Band 8, Heft 2

In view of the recent emphasis on non-conventional chemistry, application of ultrasound in isolation of plant polysaccharides represents a viable alternative to traditional extraction processes. This review presents an extensive literature survey of ultrasound-assisted extraction of polysaccharides from different plant materials, particularly herbal plants and secondary agricultural plant sources. Targeted, multistep methods were applied with respect to differences in the types of polysaccharides and their location in plant cell walls. The effectiveness of the methods was evaluated according to yield and properties of the isolated polysaccharides in comparison to classical extraction methods. Substantial shortening of extraction time, reduction of reagent consumption and/or extraction temperature are the most important advantages of the ultrasonic treatment. In combination with sequential extraction steps using different solvents, sonication was shown to be effective in separation and/or purification of polysaccharides. The disadvantages of the sonication treatment, such as degradation and compositional changes of the polysaccharide preparations are discussed as well.

This work proposes a method for determination Cu(II) concentrations, based on the formation of a copper-1-nitroso-2-naphthol complex, in the presence of micelles; formed by a triblock copolymer, made up of two blocks of polyethylene oxide (PEO), and one block of polypropylene oxide (PPO). The insoluble copper complexes, are concentrated inside the hydrophobic micelle core; formed by the PPO block. For a solution containing 0.200 mg L−1 Cu(II), the proposed method had a relative standard deviation of 2.0% (n = 3); an absolute error from 0.11 to 0.39 mg L−1; and a linear calibration range, from 0.200 to 0.800 mg L−1. Detection and quantification limits, were 43.1 mg L−1 and 144 mg L−1, respectively. We show that there is excellent agreement, between the results obtained using our novel method; and those obtained using flame atomic absorption spectrometry: In the determination of Cu(II) concentrations, in Brazilian sugar-cane spirits. The proposed method, is the first to apply macromolecular micelle systems, to the determination of copper concentrations; and improves upon the results obtained using molecular surfactants. This method is environmentally friendly (since it does not use any organic solvents for extraction), and the triblock copolymer is biodegradable and non-toxic.

An increasing interest in determination of various macro- and microelements in medicinal plants has been observed. The majority of studies are carried out using one mineralization method without any optimization. The present study demonstrates that changes in mineralization parameters can significantly affect the recovery of the elements determined. In the study, the dried plant material was mineralized in 12 ways and iron (Fe), copper (Cu), zinc (Zn), nickel (Ni) and manganese (Mn) levels were determined. The samples were mineralized in the dry or open microwave mode as well as 10 closed microwave modes. The influence of acid amounts, irradiation power and time, addition of hydrogen peroxide and perfluoric acid was examined. All parameters were shown to be critical — good efficiency was observed with larger amounts of acid. The determined content varied significantly in the same sample and were in the ranges (ug g−1): 46–136 (Fe), 1.4–11.8 (Cu), 4.0–11.3 (Ni), 15.4–53.8 (Zn) and 9.5–67.6 (Mn). Increased irradiation resulted in the loss of copper and zinc and better recovery of nickel. The results demonstrate that such determinations should include the mineralization optimization step.

Sulphonimide based organocatalyst was used to catalyze the aldol reaction in ionic liquid media. On the basis of yield and selectivity the ionic liquid mediated system was found superior in comparison with organic solvents. The added advantages of this ionic liquid mediated organocatalysis are easy recovery of product and the recyclability of the organocatalyst.

A method for the fast determination of yohimbine, a potent adrenoreceptor antagonist used for the treatment of sexual dysfunctions, is proposed in this article. MEKC under basic and acidic conditions (sodium borate, pH 9.5 and sodium phosphate, pH 2.5) with SDS was developed. The effect of the experimental parameters, e.g. pH, SDS concentration and injection time, on yohimbine migration was also studied. Both methods were validated in terms of linearity, limits of detection and quantification, accuracy, and precision using caffeine as an internal standard. The application for the determination of yohimbine in hand-made medicaments is also investigated in this study.

