Gas chromatography analysis of benzene, toluene, ethylbenzene and xylenes using newly designed needle trap device in aqueous samples

A newly designed needle trap device with Carbopack X as a sorbent material is used for sampling, preconcentration and injection of volatile analytes benzene, toluene, ethylbenzene and xylenes (BTEX) into gas chromatograph. The closed system of stripping the analytes from water samples was used. An injection port with a modified metal liner was used to desorb analytes trapped in needle trap device. The main advantage of needle trap device consists in the simple methodology and easiness and rapidity of the analysis. Needle trap device is suitable for sampling in field. The experimental parameters as breakthrough volume of stripping gas, linearity, repeatability and limit of detection (LOD) and quantification (LOQ) were investigated. LOD ranges from 0.05 to 0.07 microgL(-1) and relative standard deviation ranges from 0.5% to 11.6% at concentrations 5 and 0.1 microgL(-1), respectively.     

Electrophoretic determination of calystegines A3 and B2 in potato

Potatoes, members of the Solanaceae plant family, contain calystegines, water-soluble nortropane alkaloids, which are biologically active as glycosidase inhibitors. The content of calystegines A(3) and B(2) in different varieties of potato and in various parts of the tubers (whole potato, peel, flesh, and sprouts) were analysed by new capillary zone electrophoresis and capillary isotachophoresis methods and by the routine GC method. The optimized background electrolyte for capillary zone electrophoretic analysis was mixture of 20 mM histidine, 20 mM N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid and 20% (v/v) methanol in demineralized water. Calystegines were detected by indirect UV detection at 210 nm. A clear separation of calystegines from other components of the methanolic sample extract was achieved within 4 min. The electrolytes for isotachophoretic analysis consisted of 5 mM NH(4)OH, 10 mM N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid, 0.1% hydroxyethylcellulose and 20% (v/v) methanol in demineralized water (leading) and 5 mM histidine+10 mM acetic acid+20% (v/v) methanol in demineralized water (terminating). Calystegines were separated within 20 min and detected by a conductimeter. Method characteristics of both zone electrophoresis and isotachophoresis, i.e., linearity (10-100 ng/microl and 1-10 ng/microl), accuracy (recovery 96+/-5% and 98+/-4%), intra-assay repeatability (4.2% and 3.5%), and detection limit (3 and 0.4 ng/microl) were evaluated. Simple sample preparation, sufficient sensitivity, speed of analysis, and low running cost are important attributes of the electrophoretic methods. The overall results of electrophoretic methods were comparable with GC.     

Theoretical study of hydrated copper(II) interactions with guanine: a computational density functional theory study

Optimization of the hydrated Cu(II)(N7-guanine) structures revealed a number of minima on the potential energy surface. For selected structures, energy decompositions together with the determination of electronic properties (partial charges and electron spin densities) were performed. In the complexes of guanine with the bare copper cation and that with the monoaqua ligated cation, an electron transfer from guanine to Cu(II) was observed, resulting in a Cu(I)-guanine(+) type of complex. Conformers with two aqua ligands are borderline systems characterized by a Cu partial charge of +0.7e and a similar value of the spin density (0.6e) localized on guanine. When tetracoordination of copper was achieved, only then the prevailing electron spin density is unambiguously localized on copper. The energetic preference of diaqua-Cu-(N7,O6-guanine) over triaqua-Cu-(N7-guanine) was found for the four-coordinate structures. However, the energy difference between these two conformations decreases with the number of water molecules present in the systems, and in complexes with five water molecules this preference is preserved only at DeltaG level where thermal and entropy terms are included.     

Chemical oxidative polymerization of aminodiphenylamines

The course of oxidation of 4-aminodiphenylamine with ammonium peroxydisulfate in an acidic aqueous ethanol solution as well as the properties of the oxidation products were compared with those of 2-aminodiphenylamine. Semiconducting oligomers of 4-aminodiphenylamine and nonconducting oligomers of 2-aminodiphenylamine of weight-average molecular weights 3700 and 1900, respectively, were prepared by using an oxidant to monomer molar ratio of 1.25. When this ratio was changed from 0.5 to 2.5, the highest conductivity of oxidation products of 4-aminodiphenylamine, 2.5 x 10 (-4) S cm (-1), was reached at the molar ratio [oxidant]/[monomer] = 1.5. The mechanism of the oxidative polymerization of aminodiphenylamines has been theoretically studied by the AM1 and MNDO-PM3 semiempirical quantum chemical methods combined with the MM2 molecular mechanics force-field method and conductor-like screening model of solvation. Molecular orbital calculations revealed the prevalence of N prim-C10 coupling reaction of 4-aminodiphenylamine, while N prim-C5 is the main coupling mode between 2-aminodiphenylamine units. FTIR and Raman spectroscopic studies confirm the prevalent formation of linear N prim-C10 coupled oligomers of 4-aminodiphenylamine and suggest branching and formation of phenazine structural units in the oligomers of 2-aminodiphenylamine. The results are discussed with respect to the oxidation of aniline with ammonium peroxydisulfate, leading to polyaniline, in which 4-aminodiphenylamine is the major dimer and 2-aminodiphenylamine is the most important dimeric intermediate byproduct.     

