Band 13, Heft 1

Three particular systems are considered where transfer of a surfactant across the interface between two immiscible liquids, water and oil, is accompanied by spontaneous oscillations of relaxation type with an abrupt decrease of interfacial tension followed by its gradual increase. These oscillations cannot be explained in the frameworks of linear stability analysis, because they are related to essentially non-linear effects. The oscillations characteristics depend on the properties of a surfactant (interfacial activity, solubility, partition coefficient, density difference between the surfactant solution and pure solvent), other solutes present in one or both liquid phases, and, usually, also on the system geometry. If the transferred surfactant is an ionic one, then, the oscillations of interfacial tension are synchronised with the oscillations of electric potential across the interface. The available hypothesis about oscillations mechanism are discussed, in particular, the model proposed recently for oscillations due to Marangoni instability by surfactant transfer from a point source located in one of the liquid bulk phases. Graphical Abstract

The structure-activity relationship analysis has been performed for trans- and cis-hydroxycinnamic acids, to determine their theoretical antioxidant pharmacophore. Based on the detailed conformational studies, the most stable rotamers have been selected. We have analyzed the descriptors of four antioxidant mechanisms important in free radical scavenging: hydrogen atom transfer, sequential proton loss electron transfer, single electron transfer - proton transfer and transition metal chelation, based on the B3LYP/6-311++G(2d,2p) calculations in vacuum and polar media. The results explain the activity difference between cinnamic acid and its derivatives. The descending order of antioxidant potential is as follows: caffeic > sinapinic ~ ferulic > p-coumaric > o-coumaric > m-coumaric ~ phenol. The results have shown that transisomers indicate higher reactivity than cis- and may be considered as good antioxidants. It has been determined that the highest antioxidant ability is related to the hydroxyl group in para position, supported by planar structure and stability of radical forms. π-Type delocalization of unpaired electron on aromatic ring, double bond and para O-atom is the key to radical stabilization. The ortho-dihydroxy substitution in benzene ring positively influences the ability to neutralize free radicals and makes caffeic acid the antioxidant pharmacophore of hydroxycinnamic acids. Graphical Abstract

Structural analysis of long chain polysaccharides by electrospray ionization mass spectrometry (ESI-MS) is challenging since these molecules do not contain readily ionizable groups. Their mass spectra are dominated by singly charged ions, limiting the detection of high molecular weight species. Derivatization can enhance ionization, but analyte loss on purification decreases sensitivity. We report a method based on nanoESI-MS and MS/MS by collision induced dissociation (CID) for underivatized long chain polysaccharides. The procedure was tested on underivatized polydisperse dextrans (average molecular weight 4,000) at 2.6 kV ESI voltage and CID MS/MS at energies between 30-60 eV. 113 ions corresponding to species from Glc 2 to Glc 35 were detected. Ions at m/z 1,409.48, 1,107.35 and 1,438.47, assigned to [G 17 +2Na] 2+ ,[G 20 +H+Na+K] 3+ and [G 35 +2H+Na+K] 4+ , were sequenced and characterized by MS/MS. The component containing 35 Glc repeats is the longest polysaccharide chain detected by ESI-MS and structurally analyzed by MS/MS without prior derivatization and/or separation. Graphical Abstract

Plants from genus Seseli, have been widely used in European traditional medicine, exhibiting antibacterial, antifungal, insect repellent, emmenogogue, antiflatulence, anti-inflammatory, antinociceptive, anti-tumor, antirheumatic activities and protective effect on human lymphocytes DNA. They usually grow on mountain rocky terrains. Part of their habitat on Vidlic Mountain, located in South-east Serbia, was struck with a large wildfire. Seseli rigidum fruit essential oils (from post fire and control areas) compositions were analyzed by GC and GC-MS, identifying monoterpenes α-pinene and sabinene as most abundant. Statistical tests showed a non-significant difference in chemical composition of these two oils, but a significant difference in comparison with the herb from a geographically different origin. Antimicrobial tests showed strong activities of the oils against tested bacteria, thus confirming its administration in various inflammation processes as a quite effective remedy. Applying DPPH. and ABTS+. radical scavenging and total reducing Fe(III) to Fe(II) power assays, antioxidant characteristics of both studied essential oils were estimated as weak, though of close values. Seseli rigidum fruit essential oil was proven as a potent inhibitor of human and horse serum cholinesterase, recognizing its possible application as neural protective agent Graphical Abstract

In the present work we have calculated several DFT reactivity descriptors for quinclorac at the B3LYP/6- 311++G(2d,2p) and MP2/6-311++G(2d,2p) levels of theory in order to analyze its reactivity. Reactivity descriptors such as ionization energy, molecular hardness, electrophilicity, condensed Fukui function and total energies were determined to predict the reactivity of quinclorac. The influence of the solvent was taken into account employing the PCM model. The results indicate that the solvation modifies the values of quinclorac reactivity descriptors. The Fukui function values predict that an electrophilic attack on quinclorac might cause a dechlorination, while a nucleophilic attack might lead to a decarboxylation and a free radical attack would cause a hydrogen substitution on the quinoline ring. Quinclorac in deprotonated form would be susceptible to decarboxylation through an electrophilic attack while nucleophilic and free radical attacks would cause an attack on the hydrogens of the ring. Graphical Abstract

Complexes ZnL 2 with novel fluorinated benzazines as tridentate ligands (HL = 6,7-difluoroquinoxalinand 6,7-difluoroquinolincarboxalidin-2-aminophenol) have been prepared. The photophisical properties of the ligands and the complexes has been studied. Graphical Abstract

The aim of the studies was to establish relationships between flavonoids and elements important for human health. Therefore, total contents of flavonoids and phosphorus were determined by UV/Vis methods, flavonoids by HPLC, and Ca, Mg, Fe, Mn, Zn and Cu by FAAS in 68 infusions of medicinal herbs. Total flavonoids content in the aqueous extracts were in the range of 0.26 - 16.40 mg per 100 mL. The mean flavonoid contents (in mg per 100 mL of aqueous extract) were 2.24, 2.01, 1.83, 1.88 for rutin, myricetin, quercetin and kaempferol, respectively. The concentrations of Ca, Mg, P were determined in mg per 100 mL, and of Fe, Mn, Zn and Cu in μg per 100 mL. Total content of flavonoids was weakly correlated with quercetin (r = 0.41), kaempferol (r = 0.53), Cu (r = 0.43), and Ca (r = -0.30). Statistically significant correlations were also found among Cu, Ca, Mn, Zn and Fe. Cluster analysis grouped the studied herbs based on total flavonoids, also four flavonoids and essential elements contents, extracted from the whole population of herbs Sambuci flos, Betulae folium, and Sylibi mariani semen. Principal component analysis confirmed these findings and enabled identification of quercetin, kaempferol, Cu and Fe as the factors responsible for differentiation of the studied material. Graphical Abstract

TiO 2 -B (bronze) nanowires were synthesized via simple hydrothermal treatment of commercial titanium dioxide nanopowder in aqueous NaOH. The reaction temperature, calcination temperature, reaction time, NaOH concentration, autoclave filing fraction and precursor were systematically varied to optimize the nanowire morphology. The crystal structure, morphology and particle size were investigated by XRD, SEM and TEM. The morphology and structure are sensitive to experimental conditions. A reaction temperature of at least 150°C and NaOH concentration at least 10 M are essential, but reaction time from 24 to 72 h makes little difference. Nanowires obtained at 150°C were 60-180 nm wide and 2-4 μm long, while those after treatment at 200°C were thinner (40-100 nm) and longer (2-6 μm). The relationship between reaction conditions and morphology is discussed and practical guidelines for titanium dioxide nanowire synthesis are suggested Graphical Abstract

Aminosilane modified silica was prepared and investigated for the adsorption of textile dyes such as C.I. Acid Orange 7 (AO7), C.I. Reactive Black 5 (RB5) and C.I. Direct Blue 71 (DB71) from aqueous media and wastewaters. The values of the sorption capacities obtained from the Langmuir isotherm model were: 5.3 mg g -1 , 58.7 mg g -1 and 72.2 mg g -1 for AO7, DB71 and RB5, respectively. The affinity series of the dyes for the modified silica can be presented as follows: C.I. Reactive Black 5 > C.I. Direct Blue 71> C.I. Acid Orange 7. The influence of anionic surfactant (SDS) and sodium chloride on dye sorption was investigated in a system containing 100 mg L -1 dye and 0.1-1 g L -1 SDS or 1-25 g L -1 NaCl. The sorption capacities decrease with increasing concentration of SDS in the solution. Retention of AO7 and RB5 was reduced in the presence of NaCl. A satisfactory agreement of the experimental data with the pseudo second-order kinetic model was found. Effectiveness of the aminosilane modified silica in raw textile wastewater purification was confirmed. Graphical Abstract

The Slovak-Czech spirit distilled from Sorbus domestica was analyzed by GCxGC with headspace solid phase microextraction and liquid-liquid extraction. Two column combinations, nonpolar × medium-polar and polar × medium-polar were tested. The second column setup provided more exploited 2D separation space with better distribution of peaks in chromatogram. Effects of the first column on the elution order of γ-lactones, benzyl esters, and unsaturated aldehydes in the second separation were observed. More than 500 compounds were detected; nearly 100 were confirmed with standards. Graphical Abstract

As V ions were removed by batch equilibrium with Fe III -loaded chelating polymers containing aminophosphinic or aminophosphonic groups. It was effectively removed As V from a synthetic wastewater as well as from a real drinking water containing 40 μg As per liter. Sorption is best described by pseudo-second order kinetics and a Langmuir isotherm. Graphical Abstract

The interactions between L-glutamic acid (Glu) and 1,7-diamino-4-azaheptan (3,3-tri) and 1,8-diamino-4-azaoktan (Spd) in metal-free systems and in the appropriate Cu(II) ions complexes were studied by potentiometric and spectral methods. The composition and overall stability constants of complexes forming in the systems studied were determined and the reactions centres were identified. In the complex formation conditions, the ligands have positive and negative reaction centres, which are also the potential sites of metal coordination. Below pH 7 in metal-free systems, the terminal amine groups from both triamines and the oxygen atoms from –C (5) OO - group as well as the amine group from Glu do not take part in the weak noncovalent interactions between the ligands, but at higher pH all available active centres of the ligands are involved in the interactions in the adducts formed and the inversion effect is observed. In the Cu(II)/Glu/triamine systems, in the species MLHL’, both 3,3-tri and Spd were found to coordinate Cu(II) ions in the same way, while only in the Cu(Glu)H(Spd) complex the oxygen atoms from –C (5) OO - group of the amino acid do not take part in metallation. In the species MLL’ and MLL’OH with 3,3-tri, the chromophore formed was of different type than that formed in the corresponding species with Spd. This is related to the fact that the nitrogen atom from the amine group of Glu is inactive in the coordination. Thus, not only the length of the polyamine carbon chain but also the length of the amino acid carbon chain influence the interactions between the bioligands. The introduction of metal ions to Glu-Spd metal-free system excludes the interaction between the bioligands, and the ligands centres that do not take part in the weak interactions in the adduct (Glu)H(Spd) are involved in the metallation, but the centres that took part in the weak interactions are not involved in the coordination in a heteroligand complex. Graphical Abstract

In spite of the long history of therapeutic use of buds from different birch species in folk medicine the existing information on their chemical composition is insufficient. The main goal was to develop a method for GC-MS determination of the chemical profile of birch buds as well as their antimicrobial activity. 150 substances of different classes were identified in Betula litwinowii buds. The volatile elements of the buds were mainly represented by sesquiterpene compounds. Ether extracts also contained other biologically active components such as flavonoids and triterpenoids. However, a particular feature of this fraction was the high content of sesquiterpene phenylpropenoids, including esters of ferulic and caffeic acids with caryophyllene-type alcohols that had not been previously found in any biological samples. Apart from carbohydrates, a series of free amino acids were detected in methanol extracts. The antimicrobial activity of the ether extracts of the buds was observed against all of the microorganisms tested, with MIC values from 0.04 to 0.08 mg mL-1 for Gram-positive bacteria and Candida albicans. However, their inhibitory activities against tested Gram-negative bacteria were rather occasional. Graphical Abstract

The immobilization of Amano Lipase A from Aspergillus niger by adsorption onto Stöber silica matrix obtained by sol-gel method was studied. The effectiveness of the enzyme immobilization and thus the usefulness of the method was demonstrated by a number of physicochemical analysis techniques including Fourier Transform Infrared Spectroscopy (FT-IR), elemental analysis (EA), thermogravimetric analysis (TG), porous structure of the support and the products after immobilization from the enzyme solution with various concentration at different times. The analysis of the process’ kinetics allowed the determination of the sorption parameters of the support and optimization of the process. The optimum initial concentration of the enzyme solution was found to be 5 mg mL-1, while the optimum time of the immobilization was 120 minutes. These values of the variable parameters of the process were obtained by as ensuring the immobilization of the largest possible amount of the biocatalyst at Graphical Abstract

Immunoactive ionic liquids (2-hydroxyethyl)ammonium 1-R-indol-3-ylsulfanyl-acetates HN+R1R2(CH2CH2OH) ∙ -O(O)CCH2S-Ind-R3-1 (1-5), were synthesized by the reaction of (2-hydroxyethyl)amines with indol-3-ylsulfanylacetic- or 1-benzylindol-3-ylsulfanylacetic acid. 1: R 1 = R 2 = CH 2 CH 2 OH, R 3 = H; 2: R 1 = СН 3 ,R 2 =CH 2 CH 2 OH, R 3 = H; 3: R 1 = R 2 = CH 3 , R 3 = H; 4: R 1 = R 2 = CH 2 CH 2 OH, R 3 = СH 2 С 6 Н 5 ; 5: R 1 = СН 3 ; R 2 = CH 2 CH 2 OH; R 3 = СH 2 С 6 Н 5 . The structure of each compound was elucidated by IR, NMR 1 H, 13 С, and 15 N techniques and their composition was confirmed by elemental analysis. The crystal structure of tris-(2-hydroxyethyl) ammonium indol-3-ylsulfanylacetate was investigated by X-ray diffraction analysis. Immunoactive properties of the title compounds were screened. Graphical Abstract

A high temperature of thermal plasma provides more efficient decomposition of the wastes in comparison to traditional combustion. Due to the high temperature and high density of energy in the plasma, the destruction rate is high, which determines a high efficiency waste decomposition. The main products of pyrolysis plasma chloroorganic compounds are pyrolysis gas and pyrolysis coke. In order to reduce carbon soot, the steam supported reaction was used. Application of plasma at a temperature range from 1000 to 1750 K enabled destruction of the chloroorganic compounds with a very good yield. Several degradation products were received , which were analyzed. In the research electric arc plasma was used in the process of pyrolysis chloroorganic waste utilization. The reactor with a rotating arc was applied. Selected chloroorganic compounds were selected as the model: chloromethane (CH3Cl), carbon tetrachloride (CCl4), chlorobenzene (C6H5Cl) and dichlorobiphenyl (PCB-C12H8Cl2). Based on the amount of the individual components, chloroorganic in the exhaust gases, and the amount introduced to the plasma decomposition, percentage yield was calculated. Research results indicated that decomposition efficiency was more than 99,8% with the exception of CCl4 pyrolysis, which in the exhaust had a content of 0.2% CCl4. Graphical Abstract

Magnesium hydroxide was prepared under controlled conditions from aqueous Mg(NO3)2 and NaOH solutions. The small, nanoplate-shaped particle size distribution was monomodal from 164 to 459 nm. Functional polypropylene/Mg(OH)2 and polypropylene/polypropylene 1% maleic anhydride/Mg(OH)2 composites were prepared containing 10% or 30% Mg(OH)2. The composites have a high Young’s modulus (twice that of polypropylene) and comparable tensile strength but less ductility. EDX examination of the fractured composite surfaces suggested a homogeneous Mg(OH)2 distribution for composites produced with the addition of polypropylene grafted with maleic anhydride. The polypropylene/Mg(OH)2 composites showed good antibacterial activity. The polypropylene/polypropylene 1% maleic anhydride/Mg(OH)2 composites were less effective. Graphical Abstract

Urea is an organic molecule present in most living organisms. Historically, it was the first organic molecule synthesized in the laboratory. In prebiotic chemistry, urea readily forms in different laboratory simulations using different energy sources. Furthermore, the role of solid surfaces, particularly minerals, might have been crucial to increase the complexity of the organic matter which may have led to the subsequent emergence of life on Earth. In this work, the radiolysis of urea in presence of a clay is studied to determine to what extent the mineral surfaces influence the decomposition of organics. The results indicate that urea is relatively stable to ionizing radiation in aqueous solutions and up to 20 kGy no decomposition is observed. Moreover, the presence of sodium montmorillonite, by a mechanism until now unknown, affects the radiolytic behavior and urea remains in the heterogeneous solution without a change in concentration even at very high doses (140 kGy). These results indicate that solids could have protected some organics, like urea, from degradation enabling them to remain in the environment on the primitive Earth. Graphical Abstract

On a first attempt, the determination of 14 C and 36 Cl activity concentrations in basic operational waste (spent ion-exchange resins and perlite mixture), in decommissioning waste (construction concrete, sand, stainless steel and serpentinite) and irradiated graphite from the Ignalina NPP has been performed. The samples for measurement of the specific activity of 14 C and 36 Cl were obtained from the selected places, where the highest values of the dose rate and the activity concentrations of gamma emitters were found. The performed study of the total 14 C and 36 Cl activity concentrations was based on estimated chemical forms of 14 C (inorganic and organic compounds) and 36 Cl as Cl- ion. The tested methods used in this study were found to be suitable for estimation of activity concentrations of measured radionuclides.