Biohybrids consisting of gelatin (G) and calcium phosphate silicate/wollastonite (CPS/W) have not been prepared so far. In this work our results are focused on the possibility of obtaining G-CPS/W bioactive hybrids in vitro. XRD, FTIR, SEM/EDS techniques were employed to characterize the synthesized hybrid materials. FTIR shows that before immersion in 1.5 SBF the “red shift” of COO- band for pure G is observed. The presence of this bond could be attributed to the formation of COO-Ca2+ via non-biomimetic route. After immersion in 1.5 SBF, FTIR shows the presence of A- and B-type carbonate containing hydroxyapatite (A/B-CO3HA). ESD and FTIR show that small amount of calcite (CaCO3) are present after in vitro test in 1.5 SBF for 3 days. XRD reveals that CO3HA and small amounts of CaCO3 can be detected after in vitro test. SEM results obtained for immersed samples show that hydroxyapatite (HA) particles fully covered the surface of the hybrids by a layer composed of spherulites. At higher magnification, very small elongated crystallites could be observed.

The oxidation processes of 2,6-diisopropylnaphthalene and 4,4′-diisopropylbiphenyl with oxygen in the presence of a catalyst, composed of copper(II) chloride and tetrabutylammonium bromide, were investigated. It was found that, in essence, only one isopropyl group undergoes oxidation, and obtained mixtures contained mainly peroxide, alcohol, ketone and only small amounts of hydroperoxide.

Four Schiff base ligands, salabza-H2 = N,N′-bis(salicylidene)-2-aminobenzylamine, were synthesized by condensation of one mole of 2-aminobenzylamine and two moles of salicylaldehyde and/or two moles of substituted salicylaldehyde (5-OMe, 5-Br, 5-NO2). All the four Schiff bases and their Mn(II), Co(II), Cu(II) and Zn(II) complexes are characterized by UV-Vis, FT-IR, 1H NMR spectroscopy, mass spectrometry and elemental analysis. The formation constants and the Gibbs free energies were measured spectrophotometrically for 1:1 complexes in methanol in constant ionic strength (I = 0.1 mol dm−3 NaClO4) and at 25°C. The data refinement was carried out with the SQUAD program. The trend of formation constants of H2L1 with M(II) follows the order: Mn(II) (3.97) Also, the trend of formation constants of ligand toward a given metal (for example Mn) is as follows: H2L1 (p-OMe) (3.97) > H2L2 (p-H) (3.65) > H2L3 (p-Br) (3.37) > H2L4 (p-NO2) (3.04)

During the diazo-coupling reaction, nucleophilic displacement of a nitro group was also observed. This was the main reaction (1→7) when the starting amine bore either a chlorine or methoxy group at the para position (1b–c). The newly prepared compounds (7) might serve as convenient building blocks in synthesis of some heterocycles.

Detailed theoretical studies of azide/thioacid amidation are performed using density functional theory. The calculated results indicate that electronic properties of azide have significant effects on reaction pathways, which result in two distinct mechanisms for electron-rich and electron-poor azide coupling in the base-promoted amidation. For electron-rich azide amidation, after the concerted [3+2] cycloaddition of azide/thiocarboxylate, a new reaction channel is found challenging that recently mentioned, which follows two consecutive, unimolecular reactions with very low activation barriers (−1) to give an anionic amide and a nitrous sulfide (N2S). Distinct from electron-rich azide amidation, electron-poor azide first couples with thiocarboxylate to form a linear stable adduct, and then passes through the transition state of the rate-controlling step to afford the anionic amide, rather than the thiatrazoline. The free energy barrier of this step is 4.2 kcal mol−1 lower than that previously proposed. Comparatively, the azide/thioacid amidations undergo the concerted [3+2] cycloaddition and the subsequent retro-[3+2] cycloaddition process to give cis-enol form of the amide, which have higher activation barriers than those in the based-promoted amidation. Solvent effects investigated indicate that non-polar solvents, such as chloroform, are more preferable for the base-promoted thioacid/azide amidation.

A rapid and an efficient one-pot method for the synthesis of quinoxalines catalysed by ZnO-beta zeolite at room temperature is described. This environmentally benign method provides several advantages over methods that are currently employed such as a simple work-up, mild reaction conditions, good to excellent yields, and a process to recover and reuse the catalyst for several cycles with consistent activity.

