Band 68, Heft 5

Twenty herbs, showing medicinal benefits on human life, like Taraxacum officinale, Plantago lanceolata, Hypericum perforatum, Ocimum basilicum, Melissa officinalis, Mentha piperita, and others, were tested. The percentage content of pigments, i.e. chlorophylls, carotenoids, and flavonoids, in the chosen herbs was determined. The spectrophotometric method, which is quick and readily available, was used. Measurements required pigment extraction with a solvent. Ethanol was used for the determination of chlorophylls and carotenoids, and acetone for the determination of flavonoids. Hierarchical agglomerative cluster analysis was performed in order to confirm the experimental results. The study of flavonoids content showed an interesting regularity which can be used for the classification of herbs. Plants belonging to the Lamiaceae family showed the flavonoids content in the range from 0.18 % to 0.68 %, whereas those belonging to the Apiaceaehas family showed the flavonoids content in the 0.75–1.20 % range.

This study presents a rapid, economical and “green” N-formylation of anilines with formic acid (FA) using Fe(III)-exchanged sepiolite (IES) as a catalyst. The IES exhibited excellent catalytic properties and the reactions were complete within 20.90 min to afford products with high yields. The adsorption mechanism of FA on the IES sample was studied by infrared (IR) spectroscopy at a temperature range of 120–400°C. The thermal desorption of pyridine was detected by the IR technique to estimate the acidity of IES. Lewis acid-bound pyridine bands at 1618–1631 cm-1 and 1443–1445 cm-1 were observed even after the IES sample was heated above 400°C.

The effect of two types of catalysts on the activity of the catalytic hydrogenation of nitrobenzene was studied. Catalysts were prepared by the surface deposition of palladium hydroxide with a simultaneous reduction with formaldehyde in a basic environment and were characterised by X-ray powder diffraction, transmission electron microscopy, adsorption-desorption, and catalytic tests — hydrogenation of nitrobenzene in methanol. The influence of the supports’ (activated carbon and a mixture of activated carbon and multi-walled carbon nanotubes) surface area is discussed. Despite having a size comparable (4–5 nm) to crystallites of metallic palladium, the catalyst prepared on a mixture of activated carbon and nanotubes (Pd/C/CNT) was significantly less active than the catalyst prepared on pure activated carbon (Pd/C); the rate of this reaction was approximately 30 % lower than the initial reaction rate. This feature could be attributed to the lower specific surface area of the Pd/C/CNT (531 m2 g−1) in comparison with the Pd/C (692 m2 g−1).

This paper presents a biphasic recognition chiral extraction system developed as a new chiral separation technology for the separation of pantoprazole enantiomers, combining a hydrophilic β-CD derivative in the aqueous phase and a hydrophobic tartaric acid in the organic phase which preferentially recognise the (R)-enantiomer and (S)-enantiomer, respectively. In this study, a number of factors which influence the efficiency of the extraction were investigated including types of organic solvents, β-CD and tartaric acid esters and their concentrations, pH and temperature. As a result, enantioselectivity for pantoprazole enantiomers can be improved up to 1.42 under optimised conditions; in addition, it is clear that the combined action of β-CD and tartaric acid esters leads to formation of the biphasic chiral extraction system with a stronger separation capacity than a monophasic chiral extraction system.

Lanthanum cobaltite oxide, LaCoO3, was prepared by the evaporation technique and the amorphous metal complex method. Powders were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and surface area measurements. The effect of the synthesis route on the phase purity, particle size, surface area, and morphology of the powders was studied. A single perovskite phase was synthesized at 700°C using the amorphous metal complex route. However, the evaporation technique required higher temperature for LaCoO3 crystallization. Based on the characterization results, low temperature formation of LaCoO3 was attributed to the homogeneity of the precursors. Such behavior also results in different microstructures. Powder synthesized by the amorphous metal complex method exhibited the highest surface area and the lowest particle size.

