Band 12, Heft 4

The most important advances in planar chromatography published between November 1, 2011 and November 1, 2013 are reviewed in this paper. Included are an introduction to the current status of the field; student experiments, books, and reviews; theory and fundamental studies; apparatus and techniques for sample preparation and TLC separations (sample application and plate development with the mobile phase); detection and identification of separated zones (chemical and biological detection, TLC/mass spectrometry, and TLC coupled with other spectrometric methods); techniques and instruments for quantitative analysis; preparative layer chromatography; and thin layer radiochromatography. Numerous applications to a great number of compound types and sample matrices are presented in all sections of the review.

Polymers have been widely used in agriculture for applications including controlled release of pesticides and other active ingredients. The ability to predict their delivery helps avoid environmental hazards. Macromolecular matrices used as carriers in controlled release of agricultural active agents, especially pesticides, are reviewed. The review focuses on the advantages and mechanisms of controlled release. It includes biodegradable polymers in agriculture, their manufacturing methods, and their degradation mechanisms and kinetics. The article also presents a critical account of recent release studies and considers upcoming challenges.

A stability-indicating liquid chromatographic method was developed and validated for simultaneous determination of quinapril and hydrochlorothiazide in drug substances and dosage forms. Chromatographic separation of quinapril, hydrochlorothiazide and its degradation products was achieved on a RP-18 column, using acetonitrile and phosphate buffer (pH 4.6) as mobile phase in a gradient mode and detection at 216 nm. Stress testing was performed under hydrolytic, oxidative, thermal and photolytic conditions. The degradation products were well resolved from main peaks, proving the stability-indicating power of the method. The assay was linear for quinapril and hydrochlorothiazide concentrations of 40–200 µg mL−1 and 25–125 µg mL−1, respectively. The developed method was selective, accurate and precise for quinapril and hydrochlorothiazide determination. This method was used to quantify both drugs in combined commercial tablets. The results showed that the proposed method was found to be suitable for quantitative determination and the stability study of quinapril and hydrochlorothiazide in pharmaceutical samples.

The influence of anionic poly(acrylic acid) — PAA addition on the stability of synthesized silica, alumina and mixed silica-alumina suspensions as a function of solution pH was studied. The turbidimetry method was used to monitor the changes of the examined systems stability over time. The calculated stability coefficients enabled estimation of polymer adsorption influence on stability of metal oxide suspension. It was shown that the alumina suspension without the polymer is the most unstable at the pH values 6 and 9, whereas the silica polymer was most unstable at pH 3. PAA with higher molecular weight (240 000) is a relatively effective stabilizer of all investigated adsorbents (except silica at pH 3). These properties of poly(acrylic acid) are highly desirable in many branches of industry (e.g. production of cosmetics, pharmaceuticals, paints) where polymers are widely used as effective stabilizers of colloidal suspensions.

Effects of chlorides of univalent (LiCl, NaCl, KCl), bivalent (MgCl2, BaCl2) and trivalent (AlCl3) metals at different concentration (0.001–0.1 M) on the behavior of nanosilica A-200 (0.5–5 wt.%) in aqueous media are analyzed using photon correlation spectroscopy (particle size distribution, PSD), electrophoresis (zeta potential ζ), potentiometric titration (surface charge density), and estimation of screening length of primary particles and their aggregates. The zeta potential and the PSD are affected by silica content, pH, and concentration and type of dissolved salts. Smaller but more strongly hydrated Li+ cations caused stronger nonlinear dependences of the zeta potential on pH and salt content than Na+ or K+. This nonlinearity is much stronger at a lower content of silica (0.5–1 wt.%) than at C A-200 = 2.5 or 5 wt.%. At a high concentration of nanosilica (5 wt.%) the effect of K+ ions causes stronger diminution of the negative value of the zeta potential due to better adsorption of larger cations. Therefore, the influence of K+ on increasing screening length is stronger than that of Na+ for both primary nanoparticles and their aggregates. A similar difference in the ζ values is observed for different in size cations Ba2+ and Mg2+.

