Band 15, Heft 1

The rare coumarins stenocarpin, stenocarpin isobutyrate, oficinalin, oficinalin isobutyrate, 8-methoxypeucedanin and the known xanthotoxin, isoimperatorin, bergapten, peucedanin and 8–methoxyisoimperatorin were isolated from Peucedanum luxurians Tamamsch. (Apiaceae) and identified by means of spectral data (1D and 2D NMR). Their immunomodulating activity was evaluated by flow cytometry and their influence on HL60 cells as well as on PHA-stimulated PBLs was tested. All tested coumarins induce apoptosis (maximal in the 48 h culture) and decrease cell proliferation in a time- and dose-dependent manner, especially in HL60 cells. They also induce partial G1 block, but only in HL60 cells (at 100 µM concentrations). Dose-dependent reduction of RNA content was also found in G1 cells treated by the coumarins. All of the tested coumarins also possessed immunomodulatory activities. Bergapten and xanthotoxin were found to be the best candidates for further evaluation as anti-cancer drugs.

This paper deals with the synthesis and characterization of a novel group of potential photocatalysts, based on sol-gel-derived MgO-ZrO 2 oxide material. The material was synthesized in a typical sol-gel system using organic precursors of magnesia and zirconia, ammonia as a promoter of hydrolysis and methanol as a solvent. All materials were thoroughly analyzed, including morphology and particle sizes, chemical composition, identification of characteristic functional groups, porous structure parameters and crystalline structure. The proposed methodology of synthesis resulted in obtaining pure MgO-ZrO 2 oxide material with micrometric-sized particles and a relatively high surface area. The samples underwent an additional calcination process which led to the crystalline phase of zirconia being formed. The key element of the study was the evaluation of the effectiveness of decomposition of C.I. Basic Blue 9 dye. It was shown that the calcined materials exhibit both satisfactory adsorption and photocatalytic activity with respect to the decomposition of a selected model organic impurity. Total dye removal varied in the range of 50-70%, and was strongly dependent on process parameters such as quantity of photocatalyst, time of irradiation, and the addition of promoters.

The purpose of this review is to describe and compare selected traditional and modern extraction methods employed in the isolation of isoflavonoids from plants. Conventional methods such as maceration, percolation, or Soxhlet extraction are still frequently used in phytochemical analysis. Despite their flexibility, traditional extraction techniques have significant drawbacks, including the need for a significant investment of time, energy, and starting material, and a requirement for large amounts of potentially toxic solvents. Moreover, these techniques are difficult to automate, produce considerable amount of waste and pose a risk of degradation of thermolabile compounds. Modern extraction methods, such as: ultrasound-assisted extraction, microwave-assisted extraction, accelerated solvent extraction, supercritical fluid extraction, and negative pressure cavitation extraction, can be regarded as remedies for the aforementioned problems. This manuscript discusses the use of the most relevant extraction techniques in the process of isolation of isoflavonoids, secondary metabolites that have been found to have a plethora of biological and pharmacological activities.

Micro and nanocomposites of hydroxyl terminated polybutadiene (HTPB)-based polyurethanes (NPU) were obtained using five mineral fillers and Cloisite 20A nanoclay, respectively. Samples were prepared by the reaction of HTPB polyol and toluene diisocyanate (TDI), and the chain was further extended with glyceryl monoricinoleate to produce the final elastomeric polyurethanes. Mechanical and thermal properties were studied, showing that mineral fillers (20%w/w) significantly increased tensile strength, in particular nanoclay (at 5% w/w). When nanoclay-polymer dispersion was modified with a silane and hydantoin-bond promoter, elongation at break was significantly increased with respect to NPU with C20A. Thermal properties measured by differential scanning calorimetry (DSC) were not significantly affected in any case. The molecular structure of prepared micro and nanocomposites was confirmed by Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy. Interaction of fillers with polymer chains is discussed, considering the role of silanes in compatibilization of hydrophilic mineral fillers and hydrophobic polymer. The functionalization of nanoclay with HMDS silane was confirmed using FTIR. Microstructure of NPU with C20A nanoclay was confirmed by Atomic Force Microscopy (AFM).

Nano nickel ferrite particles were prepared at pH values 1.5, 4, 7, 10, 13 by a hydrothermal method using metal chlorides and NaOH as an oxidant and solution basicity controller. There is a phase transition from hematite to spinel ferrite that begins when the pH reaches 4. The lowest crystallite size (4 nm) was associated with a highest lattice constant (8.345 Å), at pH=4. Whereas maximum crystallite size 64.5 nm corresponds lattice constant of 8.298 Å at pH=10. The highest magnetization (48 emu/g) value was achieved for the sample prepared at pH=7, which at the same time has a lower coercivity. The samples synthesized at pH ≥4 show superparamagnetic behavior owing to its low particle size and to zero field cooling and field cooling measurements. The ferromagnetic resonance (FMR) cavity tests analysis show that the broadened linewidth (770 Oe) and high imaginary permeability or high microwave absorption which is linked to high magnetization and low coercivity of superparamagnetic particles and their aggregation. There was a shift in the resonance field due to internal fields and cation distribution.

Alkali borate glasses and alkaline earth borate glasses are commonly used materials in the field of optoelectronics. Infrared (FTIR) and Raman spectroscopy are valuable tools for structural investigation of borate glass networks. The compositional and structural variety of lithium magnesium metaborate glasses is usually determined by traditional instrumental methods. In this study a data set is classified by structural and physicochemical parameters (FTIR, Raman spectra, glass transition temperature-Tg). Characterisation of magnesium containing metaborate glasses by multivariate statistics (hierarchical cluster analysis) to reveal potential relationships (similarity or dissimilarity) between the type of glasses included in the data set using specific structural features available in the literature is conducted. The clustering of the glass objects indicates a good separation of different magnesium containing borate glass compositions. The grouping of variables concerning Tg and structural data for BO 3 and BO 4 linkage confirms that BO 4 /BO 3 ratios strongly affect Tg. Additionally, patterns of similarity could be detected not only between the glass composition but also between the features (variables) describing the glasses. The proposed approach can be further used as an expert tool for glass properties prediction or fingerprinting (identification of unknown compositions).