This work presents a nano-Al2O3 solid phase extraction technique for the determination of ultra-trace amounts of inorganic selenium species in aqueous systems using ion chromatography inductively coupled plasma-mass spectrometry (IC-ICP-MS). In this experiment, the inorganic selenium species were successfully extracted on a nano-Al2O3 solid phase column and then quantitative eluted with a 100 mmol L−1 NaOH solution. Extraction conditions such as solvent identity, solvent concentration, solvent volume, solvent pH and salt addition were optimized. Under the optimum extraction conditions (elute solvent: 100 mmol L−1 NaOH, solvent volume: 4 mL, pH: 7.0), low detection limits (Se (IV): 6 ng L−1, Se (VI): 11 ng L−1; RSD−1, R2 > 0.999) were obtained for all of the analytes. Good spiked recoveries over the range of 80–98% were obtained by applying the proposed method on real environmental water samples. These results indicated that this method is very sensitive and reliable when monitoring trace levels of inorganic selenium species in aqueous samples.

In this project, nanocrystalline SnO2 powders were successfully prepared by (a) citrate sol-gel and (b) direct precipitation methods. Powders were characterized using thermal analysis techniques (DTA-TG-DSC), X-ray powder Diffraction (XRD), surface area (BET) and electrical conductivity measurements. XRD patterns showed the presence of the cassiterite structure. SnO2 particles, prepared through sol-gel method exhibit crystallite sizes in the range from 3.1 to 22.3 nm when the gel is heat treated at different temperatures up to 900°C. SnO2 nanocrystallites prepared by the precipitation method are comparatively larger in size. The higher specific surface area was obtained for the powder prepared using sol-gel method and the obtained average grain size (d) is relatively large compared with that of the average crystallite size. The powders show a semiconducting behavior with increasing temperature. The higher conductivity obtained for SnO2 prepared by sol-gel method can be attributed to their smaller average crystallite size. XRD of alumina doped powder exhibits finer particles than pure SnO2. TEM images showed that the particles are spherical in shape and consist of a core of SnO2 surrounded by a coating of alumina. The calculated surface area was found to decrease with temperature increases. Due to the effective role of Al2O3 additive as a grain growth inhibitor for the matrix grains, the observed surface area for the coated materials are predominantly higher than for the uncoated materials.

The synthesis of metal (Fe, Co, Ni)-encapsulated carbon nanomaterials coated with cyclam-bonded silica has been described. The organic layer was identified by Fourier transform infrared spectroscopy and elemental analysis. The functionalized magnetic nanomaterials were employed to extract the divalent cations: copper, calcium, cobalt, manganese and nickel from aqueous solutions. Their adsorption capacities were studied by the batch procedure. The concentration of cations extracted was determined by inductively coupled plasma mass spectrometry. Influence of different parameters viz. pH, amount of the compound studied, contact time, on the cation extraction was investigated. Under optimum conditions copper extraction was significantly more efficient when compared with other coexisting ions.

The 1H-NMR and quantum chemical analysis of the stability of tautomers of cinnamoyl pyrone derivatives and vinylogs has been studied. The relationship between the structure of the most stable tautomer and its spectral properties has been investigated. It has been determined that the tautomer of highest stability (88–100 molar %) has an α-pyrone structure and exhibits a trans-conformation in the cinnamoyl fragment. An intense fluorescence of dyes has been observed in non-polar solvents with cinnamoyl fragments having electron-donating substituents or several double bonds in the polymethine chain. A gradient in solvent polarity resulted in fluorescence quenching which permits the use of the dyes as intensometric fluorometric probes for medium polarity examination.

Ionic liquids (IL) are gaining importance as green solvents. Imidazolium ionic liquid [bmim]+[Cl]−, an environmentally benign solvent, was found to promote the Diels-Alder reaction between anthrone and maleimides at room temperature with excellent yields. The ionic liquid played a dual role as solvent and catalyst.