A less common cyclic process of decontamination of benzene, toluene and o-xylene (BTX) using a dual function adsorbent-catalyst, referred to as the temperature swing oxidation, is introduced and discussed in this research. Preparation technique and characterization of the dual function adsorbent-catalyst CuO-CeO2/NaX are presented. The temperature swing oxidation of BTX consists of two stages: adsorption of the VOC from the stream saturating the adsorbent-catalyst at different levels and catalytic oxidation of concentrated VOC induced by raising bed temperature at different flow rates of regenerative air. The results indicate that at lower saturation levels and lower flow rates of regenerative air a complete oxidation performance is better. The highest obtained values of the overall conversion of toluene, o-xylene and benzene into CO2 and H2O were 99.3, 99.8 and 77.5%, respectively, proving that the temperature swing oxidation using a dual function adsorbent-catalyst is a promising VOC decontamination technique under properly selected operating conditions.

This article examines the extraction of rosehip to study the recovery of a number of compounds with antioxidant properties (polyphenols, flavonoids, and β-carotene). Two varieties of rosehip, cultivated and wild are used as raw material. A detailed study of the process kinetics at different operating conditions is carried out in order to determine appropriate processing parameters, which results in extracts with higher content of target compounds and higher antioxidant capacity. Data on the concentration of active components in the different parts of the fruit (skin, seeds, and pappi) are also obtained, which gives information about their distribution within the fruit. The comparison of wild and cultivated varieties demonstrates the better quality of the cultivated one. The results are useful for production of improved and enriched rosehip extracts with higher content of antioxidant substances that have proven beneficial effects on the human health.

To prepare nitrocellulose (NC), microcrystalline cellulose was treated in a mixture of nitric and sulfuric acids. Prepared NC containing a small amount of acids was studied at a different hydration degree (h = 10–1000 mg g−1) in different dispersion media (chloroform-d, acetone-d6 or their mixtures) using low-temperature 1H NMR spectroscopy. The hydration degree and the presence of residual acids affected the temperature dependence of the chemical shifts of proton resonance of water bound to NC. The Gibbs free energy of bound water became less negative with increasing hydration rate. The chloroform and acetone media affect the behavior of bound-to-NC water unfrozen at T<273 K differently. Quantum chemical calculations were performed using ab initio (HF/6-31G(d,p)), DFT (B3LYP/6-31G(d,p)) and semiempirical PM7 methods to analyze the interfacial behavior of water interacting with NC containing residual amounts of nitric and sulfuric acids.

This study was focused on the analysis of the contents (by HPLC-DAD) and antioxidant activity of phenolic compounds of aquatic higher plant Callitriche cophocarpa. The novelty of the work was: 1) the study of the species which is almost unknown in the context of investigations of bio-active compounds and, 2) the application of a unique L-band electron resonance spectroscopy (L-band EPR) to measure antioxidant activity of samples. The results were compared with those obtained for microalgae Chlorella and Spirulina which are widely distributed as the diet supplements. The obtained results are very promising with respect to the freeze-dried material of Callitriche, which revealed both high level of phenolic compounds (33 mg g−1 dry weight) and antioxidant activity (0.14 g of reduced DPPH· g−1 dry weight). An isoform of sinapic acid appeared to be the main fraction in this sample. The average content of the total phenolic compounds in Callitriche freeze-dried samples was ca. 43 or 25 times higher than in the case of the Chlorella or Spirulina samples, respectively. These samples showed also 16 times lower scavenging activity in relation to freeze-dried Callitriche material.

This paper reports a systematic study on the preparation, characterization and testing of metallosilicate macrobeads that contain chromium ions as active catalytic centers. In order to obtain hard macrospheres, four metals (Cr, Al, Zr and Zn) were incorporated into the silica matrix using chitosan as a template and shape generator. Metallosilicate macrospheres were synthesized at room temperature using tetraethylorthosilicate as silicon source and chlorohydric acid as catalyst. The size of metallosilicate macrospheres was in the range 0.9 — 1.1 mm. The catalyst was characterised by means of water sorption technique, FTIR spectroscopy and SEM/EDX analyses. FTIR spectra put into evidence the presence of metallic ions within the silica framework. EDX analyses confirmed the efficient incorporation of metals within the silica matrix (the content of metals from the calcined catalyst is almost the same as that from the initial gel mixture). Porous structure of catalyst investigated by water sorption technique and by pycnometric methods (with n-heptan and mercury respectively) proved that the synthesized catalyst had micro, meso and macropores. Catalyst was tested in the esterification reaction of acetic acid with epichlorohydrin. The temperature and the amount of catalyst exerted a marked influence on reaction rate. This work opens new perspectives for heterogeneous catalysis encouraging the replacement of powder catalysts with macrospherical catalysts that are easy to recover and to reuse.