The differences between the composting, stabilization and drying processes were discussed. The law criteria for mechanical-biological treatment plant were presented. The purpose of the article was to assess the effectiveness of biodrying MSW (municipal solid waste) in a full scale reactor taking into account the degree of biological decomposition of organic matter and its suitability for RDF (refuse derived fuel). Therefore the microbial activity was measured as the O 2 /96 h uptake. CO 2 /96 h production and the respiration activity AT4 for untreated and biodried waste were compared. The decomposition of organic matter was measured by loss on ignition (LOI) and total organic carbon (TOC). The product after the biodrying process was assessed according to the EURITS and PN-EN 15359 criteria for the quality of RDF (residual derived fuel). The result 8.48 MJ/kg of calorific value shows that bio- dried waste is ranked below the EURITS minimum level and can be classified as fifth class by PN-EN 15359 requirements. The amount of chlorine, mercury and lead fulfil the EURITS criteria. The microbial activity after processing in the biodrying reactor expressed as oxygen uptake exceeded the permissible level of 10 mg O 2 /g d.m. in the time range ten months. The regulatory parameters TOC < 20% d.m. and LOI < 35% d.m. criteria were not met.

The volatile constituents from the n -hexane extracts of the roots and rhizomes of Valeriana officinalis (VO) and Valeriana turkestanica (VT) were investigated by GC-MS analysis. Two VO samples were obtained from cultivation, one from commercially available material, while VT was collected in a mountain of Kazakhstan. The most characteristic components present in all of the analysed samples were sesquiterpenoids. The three investigated samples of VO produced mainly valerenane and kessane sesquiterpenoids. Acetoxyvalerenic acid (33.94%), valerenic acid (15.05%), valerenal (11.93%), valeric acid 2,6-dimethylnon-1-en-3-yn-5-yl ester (5.24%), valerenol (3.31%), elemol (3.19%) and ( E )-valerenyl isovalerate (2.53%), were the common components identified in the n -hexane extract from the roots of VT. In comparison to VO this species does not produce kessane sesquiterpenoids and polyunsaturated fatty acids. This study shows that the roots of VT possess compounds of high biological significance, since they have the appropriate contents of valerenic acid and its derivatives, thus VT can be considered as a substitute for VO.

Plants belonging to the genus Salvia (Lamiaceae) are known to have a wide range of biological properties. In this work, extracts obtained from the aerial parts of Salvia sclareoides Brot. were evaluated to investigate their chemical composition, toxicity, bioactivity, and stability under in vitro gastrointestinal conditions. The composition of the supercritical fluid extract was determined by GC and GC-MS, while the identification of the infusion constituents was performed by HPLC-DAD and LC-MS. The in vitro cytotoxicity of both extracts (0-2 mg/mL) was evaluated in Caco-2 cell lines by the MTT assay. The anti-inflammatory and anticholinesterase activities were determined through the inhibition of cyclooxygenase-1 and acetylcholinesterase enzymes, while β-carotene/linoleic acid bleaching test and the DPPH assays were used to evaluate the antioxidant activity. The infusion inhibited cyclooxygenase-1 (IC 50 = 271.0 μg/mL), and acetylcholinesterase (IC 50 = 487.7 μg/ mL) enzymes, also demonstrated significant antioxidant properties, as evaluated by the DPPH (IC 50 = 10.4 μg/mL) and β-carotene/linoleic acid (IC 50 = 30.0 μg/mL) assays. No remarkable alterations in the composition or in the bioactivities of the infusion were observed after in vitro digestion, which supports the potential of S . sclareoides as a source of bioactive ingredients with neuroprotective, anti-inflammatory and antioxidant properties.

Research designed to improve extraction has led to the development of microextraction techniques (ME), which involve simple, low cost, and effective preconcentrationof analytes in various matrices. This review is concerned with the principles and theoretical background of ME, as well as the development of applications for selenium analysis during the period from 2008 to 2016. Among all ME, dispersive liquid-liquid microextraction was found to be most favorable for selenium. On the other hand, atomic absorption spectrometry was the most frequently used instrumentation. Selenium ME have rarely been coupled to spectrophotometry and X-ray spectrophotometry methods, and there is no published application of ME with electrochemical techniques. We strongly support the idea of using a double preconcentration process, which consists of microextraction prior to preconcentration, followed by selenium determination using cathodic stripping voltammetry (ME-CSV). More attention should focus on the development of accurate, precise, and green methods for selenium analysis.

Laboratory scale filtration tests utilizing leachate were conducted to investigate fouling and filtration performance of nanofiltration membranes. The work presented in this study is conducted on real samples rather than model water. Physico-chemical analyses showed that the leachate contained a lot of organic substances, exceeding 20000 mg/L O 2 expressed as chemical oxygen demand. Proper pre-treatment method must be chosen in order to reduce fouling index. Coagulation pre-treatment using poly-aluminium chloride was chosen. Two thin film polysulfone membranes were used, purchased by Osmonic Desal. The focus of this research is to assess the influence of the particle size and zeta-potential of the colloidal fraction in leachate on nanofiltration performance. The isoelectric point of both membranes was 4.7 and 4.3, respectively. The fouled membranes were negatively charged over the pH range with isoelectric point shifting to the left (lower pH) indicating the foulant material mainly not charged. It was confirmed by its zeta-potential, measured at -2 mV.

Regarding the importance of nanoparticles in today’s world, and in the light of the fact that their preparation can be a rather difficult task, we focused on the applicability of a simplistic direct precipitation approach for the preparation of praseodymium tungstate nanoparticles. To maximize the effectiveness of the method, a Taguchi robust design approach was applied to optimize the reaction in terms of the operating conditions influencing its outcome and the results were monitored by characterization of the Pr 2 (WO 4 ) 3 nanoparticles. Among the four parameters studied we found the dimensions of the produced nanoparticles to be determined by the concentrations of Pr 3+ and WO 4 3− solutions and the reaction temperature, while the flow rate of adding the cation solutions to the anion solution was found to leave very negligible effects on the product characteristics. To confirm the effect of the optimizations on the outcomes of the reaction, SEM, TEM, EDX, XRD, FT-IR and UV-Vis structural and morphological characterizations of the products were performed, the results of which were in agreement with those statistically predicted in the optimization procedure. Furthermore, as-synthesized praseodymium tungstate nanoparticles under ultraviolet light exhibited an efficient photocatalyst property in the photocatalytic degradation of methylene blue.