The article describes the synthesis and characterisation of the Cr(III)-rutin complex along with an estimate of its antioxidant activity. The complex was characterised using elemental analysis, UV-VIS, IR, conductance data, thermal, and gravimetric analyses. In the UV-VIS study, a bathochromic shift of approximately 98 nm indicates the formation of a rutin complex by more than one chelating site. The FT-IR spectra clearly show the formation of the Cr—O bond between rutin and Cr(III) at 494 cm−1, while the thermal study shows the presence of eight coordinated water molecules in the complex. The gravimetric analysis quantitatively proves the presence of four chloride ions. From these data, the formula of the Cr(III)-rutin complex was deduced as [Cr2(C27H28O16)(H2O)8]Cl4. Moreover, the antioxidant study of the complex was evaluated by using 2,2′-diphenyl-1-picrylhydrazyl (DPPH) free-radical, ferric-reducing, and phosphomolybdenum assays, which show that the complex has a higher antioxidant activity than rutin.

The reaction of dppm (1,1-bis(diphenylphosphino)methane) with 2-bromo-4-phenylacetophenone and benzyl bromoacetate in chloroform produces new phosphonium salts, [Ph2PCH2PPh2CH2C(O) C6H4Ph]Br (I) and [Ph2PCH2PPh2CH2COOCH2Ph]Br (II). By allowing the phosphonium salts to react with the appropriate base, the bidentate phosphorus ylides, Ph2PCH2PPh2=C(H)C(O)C6H4Ph (III) and Ph2PCH2PPh2=C(H)C(O)OCH2Ph (IV), were obtained. The reaction of these ligands with mercury(II) halides in dry methanol led to the formation of the mononuclear complexes {HgX2[(Ph2PCH2PPh2C(H)C(O)C6H4Ph)]} (X = Cl (V); X = Br (VI); X = I (VII)) and {HgX2[(Ph2PCH2PPh2C(H)COOCH2Ph)]} (X = Cl (VIII); X = Br (IX); X = I (X)). The FTIR and 1H, 31P and 13C NMR spectra were studied. The structure of compound III was unequivocally determined by the single-crystal X-ray diffraction technique. Single-crystal X-ray analysis of the {HgBr2[(Ph2PCH2PPh2C(H)C(O)C6H4Me)]} complex (XI) revealed the presence of a mononuclear complex containing the Hg atom in a distorted tetrahedral environment. In all complexes, the ylides referred to above were coordinated through the ylidic carbon and the phosphine atom.

CaAl-layered double hydroxides (CaAl-LDHs) with various carbonate ion contents are essentially formed in Bayer liquors during the causticisation step in alumina production. Under well-defined conditions hemicarbonate is formed, which is beneficial in the process of retrieving both Al(OH)4− and OH− ions. In the current work, Ca2Al-LDHs with various carbonate contents were prepared by the co-precipitation procedure and the products were dried in different ways. Structural information was obtained by a variety of methods, such as X-ray diffractometry (XRD), scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). Elemental maps were constructed through a combination of SEM images and EDX measurements. The targeted CaAl-hydrocalumites were successfully synthesised. It was found that the method used for drying did not influence the basal spacing although it significantly altered the particle sizes.

A series of MgZnAl hydrotalcite-like compounds with different zinc content (1–25 mass % of nominal zinc content) were prepared by a simple and environmentally-friendly method. The solids were characterized by X-ray powder diffraction (XRD), thermogravimetric (TG), nitrogen adsorption-desorption at −196°C (BET), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and CO2 temperature-programmed desorption (CO2-TPD). Transesterification of castor oil with methanol was selected as a probe reaction to stress the effect of zinc incorporation. From the XRD analysis of fresh samples it was demonstrated that the incorporation of zinc is feasible in the nominal range of 1–10 mass % while in the samples with higher zinc content, zinc nitrate and ZnO as secondary crystalline phases were observed. Furthermore, the analysis of samples calcined at 450°C indicated the coexistence of the ZnO and MgO crystalline phases. From the EDS and TG characterizations, the zinc percentage and thermal decomposition of the samples were determined. It was revealed that the samples exhibited the characteristic platy-like habit of hydrotalcite-like compounds. The BET analysis confirmed that the calcined samples presented an increment in their specific surface area values compared with the pristine ones. It was established that the amount of basic sites diminished with the zinc incorporation, which also affected the conversion degree of the transesterification reaction.