Adsorption of Triton X-100 (TX-100) on silica gel has been studied as a function of temperature (308–328 K) and composition for mixtures of water with ethanol or t-butanol. The adsorption capacity of silica gel for TX-100 decreases with increase in alcohol content. Adsorption isotherms of TX-100 on silica gel are four-region and were analyzed using the ARIAN (adsorption isotherm regional analysis) model. Data in regions 2, 3 and 4 were fitted to the Temkin, bilayer and reverse desorption isotherms, respectively. The results show that adsorption of TX-100 on silica gel in water and alcohol-water binary mixtures occurs mainly through formation of monolayer surface aggregates or low bilayer coverage.

In this report, a rapid, efficient and environmental friendly synthesis of 3-carboxycoumarins under ultrasound irradiation in water media is described. The Knoevenagel condensation of Meldrum’s acid with substituted benzaldehydes in the presence of zirconium oxide chloride (ZrOCl2·8H2O) and ultrasonic irradiation in water gave the corresponding 3-carboxycoumarins in good to excellent yields.

Hydroxyapatite (HAp) was successfully produced from recycled eggshell, seashell and phosphoric acid. The phases obtained depended on the ratio of calcined eggshell/ seashell to phosphoric acid, the calcination temperature and the mechanochemical activation method (ball milling or attrition milling). The HAp structures were characterized by X-ray diffraction, scanning electron microsopy and infrared spectroscopy. Attrition milling was more effective than ball milling, yielding nanosize, homogenous and pure Hap.

Ibuprofen membrane electrodes based on different plasticizers: diisobutyl phthalate (DIBP), o-nitrophenyloctyl ether (o-NPOE), dioctyl sebacate (DOS) and tetraoctylammonium 2-(4-isobutylphenyl)propionate were prepared. All electrodes show: a near Nernstian slope of characteristic (58.3–60.9 mV decade−1) in the measurement range (10−4–10−1 mol L−1), limit of detection (5.0×10−5 mol L−1), really long lifetime (12 months), dependence of the electrode potential on pH (5.5–9.0), reproducibility of potential (0.6–1.2 mV) and selectivity coefficients in relation to some organic and inorganic anions. The electrodes were applied for the determination of ibuprofen in tablets by the calibration curve method and the standard addition method.

The two successive steps acidity constants of three azo dye derivatives D1–D3, were determined by a spectrophotometric method using 0.10 M KNO3 as supporting electrolyte in water solvent. The electronic spectra of the compounds were recorded in the course of their pH-metric titration with a standard base solution. The protolytic equilibrium constants can be solved very satisfactorily from absorbance data, by combining the data obtained in the spectrometric determinations with graphic methods as the absorbance diagrams. An A-diagram shows the relative absorbance changes at two wavelengths as a function of the pH. For a one-step system, the absorbance at any wavelength must be proportional to the absorbance at any other wavelength, so an A-diagram for all wavelength combinations for such a system must be linear (rank, s=1). However, if a system is governed by two or more equilibria, the A-diagrams corresponding to multi-step titrations will change direction every time a new equilibrium becomes dominant in the system. Analysis of the each uniform sub-region can then be used in evaluating of the corresponding equilibrium. A-diagrams for all wavelength combinations suggest that these systems have the rank two(s=2). The results revealed that the Ka(1) and Ka(2) values of different azo dyes follow the order D3>D2>D1.

An organic-inorganic composite, poly-o-anisidine Sn(IV) phosphate, was chemically synthesized by mixing ortho-anisidine into gels of Sn(IV) phosphate with different mixing volume ratios. Studies on the effect of eluant concentration, elution behavior and separation of metal ions were carried out to understand the ion-exchange capabilities. Due to Cd(II) selective nature of composite, revealed by distribution studies, Cd(II) ion selective membrane electrode was fabricated. The analytical utility of the electrode was established by employing it as an indicator electrode in electrometric titrations having fast response time, 3–5s, and long life span of six months. Some physical parameters like self-diffusion coefficient (D0), activation energy (Ea) and entropy of activation (ΔS0) have been evaluated under conditions favoring a particle diffusion-controlled mechanism by studying ion-exchange kinetics.