Various organic dyes possessing characteristic D-π-A-A configuration have been designed in this article. The analysis of the relation between polarity of charge transfer and the unsymmetrical nature of the benzothiazole group has been studied. The absorption spectra, electronic characteristic properties and non-linear optical responses were simulated using a quantum chemical approach. The results have indicated that the systems show higher polarizability ( α ) and hyperpolarizability ( β ) with commonly used polarity in comparison to the reverse polarity. A red-shifted absorption spectra were observed with systems having common polarities. This study illustrates the rule to design non-linear optical material with low energy charge transfer excited states and high value of oscillation.

The comparative adsorption studies of Cr (VI) on nano and micro-powder Fe 2 O 3 were investigated using kinetics and batch adsorption techniques. The uptake of chromate onto both the oxides of iron was observed to be dependent on the pH, contact time, temperature, media dosage and concentration of chromate anions. The values of sorption maxima were higher in the case of Fe 2 O 3 nanopowder than the micro-powder which can be ascribed to the high surface area and point of zero charge (PZC) of the former oxide. The Dubinin-Radushkivech and Langmuir models were found well fitted for the description of the batch adsorption data. The FTIR studies confirmed that the hexavalent chromium was adsorbed onto both the iron oxides in the form of the Cr 2 O 7 2− .

In the ethylene glycol generation unit of petrochemical plants, first a reaction of ethylene oxide takes place which is then followed by other side reactions. These reactions include water absorption with ethylene oxide, which leads to the generation of formaldehyde and acetaldehyde. Over the lifetime of the alpha-alumina-based silver catalyst there is an increase in side reactions, increasing the amount of the formaldehyde and acetaldehyde generated by the ethylene oxide reactor which leads to reduced MEG product purity. Given the need of a petrochemical complex to further strip the aldehyde (formaldehyde and acetaldehyde) to increase the quality of the MEG and increase the lifetime of the alpha-alumina-based silver catalyst, resin beds are designed and their surface absorption capacity is investigated to optimize aldehyde (formaldehyde and acetaldehyde) removal in the recirculating water flow of the ethylene oxide unit. Experiments show that the ion exchange system based on strong anionic resin pre-treated with a sodium bisulfite solution can reduce the aldehyde level from about 300ppm to less than 5ppm. After the resin is saturated with aldehyde, the resin can be recycled using the sodium bisulfite solution which is a cheap chemical substance.

Background Allium species extracts including Allium cepa L. contain sulfur compounds, known for their antiplatelet, antimicrobial, antineoplasic activities. Methodology Antibacterial activity of a formulation based on A . cepa extracts-liquid and lyophilized samples, has been demonstrated using two classes of bacteria: Gram-positive ( Staphylococcus aureus ) and Gram-negative ( Escherichia coli ) and three methods: discs soaked with liquid extract, the wells method in the culture medium, filled with the liquid extract and lyophilized formulation extracts transformed by the incorporation of ultrapure water. The second part of this study includes identification of thiosulfinates compounds from the studied samples by high performance liquid chromatography - mass spectrometry (HPLC-MS). Results The most important inhibition and the highest antibacterial effficiency were observed against Gram-positive bacteria, such as Staphylococcus aureus . The HPLC-MS thiosulfinates profile of the tested formulation extracts shows the presence of seven thiosulfinate compounds, MeS(O)S 1-propenyl ( E , Z ); n -PrS(O)S 1-propenyl-( E ); n -PrS(O)S 1-propenyl-( Z ); trans -zwiebelane; n -PrS(O)CHEtSS-1propenyl; 1-propenylS(O)CHEtSS1-propenyl, which may be responsible for antibacterial activity. Conclusion Testing antimicrobial effects using the three mentioned methods confirmed the antimicrobial activity of the tested samples based on A . cepa extracts, with a demonstrated content of seven thiosulfinate compounds.

The effectiveness of under-air n-hexane oxidation over monolithic catalysts made of heat-resistant foil, containing Pt, Pd or Pt-Pd, was compared. Pt and Pd precursors, either containing chlorine or devoid of chlorine, were used to prepare the catalysts. The chlorine- containing Pt (H 2 PtCl 6 ) and Pd (PdCl 2 ) precursors were found to lower the activity of the catalysts in hexane oxidation. Studies of the effect of 0.15% Pt/Al 2 O 3 catalyst (using H 2 PtCl 6 as the precursor) calcination conditions on catalyst activity showed the catalyst calcined in static air at 500°C to be the most active. Airflow calcination of the catalyst does not change its catalytic properties. In comparison with the 0.5% Pd/Al 2 O 3 catalyst obtained from Pd(NO 3 ) 2 , the use of a bimetallic 0.5% Pd/0.1% Pt/Al 2 O 3 catalyst, in which the precursors were Pd(NO 3 ) 2 and Pt(NO 3 ) 4 , resulted in the lowering of 10% and 50% n-hexane temperature by 15°C and 10°C.

Platinum(II) and vanadium(V) solid binary and ternary complexes involving naringin, a flavanone glycoside in found in grapefruit, and some phenolic acids were synthesized and fully characterized using detailed structural and spectroscopic analysis techniques such as IR, NMR, and SEM techniques. The magnetic susceptibility results as well line drawings of the platinum and vanadium complexes showed four-coordinate square-planar and remarkable low-spin diamagnetic species; which is in agreement with the structures proposed. The cytotoxic activities of the binary and ternary vanadium and platinum metal complexes of phenolic acids and naringin were tested and evaluated against HepG2 (human hepatocellular carcinoma), MCF-7 (human breast adenocarcinoma), and HCT116 (human colorectal carcinoma) tumor cell lines. Also, their antioxidant activities were examined by free radical scavenging assay. The relationship between the chemical structure of the synthesized complexes and their biological influence was studied and evaluated.