Preparation of multiwalled carbon nanotube-layered double hydroxide (MWCNT-LDH) nano-composites by (i) the co-precipitation of LDH components and pristine or surface-treated MWCNT or (ii) the delamination of LDH and application of the layer-by-layer technique has been attempted. For MWCNT, two types of surface treatment were used, either the surface was hydroxylated and deprotonated or wrapped in a tenside (dodecylbenzenesulfonate, DBS). LDH was delaminated by N,N-dimethylformamide. The obtained materials were characterized by X-ray diffractometry (XRD), and by scanning and transmission electron microscopies (SEM and TEM). Element distribution was mapped with help of the X-ray energy dispersive spectroscopy (XEDS) available as an extension of the scanning electron microscope. MWCNT could not be sandwiched between the layers of LDH by any of the methods employed; however, tenside-treated bundles of MWCNT could be wrapped in LDH thus forming a nanocomposite.

A new palladium-bidentate complex [m-C6H4(CH2ImMe)2(PdCl2)] (III) was prepared in two steps. In the first step, [m-C6H4(CH2ImMeAgCl)2] (II) (Im = imidazole moiety) was obtained by reacting imidazolium salt [m-C6H4(CH2ImMe)2]Cl2 (I) (prepared by quaternisation of Nmethylimidazole with 1,3-bis(chloromethyl)benzene) and Ag2O in CH2Cl2. In the next step, treatment of (II) with Pd(CH3CN)2Cl2 afforded complex III which was evaluated for its catalytic activity for C-C bond-formation reactions by examining the coupling reaction of 3-iodoanisole with phenylacetylene in the Sonogashira reaction. In addition, 3-methoxybiphenyls were obtained with good to excellent yields by Suzuki coupling reactions of 3-iodoanisole with phenylboronic acids or phenylborates salts in the presence of this complex.

The reduction of nitroblue tetrazolium (NBT) to formazan by folic acid, N-(4-aminobenzoyl) glutamic acid, and other amino acids was studied in this paper. The reduction involves only one of the two tetrazolium rings of NBT. The reaction is considerably more rapid with folic acid and N-(4-aminobenzoyl) glutamic acid than with the other amino acids under study. The electron donor moiety appears to be the carboxylic acid in the alpha position. N-ethyl-N′(3-dimethylaminopropyl) carbodiimide notably increases the rate of the reaction and promotes the reduction of both tetrazolium rings.

Knoevenagel condensation of phenylacetonitrile with 4-diphenylaminophenylacetonitrile in the presence of piperidine was carried out to obtain a novel conjugated compound. In addition to the expected compound 2-(phenyl)-3-(4-diphenylaminophenyl)acrylonitrile (I), the 3-((4-diphenylamino)phenyl)-2,4-diphenylpentanedinitrile (II) was also obtained with a good yield. Compound II was obtained as a result of the Michael addition of phenylacetonitrile with 2-(phenyl)-3-(4-diphenylaminophenyl)acrylonitrile (I). Conversely, when the same reaction was performed in the presence of KOH as catalyst, only the α,β-unsaturated nitrile (I) was afforded with a 92 % yield. The structures were confirmed with IR, EI-MS and NMR spectroscopy. Single crystals I and II were formed and their structures were determined by X-ray single-crystal diffraction analysis. Crystal I belongs to the monoclinic system with space group P21/n having unit cell parameters of a = 16.8589(5) Å, b = 6.68223(17) Å, c = 19.8289(7) Å, β = 111.133(4)○ and Z = 4. Crystal II belongs to the same monoclinic system with space group P21/c, having unit cell parameters of a = 10.8597(4) Å, b = 24.7533(10) Å, c = 9.7832(4) Å, β = 91.297(3)○ and Z = 4. In addition to the structural data analysis, some theoretical calculations that reveal the nature of relevant structure-property relationships are also reported.