Subnanometer-scale measurements of the interaction of ultrafast soft x-ray free-electron-laser pulses with matter

At the recently built FLASH x-ray free-electron laser, we studied the reflectivity of Si/C multilayers with fluxes up to 3 x 10(14) W/cm2. Even though the nanostructures were ultimately completely destroyed, we found that they maintained their integrity and reflectance characteristics during the 25-fs-long pulse, with no evidence for any structural changes over lengths greater than 3 A. This experiment demonstrates that with intense ultrafast pulses, structural damage does not occur during the pulse, giving credence to the concept of diffraction imaging of single macromolecules.     

Cooperative hydrogen bonds of macromolecules. 3. A model study of the proximity effect

Experimental and theoretical evidence for the proximity effect as a basic mechanism of the hydrogen bond cooperativity was obtained in a model system. Hydrogen bond (HB) interaction between poly(4-vinylpyridine) (PVP) and selected acids as HB donors was studied using PFG NMR self-diffusion measurements, 1H NMR longitudinal relaxation and quantum-mechanical DFT calculations. Bivalent HB donors, such as glutaric (GA) and adipic acid (AA), were compared to univalent donors 4-chlorobutyric acid, 4-acetylbutyric acid and 5-chlorovaleric acid. PFG NMR established substantially larger HB equilibrium constants for AA and, in particular, GA than for univalent donors, thus indicating cooperativity of COOH groups in bivalent donors. According to the values of these constants, the fraction of the transiently bound GA and AA molecules, which are bound by two hydrogen bonds, is 0.70 and 0.63, respectively. This result, which means substantial cooperativity in particular in GA, was then independently verified by a relaxation study comparing longitudinal relaxation rates of univalent and bivalent donors. Analysis of relaxation led to the same probabilities that HB of one COOH group of a bivalent donor will be accompanied by HB of another COOH group of the same molecule, namely 0.70 for GA and 0.63 for AA. Such cooperativity must be due to the proximity effect, i.e., the lowering of the entropy demand of the next binding by the motional restriction imposed by the already existing bonds. This conclusion is in excellent agreement with DFT calculations on the interaction of GA with a model vinylpyridine dimer, which predict preference of double binding of the same GA molecule over that of two GA molecules and show that this preference is due to a substantially lower entropy demand.     

Space-time discontinuos Galerkin method for solving nonstationary convection-diffusion-reaction problems

The paper presents the theory of the discontinuous Galerkin finite element method for the space-time discretization of a linear nonstationary convection-diffusion-reaction initial-boundary value problem. The discontinuous Galerkin method is applied separately in space and time using, in general, different nonconforming space grids on different time levels and different polynomial degrees p and q in space and time discretization, respectively. In the space discretization the nonsymmetric interior and boundary penalty approximation of diffusion terms is used. The paper is concerned with the proof of error estimates in “L ²(L ²)”-and “ ”-norms, where ɛ ⩾ 0 is the diffusion coefficient. Using special interpolation theorems for the space as well as time discretization, we find that under some assumptions on the shape regularity of the meshes and a certain regularity of the exact solution, the errors are of order O(h ^p + τ ^q ). The estimates hold true even in the hyperbolic case when ɛ = 0.     

Reaction force decomposition of activation barriers to elucidate solvent effects

The reaction force F(Rc) of a chemical or physical process is given by the negative derivative of the potential energy V(Rc) along the intrinsic reaction coordinate Rc. F(Rc) unambiguously and naturally divides the activation barrier in each direction into two contributions, one of which has been found to reflect preparative structural factors, Eact,prep, and the other corresponds to the first part of the transition to products, Eact,trans. We have analyzed F(Rc) for an SN2 substitution reaction in both the gas and aqueous phases. Although the overall forward and reverse activation barriers are significantly lowered by the solvent, the Eact,trans are very little affected. Thus the increased rates that are predicted for this process in aqueous solution can be attributed to the solvent facilitating the structural effects in the preparative stages, decreasing the Eact,prep. This example shows how the reaction force decomposition of activation barriers can help to elucidate the roles played by external factors, e.g., solvents.     

Development of a capillary electrophoresis method for the separation of flavonolignans in silymarin complex

CE method for the baseline separation of structurally similar flavonolignans silybin A, silybin B, isosilybin A, isosilybin B, silychristin, silydianin, and their precursor taxifolin in silymarin complex has been developed and validated. The optimized background electrolyte was 100 mmol/L boric acid (pH 9.0) containing 5 mmol/L heptakis(2,3,6-tri-O-methyl)-β-CD and 10% (v/v) of methanol. The separation was carried out in an 80.5/72 cm (50 μm id) fused silica capillary at +25 kV with UV detection at 200 nm. Genistein (10 μg/mL) was used as internal standard. The resolution between the diastereomers of silybin and isosilybin was 1.73 and 2.59, respectively. The method was validated for each analyte in a concentration range of 2.5–50 μg/mL. The calibration curves were rectilinear with correlation coefficients ≥0.9972. The method was applied to determine flavonolignans in two dietary supplements containing Silybum marianum extract. The accuracy was evaluated by comparing the results of the CE analyses of the dietary supplements with those of the reference United States Pharmacopeial HPLC method. The unpaired t-test did not show a statistically significant difference between the results of both the proposed CE and the reference method (p > 0.05, n = 3).