Purification of the organic extract of Laurencia obtusa Lamouroux by column chromatography and preparative thin layer chromatography provided four new compounds: a eudesmane-type sesquiterpenoid [eudesma-4(15),11-diene-5,7-diol ( 1 )], a cuparane-type sesquiterpenoid [10-hydroxycuparaldehyde ( 2 )], and two nor -cuparanes [3-hydroxy-15- nor -cuparan-10β-ol ( 3 ) and 2-bromo-3-hydroxy-15- nor -cuparan-10β-ol ( 4 )]. Structural identification was made possible by comparison of spectral data with those reported in the literature. Compounds 3 and 4 are significant as nor -cuparanes are rarely isolated from marine environment. 1 showed moderate anticandidal activity, whereas 2 exhibited reasonable antibacterial activity against multidrug-resistant bacteria (especially Gram-positive). All the compounds are nontoxic to Artemia salina .

Fourier transform infrared (FT-IR) and FT-Raman spectra of 1-acetyl-1 H -indole-2,3-dione ( N -acetylisatin) were recorded in the solid phase and analyzed. The molecular geometry, vibrational frequencies, infrared intensities, Raman activities and atomic charges were calculated using density functional theory (DFT/B3LYP) calculations with a standard 6-311++G(d,p) basis set. The fundamental vibrational modes of N -acetylisatin were analyzed and fully assigned with the aid of the recorded FT-IR and FT-Raman spectra. The simulated FT-IR and FT-Raman spectra showed good agreement with the experimental spectra. The stability of the molecule, arising from hyper-conjugative interactions and charge delocalization, was analyzed using natural bond orbital (NBO) analysis. The dipole moment (µ), polarization (α) and hyperpolarization (β) values of N -acetylisatin were also computed. The potential energy distribution (PED) was computed for the assignment of unambiguous vibrational fundamental modes. The HOMO and LUMO energy gap illustrated the chemical activity of N -acetylisatin. The energy and oscillator strength were calculated by DFT. Gauge–including atomic orbital NMR ( 1 H and 13 C) chemical shift calculations were performed and compared with the experimental values. Thermodynamic properties (heat capacity, entropy and enthalpy) of the compound at different temperatures were also calculated.

(5-Methoxy-1 H -indol-1-yl)(5-methoxy-1 H -indol-2-yl)methanone (MIMIM) is a bis -indolic derivative that can be used as a precursor to a variety of melatonin receptor ligands. In this work, the energetic and spectroscopic profiles of MIMIM were studied by a combined DFT and experimental approach. The IR, Raman, UV-Vis, 1 H NMR and 13 C NMR spectra were calculated by PBEPBE and B3LYP methods, and compared with experimental ones. Results showed good agreement between theoretical and experimental values. Mulliken population and natural bond orbital analysis were also performed by time-dependent DFT approach to evaluate the electronic properties of the title molecule.

The introduction of a nucleating agent in semi-crystalline polymers is a frequently utilized way to improve the crystallization performance, and the use of a nucleating agent has a very great effect on the performance of the polymer in other areas including thermal stability and mechanical properties. In this investigation, barium phenylphosphonate (BaP) was prepared as a crystallization accelerator for Poly(L-lactic acid) (PLLA), and the non-isothermal crystallization behavior, thermal stability, and mechanical properties of PLLA modified by BaP were investigated using differential scanning calorimetry (DSC), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and electronic tensile testing. Non-isothermal crystallization analysis showed that the BaP could significantly accelerate the crystallization of PLLA, and the non-isothermal crystallization peak shifted to a higher temperature with increasing concentration of BaP, however, the corresponding crystallization peak became wider. XRD results after non-isothermal crystallization confirmed the non-isothermal crystallization DSC results. Additionally, the addition of BaP did not change the crystal form of PLLA. A comparative study on thermal stability indicated that BaP decreased the onset decomposition temperature of PLLA, resulting from the formation of more tiny and imperfect crystals. Whereas the influence of BaP on the thermal decomposition profile of PLLA was negligible. In terms of mechanical properties, the tensile strength and elastic modulus of PLLA/BaP increased compared to the virgin PLLA, unfortunately, the elongation at break decreased.

A simple, fast and environmental friendly vortex assisted-supramolecular solvent based microextraction (VA-SSME) method was developed for the preconcetration of triclosan in wastewater prior to UV spectrophotometric determination. To achieve maximum sensitivity and accuracy for the target analyte, the experimental parameters affecting the VA-SSME procedure were optimized using response surface methodology (RSM). Under optimised conditions, the correlation coefficient (R 2 ) and recoveries were 0.9994 and 100.31-118.5%, respectively. The intra-day (repeatability) and inter-day (reproducibility) precisions expressed in terms of relative standard deviation (RSD) were 2-4% and 5.2%, respectively. The preconcentration factor and limits of detection (LOD) and quantification (LOQ) were found to be 90, 0.28 μg L −1 and 0.92 μg L −1 , respectively. The developed VA-SSME/UV method was applied for the determination of triclosan in real samples collected over a period of three months. The analytical results obtained showed that triclosan was frequently detected in influent wastewater samples but was not detected in effluent samples.

In this work, the O,O’-dithiophosphate derivatives of S-4-methylbenzyl-O,O’-di(phenyl) dithiophosphate (Inhi-Ph) and S-4-methyl benzyl-O,O’-di(4-bromophenyl) dithiophosphate (Inhi-BrPh) were synthesized and characterized by elemental analysis, FT-IR, 1 H, 13 C and 31 P NMR. Meanwhile, the corrosion inhibition of Q235 steel in HCl solution by synthesized inhibitors was evaluated by weight loss and electrochemical measurements. Measurement results indicate that the two inhibitors of Inhi-Ph and Inhi-BrPh are mixed-type inhibitor, the inhibition efficiency increase with inhibitor concentration increasing, decrease with HCl concentration and temperature increasing. The adsorption of Inhi-Ph and Inhi-BrPh on Q235 steel surface obeys Langmuir isotherm, which belongs to chemical adsorption.

