Development of a liquid chromatography/electrospray selected reaction monitoring method for the determination of organoarsenic species in marine and freshwater samples

Cation- and anion-exchange high-performance liquid chromatography/electrospray selected reaction monitoring (HPLC/ES-SRM) methods were developed for the determination of 15 organoarsenic compounds in marine and freshwater samples. The results demonstrate that the developed HPLC/ES-SRM methods are powerful approaches for the identification of organoarsenic species in crude sample extracts. The detection limits, linearity as well as reproducibility for most of the species are comparable or even better than those measured by the HPLC/inductively coupled plasma mass spectrometry (ICPMS) technique. The qualitative analysis of the extracts shows that the developed methods allow for the identification of arsenicals which were not detectable by ICPMS.It was also demonstrated that the signal suppression caused by matrix effects means a significant limitation in the quantification of arsenicals by ES-SRM detection. This drawback is manifested especially in the case of the slightly retained species. The three sample-cleanup chromatographic methods including off-line size-exclusion, on-line reversed-phase and on-line oppositely charged ion-exchange approaches proved to be ineffective for separation of the signal-suppressive matrix from the analytes. The standard addition calibration seems to be a suitable solution for such problems.     

Single diastereomers of polyhydroxylated 9-oxa-1-azabicyclo[4.2.1]nonanes from intramolecular 1,3-dipolar cycloaddition of omega-unsaturated nitrones

8-Benzyloxymethyl-3,4,5-tribenzoyloxy-9-oxa-1-azabicyclo[4.2.1]nonane has been prepared as the single diastereoisomer 8 from an intramolecular 1,3-dipolar cycloaddition involving 2-(benzyloxy)acetaldehyde and omega-unsaturated hydroxylamine 7 derived from methyl alpha-D-glucopyranoside. The analogous 8-methoxycarbonyl 9-oxa-1-azabicyclo[4.2.1]nonane was afforded in a similar manner, from methyl D-galactopyranoside and methyl glyoxylate, as a 3:1 mixture of diastereoisomers 15 and 16. When conducted in achiral ionic liquid 17 this ratio increased to 8:1, and in chiral ionic liquid 18, compound 15 was formed exclusively.     

Electrophoretic mobility and molecular distribution studies of poly(amidoamine) dendrimers of defined charges

Generation 5 ethylenediamine (EDA)-cored poly(amidoamine) (PAMAM) dendrimers (E5, E denotes the EDA core and 5 the generation number) with different degrees of acetylation and carboxylation were synthesized and used as a model system to investigate the effect of charge and the influence of dendrimer surface modifications on electrophoretic mobility (EM) and molecular distribution. The surface-modified dendrimers were characterized by size-exclusion chromatography, 1H NMR, MALDI-TOF-MS, PAGE, and CE. The focus of our study was to determine how EM changes as a function of particle charge and molecular mass, and how the molecular distribution changes due to surface modifications. We demonstrate that partially modified dendrimers have much broader migration peaks than those of fully surface functionalized or unmodified E5 dendrimers due to variations in the substitution of individual dendrimer surfaces. EM decreased nonlinearly with increases in surface acetylation for both PAMAM acetamides and PAMAM succinamic acids, indicating a complex migration activity in CE separations that is not solely due to charge/mass ratio changes. These studies provide new insights into dendrimer properties under an electric field, as well as into the characterization of dendrimer-based materials being developed for medical applications.     

In vivo XANES measuring technique for studying the arsenic uptake in cucumber plants

New in vivo X‐ray absorption near edge structure measuring technique was developed by using liquid nitrogen steam flow for cooling cucumber samples keeping them under cryogenic conditions during the measurement in order to preserve the original chemical states of arsenic species in the hypocotyl. The aim of this study was to determine the As oxidation state in order to identify the possible metabolic processes during the nutrient uptake in cucumber (Cucumis sativus L. cv Joker) as model plant. The plants were grown in Hoagland's modified nutrient solution. The ratio of the quantity of two As species was determined in the hypocotyls of the cucumber samples: arsenite, As(III) and arsenate, As(V). The ultimate biological goal of the in vivo experiments was to investigate the applicability of the X‐ray absorption near edge structure technique under cryogenic conditions and to specify the resistance level of the plants to arsenic toxicity when different chemical forms of iron, FeCl₃ and Fe‐ascorbate were supplied in the nutrient solution. We have examined the influence of the intense synchrotron radiation beam on the transformation of the oxidation number of both As species when the effect of the reactive oxygen forms was eliminated by the presence of ascorbate. Copyright © 2016 John Wiley & Sons, Ltd.     

Variance-reduced DSMC for binary gas flows as defined by the McCormack kinetic model

A variance-reduced direct simulation Monte Carlo method is presented for binary gas flows as defined by the McCormack kinetic model. Two types of flow configuration, namely pressure driven flow between two parallel plates and through rectangular channels, are considered. The kinetic model is transformed into one- and two-dimensional projected formalisms. Both cases are modeled by the variance-reduced DSMC. Simulations are performed to compare the method to the analytical discrete ordinate and discrete velocity methods. For both flow configurations, very good agreement is obtained between the results of different approaches. The results of the approach are also compared to the prediction of the moment method and the results of hard-sphere gases. The model can be beneficial for computing slow rarefied gaseous mixture flows, especially in nano- and microscale devices.     

Cycloaddition reactions of 1.3-benzothiazines v synthesis of new tetracyclic ring systems

New tetracyclic derivatives (3a,$\text{b}$, 5, 8) similar to protoberberines, but containing a lactam structural element and other hetero atoms besides the bridge-head nitrogen in rings B and C, were prepared by cycloaddition of 6,7-dimethoxy-2H-1,3-benzothiazine (1a) with $\text{o}$-substituted aromatic carboxylic acid derivatives (2a,$\text{b}$, 4) and from 4- methyl-6,7-dimethoxy-2$\text{H}$-1,3-benzothiazine (1b) with 3.5-dinitrobenzoyl chloride.     

HPTLC and HPLC Determination of Alkaloids in Poppies Subjected to Stress

JPC – Journal of Planar Chromatography – Modern TLC - Papaver somniferum produces secondary metabolites which have important roles in self-defense processes, in plant biochemistry, and...