The aquation reaction of the oxydiacetate cobalt(II) complex, namely [Co(ODA)(H 2 O) 2 ]•H 2 O (ODA = oxydiacetate), induced by the Fe(III) ions as the promoter has been studied spectrophotometrically (UV-Vis). Kinetic measurements were carried out in the 283.15 - 303.15 K temperature range and at a constant ionic strength of 1.0 M (NaNO 3 ). The observed rate constants were computed by a program based on global analysis. Furthermore, the reaction activation parameters were determined using the Arrhenius and Eyring equations. The changes in the enthalpy, entropy as well as activation energy barriers were calculated in the range of 0.00125 M – 0.125 M of the Fe(III) ion concentration. Based on kinetic data a mechanism for the aquation of the [Co(ODA)(H 2 O) 3 ] complex has been proposed. Graphical Abstract

Size-segregated aerosol samples were collected using six stages High Volume Cascade Impactor. Aerosol mass and water soluble ions concentrations were determined. The Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model was used to study the origin of air masses arriving to Belgrade in the investigated period. The obtained results of aerosol mass and water-soluble ion concentrations have been divided into six sub-data sets based on air mass categories. The highest average mass concentration of the fine mode (Dp ≤ 0.49 μm) was found for air masses coming to Belgrade from the southeast and northwest directions, and of the coarse mode (3.0 < Dp ≤7.2 μm) for air masses arriving from the northwest direction. The highest concentrations of SO 4 2– were found in the fine particles transported to the investigated area by air masses from southeast direction. The analysis of contribution of marine aerosol components (Na + and Cl - ), the Correlation and Cluster Analysis indicated the influence of marine aerosol on urban aerosol of the central Balkans coming from the Western Mediterranean and northern direction. NH 4 + and SO 4 2- and K + dominated in the fine mode for all air mass categories. PCA demonstrated the dominant impact of secondary aerosol formation processes on urban aerosols. Graphical Abstract

In this work, the alkali roasting of ilmenite (FeTiO 3 ) is presented as a process route for integrated beneficiation of the mineral for rutile-rich phase and rare earth oxides; the latter is released as a consequence of physical changes in the ilmenite matrix, during the water leaching after roasting. The oxidative alkali roasting transforms ilmenite mineral into water-insoluble alkali titanate and water-soluble ferrite. After roasting the insoluble alkali titanate is separated from rare-earth oxide mixture in colloidal form and water-soluble ferrite. Further leaching of alkali titanate is carried out with oxalic (0.3M) and ascorbic (0.01M) acid solution which removes the remaining Fe 2+ ions into the leachate and allows precipitation of high-purity synthetic rutile containing more than 95% TiO 2 . Iron is removed as iron oxalate. The physico-chemical changes occurred during the roasting and leaching processes are reported by comparing the role of alkali on the roasting process and product morphologies formed.

Ionic liquid (IL) synergy with other materials may influence their properties significantly. Nevertheless, their advantageous liquid state turns out to be an impediment for applications in devices which need stable solid state shaping. In the current study we present a novel method where new siloxane functionalized IL acts as a modifier for carbon nanotubes (CNTs) and titanium alkoxide-CNT coated hybrid cotton fibers. This elaborated route carried out by interconnected and entangled ionic liquid, sol-gel and solid carbon nanotube networks opens up opportunities for functionalization of sol-gel materials with different shapes and sizes. The comparison of properties of IL, ionogel, ionogel/CNT mixture and titanium alkoxide coatings is performed. Ionogel-modified cotton fibers have increased hydrophobicity, linear density, breaking force and ultimate strength as compared to the uncoated cotton fibers. These properties are ensured even after washing threads with water. A uniformly coated CNT network around the fibers strengthens the material and increases its electric conductivity. New type of hybrids can be utilized in formulations which have UV-shielding and hydrophobic properties as well as for antibacterial properties. Characterization studies of the product were carried out by energy-dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM), optical microscopy and infrared (IR) spectroscopy. Graphical Abstract

Catalytic activity of solvothermally-synthesized hexagonal molybdenum trioxide (h-MoO 3 ) in epoxidation of 1-octene by tert-butyl hydroperoxide and the effect of deposition of metal (Ag, Pd, Cu) nanoparticles on the properties of catalyst have been investigated. It has been shown that silver-modified MoO3 demonstrates the highest catalytic activity and selectivity in the reaction of 1,2-epoxyoctane formation, whereas MoO3 modified with Pd nanoparticles exhibits worse catalytic performance than bare MoO 3 ; by contrast, copper-modified MoO 3 does not catalyze the epoxidation reaction. The Ag/MoO 3 catalyst was also found to be active in the reaction of 1-octene oxidation by molecular oxygen at the initial stage of the oxidation process. Graphical Abstract

This review classifies and analyzes over fifty heterohepta- and heterooctanuclear platinum clusters. There are eight types of metal combinations in heteroheptanuclear: Pt6M, Pt5M2, Pt4M3, Pt3M4, Pt2M5, PtM6, Pt3Hg2Ru2 and Pt2Os3Fe2. The seven metal atoms are in a wide variety of arrangements, with the most common being one in which the central M atom (mostly M(I)) is sandwiched by two M3 triangles. Another arrangement often found is an octahedron of M6 atoms asymmetrically capped by an M atom. The shortest Pt-M bond distances (non-transition and transition) are 2.326(1) Å (M = Ga) and 2.537(6) Å (M = Fe). The shortest Pt-Pt bond distance is 2.576(2) Å. In heterooctanuclear platinum clusters there are eight types of metal combinations: Pt6M2, Pt4M4, Pt3Ru5, Pt2M6, PtM7, Pt2W4Ni2, PtAu6Hg and PtAu5Hg2. From a structural point of view, the clusters are complex with bicapped octahedrons of eight metal atoms prevailing. The shortest Pt-M bond distances (non-transition and transition) are 2.651(3) Å (M = Hg) and 2.624(1) Å (M = Os). The shortest Pt-Pt bond distance is 2.622(1) Å. These values are somewhat longer than those in the heteroheptanuclear clusters. Several relationships between the structural parameters were found, and are discussed and compared with the smaller heterometallic platinum clusters Graphical Abstract

The aim of this paper is to determine the influence of Ki-67 proliferation index on somatostatin receptor scintigraphy (SSRS) with Tc-99m-EDDA-HYNIC-TOC (Tc-99m-Tektrotyd) somatostatin analogue in patients with carcinoid tumors. Sixty-one patients (31 female, 30 male; age range: 33-76 years) were examined: 13 patients highly suspected of having a carcinoid, and 48 patients who had undergone the surgical removal of the tumor. Whole body SSRS at 4 h postinjection, spot scintigrams and SPECT of the selected regions were obtained for all patients. Tc-99m-Tektrotyd scintigraphy was classified as true positive in 26 out of 30 and true negative in 24 out of 28 patients. The sensitivity of Tc-99mTc-Tektrotyd scintigraphy was found to be as high as 94.74% in the group of patients with low mitotic index Ki67 (<2%), and it progressively decreased in patients with higher mitotic index (77.78% for Ki67 2-15% and 20% for Ki67% >20%). The likelihood of Tc-99m-Tektrotyd scan being positive when a carcinoid is present was found to be inversely proportional to the value of Ki67 proliferation index. The results showed that Tc-99m-Tektrotyd SSRS is a sensitive method for diagnosing and staging patients with well-differentiated carcinoid tumors. However, in poorly differentiated tumors with high Ki67 proliferation index, additional analyses are necessary for precise staging.

A potentiometric titration method (PT) and a stopped-flow kinetic technique monitored by a UV−Vis spectroscopy have been used to characterize the stability of series of Co(II)- and Ni(II)-thiodiacetato complexes, M(TDA), in the presence of 1,10-phenanthroline (phen) or 2,2’-bipyridine (bipy) in aqueous solutions. The stability constants of the binary (1:1), ternary (1:1:1) as well as the resulting hydroxo complexes were evaluated and compared to the corresponding oxydiacetate complexes. Based on the species distribution as a function of pH the relative predominance of the species in the system over a pH range was discussed. Furthermore, the kinetic measurements of the substitution reactions of the aqua ligands to phen or bipy in the coordination sphere of the binary complexes M(TDA) were performed in the 288–303 K temperature range, at a constant concentration of phen or bipy and at seven different concentrations of the binary complexes (0.2–0.5 mM). The kinetic stability of the M(TDA) complexes was discussed in relation to the experimental conditions and the kind of the auxiliary ligands (phen/bipy). Moreover, the influence of the type of primary ligand (thiodiacetate/oxydiacetate) on the substitution rate of the auxiliary ligands was also compared. Graphical Abstract

Some efficient polymer-supported platinum catalysts have been synthesized through the novel application of epoxy resin D.E.R.TM332 cured with polythiourethanes. Epoxide supports were obtained as a result of the use of polythiourethane hardeners. The activity, stability and selectivity during long-term use of the investigated catalytic systems were tested in a hydrogenation reaction of cinnamaldehyde. The results of this study indicate that polythiourethanes used to cure epoxy resin can also greatly affect the catalytic properties of the epoxide-supported platinum catalysts. To fully characterize both polymeric supports and heterogenized catalysts numerous research methods like time-of-flight secondary ion mass spectrometry (ToF-SIMS), infrared spectroscopy (IR), X-Ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM-EDX) and nitrogen BET surface area measurements were used. Graphical Abstract

The major aim of the newly adopted Mercury Convention is to reduce global mercury (Hg) emissions to the environment. In high temperature industrial processes, including coal combustion, Hg compounds present as impurities in solid materials are decomposed and evaporated leading to the emission of Hg to the atmosphere. The behaviour of different Hg compounds and their mixtures during heating have been the subject of numerous studies, and is the topic of the present work. Controlled heating can be used to fractionate Hg compounds in solid substrates, offering the possibility of identification and quantification of Hg compounds. In the attempt to develop a method for temperature fractionation of Hg, experiments were conducted with pure Hg compounds, and the compounds mixed with different substrates (SiO2 and CaSO4 • 2H2O), for calibration purposes. Detection was performed by two methods, namely Cold Vapour Atomic Absorption Spectrometry (CV AAS) with Zeeman background correction, and Nier-type Mass Spectrometry with a Knudsen cell (MS). Further investigation is in process. Graphical Abstract

This review classifies and analyses fifty heteronona- and heterodecanuclear Pt clusters of metal composition: Pt4Ru5, Pt3Ru6, Pt20sr PtRh8, PtAu8; Pt6M4, Pt5M5, Pt4M6, Pt3M2, Pt2M8, PtM9, Pt3Ru6M and PtAu8M. There are nine different heterometals: M = Ru, Au, Ag, Cu, Hg, Os, Rh, Ir and Fe, of which Ru and Au are the most frequent. The clusters crystallize mostly into two crystal classes, monoclinic (74%) and triclinic (18%), and their structures are complex. Three triangular layers of nine metal atoms arranged in the form of a face-shared bioctahedron are common in the series of heterononanuclear clusters. In the series of heterodecanuclear clusters distorted skeletal icosahedrons, where a central platinum atom is surrounded by nine metal atoms, and face (edge) shared (fused) bioctahedral cluster of the metal atoms are the most common. The most frequent ligands are CO and PPh3. The shortest metal-metal bond distances are: 2.540(4) Å (Pt-Fe), 2.580(2) Å (Ru-Ru), 2.584 Å (Pt-Pt) and 2.629(4) Å (Cu-Au). Several relationships between the structural parameters were found and are discussed. Some clusters contain two crystallographically independent molecules within the same crystal and are examples of distortion isomerism. Graphical Abstract

A simple and selective differential pulse anodic stripping voltammetry (DPASV) method for the determination of Ag+ and Cu2+ ions in mixture samples obtained in the microwave assisted polyol process was developed and validated. Analytical methods for the preparation of the reaction mixture for voltammetric analysis (dilute samples in the supporting electrolyte) were worked out and optimized. All measurements were conducted in three-electrode cell system equipped with glassy carbon electrode (GCE) as a working electrode, silver/silver chloride (Ag|AgCl|KCl(sat.)) as a reference and platinum wire as a auxiliary electrode. The optimal conditions for quantitative determination were obtained in an mixture Britton–Robinson buffer at pH 4.1 / ethylene glycol (100/1; v/v). The calibration curves of analysed compounds are linear within the range of concentration: 0.032 − 0.420 μg mL-1 and 0.075 − 0.960 μg mL-1 for Ag+ and Cu2+, respectively. Good linear behaviour over the investigated concentration ranges were observed with the values of r2 higher than 0.996 for the silver and cooper ions. The accuracy of analytical determinations ranged from 0.4 to 3.6%. The levels of analysed ions in the reaction mixture can be successfully determined using this developed method with no matrix effect. Graphical Abstract

This paper reports the synthesis and investigation of a polymer composite based on poly(4-styrenesulfonic acid) (PSSA) and polyaniline (PANI) directly obtained in an aqueous PSSA medium, with improved conductivity and solubility in polar solvents. The oxidative polymerization reaction of aniline takes place in-situ with PSSA as protonating agent. The synthesis was tested at three PSSA/PANI molar ratios, an intense green colored aqueous composite solution being obtained in each case. For comparison purposes, commercially available polyaniline and PSSA were also investigated. PSSA-PANI composites, PANI and PSSA were investigated through thermal analysis, Fourier Transform Infrared Spectroscopy (FTIR) and Raman spectroscopy. Thin films of PSSA/PANI complex were spin coated on glass substrates which were further investigated through Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). Also, thin films of PSSA-PANI were deposited on interdigitated electrodes for dielectric measurements. Graphical Abstract

A well network at a potential new nuclear site in Lithuania examined a semi-confined intertill aquifer 10–19 m deep and an unconfined aquifer 4.5–9 m deep. Tracer results indicate a northwest flow direction and great hydraulic connection between observation and injection wells. Natural conditions affect tracer flow velocities. Graphical Abstract

Consecutive hydroconversion of acetic acid (AA) to ethanol was compared over monometallic and novel bimetallic (containing In as guest metal) catalysts on alumina and silica supports (inter alia highly ordered SBA-15) of different porosity and pore structure. The transformation was studied in a fixed bed, flow-through reactor in the temperature range of 220–380°C using hydrogen flow at 21 bar total pressure. AA hydroconversion activity of Cu and Pt catalysts and the yield of selectively produced alcohol were increased drastically by applying SBA-15 as highly ordered, mesoporous silica support instead of alumina. The most active nickel catalysts do not allow the selective addition of hydrogen to carbon-oxygen bonds independently of supports producing mainly CH4; however, indium doping can completely eliminate the hydrodecarbonylation activity as found in earlier studies. The textural properties of studied silica supports of various textures such as SBA-15, CAB-O-SIL, and Grace Sylobead have a profound impact on the catalytic performance of Ni and Ni2In particles. Graphical Abstract

In many countries, spent nuclear fuel is considered as a waste form to be disposed of in underground disposal. Under deep host rock conditions, a reducing environment prevails. In the case of water contact, long-term radionuclide release from the fuel depends on dissolution processes of the UO2 matrix. The dissolution rate of irradiated UO2 is controlled by oxidizing processes facilitated by dissolved species formed by alpharadiolysis of water in contact with spent nuclear fuel. To understand the effect of the radiation, the information of the dose rate at the surface of the fuel and its proximity is needed. α particles contribute strongly due to their high linear energy transfer. However, their dose rate and the energy deposition at the fuel surface are difficult to measure. Cylindrical fuel pellets as used in fuel rods show specific features, such as the rim zone, where a higher Pu concentration and a different porosity of the fuel matrix is present. The a particle dose rate was determined by simulations with the code MCNPX with focus on the rim zone of a pellet. As a result a 40% increased dose level in the rim zone exists in comparison to the center of a pellet. The potential dominant and inhomogeneous α-dose distribution is supposed to have a strong impact on radiolysis phenomena and in turn on an inhomogeneous dissolution of elements over the surface.