Surface water is often used as alternative source of drinking water in many regions of the world where the potable water supply is erratic or not present. The concentration of heavy metals was assessed using an Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES). The impact of temporary seasonal variation on the contamination level was also assessed. Contamination factor (CF) and Hakanson’s potential ecological risk (E r and RI) indices were used to evaluate the toxicity levels of the metals in the sediments of the river. Higher concentrations of Fe, Mn, Pb, Cu and Zn were determined in the dry season in the river water whereas in the sediments higher levels were recorded for Al, Fe, Cd, Cr, Cu and Zn in the wet season. The average CF values for all the metals showed a low contamination level in the sediment, except for Cu and Cd which had moderate and considerable contamination levels, respectively. Similarly, Cu showed a moderate ecological risk level (E r = 62.90) only in March 2014, for other months Cu and the other metals investigated had E r values < 40 which implies low ecological risk. The mean relative abundance of heavy metals in the sediments follows the trend Al>Fe>Mn>u>Zn>Cr>Pb>Cd.

The requirement for materials which exhibit good second and third order non-linear optical properties and also for materials which could sense metals in trace quantities has kindled renewed investigations. Organometallics and coordination compounds show a lot of promise as new NLO materials combining the variety of organic moieties with the strength and variable oxidation states of metals. Especially ligands which selectively detect industrial pollutants like Cd and biologically significant metals like Zn are necessary. In the current work the ligand 1,10-phenanthroline-2,9-di(carboxaldehyde phenylhydrazone) (L) and its Ni 2+ , Co 2+ , Fe 2+ , Zn 2+ , Cd 2+ and Ir 3+ complexes were synthesized. These were characterized by UV-Vis, FT-IR, 1 H NMR, MS and CHN microanalysis techniques. The complexes were shown to have the formula [ML] 2+ . The second and third order NLO of the ligand and its complexes were recorded These new compounds were found to have same order of third order nonlinear optical susceptibility as that of CS 2 and their second hyperpolarizability was an order of magnitude greater than that of C 60 . Furthermore the ligand also displays selective luminescence sensing of metals ions Fe 2+ and Ir 3+ even in the presence of other metal ions.

A simple, rapid, cost-effective, and sensitive TLC-spectrodensitometric method for simultaneous determination of esomeprazole and domperidone was developed and tested in human plasma. Ethyl acetate: methanol: benzene: acetonitrile (5: 4: 8: 3, v/v/v/v) mobile phase was used for separation on TLC plates detected at 286 nm. The linearity ranges were 5-1200 and 2-600 ng/ spot for esomeprazole and domperidone, and limits of detection were 1.73 and 0.59 ng/spot. The effects of four variables affecting R f were evaluated by fractional factorial design. The benzene volume and saturation time had significant effects.

Capuramycin and a few semisynthetic derivatives have shown potential as anti-tuberculosis antibiotics.To understand their mechanism of action and structureactivity relationships a 3D-QSAR and molecular docking studies were performed. A set of 52 capuramycin derivatives for the training set and 13 for the validation set was used. A highly predictive MFA model was obtained with crossvalidated q 2 of 0.398, and non-cross validated partial least-squares (PLS) analysis showed a conventional r 2 of 0.976 and r 2 pred of 0.839. The model has an excellent predictive ability. Combining the 3D-QSAR and molecular docking studies, a number of new capuramycin analogs with predicted improved activities were designed. Biological activity tests of one analog showed useful antibiotic activity against Mycobacterium smegmatis MC2 155 and Mycobacterium tuberculosis H37Rv. Computer-aided molecular docking and 3D-QSAR can improve the design of new capuramycin antimycobacterial antibiotics.

The novel Schiff base ligand 2-(2-hydroxyphenyl)-3-{[(E)-(2-hydroxyphenyl)methylidene]amino}-2,3-dihydroquinazolin-4(1H)-one (H-HHAQ) derived from 2-aminobenzhydrazide was synthesized and characterized by elemental analyses, ES + -MS, 1 H and 13 C{ 1 H}-NMR, and IR studies. The characterization of the ligand was further confirmed by single crystal analysis. The Schiff base ligand was complexed with metal ions like Co(II), Ni(II), Cu(II) and Zn(II) to obtain the bis-octahedral complexes. The ligand and its metal complexes were also studied for their urease inhibitory activities. All the tested compounds show medium to moderate activities for the enzyme, whereas the copper based complex was found to be much more active against urease with an IC 50 = 0.3 ± 0.1 μM±SEM, which is even more potent than the standard thiourea. The IC 50 of the cobalt complex was 43.4±1.2 μM±SEM, whereas that of the nickel complex was 294.2±5.0 μM±SEM. The ligand H-HHAQ and the zinc complex were inactive against the tested enzyme.

Two series of novel ammonium salts containing the quinuclidine moiety were prepared in order to evaluate their antioxidative, antibacterial and antifungal potential. The synthesized homologues of 3-hydroxy (QOH) and 3-chloroquinuclidine (QCl) with the different N-benzyl substituents at the para -position (bromo, chloro or nitro group) were obtained in very good yields and characterized by IR and NMR spectroscopies and elemental analysis. All compounds were tested for antioxidative activity using the oxygen radical absorbance capacity (ORAC) assay and among tested samples, N-p-nitrobenzyl-3-hydroxyquinuclidinium bromide (QOH-4) exhibited the highest antioxidative potential (293.80 nmol (TE) mL -1 ), which was further investigated by the DNA nicking assay. The biological activity of selected compounds was evaluated by measuring the zone of inhibition and by determining the minimal inhibitory concentration (MIC) against three Gram-positive bacteria ( B. cereus, E. faecalis and S. aureus ), three Gram-negative bacteria ( E. coli, P. aeruginosa and C. sakazakii ) and three fungi species ( C. albicans, A. niger and P. notatum ). The bioactivity assay showed that some newly synthetized quaternary quinuclidinium compounds display a comparable or even better antibacterial and antifungal activity than the reference drugs such as gentamicin (GEN), cefotaxime (CTX) and amphotericin B (AMPHB). Among the tested compounds, N-p-chlorobenzyl-3-hydroxyquinuclidinium bromide (QOH-3) exhibited a considerable antibacterial efficiency against P. aeruginosa (MIC=0.39 µg mL -1 ) and QOH-4 displayed a potent antifungal activity against C. albicans (MIC=1.56 µg mL -1 ).