Phosphate esters play an important role in genetic information transfer, cell signal transduction, energy transmission and metabolic processes of living beings. Efficient catalytic hydrolysis of phosphate esters is still an attractive and challenging problem. Here, a new 2-amino-N-dodecyl-3-(1H-imidazol-5-yl)propanamide (L2) surfactant was synthesized and its metallomicelles of La3+, Cu2+, Co2+, and Zn2+ complexes were used as mimic metalloenzymes to catalyze the hydrolysis of glucose-1-phosphate (G1P) in a buffer solution at 35°C. The metallomicelle systems can efficiently catalyze the hydrolysis of G1P. The rare-earth metallomicelle LaL2 has the highest catalytic activity compared with those of the transition metal micelles CuL2, CoL2, and ZnL2. Different association behaviors of metallomicelles and substrate G1P were proposed. The imidazole group might accelerate the hydrolysis by activating H2O associated with the metal into a metal-OH− group. A possible catalytic mechanism was also discussed.

A combined experimental and computational study of the dinuclear rhenium(V) complex containing (ReO)2(µ-O) core is presented in this article. The solid-state [Re2Cl4(O)2(µ-O)(3,5-lut)4] (3,5-lut = 3,5-dimethylpyridine) complex was characterised structurally (by single crystal X-ray diffraction) and spectroscopically (by IR, NMR, UV-VIS). The electronic structure was examined using the density functional theory (DFT) method. The spin-allowed electronic transitions were calculated using the time-dependent DFT method, and the UV-VIS spectrum was discussed.

Aromatase is a member of the cytochrome P450 family responsible for catalyzing the rate-limiting conversion of androgens to estrogens. In the pursuit of robust aromatase inhibitors, quantitative structure-activity relationship (QSAR) and classification structure-activity relationship (CSAR) studies were performed on a non-redundant set of 63 flavonoids using multiple linear regression, artificial neural network, support vector machine and decision tree approaches. Easy-to-interpret descriptors providing comprehensive coverage on general characteristics of molecules (i.e., molecular size, flexibility, polarity, solubility, charge and electronic properties) were employed to describe the unique physicochemical properties of the investigated flavonoids. QSAR models provided good predictive performance as observed from their statistical parameters with Q values in the range of 0.8014 and 0.9870 for the cross-validation set and Q values in the range of 0.8966 and 0.9943 for the external test set. Furthermore, CSAR models developed with the J48 algorithm are able to accurately classify flavonoids as active and inactive as observed from the percentage of correctly classified instances in the range of 84.6 % and 100 %. The study presented herein represents the first large-scale QSAR study of aromatase inhibition on a large set of flavonoids. Such investigations provide an important insight on the origins of aromatase inhibitory properties of flavonoids as breast cancer therapeutics.

Sharp variations of different climatic parameters influence the transport, transfer, and deposition of contaminants in nature. Investigations of the impact of environmental temperature on the fractionation of radionuclides in soil are necessary for adequate assessment of their distribution and bioavailability in case of a nuclear accident. The impact of a sharp decrease of environmental temperature shortly after radioactive contamination on the physicochemical fractionation of natural and technogenic radionuclides in Chernozem soil and its influence on their potential migration ability and bioavailability in case of subsequent warming were evaluated. The soil was contaminated in a laboratory with 241Am, 60Co, 137Cs, 228Ra, 234Th, and U and two temperature regimes were used for storage. Changes of the radionuclides association with various soil phases in the first weeks after contamination were studied. Physicochemical forms of 241Am, 60Co, 228Ra, 234Th, and U were determined using two sequential extraction procedures. The ion-exchangeable forms of 137Cs were evaluated by single extraction with 1 M NH4NO3. The data showed that the freezing, following the radioisotope contamination of the soil, causes an increase of the amount of potentially mobile forms of radiocobalt, radiocesium, radium, and thorium and has an insignificant impact on the fractionation of americium and uranium.

A novel series of indeno-benzothiazepine derivatives was synthesised via a “green” route. Synthesis of these compounds involves the treatment of dinucleophiles such as 2-aminobenzenethiols with α,β-unsaturated ketones in poly(oxyethylene) (poly(ethylene glycol), PEG-400) catalysed by acetic acid. The synthone α,β-unsaturated ketones were obtained by Claisen-Schmidt condensation of indan-1-one with substituted pyrazole-2-carbaldehydes prompted by bleaching earth (pH 12.5) as catalyst and PEG-400 as “green” reaction solvent. Screening of all the synthesised compounds for antimicrobial activity revealed that most of these compounds exhibited moderate to significant antimicrobial activity.