In stoichiometric network analysis (SNA) the instability condition is calculated by the current rates. Recently, we have shown that in the final result the current rates can be substituted by reaction rates, which is a more appropriate value for the examination of instability from experimental point of view. Here, we elaborate the problem of whether the current rates are necessary parameters in the calculation, with the aim of obtaining the region of instability. All calculations are performed on a model for Belousov-Zhabotinsky (BZ) reaction, which has not been examined by SNA.

The natural radionuclide ( 238 U, 226 Ra, 232 Th and 40 K) contents in soil were determined for three different regions of Bulgaria using high-resolution gamma-ray spectrometric analysis. A comparison of the dynamics of their behavior throughout the years was performed. Bulgaria is a country with intensive uranium mining activities. That is why radiological monitoring of closed uranium mining facilities in different regions of the country are obligatory and of great interest. This work presents results from such investigations made in regions where remediation was necessary. The results have been evaluated according to Bulgarian radionuclide environment contamination legislation. Graphical Abstract

Anodic oxidation of VT1-0 titanium and E-125 zirconium alloy in aqueous electrolyte solutions based on H 2 SO 4 and K 4 P 2 O 7 was used to obtain oxide coatings composed of Zr/ZrO 2 , Ti/TiO 2 , and mixed oxide systems Ti/Ti n O m ∙ Zr x O y . It was shown that, depending on the electrolyte рН, the films contained from 0.17 to 2.1% wt. of zirconium. The catalytic activity of the synthesized coatings in the oxidation reaction of the methyl orange azo dye under UV irradiation was established. The process rate constants and synergy factors for the mixed systems were calculated.

A novel synthesis route for the fabrication of p-type nanostructured skutterudite, FexCo1-xSb3 in large quantity is reported. This scalable synthesis route provides nano-engineered material with less impact on the environment compared to conventional synthesis procedures. Several Fe substituted compositions have been synthesized to confirm the feasibility of the process. The process consists of a nano-sized precursor fabrication of iron and cobalt oxalate, and antimony oxides by chemical co-precipitation. Further thermochemical processes result in the formation of iron substituted skutterudites. The nanopowders are compacted by Spark Plasma Sintering (SPS) technique in order to maintain nanostructure. Detailed physicochemical as well as thermoelectric transport properties are evaluated. Results reveal strongly reduced thermal conductivity values compared to conventionally prepared counterparts, due to nanostructuring. P-type characteristic was observed from the Seebeck measurements while electrical conductivity is high and shows metallic behavior. The highest TE figure of merit of 0.25 at 800 K has been achieved, which is strongly enhanced with respect to the mother compound CoSb3. This suggests the promise of the utilized method of fabrication and processing for TE applications with improved performance. Graphical Abstract

The homogeneity of fertilizer samples for interlaboratory γ-ray spectrometry comparison was tested by determination of the total γ count rate and the count rates for two 238 U γ lines, one 40 K line and one common 235 U and 226 Ra line. Homogeneity testing was accomplished by determination of the minimum, maximum, mean and standard deviation for each parameter and comparison of their standard deviations with predefined tolerances, by Cochran’s test, and by a one-way ANOVA. The standard deviations were all less than these tolerances. All samples passed Cochran’s test and the one-way ANOVA test for homogeneity. Graphical Abstract

[M+CuCl+H] 2+ ions were generated using electrospray ionization (ESI); where M is a molecule of 3,5-bis(2,2’-bipyridin-4-ylethynyl)benzoic acid or its methyl ester (1 and 2, respectively). The ions were subjected to CID-MS/MS analysis. It was found that their gas phase decomposition lead to the formation of rare di-cations [M] 2+ , namely [1] 2+ and [2] 2+ ions. The formation of [1] 2+ ion from [3+H+CuCl] 2+ ion in the second fragmentation, where 3 is ethyl ester of 3,5-bis(2,2-bipyridin-4-ylethynyl)benzoic acid, was also observed since in the first fragmentation step the loss of ethylene molecule from [3+H+CuCl] 2+ ion took place. To the best of our knowledge, it is the first time that [M] 2+ ions formation from respective metal complexes has been reported. It is also unusual that formation of [M] 2+ ions is not accompanied by formation of [M] +∙ ions. Furthermore, as expected, theoretical calculation and electron ionization mass spectra show that 1 and 2 are not especially prone to form [M] 2+ ions. Thus formation of [M] 2+ ions under CID conditions is very surprising. Graphical Abstract

Measurement of the gross alpha and beta activity concentrations in various matrices is suitable as a preliminary screening procedure to determine whether further analysis related to specific radionuclide is necessary. In Serbia, according to current regulations, radioactivity concentrations in drinking water for gross alpha and gross beta should be < 0.5 and < 1.0 Bq L −1 , respectively. The generally accepted methods for gross alpha and beta activity analysis of drinking water in different countries are: EPA 900.0 and ISO methods (ISO 9696, water quality – measurement of gross alpha activity in non-saline water – thick source method, and ISO 9697, water quality – measurement of gross beta activity in non-saline water). This paper describes comparison of preparations and measurement gross alpha and beta activity in bottled mineral waters as well as in tap waters in Serbia using two methods: EPA 900.0 with and without ash, and ISO methods. Concentration of total dissolved solids (TDS) in investigated water samples was determined. Based on obtained TDS, certain volume was evaporated. The instrumentation used to count the gross alpha and gross beta activities for both methods is α/β low level proportional counter Thermo Eberline FHT 770 T. Graphical Abstract

Glycosylation of biomolecules is one of the most prevalent post- and co-translational modification in a human body, with more than half of all human proteins being glycosylated. Malignant transformation of cells influences glycosylation machinery resulting in subtle changes of the glycosylation pattern within the cell populations as a result of cancer. Thus, an altered terminal glycan motif on glycoproteins could provide a warning signal about disease development and progression and could be applied as a reliable biomarker in cancer diagnostics. Among all highly effective glycoprofiling tools, label-free electrochemical impedance spectroscopy (EIS)-based biosensors have emerged as especially suitable tool for point-of-care early-stage cancer detection. Herein, we highlight the current challenges in glycoprofiling of various cancer biomarkers by ultrasensitive impedimetric-based biosensors with low sample consumption, low cost fabrication and simple miniaturization. Additionally, this review provides a short introduction to the field of glycomics and lectinomics and gives a brief overview of glycan alterations in different types of cancer. Graphical Abstract

Concentrations of several heavy metals in soil, water and grape samples (variety Plovdina) collected at five locations at different distances from the road in Southeast Serbia were determined using the Flame Atomic Absorption Spectrophotometry. There was a decrease in analyzed samples with an increase in distance from the road. A complete absence of several examined, very harmful heavy metals (Mn, Ni, and Cd) in all analyzed samples was found. The analysis of grape samples proved the presence of iron, zinc and copper in concentration ranges 3.3-19.8, 0.31-0.63, and 3.4-13.6 μg g -1 , respectively. The content of heavy metals in soil, water and grapes were below allowable limits. Correlation analysis showed a significant relationship between the concentrations of metals in soil and grape samples. Graphical Abstract

Activated carbon monoliths with different surface characteristics were prepared by impregnating oil palm stone with diluted aqueous CaCl 2 solutions (with concentrations between 2 and 7% w/v) without binders. The solids were characterized by determination of nitrogen adsorption isotherms at 77 K and carbon dioxide adsorption isotherms at 273 K using volumetric adsorption equipment. Surface area and micropore volume values were calculated from the nitrogen isotherms using the BET and DR models, respectively, obtaining solids with low percentages of mesoporosity. Immersion enthalpies of the activated carbon monoliths were determined in benzene, with values between -173 and -104 J g -1 , and water, with values between 61 and 30 J g -1 , indicating that the monoliths have a hydrophobic character. Graphical Abstract

This work is a systematic review of the literature over the past decade of the application of activated carbon (microporous or mesoporous) as adsorbents for the removal of heavy metals, focusing especially on lead (Pb) and arsenic (As) ions from the aqueous phase. Classical examples from our lab are also given. Activated carbon is known to provide a high surface area for adsorption. Generally, surface modification is typically required, such as oxidation, treatment with ammonia or even impregnation with ferric ion, etc. and the adsorbent material may originate from various sources. The pristine materials, after modification and those after batch-wise adsorption, were characterized by available techniques (BET analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, thermal analyses, X-ray photoelectron spectroscopy). Adsorption isotherms, thermodynamics and kinetics of the process are also discussed. Selected studies from the literature are examined in comparison with other adsorbents. The role of chemistry in the metals adsorption/removal was investigated. Graphical Abstract

This review classifies and analyzes over thirty heterooligonuclear platinum clusters with a wide variety of metal frameworks, from twelve to forty-four. There are thirteen heterometals (Ge, Sn, Hg, W, Mo, Ru, Rh, Pd, Os, Ni, Cu, Ag, Au) which are the partners of platinum. The clusters mostly crystallize in monoclinic (36,4%) and triclinic (30,3%) crystal classes. Their structures are complex, with platinum most commonly preferring interstitial sites, such as the centroids of icosahedrons. There are examples of distortion isomerism. The most common ligands are CO and PPh3, and it is interesting that the mean Pt-CO and M-CO bond distances are identical at 1.84 Å. In contrast, the mean Pt-μCO and M-μCO are of values of 2.02 and 1.97 Å, respectively, while the Pt-PPh3 and M-PPh3 bond distances are 2.30 and 2.28 Å, respectively. The shortest Pt-Pt, Pt-M (non-transition) and Pt-M (transition) bond distances are 2.559(2) Å, 2.412(2) Å (M = Ge) and 2.510(2) Å (M = Ni). Graphical Abstract

The purpose of this study was to investigate the structural and morphological properties of hydroxyapatite – zinc oxide (HA-ZnO) powders prepared to be used in an endodontic sealer formulation. The HA-ZnO was synthesized from hydroxyapatite (HA) in the presence of zinc oxide (ZnO) sol. The starting reagents were CaO, H 3 PO 4 and a suspention of ZnO (25% in water). Following precipitation, the obtained sol was subjected to heat treatment at 110°C, 400°C, 850°C and 1050°C. The study focused on the influence of the thermal treatment on the cristallinity of precipitated powders. X-ray diffraction was used in order to study the structural properties of the obtained powder. Fourier Transform Infrared Spectroscopy (FT-IR) was used in order to evaluate the interactions between HA and ZnO. The morphology of the samples was studied by Scanning Electron Microscopy (SEM). Transmission Electron Microscopy and High Resolution Transmission Electron Microscopy (TEM, HRTEM) were used for the determination of particle size and fractal analysis. The fractal analysis of images using the standard box-counting method is presented and the results are discussed. It was demonstrated that the fractal dimension analysis is a useful method to quantitatively describe the complex microstructures and it can reveal the relation between fractal parameters. Graphical Abstract

Ab-initio calculations using density functional theory (DFT) are used to investigate the non-covalent interactions between single wall armchair boron nitride nanotubes (BNNTs) with open ends and several heterocyclic molecules: thiophene (T; C 4 H 4 S), benzothiophene (BT; C8H6S) and dibenzothiophene (DBT; C 12 H 8 S). In the armchair model the nanotubes exhibit (n, n) chirality; here we consider n = 5. The exchange-correlation energies are treated according to the Hamprecht-Cohen-Tozer-Handy functional in the generalized gradient approximation (HCTH-GGA). A base function with double polarization is used. The geometry optimization of (5,5) BNNT-X; X = T, BT and DBT has been carried out using the minimum energy criterion in 5 different configurations of the molecules adsorbed on the nanotube. Our computer simulations have found that the preferential adsorption site of the molecule on the nanotube surface is the parallel configuration for BT and DBT, and at one nanotube end for the T fragment, with all cases having physical interactions. The polarity exhibits an increase which favors the possible dispersion, provided the electrons are polarized. The nanostructure functionalization increases the chemical reactivity which in turn enhances interactions between the molecule and the nanotube. The BNNT-dibenzothiophene work function reduction as compared with the pristine case yields the improvement of the field emission properties. Graphical Abstract

Dye pollution in waste waters causes serious environmental and health risk, legislation problems and is a serious challenge to environmental scientists. In this work the treatment of waste waters resulted from ink jet cartridges manufacturing, using different nanocrystalline ferrites M II Fe 2 O 4 (M II = Mg, Cu) as adsorbent materials, has been investigated. The ferrites were obtained by thermal decomposition at 500°C of the magnesium and copper ferrioxalate coordination compounds. The nanocrystalline ferrites powder was investigated by various methods such as XRD, IR, SEM and EDX. The discoloration of the waste waters has been spectrophotometrically studied. The ferrites could be removed easily after adsorption by using a magnetic filtration process. The results indicated that the maximum adsorption efficiency was obtained after 60 min of treatment, magnesium ferrite showing a higher efficiency than the copper ferrite in the treatment process of waters resulted from ink jet cartridges manufacturing. Graphical Abstract

Dummy molecularly imprinted mesoporous silicates (MIMS-2) were made by co-condensation of tetraethyl orthosilicate (TEOS) with precursors of bi-functional mimic of 2-naphthol, 2,7-dihydroxynaphthalene, around triblock copolymer surfactant Pluronic (P123) micelles. The bi-functional template was linked to two functional monomers through thermally cleavable covalent bonds to generate imprint precursor. This provides the possibility of incorporating the target into the cross-linked mesoporous silicate matrix in the non-ionic surfactant templated sol-gel process. P123 was eluted by ethanol extraction and template molecules were removed by refluxing the materials in a mixture of dimethyl sulfoxide (DMSO) and water. MIMS-1 was prepared similarly except that 2-naphthol was used as template instead of 2,7-dihydroxynaphthalene. Solid phase extraction studies showed that MIMS-2 exhibited good retention and selectivity for 2-naphthol among its structural analogues. The mono-functional molecule 2-naphthol was unable to be incorporated into the silica matrix of mesoporous material by the identical method, and the resulting material MIMS-1 exhibits poor selectivity to the template analogues. Graphical Abstract

A QuEChERS in house method for determining the marker residue of eprinomectin (eprinomectin B 1a ) by HPLC-FLD in bovine tissues and milk provided from treated animals was developed and applied. Briefly: all samples were extracted with acetonitrile using a dispersive SPE purification stage. The ascertained detection limits were 1 μg kg -1 and the quantification limits 2 μg kg -1 . Recoveries on tissue samples fortified in the range of 10 μg kg -1 to 200 μg kg -1 were from 80.0% to 87.2%, with variation coefficients between 2.7% to 10.6%. The confirmation of residues in the purified extracts was made by LC-MS/MS after separation on an XTerra MS C18 (10 cm × 2.1 mm, 3.5 μm) column with a mobile phase of acetonitrile / formic acid 0.1% (97:3, v/v) at a flow rate of 0.2 mL min -1 and MRM monitoring of three characteristic ions (m/z 896.1, m/z 467.9 and m/z 329.9), resulting from the fragmentation of molecular ions [M-H]+ (m/z 914.6) of eprinomectin and the comparison of the abundance ratio of fragmented ions was obtained in the booth, sample and standard at comparative concentrations. In conclusion, this method has proven its advantage and versatility as a routine drug residues analysis method. Graphical Abstract

This review covers heteropolynuclear platinum complexes. There are over sixty examples with heterometal atoms as partners including non- transition metals, K, Cs, Mg, Ca, Sr, Tl, Sn, Pb, Zn, Cd, and transition metals: Cu, Ag, Fe, Co, Ni, Rh and Pd. In addition, there are examples for the lanthanides, Eu and Yb. The most common are Ag (x16) and K (x14). The predominant geometries for Pt(II) is square-planar and for Pt(IV) is octahedral. The overall structures are complex. In spite of the wide variety of heterometal atoms partners of platinum, there is “real” Pt-M bonds only with silver, ranging from 2.678 to 2.943(I) Å (ave 2.855 Å). The mean Pt-Pt bond distance is 2.869 Å. Graphical Abstract

Separation of a methane/nitrogen gas mixture was investigated by means of carbon molecular sieves (CMS) obtained from a newly discovered “green” resource: Salix viminalis . This plant grows quickly, yields hard wood and is frequently cultivated for energy purposes (renewable green fuel). Unconventional applications such as charcoal fabrication using this sort of wood are very rare. Carbonization of the wood (1–3 h, 600–700°C) yields carbons with a very narrow pore size distribution (determined by N2 adsorption at -196°C) resembling a perfect CMS. The diameter of most pores (ca. 0.8 nm) is comparable to the size of simple molecules, thus enabling separation. The sieving effect was proven in an industrially important process of CH 4 /N 2 separation at 30–70°C. Despite relatively minor differences of the size of the molecules, the experiment demonstrated that separation factors are placed in the range 3.64–10.20. Additional experiments involving krypton proved that the separation mechanism is based on a geometric factor i.e. the known size and shape of the molecules under separation. Graphical Abstract

Slow-release microencapsulated N, P, and K fertilizer synthesis was optimized and the products exhaustively characterized. Four NPK formulations with nutrient mass ratios of 1:0:0, 1:1:0, 1:1:1, and 2:1:1 were characterized following European Council Regulation 2003/2003 for fertilizers as well as ICP-AES, 1H-NMR, FT-IR, HPLC, elemental analysis, XPS, SEM, dynamic light scattering, thermogravimetry, differential thermogravimetry, activity index, and leaching rate. These fertilizers have good slow-release properties and decrease waste and crop contaminants, improving environmental protection. Compared to classic granulated fertilizers, plant nutrient availability was improved allowing reduced application. Nutrient leaching parameters describing four different kinetic models were evaluated. Graphical Abstract

The cellulose matrix was characterized by FTIR, 13 C NMR, XRD, TG, SEM and applied in the removal of the reactive red RB dye in an aqueous medium, with a capacity of adsorption at a pH of 2.0, and an adsorption equilibrium time which was reached at around 200 mins. The kinetic study for the system followed the Elovich model. The adsorption isotherms for the system at temperatures of 35°C, 45°C, and 55°C were adjusted to the Langmuir, Freundlich, Sips, and Redlich-Peterson non-linear models, with a capacity of adsorption for adsorbent of 5.97 mg g -1 , 5.64 mg g -1 , and 4.62 mg g -1 , respectively. The adsorption occurred by electrostatic interactions and it was favorable and spontaneous, with the influence of temperature.