There are numerous sources of chemical pollutants which can impact the mangrove ecosystem through adjacent waters, industrial and sewage discharges and air depositions. Polycyclic aromatic hydrocarbons (PAHs) are semi volatile ubiquitous anthropogenic pollutants detected in all environmental compartments. In the monitoring framework for the mangrove ecosystem along the Red Sea coast of Saudi Arabia, nine mangrove stands were examined for the accumulation of PAHs. Polycyclic aromatic hydrocarbons were measured using Gas Chromatography-Mass Spectrometry (GC-MS). The mean values detected for total PAHs in sediments, roots and leaf were 2.98, 8.57 and 23.43 ng/g respectively. The trend of the total PAHs concentration in all sites showed the descending order: leaf > roots > sediments. Beside the sandy nature of the sediments, the presences of all stands in remote areas fare from the direct anthropogenic effects lead to these relative low values. PAH bio-concentration factors for leaf are two to three magnitudes higher than that in roots, suggesting atmosphere deposition /leaf uptake mechanism in addition to the sediment/root mechanism. The diagnostic ratios revealed that the sources of PAHs are mainly pyrogenic.

Natural high-quality iron can be directly applied to pyro-metallurgy process, however, the availability of these ores has become less and less due to exploitation. This research reports a systematic approach using reduction roasting and magnetic separation for oolitic iron ores from west Hubei Province. Firstly, a mineralogical study was performed and it was shown that the oolitic particles were mainly composed of hematite, with some silicon-quartz inside the oolitic particle. Then, the roasting temperature was examined and shown to have significant influence on both Fe recovery and the Fe content of the concentrate. Also the Fe content gradually increased as the temperature increased from 700 to 850 °C. The most important aspects are the quantitative investigation of change of mineral phases, and reduction area (with ratio) during the reduction roasting process. The results showed that Fe 2 O 3 decreased with temperature, and Fe 3 O 4 (magnetite) increased considerably from 600 to 800 ° C. The reductive reaction was found to occur from the outside in, the original oolitic structure and embedding relationship among the minerals did not change after roasting. Finally, 5% surrounding rock was added to mimic real industrial iron beneficiation. This study could provides useful insight and practical support for the utilization of such iron ores.

The aim of this study was to reveal the photobleaching characteristics of α-(8-quinolinoxy) zinc phthalocyanine (ZnPc-F7), a new type of amphiphilic complex. Normal saline (NS), pure Roswell Park Memorial Institute (RPMI)-1640 medium (1640), RPMI-1640 medium containing 10% fetal calf serum, and cell suspension were used as solvents to study the photobleaching of ZnPc-F7 in different solutions. Absorbance and fluorescence spectra were measured. Photobleaching kinetics were observed after irradiation for 3–180 min with ZnPc-F7 concentrations of 1–40.00μg/mL. An in vivo imaging system was used to observe the distribution and photobleaching of ZnPc-F7 in mice. ZnPc-F7 was bleached both in vitro and in vivo after exposure to laser energy at 670 nm. ZnPc-F7 was not bleached without irradiation. ‘The type of solvent, irradiation time, and initial concentration influenced the photobleaching rate. Rapid initial phases followed by a slower rate of photobleaching were observed in all four solutions. Fluorescence of ZnPc-F7 in mouse skin was steady and then increased 24 h after injection. There was no significant difference in the extent of fluorescence between normal and psoriasis-like mice. Local administration of ZnPc-F7 showed higher fluorescence intensity in skin at an early time than intravenous injection and lower content in organs after 24 h.

Ce 0.5 Zr 0.5 O 2 mixed oxides were prepared in a flow reactor in supercritical isopropanol with acetylacetone as a complexing agent. Variation of the nature of the Zr salt and the temperature of synthesis affected the phase composition, morphology and specific surface area of oxides. X-ray diffraction and Raman spectroscopy studies revealed formation of metastable t” and t’ phases. Oxides are comprised of agglomerates with sizes depending on the synthesis parameters. Loading NiO decreases the specific surface area without affecting X-ray particle sizes of supports. Such sintering was the most pronounced for a support with the highest specific surface area, which resulted in the lowest surface content of Ni as estimated by X-ray photoelectron spectroscopy and in the formation of flattened NiO particles partially embedded into the support. The catalytic activity and stability of these samples in the dry reforming of methane were determined by the surface concentration of Ni and the morphology of its particle controlled by the metal-support interaction, which also depends on the type of catalyst pretreatment. Samples based on ceria-zirconia oxides prepared under these conditions provide a higher specific catalytic activity as compared with the traditional Pechini route, which makes them promising for the practical application.

This paper addresses the compatibility, morphological characteristics, crystallization, physico-mechanical properties and thermal stability of the melt mixed EMA/NBR blends. FTIR spectroscopy reveals considerable physical interaction between the polymers that explain the compatibility of the blends. DSC results confirm the same (compatibility) and reveals that NBR hinders EMA crystallization. Mechanical and thermal properties of the prepared EMA/NBR blends notably enhance with increasing the fraction of EMA in the blends. Morphology study exhibit the dispersed particles in spherical shape in the nanometer level. Swelling and oil resistance study have also been carried out in details to understand the performance behaviour of these blends at service condition

The real/atomic structure of single phase homogeneous nanocrystalline Ce 0.5 Zr 0.5 O 2±δ oxides prepared by a modified Pechini route and Ni-loaded catalysts of methane dry reforming on their bases was studied by a combination of neutron diffraction, synchrotron X-ray diffraction, total X-ray scattering and X-ray absorption spectroscopy. The effects of sintering temperature and pretreatment in H 2 were elucidated. The structure of the mixed oxides corresponds to a tetragonal space group indicating a homogeneous distribution of Ce and Zr cations in the lattice. A pronounced disordering of the oxygen sublattice was revealed by neutron diffraction, supposedly due to incorporation of water into the structure when in contact with air promoted by the generation of anion vacancies in the lattice after reduction or calcination at high temperatures. However, such disordering has not resulted in any occupation of the oxygen interstitial positions in the bulk of the nanodomains.