Several monoterpenes, i.e., (+)-α-pinene, (−)-camphene, sabinene, (−)-β-pinene, myrcene, R-(+)-limonene, (−)-bornylacetate, (−)-trans-caryophyllene and a-humulene were identified and determined by gas chromatography-mass spectrometry (GC-MS) in needles of Pinaceae (Picea abies, P. omorika, P. pungens, P. Breweriana, Pinus nigra, P. mungo turra, P. black, P. sylvestris, Abies pinsapo, A. holophylla, A. Bronmuelleris, A. alba, Larix Kaempferi L. decidua) and tree-leaves of Juglandaceae (Juglans regia, J. nigra, J. sieboldiana var. Cordiformis) families. Supercritical fluid extraction (SFE) was found to be very useful for their isolation at optimised conditions (needles/leaves: pressure 20/30 MPa, temperature 80/130°C, time of extraction 60/60 min, modifier chloroform/chloroform). Their seasonal distribution, evaluation of differences in concentrations and relative amounts in different trees and their varieties grown in different localities were evaluated.

A series of CoAlxCrxFe2−2xO4 systems (x = 0.1 to 0.5 in steps of x = 0.1) spinel ferrites have been synthesized successfully using wet chemical co-precipitation technique. The samples were characterized by X-ray diffraction (XRD), infrared spectroscopy (IR) and magnetization measurements. The powder XRD patterns confirm the single phase spinel structure for the materials synthesized. X -ray diffraction measurements were performed to yield the lattice constant as function of the amount x corresponding to Al-Cr substitution. Lattice parameters, X-ray density, bulk density and particle size decrease whereas porosity increases with the increase in Al-Cr content, ‘x’. Infrared studies show two absorption bands at about 400 cm−1 and 600 cm−1 for octahedral and tetrahedral sites, respectively. Saturation magnetization decreases with the increase in Al-Cr content x. AC magnetic susceptibility measurements were carried out as a function of temperature to measure the Curie temperature, which was found to decrease with Al-Cr content x. The decrease of Curie temperature has been explained by A-B interaction.

Based on a biodegradable cross-linker, N-maleyl chitosan (N-MACH), a series of Poly(N-isopropylacrylamide) (PNIPAAm) and Poly(N-isopropylacrylamide-co-acrylamide) [P(NIPAAm-co-Am)] hydrogels were prepared, and their lower critical solution temperature (LCST), swelling kinetics, equilibrium swelling ratio in NaCl solution, and enzymatic degradation behavior in simulated gastric fluids (SGF) were discussed. The LCST did not change with different cross-linker contents. By altering the NIPAAm/Am molar ratio of P(NIPAAm-co-Am) hydrogels, the LCST could be increased to 39°C. The LCST of the hydrogel was significantly influenced by the monomer ratio of the NIPAAm/Am but not by the cross-linker content. In the swelling kinetics, all the dry hydrogels exhibited fast swelling behavior, and the swelling ratios were influenced by the cross-linker content and NIPAAm/Am molar ratios. Equilibrium swelling ratio of all the hydrogels decreased with increasing NaCl solution concentration. In enzymatic degradation tests, the weight loss of hydrogels was dependent on the cross-linker contents and the enzyme concentration.

Hierarchical nickel microwires with nanothorns were fabricated through a reduction of nickelous salt with hydrazine in diethanolamine. The product was characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDS). The growth mechanism of the nickel microwires with nanothorns is proposed, based on the evolution of the structures and morphologies, which could be ascribed to the cooperative effect of the complexant of diethanolamine and inherent magnetic interactions. Magnetic properties of the product were measured at room temperature and compared with other shaped counterparts.