Backround: The present review focuses on electrochemical methods for antioxidant capacity and its main contributors assessment. The main reactive oxygen species, responsible for low density lipoprotein oxidation, and their reactivity are reminded. The role of antioxidants in counteracting the factors leading to oxidative stress-related degenerative diseases occurence, is then discussed. Antioxidants can scavenge free radicals, can chelate pro-oxidative metal ions, or quench singlet oxygen. When endogenous factors (uric acid, bilirubin, albumin, metallothioneins, superoxide dismutase, catalase, glutathione peroxidase, glutathione reductase, glutathione-S-transferase) cannot accomplish their protective role against reactive oxygen species, the intervention of exogenous antioxidants (vitamin C, tocopherols, flavonoids, carotenoids etc) is required, as intake from food, as nutritional supplements or as pharmaceutical products. Literature study: The main advantages of electrochemical methods with respect to traditional, more laborious instrumental techniques are described: sensitivity, rapidity, simplicity of the applied analytical procedure which does not require complicated sample pre-treatment etc. The paper reviews minutiously the voltammetric, amperometric, biamperometric, potentiometric and coulometric methods for total antioxidant capacity estimation. For each method presented, the electroactivity and the mechanism of electro-oxidation of antioxidant molecules at various electrodes, as well as the influences on the electroactive properties are discussed. The characteristics of the developed methods are viewed from the perspective of the antioxidant molecule structure influence, as well as from the importance of electrode material and/or surface groups standpoint. The antioxidant molecule-electrode surface interaction, the detection system chosen, the use of modifiers, as well as the nature of the analysed matrix are the factors discussed, which influence the performances of the studied electrochemical techniques. Conclusions: The electrochemical methods reviewed in this paper allow the successful determination of the total antioxidant capacity and of its main contributors in various media: foodstuffs and beverages, biological fluids, pharmaceuticals. The advantages and disadvantages of the electrochemical methods applied to antioxidant content and antioxidant activity assay are treated and interpreted, in the case of various analysed matrixes. Combining advanced materials with classical electrode construction, provides viable results and can constitute an alternative for the future. Graphical Abstract

The present work deals with nitrogen-doped stoichiometric TiO2:N and non-stoichiometric TiO2−x:N thin films deposited by means of dc-pulsed reactive sputtering for application as photoanodes for hydrogen generation from water, using solar energy. Stoichiometric thin films of TiO2 crystallize as a mixture of anatase and rutile while rutile phase predominates in TiO2:N at higher nitrogen flow rates as shown by X-ray diffraction at grazing incidence, XRD GID. Lack of bulk nitridation of stoichiometric TiO2:N is indicated by valence-to-core X-ray emission spectroscopy, XES, analysis. The energy band gap as well as flat band potential remain almost unaffected by increasing nitrogen flow rate in this case. In contrast to that, non-stoichiometric thin films of TiO2‑x:N demonstrate systematic evolution of the structural, morphological, optical and photolectrochemical properties upon increasing level of nitrogen doping. Pronounced changes in the growth pattern of non-stoichiometric TiO2-x:N upon varied nitrogen flow rate, demonstrated by scanning electron microscopy, SEM, can be easily correlated with the crystallographic properties studied by XRD GID. Relative positions of Kβ’’ XES lines of the TiO2-x:N thin films, which depend strongly on the nature of the ligands and their local coordination, change with the increasing nitrogen flow. Doping of nonstoichiometric titanium dioxide with nitrogen shifts the absorption spectrum towards the visible range and increases considerably the flat band potential which is beneficial for water photolysis. Graphical Abstract

Micellar liquid chromatography (MLC) is a simple well-established branch of high-performance liquid chromatography. The applications of MLC for the determination of numerous compounds in pharmaceutical formulations, biological samples, food, and environmental samples have been growing very rapidly. MLC technique has several advantages over other techniques, such as simultaneous separation of charged and uncharged solutes, rapid gradient capability, direct on-column injection of physiological fluids, unique separation selectivity, high reproducibility, robustness, enhanced luminescence detection, low cost, and safety. This review is devoted to the evaluation of the agreement of MLC with the principles of green chemistry which recently represents a universal trend. Also, it provides an overview on the basics of MLC, in addition to a survey of MLC methods published in the past five years for the assay of various compounds in different matrices. Graphical Abstract

This study determines the basic parameters of Monod kinetics for microbial growth within a membrane bioreactor using the Zenon ZeeWeed 10 MBR system. The influent nitrate concentration was kept at 70 ± 2 mg L -1 NO 3 ˉ . During the experiments a constant concentration of activated sludge was maintained at approximately 0.76 g L -1 under anoxic conditions. Sucrose was added to the activated sludge as a carbon source. The Monod kinetic parameters were calculated by numerical interpolation, by considering experimental data. The maximum specific growth rate of the biomass was determined to be 0.31 h -1 , half-saturation constant 5.4 mg L -1 , and yield coefficient 0.35 mg biomass mg -1 COD. Afterwards, a dynamic simulation was performed within the calculated parameters. The dynamic concentration profiles for substrate and biomass were determined at different dilution rates within the range of 0.8 to 5 d -1 . Graphical Abstract

The structural changes induced in extra virgin olive oil (EVOO) by adulteration with soybean oil (SBO) and heat treatment at 185°C for 4 and 8 h were investigated using Attenuated Total Reflectance – Fourier Transform Infrared (ATR-FTIR) spectroscopy. Our results revealed that the band around 3006 cm–1 recorded shifts versus the percentage of adulterant. The changes in the absorbance at 3006 cm −1 (A3006) and in the ratio of the maximum heights of the bands at 3006 and 2925 cm −1 (A3006/A2925) were used to evaluate the EVOO adulteration. The regression analysis of A3006 and A3006/A2925 versus the percentage of adulterant was used to calculate the detection limits of adulteration. The time course of spectral changes showed that the oil heating caused notable modifications in the intensity of the absorption bands and induced no shifts in their exact position. The most relevant changes were reflected by conjugation and cis-trans isomerisation of double bonds, the formation of epoxides and widening of the band in the C=O region due to formation of secondary oxidation products. This study highlights that ATR-FTIR spectroscopy may be a promising means to differentiate among pure and adulterated oils and to study the thermooxidative processes in oils undergoing thermal stress. Graphical Abstract

This work was aimed at testing gastroprotective effects of Centaurea cyanus L. (herba) polysaccharides (P) and polyphenols (A) fractions on stress-induced rat ulcer model. Studies evaluating acute toxicity in rats and antioxidant (chemiluminescence method) and antimicrobial (on Staphylococcus aureus ATCC6538 and Escherichia coli ATCC8739 strains) activities of Centaurea cyanus L. ( herba ) product, which combined polysaccharides and polyphenols fractions (PA), have also been done. Accordingly, in vivo pharmacological studies revealed high influence of PA product (500 mg kg -1 of body weight) on deep, moderate and superficial gastric mucosal lesions, greater than that of chemical reference, Ranitidine. P product was proven more effective than Ranitidine in opposing the emergence of deep necrotic lesions only, suggesting the ability of polysaccharides compounds to consolidate gastric mucous layer as well as their certain tendency for cooperation with polyphenols fractions. The acute toxicity study indicated the lack of toxicity of PA product and maximum tolerated doses greater than 1875 mg kg -1 of body weight. PA product provided augmented scavenger activity and week antimicrobial activity on Staphylococcus aureus ATCC6538 and Escherichia coli ATCC8739 strains, resulting in better opportunities for valorisation of the aerial part of Centaurea cyanus L. species in order to obtain new and effective natural medicines.

The time-resolved fluorescence quenching method was applied to determine the micelle aggregation number of cationic single-chain surfactants dodecyltrimethylammonium bromide (DTAB), cetyltrimethylammonium bromide (CTAB) and anionic surfactant sodium dodecyl sulfate (SDS). The concentration dependence of micelle aggregation number was found to be linear for all investigated surfactants in the concentration range 2‒15 × the value of critical micelle concentration of the respective surfactant. The values of micelle aggregation number were found in the range 30‒77. Different trends in the linear concentration dependence of micelle aggregation number were observed for cationic surfactants and for the anionic surfactant SDS. A small slope value was found for cationic surfactants, while the SDS micelle aggregation number concentration dependence showed significantly a larger slope value. The aggregation number increase with the increasing SDS concentration results in the micellar growth. Results from a simple analysis based on computer models of cationic and anionic surfactant molecules with dodecyl chains supports, the formation of intramicellar hydrogen bonding between surfactant molecules in SDS micelle shell. Graphical Abstract

Theoretical studies of the intermolecular potential energy surfaces (PESs), the intermolecular vibrational states and the wavefunctions for the C 3 -Ar complex have been performed at the CCSD(T) level with four different basis sets,. Each PES can be characterized by two symmetrical T-shaped global minimum at ɵ = 75° and ɵ = 105°, a saddle point between them at ɵ = 90°, and two collinear saddle points at ɵ = 0° and ɵ = 180°. Moreover, we also calculated the intermolecular vibrational frequencies and the average structural parameters of the ground vibrational states for the C 3 -Ar complex. The vdw bending and stretching frequencies are calculated to be 8.682 and 34.511 cm-1, which are in agreement with the experimental results and a more accurate result was determined for the bending mode. Studies show that the larger the basis set is used, the more accurately the results are calculated. Graphical Abstract

Microtubular Solid Oxide Fuel Cells (mSOFCs) are one of the most promising and efficient devices that convert chemical energy of fuels into electrical energy. However, mSOFC stacks work at high operating temperature over 650°C, which leads to thermally induced mechanical stresses and in consequence may cause failure of stack components. In order to reduce the local thermal gradients and prevent high stresses in the stack components, it is desirable to study the effect of stack design on its performance. For this purpose a 3D numerical approach was developed to estimate thermal expansion of fuel cell inside an mSOFC stack and to reduce the associated experimental efforts and costs. Initially, a Computational Fluid Dynamics (CFD) model was used to calculate the temperature and species concentration profiles. During the second modeling step temperature profiles were used in the thermo-mechanical model to calculate the thermal stress distribution in the mSOFC stack. The results maximum thermal axial elongation that equals 1.4 mm for the mSOFC stack. The modelled maximum radial elongation was equal to 0.5 mm in the contact areas of the cylindrical housing and manifolds on the fuel inlet side. Graphical Abstract

This paper discusses the biosorption in a multi-cation system as an example of advances in the method of ions removal/binding to the biomass. Biosorption experiments were conducted on Chlorella kessleri biomass. The ions used in the experiment were Co(II), Cu(II), Mn(II) and Zn(II) and had the following configurations: binary, ternary and quaternary system. Also, the effect of the following anions Cl-, NO 3 - , SO 4 2- on the biosorption process in the quaternary system (initial concentration of each ion was 0−300 mg L-1) was examined. The affinity order determined in the experiment was as follows: Cu(II)>Zn(II)>Mn(II)>Co(II). At higher concentrations of Cu(II) cations, the strong competition effect between Cu(II) cations with the remaining cations was observed. The modified Langumir competition model was proposed to support the biosorption method in the description of the experimental data of inhibited metal ions biosorption. After the influence of anions was examined, the highest total biosorption capacity was obtained for 1:1:2 system (Cl-: NO 3 - : SO 4 2- ). Graphical Abstract

Eight new rod-like liquid crystal molecules composed by a long rigid core of three six-member rings (cyclohexane ring or benzene ring), azo, ester and terminal aldehyde groups have been prepared. These rod-like liquid crystalline molecules were designed to construct new structures to further study photo-isomerization in their mesophases. All the compounds have been characterized based on their basic spectral data, differential scanning calorimeter (DSC) and hot stage polarizing optical microscope (HS-POM). The result showed that all the molecules, even those with the shortest terminal methyl group, have liquid crystalline properties. Their mesophases are nematic within the temperature ranges from 85 to 145°C. They exhibit photo-sensitivities not only in methanol solutions but also in a mesophase when exposed to UV light. The highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) and the differences between the frontier molecular orbitals (E g ) of these compounds were determined by cyclic voltammetry. The effect of even-odd carbon number of the terminal straight alkyl chain on the UV spectral data and the E g were observed. The difference between the E g of these compounds are in excellent agreement with the difference of their maximum absorption wavelength in UV spectra. Graphical Abstract

The aim of study was to evaluate the usefulness of FT-Raman spectroscopy in assessing stress-induced metabolic changes in plants. 20-d-old optimally watered plants of soybean were exposed to drought. Metabolic changes in optimally watered and drought-stressed plants were monitored using FT-Raman spectroscopy. In parallel, analyses were carried out of fatty acid composition and pigment content using analytical methods. These compounds are associated with the response of plants to environmental stress. While fatty acid assays in study were inconclusive, the pigment content analysis gave promising results. FT-Raman experiment demonstrated a decrease in carotenoid content in leaf, as a result of drought, which was confirmed by spectrophotometric analysis. In addition to the analysis of aforementioned compounds, FT-Raman spectroscopy allowed the simultaneous observation of a wider spectrum of compounds scattering the radiation in the leaves tested, and their subsequent comparative analysis. The impact of drought on metabolism of soybean was clearly visible on spectra and confirmed using cluster analysis. The technical problem of the influence of leaf water content on measurements, which appeared in studies, will be discussed. To conclude, FT-Raman spectroscopy may be a good complement to other non-invasive methods, e.g., fluorescent methods, in assessing the stress-induced damage of crops.