This paper presents properties of filtrate obtained from pig manure using the AMAK treatment process, which includes the mineralization of macro- and microfertilizer components by the hydrolyzing of organic matter into forms that are bioavailable to plants. Filtration produced two products, sediment and filtrate. The quality of the filtrate allowed for its use as a substitute of water to irrigate crops. Concentrations of heavy metals are very low and therefore the quality of the filtrate fully complies with European standard concerning fertilizers. The used mineralization process practically eliminated odors from the filtrate. The reduction of specific odor emission by 99.1-99.5% in samples taken from above the filtrate, respectively compared to the odor concentration found in samples taken from above raw pig manure. Sediment could be used as raw material for production of mineral-organic fertilizer. Filtrate and filtration sediments analyses show that the majority of nitrogen and other fertilizing compounds included in raw pig manure remains in sediment.

Due to the simplicity of tea preparation (pouring hot water onto different dried herbs) and its high popularity as a beverage, monitoring and developing a screening methodology for detecting the metal content is very important. The concentrations of Cd, Ca, Cu, Fe, Pb, Mg and Mn in 11 different samples of sage (Salvia officinalis L.), linden (Tilia L.) and chamomile (Matricaria chamomilla L.) purchased at local herbal pharmacy were determined using electrothermal atomizer atomic absorption spectrometry (ETAAS) and flame atomizer atomic absorption spectrometry (FAAS). The concentrations determined were: Cd (0.012 – 0.470 mg kg −1 ), Ca (5209 – 16340 mg kg −1 ), Cu (22.01 – 33.05 mg kg −1 ), Fe (114.2 – 440.3 mg kg −1 ), Pb (0.545 – 2.538 mg kg −1 ), Mg (2649 – 4325 mg kg −1 ) and Mn (34.00 – 189.6 mg kg −1 ). Principal Component Analysis (PCA) was applied to identify factors (soil and climate) influencing the content of the measured elements in herbal samples. The proposed methodology developed in this work was successfully applied to the detection of metals in herbal samples. The analysis showed that the content of toxic metals in herbal teas was below the maximum dose recommended by the World Health Organization (WHO).

In the work presented, a lead film electrode was prepared in situ on a screen-printed carbon support using a reversibly deposited mediator (Zn) and applied to the determination of Cd(II) by anodic stripping voltammetry. The electrochemical method for lead film formation is based on a co-deposition of a metal of interest (Pb), with a reversibly deposited zinc mediator, followed by oxidation of zinc, with additional deposition of lead at the appropriate potential. It serves to increase the density of lead particles, promoting lead film growth, and consequently helps to improve the electrochemical properties of the electrode. This was confirmed by microscopic and voltammetric studies. The obtained detection limit of Cd(II) is equal to 6.6 × 10 −9 mol L −1 (−1.6 V for 180 s and then −0.95 V for 5 s). The presented procedure was successfully applied to cadmium determination in Bystrzyca River water samples.

This work aimed to study the potential effects of four Arctii folium extracts, 5 mg gallic [GAE] acid equivalents per 1 mL sample, on six antibiotics (Ampicillin/AM, Tetracycline/TE, Ciprofloxacin/CIP, Sulfamethoxazole-Trimethoprim/SXT, Chloramphenicol/C and Gentamicin/CN) tested on four Gram-positive ( Staphylococcus aureus ATCC 6538, Staphylococcus aureus ATCC 25923, Enterococcus faecalis ATCC 29212, and Staphylococcus epidermidis ATCC 12228) and five Gram-negative ( Proteus mirabilis ATCC 29245, Escherichia coli ATCC 35218, E. coli ATCC 11229, E. coli ATCC 8739, and Bacillus cereus ATCC 11778) bacteria. Arctii folium extracts were the whole ethanol extract/W and subsequent ethyl acetate/EA, aqueous/AQ, and chloroform/CHL fractions. Chemical qualitative analysis (HPTLC method) emphasized five main polyphenol compounds in Arctii folium polar extracts: chlorogenic acid (Rf≈0.52/0.55) and its isomer, 1,5-di- O -caffeoylquinic acid (Rf≈0.90/0.92), plus cynarin (Rf≈0.77), hyperoside (Rf≈0.68/0.64) and isoquercitrin (Rf≈0.69/0.71). Microbiological screening indicated Arctii folium polar extracts (AQ and W) efficacy on S. epidermidis ATCC 12228; the MIC values were in the range of common antibiotics, being 32 and 128 μg GAE per mL sample respectively. The unpredictable effects (stimulatory or inhibitory) of Arctii folium extracts in combination with typical antibiotics as well as a potential use of the whole ethanol extract/W for restoring the antimicrobial potency of susceptible antibiotics have also been evidenced.

Aedes aegypti L. is the major vector of the arboviruses responsible for dengue fever, one of the most devastating human diseases. Some bacterial, fungal and plant metabolites belonging to different chemical subgroups, including Amaryllidaceae alkaloids, anthracenes, azoxymethoxytetrahydropyrans, cytochalasans, 2,5-diketopiperazines, isochromanones, naphthoquinones, organic small acids and their methyl esters, sterols and terpenes including sesquiterpenes and diterpenes, were tested for their larvicidal and adulticidal activity against Ae. aegypti . Out of 23 compounds tested, gliotoxin exhibited mosquitocidal activity in both bioassays with an LC 50 value of 0.0257 ± 0.001 µg/µL against 1 st instar Ae. aegypti and LD 50 value of 2.79 ± 0.1197 µg/mosquito against adult female Ae. aegypti . 2-Methoxy-1,4-naphthoquinone and cytochalasin A showed LC 50 values of 0.0851 ± 0.0012 µg/µL and 0.0854 ± 0.0019 µg/µL, respectively, against Ae. aegypti larvae. In adult bioassays, fusaric acid (LD 50 = 0.8349 ± 0.0118 µg/mosquito), 3-nitropropionic acid (LD 50 = 1.6641 ± 0.0494 µg/mosquito) and α-costic acid (LD 50 = 2.547 ± 0.0835 µg/mosquito) exhibited adulticidal activity. Results from the current study confirm that compounds belonging to cytochalsin, diketopiperazine, naphthoquinone and low molecular weight organic acid groups are active and may stimulate further SAR investigations.