The activity of fungicide agents containing a quinazolinone ring was described using the quantitative structure-activity relationship (QSAR) model by applying it to data taken from literature. The title compounds exhibit two important types of activity against certain fungal pathogens, i.e. activity against yeast and activity against filamentous fungi. A correlation between both antifungal activities (e.g. FA(yst) and FA(ff)) and physicochemical parameters such as the logarithm of the n-octanol/water partition coefficient (log P), the polarizability (P), the global minimum energy (TE), the energy difference between the frontier molecular orbital (DELH) and the molar refractivity (MR), was established using multiple linear regression. The molecular descriptors of the antifungal agents were obtained by quantum chemical calculations combined with molecular modeling calculations. Statistical analysis shows that the antifungal activity depends mainly on the calculated partition coefficients, log P, of the compounds. Bi-parametric models reveal that antifungal activity relates linearly to log P and P.

Ag4[Fe(CN)6]→Ag reduction process occurring in Ag4[Fe(CN)6]- gelatin-immobilized matrices, has been studied. In the course of reduction, these matrices are in a contact with water-alkaline solu-tion containing tin(II) dichloride along with an organic or inorganic compound capable of forming a stable soluble complex with Ag(I). It has been found that the substance formed in the gelatin matrix, is almost pure elemental silver, which consists two various phases which are distinguished by their optical and X-ray diffraction parameters.

A set of transition metal doped nanosized TiO2 particles with anatase structure were synthesized by the pulverization method and their ability to photocatalytically degrade the dye Alizarin Red S was investigated. Characterization of the Zr-, Co- and Mo-doped photocatalysts was conducted with the aid of XRD, SEM, EDX, TEM, BET and spectral analysis. X-ray diffraction patterns did not reflect the appearance of any peaks due to dopants, however dopants were observed in SEM-EDX analysis. Particle sizes were in the range of 25 nm as per TEM and XRD analysis. Upon doping, a prominent decrease in surface area was observed. The percentage composition of each of the dopants was confirmed by EDX analysis. Doped samples depicted many mid-bands in the Kubelka Munk plots due to d-d transition of dopants. Experiments were conducted to compare the photocatalytic activity under identical UV and solar light exposure. Zr-doped TiO2 at the molecular scale exhibited better photocatalytic activity in degradation of Alizarin, with a lower band-gap energy that can respond to visible light. However, Co- and Mo-doped TiO2 appeared to suppress the photoactivity. A rise in the number of mid-bands causing effective separation or recombination of charge carriers strongly influences the rate of the degradation process.

Complex formation and liquid-liquid extraction have been studied for ternary complexes of vanadium(IV) with 4-(2-pyridylazo)-resorcinol (PAR) and ditetrazolium chlorides (DTC) in a water-chloroform medium. The specific ditetrazolium compounds investigated were i) 3,3′-(4,4′-biphenylene)-bis(2,5-diphenyl-2H-tetrazolium) chloride (Neotetrazolium chloride, NTC); ii) 3,3′-(3,3′-dimetoxy-4,4′-biphenylene)-bis(2,5-diphenyl-2H-tetrazolium) chloride (Blue Tetrazolium chloride, BTC); and iii) 3,3′-(3,3′-dimetoxy-4,4′-biphenylene)-bis[2-(4-nitrophenyl)-5-phenyl-2H-tetrazolium] chloride (Nitro Blue Tetrazolium chloride, NBT). Molar absorptivity coefficients and the composition of the complexes have been calculated. Association constants (β) have also been obtained for the interactions between the vanadium(IV) — PAR anionic chelates [VO(PAR)2]2− (I) and [VO(OH)2(PAR)2]4− (II), and ditetrazolium cations (DT2+). Some special features of NBT as an extraction-spectrophotometric reagent for vanadium(IV) have been discussed. Unlike NTC and BTC which form complexes with both I and II, NBT associates only with II. The pH interval for complete extraction of (NBT2+)2[VO(OH)2(PAR)2] is broader and allows work at lower pH values the other ion-associates of V(IV,V)-PAR that were studied. NBT is -therefore the appropriate reagent both for direct V(IV) determination and for V(IV)/V(V) separation. Some additional characteristics for the V(IV)-PAR-NBT-water-chloroform system have been determined: extraction constant, distribution constant, recovery factor, limit of detection and limit of quantification. Beer’s law is valid up to 1.4 μg mL−1 vanadium(IV) with molar absorptivity coefficient of 3.55×104 L mol−1 cm−1 at λmax=559 nm.