A series of seven 2-amino-4-arylthiazoles were prepared following Hantzsch’s modified method under microwave irradiation. A set of 50 derivatives was obtained and the in vitro activity against Giardia intestinalis was evaluated. The results on the biological activity revealed that, in general, the N-(5-bromo-4-aryl-thiazol-2-yl)-acetamide scaffold showed high bioactivity. In particular, compounds 6e (IC50 = 0.39 μM) and 6b (IC50 = 0.87 μM) were found to be more potent than the positive control metronidazole. Citoxicity and acute toxicity tests performed showed low toxicity and high selectivity of the most active compounds (6e SI = 139, 6b SI = 52.3). A QSAR analysis was applied to a data set of 37 obtained 2-amino-4-arylthiazoles derivatives and the best model described a strongly correlation between the anti-giardiasic activity and molecular descriptors as E2M, RDF115m, F10, MATS6v, and Hypnotic-80, with high statistical quality. This finding indicates that N-substituted aminothiazole scaffold should be investigated for the development of highly selective anti-giardial agent. Graphical Abstract

This study describes the influence of the phosphorothioate internucleotide bond on the deoxyribonucleic acid (DNA) oxidation process. The interaction of an ultraviolet radiation (UVA) with a targeted double-stranded (ds) oligonucleotide, in which one strand contains an antraquinone (AQ) moiety on the 5’-end, may lead to a hole migration process through the double helix. In the end, the migration of theformed radical cation terminates in a suitable place. Usually, this is a guanine-rich sequence. In another experiment, phosphorothioate internucleotide bonds were detected in the bacterial genome as a natural modification. In this study, a polyacrylamide gel electrophoresis (PAGE) autoradiogram analysis of irradiated ds-DNA showed that the oxidation reaction was not inhibited by an isolated guanine. Instead, irrespective of the absence or presence of a phosphorothioate bond, the termination of the ds-DNA oxidation process was predominantly observed on the thymine moieties. Based on the obtained results, it can be concluded that in the discussed case, a hole migration by a hopping mechanism is in competition with an oxidation reaction with a superoxide radical anion. Alternatively, the radical cation migration process is sequence-dependent due to its different ionization potentials. Therefore, the presence of a phosphorothioate internucleotide bond did not change the stability of ds-DNA under UVA irradiation conditions. Graphical Abstract

New simple, rapid, and accurate spectrophotometric techniques for sulphanilamides assay in combination drugs have been elaborated. The method is based on the formation of coloured products of sulphanilamides diazonium salt azoсoupling with heterocyclic azo reagent 4-(2-thiazolylazo)-resorcinol (TAR) in alkaline medium (pH 9.5) with the following measurement of their absorbance at λmax = 615 nm. Formed products are stable for 1 hour at room temperature. Effective molar absorptivities at absorbance maximum 615 nm for disazo dyes were ~ 104 M-1 cm-1. Linear ranges for sulphanilamides determination were 0.5−30.0 μg mL-1. The developed method was used for the suphanilamides determination in tablets, powder, solutions, suspensions and ointments. Graphical Abstract

An analytical method for the determination of tannic acid is proposed by the sequential perturbation caused by different amounts of tannic acid on the Belousov-Zhabotinskii oscillating system. The oscillating system is catalyzed by tetraazamacrocyclic complex [CuL](ClO4)2, where L is 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene. The method relies on the linear relationship between the changes in the inhibition time and the logarithm of the concentration of tannic acid. The calibration curve obeys a linear equation very well when the concentration of tannic acid is over the range of 6.25 × 10-7 ~ 1.56 × 10- 5 M (n = 16, R = 0.9984). This analytical method, equipped with a simple instrument, provides a new way to accurate determination of tannic acid. Graphical Abstract

This paper presents results on electric discharge generation by high frequency high voltage (15–100 kHz) in NaCl solutions with different initial conductivity (100–1300 mS cm -1 ), and compares them with DC discharge in the same electrode configuration. A batch plasma reactor in the pin-hole configuration contained a ceramic dielectric barrier separating two planar stainless steel electrodes; barrier thickness of 0.6 mm and pin-hole diameter of 0.6 mm was used. Lissajous charts were evaluated from electric measurements for different discharge phases (electrolysis, bubble formation and discharge regular operation). Breakdown moments for different solution conductivities were determined from discharge power evaluation as a function of applied frequency. Breakdown voltage amplitude was decreased by the increasing conductivity in both regimes while frequency and current decreased. Changes of physical parameters (temperature, solution conductivity and pH) as well as production of hydrogen peroxide at different solution conductivities were compared. Solution conductivity was increased in both discharge regimes and with the initial conductivity value. Solution temperature was increased by the discharge in both regimes and with the increasing initial conductivity, too. Solution pH dropped to acidic conditions when HF or DC positive regime was applied while it was enhanced by DC negative regime.

The application of non-thermal atmospheric pressure plasma raises a hope for the new wound healing strategies. Next to its antibacterial effect it is known to stimulate skin cells. However, monocytes are also needed for the complex process of a wound healing. This study investigates the impact of plasma on the intracellular signaling events in the primary human monocytes. The proliferative MEK-ERK (MAPK/ERK kinase-extracellular signal-regulated kinase) pathway was activated by short plasma treatment times. In contrast, an induction of the apoptotic JNK (c-Jun N-terminal kinase) cascade as well as activation of caspase 3 were observed after long plasma exposure. These findings indicate that monocytes can be differentially stimulated by plasma treatment and may contribute to the proper wound recovery. Graphical Abstract

The emission characteristics of a scheme combining laser ablation as sample introduction source and hollow cathode discharge as excitation source are presented. The spatial separation of the sample material introduction by laser ablation and hollow cathode excitation is achieved by optimizing the gas pressure and the sample-cathode gap length. At these conditions the discharge current is maximized to enhance the analytical lines intensity.

The spatially resolved concentration of OH radicals in the effluent of a microwave (MW) surfatron plasma jet was measured by planar laser-induced fluorescence. Two cases were compared – constant MW power and MW power modulated by 80 Hz. In both cases the maximal concentration was at the tip of the visible discharge, but for constant MW power the OH was spread over a larger volume. The maximum concentration in both cases was on the order of 10 22 m -3 . Graphical Abstract

The purpose of this work was to deposit Zn-containing films on Si substrates using the commercial atmospheric pressure plasma jet “kINPen’09.” In preliminary experiments Zn-containing films were deposited on the silicon substrates immersed in water solutions of Zn(NO 3 ) 2 •6H 2 O salt. The surface composition of deposited films was analyzed by the XPS (X-ray photoelectron spectroscopy) technique while the bulk composition was studied by means of XRD (X-ray diffraction) mesurements. The film thickness was measured by a profilometer. We have determined that the concentration of the zinc nitrate solution as well as changes in the deposition time resulted in a large fluctuation of the deposited film thickness. However, the successful deposition of the Zn-containing films on the Si substrate was definitely confirmed. Graphical Abstract

Advantages of the electron-beam plasma (EBP) for production of bioactive titanium oxide coatings were experimentally studied. The coatings were synthesized in EBP of oxygen on the surface of plane titanium substrates. A number of analytical techniques were used to characterize morphology, chemical composition, and structure of the synthesized titanium oxide. The analysis showed the titanium oxide (IV) in the rutile form to predominate in the coatings composition. The samples with plasmachemically synthesized TiO 2 -coatings were more hydrophilic than untreated titanium. The effect was stable during two weeks and then the degradation of the wettability began. The EBP-stimulated TiO 2 synthesis improved the hydroxyapatite formation on the surface of plane titanium substrates. The EBP-stimulated TiO 2 synthesis is promising technique to produce bioactive coatings on the surface of titanium medical dental and bone implants. The computer simulation of plasma-surface interaction was carried out to predict the plasma composition, to find the spatial distribution of the sample temperature, and to calculate the flows of the chemically active plasma particles bombarding the tube wall. The flows of atomic and singlet oxygen were found to be the most intensive and, therefore, these particles are likely to be responsible for the formation of the biocompatible TiO 2 -coaings.

Gliding discharge plasma in a large scale reactor was used for decomposition of tetrachloromethane. The new power supply system based on a power inverter was used. The conversion of CCl 4 was investigated in air at normal pressure. The reactor was made of a quartz-glass tube 60 mm in diameter and contained three converging electrodes 140 mm long. Effects of the initial CCl 4 concentration, gas flow rate and discharge power on CCl 4 conversion have been studied. The conversion of CCl 4 was high in all cases reaching a maximum of 90%. The conversion of tetrachloromethane decreased with increasing initial concentration of CCl 4 in the reaction mixture. Changing the gas flow rate from 1000 Nl h -1 to 1400 Nl h -1 decreased the conversion of tetrachloromethane. Graphical Abstract

In this work, several materials were studied as electrodes in a pinhole configuration of a DC plasma discharge to estimate their effect on the efficiency of the discharge, indicated by hydrogen peroxide production. Detection was carried out using a specific titanium reagent. This was combined with ICP-OES analysis of the final solutions to determine the difference between the amount of electrode material released during the discharge operation and electrolysis experiment carried out under the same conditions. It was found that from seven studied electrode materials, graphite gives the best results, while lower cost aluminum and titanium-zinc still work well. The most unsuitable materials were copper and brass; in these cases, no hydrogen peroxide was detected in the cathode part of the reactor. Results obtained by ICP analysis indicate that even in the case of brass, the absence of hydrogen peroxide is due to the presence of copper in the material. It probably affects both directly the phase of discharge creation and propagation and the decomposition reactions. Graphical Abstract

A 6-carboxycellulose (in medicine known as “oxidized cellulose” or “oxycellulose”) is one of the cellulose derivatives popular in the field of surgery. Health products based on oxidized cellulose are great local hemostatics with unique bactericidal and fully bioabsorbable effects. Traditional process of native cellulose oxidation is described as a complex radical reaction in strong acidic liquid medium doped by toxic nitrous radicals (NO*). Our plasma-chemical reaction demonstrates a new synthesis method of oxidized cellulose with unique bactericidal effect. This plasma-chemical treatment is based on atmospheric plasma discharge in liquid medium leading to the oxidation of polysaccharide molecules resulting in oxycellulose. Final oxycellulose properties were evaluated by infrared spectroscopy and carboxyl content determination. The biological impact showed a strong germicidal effect. Graphical Abstract

The plasma treatment of polypropylene fibres used as concrete admixtures for improving its mechanical properties is the focus of this research paper. A plasma treatment was conducted in a low-temperature plasma environment at atmospheric pressure in a DCSBD (Diffuse Coplanar Surface Barrier Discharge). The degree of hydrophilicity caused by the plasma treatment was determined by measuring the rate of penetration of water into the porous media, commonly referred to as the Washburn method. The influence of the addition of PP (polypropylene) fibres to the concrete matrix was investigated using a three point bending test which determined the flexural strength of concrete samples. Our experiments demostrate that plasma improves both the wettability of PP fibres and its adhesion to the concrete matrix. The tests of flexural strength show, that even a short plasma treatment (5 s) can have a significant impact on the mechanical properties of fibre-reinforced concrete composite. Graphical Abstract

A rapid growth of interest in low temperature plasma in medicine in recent years has given a rise to a number of different applications. We report a low cost kHz driven argon plasma jet with flow rate less than 0.15 L min -1 suitable for treatment of small areas infected with the wide-spread yeast pathogen Candida albicans . The plasma jet has been applied for inactivation of C. albicans seeded on an agar surface as well as yeast suspensions. The effects of different treatment parameters (gas composition, distance and treatment time) have been studied on the efficiency of yeast inactivation. C. albicans viability was evaluated by XTT assay and by measuring diameters of circular transparent zones. Graphical Abstract

Zero phonon line (ZPL) shape, position and integral intensity of SiV defect center in diamond is presented for nanocrystalline diamond (NCD) films grown at different conditions, NCD films of average grain sizes from ~50 nm up to ~180 nm have been deposited onto c-Si wafer at substrate temperature of 700 and 850oC from mixture with different CH 4 and H 2 ratios using MWCVD process. Light emission of SiV defect center and Raman scattering properties of NCD samples were measured on a Renishaw micro-Raman spectrometer with 488 nm excitation. Scanning electron microscopy images were used for monitoring surface morphology and for the analysis of the average grain sizes. Sample thickness was determined by in situ laser reflection interferometry. Characteristics of SiV ZPL are discussed in light of the morphology, bonding structure and average grain size of NCD films.

Complex theoretical and experimental investigation of ethanol into syngas conversion assisted by DC atmospheric pressure discharge with plasma cathode is presented. Infrared absorption spectroscopy together with the equation for the conservation of the number of atoms at the inlet and outlet of the reactor are used to determine the composition of syngas, the main components of which are hydrogen, carbon monoxide, methane and acetylene. It is shown that the plasma-chemical reactor enables efficient (over 90%) ethanol into syngas conversion with an output of 2 L min-1 and at energy costs of about 3 electron-volts per one hydrogen molecule. Numerical modeling of conversion kinetics at discharge conditions was performed assuming thermal nature of the process. Experimental and calculated data are in good agreement. Graphical Abstract

Hydrogen seems to be one of the most promising alternative energy sources. It is a renewable fuel as it could be produced from e.g. waste or bio-ethanol. Furthermore hydrogen is compatible with fuel cells and is environmentally clean. In contrast to conventional methods of hydrogen production such as water electrolysis or coal gasification we propose a method based on atmospheric pressure microwave plasma. In this paper we present results of the experimental investigations of hydrogen production from ethanol in the atmospheric pressure plasma generated in waveguide-supplied cylindrical type nozzleless microwave (2.45 GHz) plasma source (MPS). Nitrogen was used as a working gas. All experimental tests were performed with the nitrogen flow rate Q ranged from 1500 to 3900 NL h -1 and absorbed microwave power P A up to 5 kW. Ethanol was introduced into the plasma using the induction heating vaporizer. The process resulted in an ethanol conversion rate greater than 99%. The hydrogen production rate was up to 728 NL[H 2 ] h -1 and the energy efficiency was 178 NL[H 2 ] per kWh of absorbed microwave energy. Graphical Abstract

In this work, degradation of the anthraquinonic dye Acid Blue 25 by non-thermal plasma at atmospheric pressure with and without photocatalyst is investigated. Titanium dioxide (TiO 2 ) is used as a photocatalyst. The dye degradation by plasma in the presence of TiO 2 is investigated as a function of TiO 2 concentration, dye concentration and pH. The degradation rate is higher in acidic solutions with pH of 2 to 4.3, especially at pH 2, and decreases to 0.38 mg L -1 min -1 with the increase of pH from 2 to 5.65. A similar effect is observed in basic media, where a higher degradation rate is found at pH = 10.3. The degradation rate increases in the presence of TiO 2 compared to the discharge without photocatalysis. The results show that the degradation of the dye increases in the presence of TiO 2 until the catalyst load reaches 0.5 g L -1 after which the suppression of AB25 degradation is observed. The results indicate that the tested advanced oxidation processes are very effective for the degradation of AB25 in aqueous solutions. Graphical Abstract

In this paper we will present results for plasma sterilization of planktonic samples of two reference strains of bacteria, Pseudomonas aeruginosa ATCC 27853 and Enterococcus faecalis ATCC 29212. We have used a plasma needle as a source of non-equilibrium atmospheric plasma in all treatments. This device is already well characterized by OES, derivative probes and mass spectrometry. It was shown that power delivered to the plasma is bellow 2 W and that it produces the main radical oxygen and nitrogen species believed to be responsible for the sterilization process. Here we will only present results obtained by electron paramagnetic resonance which was used to detect the OH, H and NO species. Treatment time and power delivered to the plasma were found to have the strongest influence on sterilization. In all cases we have observed a reduction of several orders of magnitude in the concentration of bacteria and for the longest treatment time complete eradication. A more efficient sterilization was achieved in the case of gram negative bacteria.