The investigation of natural products used in Traditional Medicine in Africa is complicated as modern analytical and screening methods are often not available. Computer aided product identification from traditional usage records (CAPITURE) may provide an interesting alternative and has been evaluated in the context of an ethnobotanical survey on fungal diseases and their traditional treatment in Tchamba District (Togo). 53 traditional healers were interviewed and their knowledge recorded. Several indicators, the Use Value (UV), Plant Part Value (PPV), Specific Use (SU) Value, Intraspecific Use Value (IUV) and Informant Consensus Factor (ICF), were applied to the data. Those indices, in addition to a bibliographic review, were then fed into a computer-aided approach which predicted two interesting plants out of the 43 species survey-recorded and their specific activities: Pterocarpus erinaceus sap against ringworm, Daniellia oliveri sap against intertrigo and respectively their roots and trunk barks against candidiasis. Subsequent laboratory-based studies have confirmed the predicted antimicrobial activities with MIC (128 μg/mL to 30 mg/mL) and without any notable toxicity on a normal human cell (MRC-5 cells). Although such a method may not be flawless, it is able to provide first leads, and in the face of limited resources, is an attractive alternative worth considering.

Alzheimer’s disease (AD) is by far the most prevalent of all known forms of dementia. Despite wide-spread research, the main causes of emergence and development of AD have not been fully recognized. Natural, low-molecular, lipophilic terpenoids constitute an interesting group of secondary plant metabolites, that exert biological activities of possible use in the prevention and treatment of AD. In order to identify secondary metabolites possessing both antioxidant activity and the potential to increase the level of acetylcholine, selected terpenoids have been screened for possible acetylcholinesterase inhibitory activity by use of two methods, namely Marston (chromatographic assay) and Ellman (spectrophotometric assay). In order to describe the interaction between terpenes and AChE active gorge, molecular docking simulations were performed. Additionally, all analyzed terpenes were also evaluated for their cytotoxic properties against two normal cell lines using MTT assay. The obtained results show that: carvone (6), pulegone (8) and γ -terpinene (7) possess desirable AChE inhibitory activity. MTT assay revealed low or lack of cytotoxicity of these metabolites. Thus, among the investigated terpenes, carvone (6), pulegone (8) and y -terpinene (7) can be recognized as compounds with most promising activities in the development of multi-target directed ligands.

Essential oils (EOs) exhibit a wide range of pharmacological properties, which have been reported over the years in various studies. The aim of this literature review is to present the latest findings of the immunomodulatory effects of EOs. From 2008 to 2016 in vivo - and/or in vitro -studies, most of which were published in the last couple of years, have been selected based on their topic relevance, namely immunomodulatory, anti-inflammatory, antileishmanial, antiallergic, and anticancer effects of various EOs. These findings show modulation of pro- and anti-inflammatory cytokines, antiproliferative, chemotactic properties and also exert antiparasitic effects by inhibiting the pro, axenic and intramacrophagic amastigote forms of Leishmania parasites or by modulating the T H 1 and T H 2 immune responses. Furthermore, the EOs of some plants show the ability to reduce the mast cell degranulation and improve the airway inflammation and mucus obstruction in the cases of immediate hypersensitivity in murine models. Additionally, the cytotoxicity of some EOs against human melanoma, hepatoma, lung, prostate and breast cancer cell lines proposed their potential antitumor effect by an increased immunosuppressive (cytostatic) activity.

The current study supports the phytochemical screening, evaluation of antioxidant and enzyme inhibition potential and correlations between antioxidant activities and phenolics of Rumex dentatus (Family: Polygonaceae ), Mentha spicata (Family: Lamiaceae ), Withania somnifera (Family: Solanaceae ), Nerium indicum (Family: Apocynaceae ) and Artemisia scoparia (Family: Asteraceae ). The herbal materials were extracted in ethanol (90%) and partitioned between several solvents based on polarities. Total phenols were determined with FC method and ranged 21.33 ± 1.53 - 355.67 ± 6.03 mg GAE/ mg of the extract. Antioxidant activities (DPPH, total iron reducing capacity, phosphomolybdate assay & FRAP) and enzyme inhibition potential (Protease, AChE & BChE) were performed by the standard protocols. The results showed that all extracts exhibited significant DPPH activity ranging from 12.67 ± 2.08 - 92.67 ± 1.53%. The extracts that were active in DPPH activity also potrayed marvelous FRAP, total iron reducing and phosphomolybdate values. Correlation studies of antioxidant activities and the content of phenolic compounds in plant materials exhibited positive correlation between them. The outcome of enzyme inhibition activity exhibited that about 80% of the fractions under surveillance plants intimated more than 50% inhibition. Isolation of bioactive compounds from these plants is in progress.

The total phenolic content (TPC), total tannin content (TTC) and total flavonoid content (TFC) as well as the antioxidant activity and the cytotoxic effect of the extract from leaves of Erythrochiton brasiliensis Nees & Mart. (Rutaceae) were evaluated. Raw material was collected in different European botanical gardens. Statistical analysis revealed a clear grouping of populations according to their climatic zone. The average TPC, TTC and TFC in tested samples were 35.92 (± 7.11) mg GAE·g –1 DW, 14.98 (± 4.08) mg PyE·g –1 DW and 2.92 (± 0.76) mg QuE·g –1 DW, respectively. The scavenged DPPH and Trolox equivalents determined by EPR spectroscopy were 1.23–4.14 and 0.50–1.44 mmol·g –1 of dry extract, respectively. Thirteen compounds (derivatives of bezoic acid acid and trans -cinnammic acid) were identified in the samples. The flavonoid vitexin was also present as the major component in three investigated samples. The in vitro cytotoxicity test of the extract on Vero cells provided IC 50 and IC 10 values of 175.6 and 72.5 μg·mL –1 , respectively. Incubation of samples with HHV-1 infected Vero cells had no effect on the occurrence of cytopathic effect.