Two types of capacitive dual-frequency discharges, used in plasma processing applications to achieve the separate control of the ion flux, Гi, and the mean ion energy, <Ei>, at the electrodes, operated in CF4, are investigated by particle-in-cell simulations: (i) In classical dual-frequency discharges, driven by significantly different frequencies (1.937 MHz + 27.12 MHz), <Ei> and Гi are controlled by the voltage amplitudes of the low-frequency and high-frequeny components, ΦLF and ΦHF, respectively. (ii) In electrically asymmetric (EA) discharges, operated at a fundamental frequency and its second harmonic (13.56 MHz + 27.12 MHz), ΦLF and ΦHF control Гi, whereas the phase shift between the driving frequencies, θ, is varied to adjust <Ei>. We focus on the effect of changing the control parameter for <Ei> on the electron heating and ionization dynamics and on Гi. We find that in both types of dual-frequency strongly electronegative discharges, changing the control parameter results in a complex effect on the electron heating and ionization dynamics: in classical dual-frequency discharges, besides the frequency coupling affecting the sheath expansion heating, additional frequency coupling mechanisms influence the electron heating in the plasma bulk and at the collapsing sheath edge; in EA dual-frequency discharges the electron heating in the bulk results in asymmetric ionization dynamics for values of θ around 45°, i.e., in the case of a symmetric applied

The aim of this work is the application of low-temperature low-pressure hydrogen plasma on artificially prepared corrosion layers, so called plasma chemical reduction. It is necessary to use samples with artificially prepared corrosion layers because it is impossible to use the real artifacts for fundamental research. The bronze was chosen as a sample material. Formation of corrosion layers on the bronze samples was carried out in concentrated hydrochloric acid vapors with the addition of sand. The radio-frequency hydrogen plasma was generated in the flowing regime at a pressure of 160 Pa. Different values of supplied power were chosen as well as different discharge modes: continuous or pulsed mode with varied duty cycles. By the combination of supplied power and mode factors, we selected two values of effective power. The process of plasma chemical reduction was monitored by optical emission spectroscopy (OES) and simultaneously, the sample temperature was measured. Rotational temperatures were calculated from OH radicals spectra. Changes in the structure and elemental composition were determined using scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX). Graphical Abstract

In this research a new process of plasma oxidation of crystalline silicon at room temperature is studied. The plasma oxidation was carried out using Diffuse Coplanar Surface Barrier Discharge (DCSBD) operating in ambient air and oxygen at atmospheric pressure. The influence of exposition time, plasma parameters and crystallographic orientation of silicon on oxidized layers and their dielectric properties were investigated. Thickness, structure and morphology of these layers were studied by ellipsometry, infrared absorption spectroscopy and scanning electron microscopy. During the treatment time, from 1 to 30 minutes, oxidized layers were obtained with thickness from 1 to 10 nm. Their roughness depends on the crystallographic orientation of silicon surface and exposure time. Electrical parameters of the prepared layers indicate the presence of an intermediate layer between silicon substrate and the oxidized layer. Graphical Abstract

The surface of a polyamide-12 (PA-12) foil was modified in order to improve the adhesive properties by two types of atmospheric pressure plasma sources. The samples were characterized using contact angle measurement, adhesive properties measurement and X-ray photoelectron spectroscopy (XPS). The ageing of the plasma modification was also studied. A significant increase in wettability was observed at different treatment times. The same effect was also seen in the adhesive properties - the adhesion was increased almost 12 times for 10 s DCSBD treatment in comparison to untreated PA-12. XPS analysis confirmed chemical changes due to the plasma modification of the PA-12. It was concluded that both plasma sources improve the adhesive properties of PA-12, with DCSBD obtaining better results. Graphical Abstract

The active DC glow discharge sustained in the pure oxygen can be employed in various technological applications, such as thin layer deposition or sterilization. Considering applied pressures of hundreds of Pascals, two different forms of the positive column of the discharge can co-exist: T- and H-form. These forms are commonly distinguished according to the values of the axial electric field strength: values in the H-form are generally one order of magnitude higher compared to the T-form. However, electric measurement itself may often affect the discharge plasma. Optical emission spectroscopy as a non-invasive diagnostic was therefore employed as an alternate characterization of both forms. We found that the H- and T-forms can be clearly recognized by values of intensities of particular oxygen spectral lines. This characterization enabled us to observe transition between the both particular forms when spatial distribution measurements were employed. Moreover, transition in the rotational temperature Trot was also observed. Graphical Abstract

The parameters for microdischarges of plasma medicine in air and argon vortex flows at atmospheric pressure for different shapes of electrodes (outlet nozzle and axis electrode diameters ratio set) have been investigated. The current-voltage characteristics of the designed systems have been analyzed, the parameters of the generated jets plasma have been investigated by means of the optical emission spectroscopy, and the form of plasma jets has been studied by using video camera.

Well-ordered nano-carbon materials, like multi-wall carbon nanotubes, graphene oxide, graphene due to their unique physical and chemical properties, are candidates for promising applications. In this work thin multilayered graphene, single layer graphene oxide layers and highly oriented pyrolytic graphite (HOPG) surface were treated by RF activated N2 gas plasma at nominally room temperature. Negative bias in the 0–200 V range and treatment time of 10 min was applied. Surface chemical alterations were followed by X-ray photoelectron spectroscopy (XPS). The applied treatments resulted in a significant build-up of nitrogen in the surface of these nano-carbon materials. The amount of nitrogen varied between 4 and 10 atomic %, depending on type of carbon and on biasing conditions. Evaluating the high-resolution N1s XP spectral region, typically three different chemical bonding states of the nitrogen were delineated. Peak component at 398.3 eV is assigned to C=N–C type, at 399.7 eV to sp2 N in melamine-type ring structure and at 400.9 eV to N substituting carbon in a graphite-like environment. Identical chemical bonding of the nitrogen was detected on the surface of HOPG treated in the same way for comparison. Graphical Abstract

Atmospheric-pressure air and nitrogen plasmas generated by surface dielectric barrier discharges have been used to incorporate new functionalities at the surface of polypropylene nonwoven fabric. The main goals were to activate the polymer surfaces for subsequent immobilization of chitosan from water solution without using any crosslinking and wetting agents. The samples were analyzed by diffuse reflectance infrared Fourier transform spectroscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy. The nitrogen plasma treatment resulted in relatively high oxygen incorporation, about 9 atomic % mainly in aliphatic C=O type bonds and about 4 at.% of nitrogen incorporation in amine and other nitrogen functionalities. Chitosan was immobilized on the fabric fibers surfaces very homogeneously in amount of 2 - 5 g m-2. The chitosan coated samples exhibited a good laundering durability and strong antimicrobial activity against Bacillus subtilis and Escherichia coli. Graphical Abstract

This contribution attempts to establish an easy-to-apply non-thermal plasma reactor for efficient toluene removal. Derived from the already established knowledge of the so called Dielectric Barrier Discharge (DBD) Stack Reactor a new model reactor was used in this work. The DBD Stack Reactor is a multi-elements reactor but in this work only one stack element was used to investigate the efficiency and efficacy of toluene removal. In case of reliable results the scalability process for industrial application is already well known. Therefore, laboratory experiments were conducted in dry and wet synthetic air with an admixture of 50 ppm toluene. Along with the toluene removal process the electrical behaviour of the discharge configuration was investigated. It was found that the electrical capacitance of the dielectric barrier changes with variations of the operating voltage. This could be due to the changes in the area of the dielectric barrier which is covered with plasma. Additionally, it was found that the power input into the plasma, at a fixed operating voltage, is proportional to the frequency, which is in agreement with the literature. Regarding the decomposition process, the total removal of toluene was achieved at specific input energy densities of 55 J L-1 under dry conditions and 110 J L-1 under wet conditions. The toluene removal was accompanied by the production of nitric acid (dry conditions) and formic acid (wet conditions). The latter suggested a combination of the plasma reactor with a water scrubber as an approach for total removal of pollutant molecules. Graphical Abstract

Mulitlayer graphene reinforced silicon nitride composites were prepared by spark plasma sintering to investigate the effect of the graphene addition on mechanical properties. The composites contained multilayer graphene (MLG) in various (0, 1, 3 and 5 wt%) content. Significantly higher fracture toughness of 8.0 MPa m 1/2 was obtained at 1% MLG content, however, on further increasing the graphene content the toughness did not increase, but dropped to the value of the monolithic silicon nitride. The maximum hardness of 18.8 MPa was also obtained at 1% MLG, while at higher MLG contents it gradually decreased. Graphical Abstract

Polyethylene terephthalate (PET) foils have been exposed to oxygen plasma and its afterglow in order to reveal compositional and structural modifications of the surface layer. Oxygen plasma was created by electrode-less RF discharge in a glass chamber so the O-atom density was close to 1022 m -3 although the density of charged particles was only about 1 × 10 16 m -3 . Long-living reactive particles created in plasma were leaked into the afterglow chamber using a two-stage rotary pump of pumping speed 4.4 × 10 -3 m 3 s -1 . The density of O-atoms in the afterglow as measured with a catalytic probe was 3 × 10 21 m -3 , while the density of reactive oxygen molecules was estimated theoretically. The functionalization was accomplished even after a brief exposure to either plasma or afterglow since all samples were saturated with oxygen-rich functional groups as revealed by XPS. The water contact angle measurements, however, showed that only plasma treatment allowed for super-hydrophilicity, explained by rich surface morphology as detected by AFM. The differences in morphological properties between plasma and afterglow treated samples were explained by different interaction mechanisms between low and high energy particles impinging the polymer surface. Graphical Abstract

The objective of the paper consists of a theoretical prediction of radiative heat transfer in arc plasmas of SF 6 (sulphur hexafluoride) with various admixtures of copper vapours. The P1-approximation was used as a mathematical tool. Due to the very complicated frequency dependence of absorption coefficients, the Planck and Rosseland mean absorption coefficients have been derived from the calculated absorption spectrum. The main radiation quantities (radiation intensity, radiation flux density and its divergence – net emission) have been determined in cylindrical arc plasmas for several model temperature profiles. Contribution to the net emission of copper admixtures is discussed. Conclusions have been made concerning validity and utilization of various absorption means. Graphical Abstract

The decomposition of CCl 4 in air was investigated at atmospheric pressure in two discharges. Reactors used to generate electrical discharges were powered by the same electric power supply. In both reactors, nearly 90% conversion of CCl 4 was obtained. All chlorine was in the form of Cl 2 in the process carried out in the barrier discharge, while in the spark discharge, COCl2 was formed. The conversion of CCl 4 to COCl 2 ranged from 2 to 12%. NO was formed in both discharges but the NO content in the gas leaving the reactors was 1.7–2.7% for the spark discharge and 0.045–0.06% for the barrier discharge. O 3 was produced only in the barrier discharge and its content ranged from 0.1 to 0.2%. Graphical Abstract

Diffuse Coplanar Surface Barrier Discharge (DCSBD) is a novel type of atmospheric-pressure plasma source developed for high-speed large-area surface plasma treatments. The statistical behavior of microdischarges of DCSBD generated in artificial air atmosphere was studied using time-correlated optical and electrical measurements. Changes in behavior of microdischarges are shown for various electrode gap widths and input voltage amplitudes. They are discussed in the light of correlation of the number of microdischarges and the number of unique microdischarges’ paths per discharge event. The ‘memory effect’ was observed in the behavior of microdischarges and it manifests itself in a significant number of microdischarges reusing the path of microdischarges from previous half-period. Surprisingly this phenomenon was observed even for microdischarges of the same half-period of the discharge, where mechanisms other than charge deposition have to be involved. The phenomenon of discharge paths reuse is most pronounced for wide electrode Graphical Abstract

In this study, the variations of properties of a microwave plasma jet (surfatron) along the discharge axis have been investigated using optical emission spectroscopy. As the argon jet is not enclosed, the spatial distribution of individual species in effluent plasma is the result of rather complicated interplay between energy loss and gradual mixing with the air. Spatial 2D relative intensity profiles of atomic lines and molecular bands at 310 nm, 336 nm, 391 nm and 656 nm are presented in the form of colour maps revealing different positions of maximum emission intensity for 310 nm and 336 nm (in the effluent plasma) and for 391 nm and 656 nm (inside the discharge tube). The plasma jet was used for surface treatment of heat resistant samples (stainless steel, aluminium, silicon wafer) and the effectiveness of the plasma treatment was evaluated by measuring the sessile drop contact angle, with water and glycerol as testing liquids. The optimal position for plasma treatment (close to the tube nozzle) combined with longer treatment time (10 s) lead to hydrophilic properties of samples with contact angles as low as 10°. Graphical Abstract

Decomposition of poly(vinyl chloride) (PVC) was investigated in radiofrequency thermal plasma in neutral, oxidative and reductive conditions. Optical emission spectroscopy (OES) was applied for the characterization of the plasma column. OES was used to identify active plasma components such as excited atoms, ions, radicals and molecules. The spectra were dominated by molecular C2, CN, OH, and CH bands, and atomic H, Ar, C, Cl and O lines. Emission intensities of main species were monitored versus various experimental parameters. The rotational-vibrational temperatures determined from different bimolecular species were considered in the range of 2000–6400 K. Solid soot samples were collected and purified to investigate the possibility of graphene formation as a by-product of the decomposition process. Graphical Abstract

An air diffuse coplanar surface barrier discharge is used to activate the surface of polytetrafluoroethylene (PTFE) samples, which are subsequently coated with polyvinylpyrrolidone (PVP) and tannic acid (TAN) single, bi- and multilayers, respectively, using the dip-coating method. The surfaces are characterized by X-ray Photoelectron Spectroscopy (XPS), Attenuated Total Reflection – Fourier Transform Infrared Spectroscopy (ATR-FTIR) and Atomic Force Microscopy (AFM). The XPS measurements show that with plasma treatment the F/C atomic ratio in the PTFE surface decreases, due to the diminution of the concentration of CF2 moieties, and also oxygen incorporation through formation of new C–O, C=O and O=C–O bonds can be observed. In the case of coated samples, the new bonds indicated by XPS show the bonding between the organic layer and the surface, and thus the stability of layers, while the gradual decrease of the concentration of F atoms with the number of deposited layers proves the creation of PVP/TAN bi- and multi-layers. According to the ATR-FTIR spectra, in the case of PVP/TAN multilayer hydrogen bonding develops between the PVP and TAN, which assures the stability of the multilayer. The AFM lateral friction measurements show that the macromolecular layers homogeneously coat the plasma treated PTFE surface.

Polylactic acid (PLA) is suitable for applications in packaging and biomedicine due to its biodegradability. To improve PLA surface adhesion a plasma-chemical treatment using nonthermal plasma generated in ambient air via diffuse coplanar surface barrier discharge (DCSBD) was used. The optimal treatment time and power were investigated. Interaction between active plasma species and the polymer surface, and the resulting surface changes were studied by contact angle measurement, surface energy determination, FTIR, and XPS. The most hydrophilic surface was obtained after only 3–4 s treatment. Treatment up to 10 s did not damage the polymer but longer treatments (30 and 60 s) caused partial degradation. The plasma broke C-C/C-H bonds and formed more C-O, O-C=O and C-O-C bonds. During storage surface oxygen decreased and a negligible amount of nitrogen was adsorbed. The oxygen-containing functional groups probably sank into the PLA volume after treatment. Graphical Abstract

In this research, a diffuse coplanar surface barrier discharge (DCSBD) type plasma reactor was used for the surface modification of raw linen fabric. Changes in physical properties and chemical composition of the fiber surface as well as color of the fabric were measured as a function of time of the atmospheric air plasma treatment. Furthermore, ageing of the effects created on the fiber surface by plasma treatment was also characterized in a period of 0-14 days elapsed after the plasma treatment. Significant differences were found between the properties of the raw and plasma treated linen fabrics, including increase of wettability, wickability, surface energy and O/C ratio, and decrease of water contact angle and deterioration of the waxy outer layer of the fibers. Most of the parameters depended on the time of plasma treatment (0–180 s). O/C ratio increased steadily with the increase of duration of the plasma treatment, which was explained by destruction of the waxy surface layer, creation of polar groups and exposure of cellulosic components. Most of the properties tested were found to be stable during two weeks of storage after the plasma treatment, indicating that the surface ‘topography’ created by plasma remained almost unaltered and the recovery of the etched waxy coverage of the fiber did not occur. Graphical Abstract

In this paper, the effects of the power modulation on atmospheric pressure plasma jet, operated in Ar+2%N2 mixture, are studied. Time resolved optical emission spectroscopy is used for the investigation. From line and band intensities, the excitation, vibration and rotation temperatures are calculated. Their evolution during the modulation period exhibits a strong dependence on modulation frequency. For higher modulation frequencies, there is significant discrepancy in rotational temperatures calculated from OH spectra and from N2+ spectra, which indicates that thermalisation time can reach milliseconds. Graphical Abstract

Nowadays, chromatographic methods coupled with mass spectrometry are the most commonly used tools in metabolomics studies. These methods are currently being developed and various techniques and strategies are proposed for the profiling analysis of biological samples. However, the most important thing used to maximize the number of entities in the recorded profiles is the optimization of sample preparation procedure and the data acquisition method. Therefore, ultra high performance liquid chromatography coupled with accurate quadrupoletime- of-flight (Q-TOF) mass spectrometry was used for the comparison of urine metabolomic profiles obtained by the use of various spectral data acquisition methods. The most often used method of registration of metabolomics data acquisition – TOF (MS) was compared with the fast polarity switching MS and auto MS/MS methods with the use of multivariate chemometric analysis (PCA). In all the cases both ionization mode (positive and negative) were studied and the number of the identified compounds was compared. Additionally, various urine sample preparation procedures were tested and it was found that the addition of organic solvents to the sample noticeably reduces the number of entities in the registered profiles. It was also noticed that the auto MS/MS method is the least efficient way to register metabolomic profiles. Graphical Abstract

The determination of phenolic acids’ and flavonoids’ content in daily food rations (DFRs) of a selected group of male and female students and the development of chromatographic conditions is the primary goal of the study. The presence of 7 phenolic components were confirmed in the prepared extracts from all diets reconstructed within a period of 3 years. The highest concentrations were determined for hesperidin (124 and 55.6 mg for women and men, respectively), naringin (47.6 mg in female and 37 mg in male diets) and chlorogenic acid (19.7 and 19.8 mg for women and men). The antioxidant potential of the daily food rations, measured with a DPPH test, was higher for women (range 47.1‒78.8%) than for men (range 34.5‒78.0%) and was found to strongly correlate with the total phenolics content of the samples (Folin-Ciocalteu test) (correlation coefficient 0.90). Graphical Abstract

Inverse gas chromatographic characterization of resins and resin based abrasive materials, polymerpolymer and polymer-filler systems, as well as dental restoratives is reviewed. Graphical Abstract

Astragalus mongholicus, commonly used in Traditional Chinese Medicine (TCM), contains significant amounts of triterpene saponins – astragalosides, which possess a wide variety of pharmacological actions, including the treatment of cardiovascular and respiratory diseases. The present study was performed to develop a fast and effective extraction method of saponins from crude plant material using Twisselmann-type apparatus. Moreover, a detailed comparison between Soxhlet and Twisselmann apparatus was performed to explain the advantages and disadvantages of their applications. The content of astragaloside IV – the major saponin of A. mongholicus extracts and chosen as an extraction efficiency marker ‒ was determined by means of RP-HPLCELSD chromatography in an herein optimized method. Twisselmann extraction shortened its duration from 4 to 2 hours in comparison with the Soxhlet method ‒ a generally accepted method preparation for this extract. The effectiveness of both apparatus was alike (3.24 ± 0.44 mg and 3.48 ± 0.26 mg of astragaloside IV/ 4g of powdered root for 2 hours in Twisselmann and 4 hours in Soxhlet apparatus). Compared with a pharmacopoeial method, the application of Twisselmann apparatus enabled a decrease in analysis time of 50%, which is of high significance, especially for large, scaled-up industrial scale. Graphical Abstract

Retention parameters of psychotropic drug standards were determined on different columns, i.e., Octadecyl silica, Phenyl, Phenyl-Hexyl, Polar Reverse Phase, Pentafluorophenyl, and Cyanopropyl using aqueous eluent systems containing methanol or acetonitrile as organic modifiers, acetate buffer at pH 3.5 and addition of silanol blocker − diethylamine (DEA). The retention, separation selectivity, and sequence of elution were different when using eluents containing various organic modifiers. The significant differences were observed in retention parameters with a change of the used stationary phase. The various properties of stationary phases resulted in differences in analyte retention, peaks shape, systems efficiency and separation selectivity. The best shape of peaks were on Cyanopropyl (CN) column and the highest efficiency for most investigated psychotropic drugs were obtained on Phenyl-Hexyl and Polar RP columns. Graphical Abstract

A comprehensive review is presented on the recent developments and trends in the QuEChERS (quick, easy, cheap, effective, rugged, and safe) sample preparation approach. This technique involves liquid-liquid partitioning using acetonitrile and purifying the extract using dispersive solid-phase extraction (d-SPE). Originally, the QuEChERS was introduced for pesticides residues analysis in high moisture fruits and vegetables, but more recently it is gaining significant popularity in the analysis of broad spectrum of analytes in huge variety of samples. The wide range of the technique applications is possible due to introducing various modifications based on the use of different extraction solvent and salt formulation and buffer additions for salting-out partitioning step and the application of various d-SPE sorbents for clean-up step. Therefore, the QuEChERS approach is useful for analysis of, among others pesticides, veterinary drugs and other pharmaceuticals, mycotoxins, polycyclic aromatic hydrocarbons (PAHs), dyes, acrylamide, synthetic musks and UV filters, bisphenols, polybrominated diphenyl ethers and other flame retardants, endocrine disruptors, and other chemical compounds. Thanks to the QuEChERS approach, high-throughput multiresidue methods operate in a routine contaminant control of food products, feedstuff, and environmental samples. Graphical Abstract

Oxidative stress (OS) can be defined as an imbalance between antioxidant systems and various pro-oxidants. This loss of balance is closely associated with initiation and development of a wide range of systemic or organ specific diseases. Exhaled breath of healthy humans contains a large number of volatile organic compounds (VOCs) derived from cellular metabolism, released by microorganisms or taken up from the environment. Qualitative or quantitative changes in their composition are associated with diseases and various pathological conditions, also characterized by increased production of reactive oxygen species (ROS), such as superoxide radical, hydrogen peroxide, hydroxyl anion, peroxinitrite, etc. Several volatile organic compounds such as ethane and pentane are direct end-products of the reaction of ROS with various biological compounds (e.g., lipid peroxidation, DNA or protein damage). Being able to accurately identify ROS-generated VOCs could be of particular importance in devising sensitive tests that can diagnose and follow-up oxidative stress-related diseases. This review describes current knowledge on the associations between oxidative stress and free radicals and the release of several marker volatile organic compounds in a number of diseases. A special focus will be placed on such VOCs in the cardiovascular pathologies, pulmonary diseases and gastro-intestinal tract affections. Graphical Abstract

Glyphosate and AMPA determinations in rapeseed extracts by (a) liquid chromatography with triple quadrupole MS detection (LC-MS/MS), or (b) liquid chromatography with post-column OPA derivatization and fluorescence detection (LC-FLD) were developed. Mean recoveries for glyphosate and AMPA were (a) 88.8–95.0% and 82.1–86.1%, and (b) 70.8–74.1% and 62.4–72.6%. RSD were below (a) 11% and (b) 22%. Correlation coefficients were above 0.997 for both methods. LOD were 0.01 mg kg -1 for (a) and 0.05 mg kg -1 for (b). Both methods are simple and efficient for routine analysis of glyphosate and AMPA in a fatty matrix. Graphical Abstract

Antioxidant activity is one of the most desirable properties of natural compounds. Among these substances are phenolic compounds which exhibit excellent antiradical activity. The main aim of the present study was determination of the free radical scavenging activity of gruels with 5, 10 and 20% addition of linden inflorescence. The studies were based on two methods: TLC-bioautographic assay and spectrophotometric analysis using DPPH (2,2-diphenyl-1-picrylhydrazyl radical). The obtained results indicate that the radical scavenging properties of the extracts are positively correlated with the content of phenolic compounds in gruels and that a high-temperature extrusion process does not deactivate antioxidant polyphenolic compounds. Graphical Abstract

LSE (liquid-solid extraction), MSPD (matrix solid phase dispersion) and QuEChERS (quick, easy, cheap, effective, rugged and safe) extractions followed by GC-μECD/NPD to determine 223 pesticide residues in tobacco simultaneously were developed and compared. The identities of ten model pesticides were confirmed by GC-MS/MS. The type and amount of dispersant (Florisil, silica gel and alumina), sample mass, cleanup adsorbent, and the eluent (hexane, acetone and acetonitrile) were optimized. Linearity, recovery, LOQ, LOD, and matrix effect were compared. Most recoveries were 71−120% (RSD < 18%). LOD and LOQ were much lower than the CORESTA GRLs. The best method was QuEChERS: acetonitrile extraction and dispersive solid-phase extraction using primary-secondary amine and graphitized carbon. Graphical Abstract

Extrusion-cooking of plant materials may enhance antioxidant activity and improve health benefits. Selected antioxidant polyphenols in extruded corn gruels enriched with different amounts of linden flowers were determined by LC-ESI-MS/MS and quality characteristics were determined. Phenolic content increased with Tiliae inflorescentia addition and was not decreased by high-temperature extrusion. Linden flower incorporation into instant gruels should be limited to 10% to retain acceptable sensory properties. Graphical Abstract

Technology of molecularly imprinted polymers (MIP) has become very popular in recent decades. MIPs are primarily used in medical diagnostics, chromatographic separation and solid phase extraction (SPE); also as sensors and catalysts. In recent years there have been reported benefits of combining molecular imprinted polymers with additional features, e.g. magnetic properties, through the build-up of this type of material on magnetite particles (Magnetic Molecularly Imprinted Polymer – MMIP). This method produces a multifunctional material which has high selectivity and the ability to isolate the analyte from biological and environmental samples, allowing effective purification from such interferents as proteins and fats. This developing branch of new materials for the preparation and purification of complex sample matrices is an interesting alternative to materials routinely used to date, particularly with regard to the immunosorbents. This paper summarizes recent reports regarding MMIP preparation and their application for purification and isolation of compounds from biological matrices. Graphical Abstract

The main aim of the present investigation was to determine retention behavior and interactions of oligonucleotides with alkylamide stationary phase. Five oligonucleotides, differing in the sequence, were tested. Changes in the composition of the mobile phase, i.e. pH (5.0−7.0) and buffer concentration (30−75 mM) were investigated in detail. In addition, the hydrophobic and electrostatic parameters were measured for the different pH’s and salt concentrations. The theoretical model of interactions between individual elements of the separation system, (e.g. solute, stationary phase, and mobile phase) based on zeta potential measurements, hydrophobic and electrostatic parameters calculation, and molecular modeling, has been considered. Graphical Abstract

Essential oils from eleven Mentha species were obtained by Deryng hydrodistillation and analysed by GC–MS: 44 compounds were identified. The most abundant were menthone, isomenthone, menthol, carvone, piperitone oxide, D-limonene and eucalyptol. Chemometric similarity measures and principal component analysis were calculated, allowing comparisons based on secondary metabolite content. The fingerprints may be helpful in chemotaxonomy. Graphical Abstract

Concern for the natural environment increasingly devotes more attention to growing potential hazards resulting from the release of various substances. Currently, one of the main problems associated with environmental pollution is the derivation of organic compounds from wastewater. Substances derived from sewage leaks into the environment in the form of a multicomponent mixtures often enhances the toxic effects caused by these compounds. While analyzing the reports in the literature of the last two decades it can be seen that substantial efforts are devoted to the determination of selected trace contaminants present in wastewater. Among the most marked there are endocrine disrupting compounds, residues of pharmaceuticals and personal care products, plastics and sunscreens. Recently, a new group of compounds joined the aforementioned contaminants, namely drugs, whose legality and availability is increasing every year. Exposure to these type of compounds, named in the literature as emerging contaminants (ECs), involves, among others, such effects as hormonal imbalance, reduction of the survivability of aquatic organisms and reproductive problems. This paper provides a review of the types of emerging organic groundwater contaminants (EGCs) which are beginning to be found in the natural environment in many countries all around the world. Graphical Abstract

The paper reports state of the art research in the field of novel bio-based products for agriculture. Biopesticides, biostimulants and biofertilizers were shown as a potential alternative or additional products to the currently used agrochemicals. The present situation on the market of agrochemicals was discussed. Difficulties related to products registration were taken into account. Research on supercritical algal extracts as a biostimulant of plant growth and health supporting feed additive for laying hens was presented, as well as the perspectives of the use of biomass as the carrier of fertilizer nutrients. The method of production of new fertilizer components with micronutrients was biosorption. The concept of new phosphorus biofertilizers containing living microflora that solubilizes phosphorus was reported. Graphical Abstract

In this article, the phytotoxicity of biofertilizer produced from bones and its utilitarian properties are presented. Biofertilizer was obtained from bones in a solubilization process of phosphates conducted by bacteria Bacillus megaterium. Two in vivo tests were used for examination of the utilitarian properties of the biofertilizer: a hydroponic and a germination test. The experiment was performed using three groups of plants and four replications: group 1 − not treated (control 1), group 2 − with a conventional fertilizer (control 2), and group 3 – with the biofertilizer (experimental group). In the hydroponic tests, the best growth parameters were found for the samples where the biofertilizer was applied. The greater dry mass of plants was observed for plants collected from this group compared to the control 1 group and the group where the commercial fertilizer were used. In the case of the plant length and the intensity of green color, statistically significant differences were found. The utilitarian properties of the biofertilizer, evaluated from a germination test, were similar to those of the classical fertilizer. Statistically significant differences were found between the mass and intensity of green color of the experimental group (with the biofertilizer) and the control 1 group. Graphical Abstract

Odor mitigation techniques are widely investigated due to the problem of odor nuisance generated by intensive livestock production. The goal of this research was to investigate the use of aluminosilicate sorbents as filter packs in the air scrubber ODOR1, which enables cleaning of air inside the livestock building. The following sorbents were examined: raw halloysite, roasted halloysite, activated halloysite, raw bentonite, roasted bentonite and expanded vermiculite. The experiment was conducted in chambers where poultry manure was placed, the time of air treatment was 24 hours. A manual SPME (solid-phase microextraction) holder with DVB/Carboxen/PDMS fiber was used for extraction of odor compounds, and analyses were carried out using gas chromatography-mass spectrometry. Ammonia concentrations were determined according to Polish standards (Nessler method) using a spectrophotometer. It was found that all examined aluminosilicates had the potential for removal of ammonia as well as 24 volatile compounds emitted from poultry manure. The highest efficiency was noted for activated halloysite (81%) and roasted bentonite (84%) in the case of ammonia and odors, respectively. Despite the limitations of the study, the results showed the effectiveness of the air scrubber packed with aluminosilicates for the reduction of volatile odorous compounds in the air of livestock buildings. Graphical Abstract

The effects of the impact of four organic compounds (ascorbic acid, biotin, glucose and sucrose) on ash, protein, fiber, fat and amino acid contents in the freshwater Aegagropila linnaei biomass were examined in 7 and 14 days of cultivations in high concentrations of tested compounds (100 mg L -1 ). The presence of examined organic compounds had a negligible effect on the development of algae and their biomass composition. There were no significant differences in the amino acids composition in the biomass in the presence of organic compounds compared to the test system. However, the increase in ash content was observed irrespective of the cultivation time in the case of all used organic compounds. Only slight differences in crude fat concentration were observed in the case of 7 days cultivation with ascorbic acid, biotin and sucrose, while the highest increase of ash content was observed after 14 days of supplementation with glucose. None of the compounds affected changes in amino acid content in the Aegagropila linnaei biomass. The results suggest that an environment enriched with the test organic compounds had only minimal, or at most short-term, effects on the algal biomass composition. Graphical Abstract

The research results concerning the application of magnesium and ammonium ions for continuous removal of phosphate(V) ions from solution containing 1.0 or 0.20 mass% of PO 4 3– and from 0.10 to 0.50 mass% of SO 4 2– are presented. A continuous struvite MgNH 4 PO 4 × 6H 2 O reaction crystallization process was carried out both under stoichiometric conditions and using 20% excess of magnesium ions. The research was conducted in a DT MSMPR type crystallizer with internal circulation of suspension driven by a propeller stirrer, in constant temperature 298 K. The pH varied from 9 to 11 and mean residence time of suspension in a crystallizer τ varied from 900 to 3600 s. It was concluded, that sulphate(VI) ions influenced product quality disadvantageously. Depending on process parameter combinations struvite crystals of mean size from ca. 18 to ca. 44 μm and of moderate homogeneity: CV 7–95% were produced. Presence of sulphate(VI) ions favored crystallization of struvite as prismatic crystals, but tubular forms were also identified. The best shaped struvite crystals were produced at relatively low concentration of sulphate(VI) ions, pH 9 and for mean residence time of suspension in a crystallizer elongated up to 3600 s.

In this paper, the production of phosphate biofertilizers from bones by phosphate-solubilizing bacteria Bacillus megaterium is presented. The biofertilizers used in this study contain phosphorus compounds that are in available form to plants as well as components of growth medium. The solubilization was performed under two conditions; with chlorides and with sulphates instead of chlorides. Three biofertilizer forms are proposed in relation to the doses of bones applied in the solubilization process (4, 10 or 20 g L-1). The solubilization degree varied according to the bacterial medium formulation and the bones doses. The replacement of chlorides with sulphates yielded a lower growth rate, and resulted, in a lower solubilization. The specific growth rate of the cells of B. megaterium in a sulphate medium was lower than compared with the specific growth rate of cell culture in a medium of chlorides of about 22.4, 39 and 14%, for 4, 10 and 20 g L-1 of bones concentration, respectively. In the stationary phase, the solubilization factor (SF) was higher (61.7%) for the solubilization process conducted in a medium with chlorides − C bone 4 g L -1 , compared with the solubilization process conducted in the medium of sulphates (52.7%). Graphical Abstract

The objective of our study was to assess the residual effect of sewage sludge on the growth and yield of Prairie cordgrass and the content of crude ash, macroelements and heavy metals in the plant biomass. Field trials conducted in the years 2011 to 2013 focused on the assessment of the impact of municipal sewage sludge applied from 2008 to 2010on the growth and yield of Prairie cordgrass. The experiments followed the split-plot design with two variables: the rate of sewage sludge (DM-dry matter) at 0, 1.4, 2.8 and 4.2 t ha -1 , corresponding to nitrogen fertilization with: 0, 50, 100, 150 kg ha -1 , and the harvest time - fall and winter. The total dose of sewage sludge applied in 2008−2010 was 0, 4.2, 8.4 and 12.6 t DM ha -1 , which corresponded to the total dose of nitrogen fertilization: 0, 150, 300 and 450 kg ha -1 , respectively. The municipal sewage sludge at a rate of 8.4 t DM ha -1 , compared to the Control, significantly increased the number of leaves per plant, the leaf and culm matter, the number of shoots per 1 m 2 , the dry matter yield, crude ash deposition and uptake of macroelements and heavy metals. Graphical Abstract

This study was undertaken to determine mineral content, amino acid and fatty acid composition of the freshwater macroalga – Cladophora glomerata. The studies were based on the content comparison in algal biomass collected from a lake and cultured in a laboratory. To determine the ability of copper cumulating by macroalgae, Cladophora was cultured in the medium supplemented with Cu ions. This study indicated that the relative abundance of metals in filaments decreased in the following order: Ca > K > Mg > Na > Fe > Cu > Zn > Pb > As > Ni > Cd > Mn > Cr > Co. Total protein content ranged from 14.45% in Cladophora from a lake to 26.55% in Cladophora from a laboratory. The main amino acids analyzed were aspartic and glutamic acid. The fatty acid content in the dry matter of the extract varied depending on the extraction method used: ethylene alcohol (19.0%), acetone (34.5%) or supercritical fluid extraction (62.5%). Freshwater C. glomerata due to the macrominerals, trace elements, amino and fatty acids composition in the extracts can be a valuable resource for nutritional and cosmetic applications. Graphical Abstract

The aim of the present work was to examine the effect of the application of Spirulina platensis post-extraction residues enriched with Zn(II), Mn(II), Cu(II) via biosorption as micronutrient fertilizer for the biofortification of maize grains with micronutrients in field tests. As a nominal dose 2.5 kg ha-1 of zinc, 1.0 kg ha-1 of manganese and 0.5 kg ha-1 of copper were applied. The preparation was applied also in higher doses (150%, 200%) to investigate agronomic biofortification of maize grains. In field trials, obtained grain yield (7.2 Mg ha-1 for Spirulina 100%) was higher than in control group (6.2 Mg ha-1) and commercial reference product (6.6 Mg ha-1). For the same dose of micronutrients, their bioavailability was higher for bio-preparations than for reference fertilizer. The highest content of micronutrients delivered to plants (2.15 mg kg-1 – Cu, 7.07 mg kg-1 – Mn, 29.0 mg kg-1 – Zn) was observed for maize grains fertilized with preparation of Spirulina 150%, which signifies that biofortified maize grain was obtained. Corn grains biofortified with micronutrients can be used as staple food or feed preventing from micronutrient malnutrition. The application of micronutrient biocomponents based on Spirulina biomass allows to manufacture a valuable fertilizer with bioavailable micronutrients. Graphical Abstract

Activated carbons from biomass material of giant knotweed Reynoutria sachalinensis (F. Schmidt ex Maxim.) Nakai were obtained. Use of this plant for manufacturing activated carbon has not been studied yet. Therefore, the first activated carbons of giant knotweed origin are described. Both physicochemical (by steam and CO2) and chemical (by KOH) activation methods were applied. Influences of temperature (500, 600, 700 and 800°C), burn-off [10, 25 and 50 wt. % (daf)] and KOH concentration on pores surface area and volume distribution of the obtained activated carbons were explored. Porosity of the elaborated sorbents was determined by benzene and carbon dioxide sorption measurements. Sorbents obtained by steam activation were micro- and mesoporous with surface area and volume of pores increasing with temperature and burn-off to V = 0.351 cm3 g-1 and S = 768 m2 g-1 at 800°C at 50% burn-off. Carbon dioxide activation resulted with notably microporous activated carbons with porous texture parameters also increasing with burn-off to V = 0.286 cm3 g-1 and S = 724 m2 g-1 at 50% burn-off. The highest BET surface area of 2541 m2 g-1 was achieved when chemical (KOH) activation was performed using KOH to char ratio 4:1. Graphical Abstract

The present study aims to characterize the effect of the annual potassium variable rates fertilization (VRF) on the content of the soluble K, with this being investigated in both light and heavy soils. The study was performed between 2007 and 2013 in two separate areas differing in the soil texture classes. The initial levels of potassium determined in both experimental areas were classified as very high. The data obtained confirmed the positive effect of the variable fertilization techniques on the equalization of the K contents in the experimental fields, as determined by the decrease in the variance, standard deviation, and range of the elements content in both types of the soils studied. As assumed, the controlled withholding of fertilization applied in the early stages of the experiment resulted in a decrease of K content toward the preferred, medium to optimal, levels. In addition, we found that the progressive initiation of the potassium VRF on the experimental areas, to prevent an excessive decreases, resulted in earlier global adjustment of K contents in the light soils in contrast to the heavy ones, with the final spatial equalization being better in the latter, however.

Extracts obtained from hops (Humulus lupulus L., Cannabaceae) by supercritical fluid extraction (SFE), SFE followed by isomerization, as well as by conventional technique, were investigated for their chemical composition and antibacterial activity against selected foodborne pathogens and microorganisms capable to cause the food spoilage. The antibacterial activity of the extracts was compared with the antibacterial activity of xanthohumol, compound known for its broad pharmacological properties, isolated from the raw material remained after the SFE. Xanthohumol (XH, 96%) proved to posses the most prominent activity against all the tested strains, with the MIC values ranged between 2.5 and 20 μg mL-1. Supercritical hops extract and potassium isomerized supercritical hops extract showed strong antibacterial activity against the tested strains as well. Escherichia coli was not affected by the extracts, meaning that their oral admission would not cause the same problem as antibiotic application in intestinal flora. The chemical composition of the investigated hops extracts was analysed by GC-MS. Contents of α-acids, β-acids, iso-α-acids and xanthohumol in the samples were determined by HPLC. Graphical Abstract

The purpose of this study was to show relationships among the levels of essential metals (zinc, iron, sodium, magnesium, calcium and potassium) and phenolic acids (caffeic, chlorogenic, ferulic, gallic, rosmarinic and syringic) in commercial herbs (lemon balm, thyme, rosemary, mint, sage and angelica) and spices (caraway, lovage, hyssop and oregano). In the herbs higher quantities of metals and phenolic compounds were found than in spices. All plants contained high levels of calcium, potassium and rosmarinic acid, but low levels of zinc and gallic acid. By using principal component and hierarchical cluster analyses several clusters were identified grouping samples originating from a plant of a particular botanical species. Multivariate analysis has also shown that the contents of phenolic acids had a stronger impact on the scattering of herbs and spices than the metals levels. Furthermore, statistically significant correlations were found between calcium and ferulic, gallic, rosmarinic and syringic acids as well as between zinc and sodium and caffeic acid. This suggests co-operate between these biologically active constituents in metabolic processes occurring in plants. Graphical Abstract

Microwave Assisted Extraction (MAE) was used to obtain aqueous extracts of Baltic seaweeds. Three different temperatures: 25, 40, 60°C were examined. Algal extracts were characterized in terms of polyphenols, micro- and macroelements, lipids content and antibacterial properties. This is the first study that examines the effect of algal extract obtained by MAE in plant cultivation. The utilitarian properties were checked in the germination tests on Lepidium sativum for three dilutions of extract (0.5, 2.5 and 10%). Results showed that the content of polyphenols in extracts decreased with temperature, whereas the content of micro- and macroalements increased with temperature. The aqueous extracts did not contain fatty acids and did not show inhibitory effect on Escherichia coli and Staphylococcus aureus. Germination tests showed that plants in the experimental groups with an optimal concentration of extract had a higher height, weight, chlorophyll and micro- and macroelement content than plants in the control group. The algal extracts did not significantly influence the morphology of plants as shown in SEM pictures. Results show that algal extracts obtained by MAE have the highest potential applied in agriculture as biostimulants. Graphical Abstract

Effect of the application of blackcurrant seed post-extraction residues (BS) enriched via biosorption with Zn(II), Mn(II) and Cu(II) was examined in field tests on maize. As a nominal dose (100%), 2.5 kg of zinc, 1 kg of manganese and 0.5 kg of copper per hectare, were applied. The preparation was applied, also, in higher doses (150%, 200%). Crop yield and quality were assessed and multielemental analysis of grains was conducted. Grain yield obtained for maize treated with different doses of micronutrients (7.3 and 7.2 Mg ha-1 for BS 100% and BS 200%, respectively) was higher than in control group (6.2 Mg ha-1) and similar to a commercial reference product (7.1 Mg ha-1). Bioavailability of micronutrients from BS was shown to be higher than from reference commercial fertilizer. The highest content of micronutrients delivered to plants was observed for groups fertilized with BS in nominal dose of micronutrients (1.79, 7.08 and 28.55 mg kg-1 for Cu, Mn and Zn, respectively). The content of each micronutrient was 5.6% (Cu) 12.1% (Mn) and 12.6% (Zn) higher than in untreated group and 8.9% (Cu) 9.7% (Mn) and 8.7% (Zn) higher than commercial reference micronutrient fertilizer. New biocomponents are cheap and biodegradable carriers of nutrients which can be released in controlled way. Graphical Abstract

Spirulina has been studied due to its commercial importance as a source of essential amino acids, protein, vitamins, fatty acids etc. Most of the culture systems in use today are open ponds. The new approach proposed in this paper is to use the geothermal water as a medium for microalgae cultivation. Poland has beneficial conditions for wide geothermal use, as one of the environmentally friendly and sustainable renewable energy sources. In the planned research, geothermal water could be used to prepare microalgal culture medium, to heat greenhouses with bioreactors used for the growth of Spirulina, to dry the obtained biomass, as well as to heat the ground in foil tunnels. Using geothermal water gives the possibility to produce algae in open ponds covered with greenhouses and to cultivate plants during winter. The obtained algae can be used for the production of algal bio-products (e.g. homogenates), having the potential application in plant cultivation. Graphical Abstract

The paper presents the results of the selection of the flocculent and coagulant types as well as the evaluation of the best parameters of treatment of wastewater deriving from meat-bone meal (MBM) production. The efficiency of purification depends on the composition of the coagulant and flocculent as well as the magnitude of the applied dose. The use of ferrous sulfate PIX 113 coagulant assured the highest reduction of the contamination content in filtrate, resulting in the reduction of color of wastewater by 96.8%, turbidity by 99.2%, and the phosphorus content by 99.9% and nitrogen by 92.4%, with the Chemical Oxygen Demand (COD) being reduced by 62.8%. The X-ray method proved the significant presence of phosphorus salts in the content of sediment. The moisture content in the sediment varied from 45 to 78.5%. The elaborated method of pretreatment of wastewater from meat-bone meal unit was verified on an industrial scale. A very high reduction of the phosphorus content in filtrate (> 99.9%), and a significant reduction of COD as well as nitrogen and suspended solid contents (90−95%) were presented. A high reduction of contamination in filtrate increases the production capacity of the existing biological treatment plant, in the next step of treatment of filtrate in the biological treatment unit. Graphical Abstract

This study aimed to assess levels of silver nanoparticle residues in eggshells and tissues as well as the levels of selected biochemical parameters and oxidative stress indices in chickens hatched from nanosilver disinfected eggs. The samples included 40 Greenleg Partridge chicks allocated into two groups. The experimental group (group D) consisted of chickens hatched from eggs disinfected with a nanosilver preparation prior to incubation, while the control group (group C) included chickens whose eggs were exposed to UV radiation for disinfection. The eggshells and kidney sections obtained from group D chickens showed a significantly higher silver level compared to group C. For the biochemical parameters, only the uric acid content was higher in group D compared to group C. Analysis of the antioxidative stress biomarkers (superoxide dismutase and catalase), showed a significant increase in group D in relation to group C. Graphical Abstract

Fruits of several, mainly Polish cultivars of floricane- and primocane-fruiting red raspberry (Rubus idaeus), black raspberry (Rubus occidentalis) and blackberry (Rubus fruticosus), grown in central Europe during two successive vegetation periods, were investigated. The content of phenolic compounds, including anthocyanins, as well as antioxidant properties of fruit extracts were analysed. A number of methods were employed: ferric ion reducing antioxidant power (FRAP), cupric ion reducing antioxidant capacity (CUPRAC), 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging capacity involving both colorimetric and EPR spectrometric measurements. From among all the tested fruits black raspberries had the largest antioxidant capacity as verified by all methods used in this study. These berries were also the most abundant in phenolic and anthocyanin compounds. Blackberries were characterised by larger antioxidant capacity than red raspberry fruits which were accompanied by higher content of total phenolics and anthocyanins. Berries of primocane-fruiting cultivars, often used for intensive agricultural production, generally did not differ in the total phenolic and anthocyanin content as well as in the antioxidant capacity as compared to the traditional, floricane-fruiting ones. The research contributes to deep characterisation of central European berry fruits which due to their high content and large diversity of health-beneficial compounds are classified as natural functional food. Graphical Abstract

The objective of the study was to investigate the effects of selenium modulation on the alteration of carbonyl and sulfhydryl groups in proteins in chicken breast and leg meat. Selenium, in the form of sodium selenite and selenized yeast, was applied to broiler chicken at 0.26, 0.38 and 0.50 mg Se kg-1. The alteration of protein carbonyl and sulfhydryl groups, as well as total antioxidative potential of breast and leg meat were analyzed in fresh, chilled and frozen material. Protein reactive groups were effectively protected against oxidatively induced changes (carbonyl groups formation) by dietary selenium supplementation, during frozen storage of both types of chicken muscles, either with white fibre domination (breast) or with red fibre domination (leg). The inorganic form of selenium was effective in decreasing the loss of protein sulfhydryl groups in muscles with red fibre domination during frozen storage. In conclusion, selenium compounds can be used in broiler nutrition as a protein antioxidizing agent, especially in perspective of the long storage of meat under freezing conditions. Graphical Abstract

Natural compounds are an important source of desired biological activity which help to improve nutritional status, enhance productivity and bring many health benefits. The leaves of the Ilex paraguariensis (Aquifoliaceae) are used for preparing a beverage known as yerba mate and represent a proven source of natural polyphenols which are known to foster biological activity with the emphasis on antioxidant properties. In present work we focused on the polyphenolic content of air-dried leaves of Ilex aquifolium L., Ilex aquifolium ‘Argentea Mariginata’, Ilex meserveae ‘Blue Angel’, and a commercially available mate as the reference product. Liquid chromatography combined with mass spectrometry (HPLC and LC-MS) and thin layer chromatography (TLC), were used to establish polyphenolic substances content in aqueous methanolic extracts obtained from the biological matter. Up to 20 polyphenolic compounds were identified in the extracts, including rutin, quinic acid and its caffeoyl esters, i.e. chlorogenic acid and its isomers as well as dicaffeoyl derivatives. We took chlorogenic acid and rutin as reference compounds to quantify their levels in the extracts. It was determined that in all tested plants, high levels of these antioxidants were present. This led us to the conclusion that their leaves might serve as valuable food additives.

The aim of the study was to perform feeding experiments on growing pigs in order to assess the impact of macroalga Enteromorpha sp. enriched with Zn(II) and Cu(II) ions via the biosorption process on the mineral composition of blood, meat, liver, feces and urine. In the control group, microelements were supplemented as inorganic salts, whereas in the experimental groups they were replaced by enriched macroalga. After 3 months of the feeding experiment, it was found that the meat was biofortified with Cr, Mn, Fe, Cu and Zn. The average content of Zn in the blood from the pigs fed with algae was higher by 9.5%, compared to that in the blood from pigs in the control group. The liver of growing pigs from the experimental group contained 16% less Cu and 18% less Zn than the liver in the control group. Growing pigs fed with macroalgae excreted in feces 27% more Zn than growing pigs in the control group, but 3.5 times less Cu. It could be concluded that the bioavailability of microelements to pigs from algae was higher than from the inorganic salts. Baltic macroalgae enriched with microelement ions could be potentially used as a biological feed additive. Graphical Abstract

The paper presents the technology of processing Baltic cod (Gadus morhua callarias) and Atlantic salmon (Salmo salar) backbones – by-products from fish processing – for the production of calcium preparations. The raw material for the process consisted of backbones with remaining muscle tissue, devoid of heads and fins (30 kg of each type of backbones). The processing included the following stages: cutting, preliminary processing in an alkaline environment (soaking in 2 M NaOH), processing with 0.1% citric acid, aroma removal and material disinfection (5% H2O2), rinsing with tap water, drying, and grinding the end-product. Calcium preparations from cod (BCP) and salmon (ASP) in the amounts of 1.20 kg and 1.62 kg, respectively, characterized by high calcium content (27.79% in BCP, and 24.92% in ASP) and low protein and fat content (14.20% and 0.25% for BCP, and 10.78% and 0.12% for ASP, respectively) were obtained. The study demonstrated the effectiveness of this technology for production of calcium preparations from fish backbones. Graphical Abstract