Simultaneous scission and crosslinking of polystyrene chains on irradiation by ultraviolet light in CCl4 and CHCl3 solutions

This work is the continuation of the investigations of changes in the structure of polystyrene initiated by radiation of wavelengths λ ≥ 270 nm in oxygen-free solutions in CCl₄ and CHCl₃. Coupled integral and quasielastic light scattering techniques have been applied, enabling observations of changes in the molecular weight distribution function w(M). On the basis of the experimental data and application of Saito and Inokuti's theoretical results, it is shown that in the irradiated solutions polystyrene undergoes simultaneous chain scission and crosslinking. The average number of scissions and crosslinks per macromolecule as a function of irradiation time is calculated. The effect of macromolecular mobility on both photochemical processes is also discussed.     

Direct sampling and analysis from solid-phase extraction cards using an automated liquid extraction surface analysis nanoelectrospray mass spectrometry system

Direct liquid extraction based surface sampling, a technique previously demonstrated with continuous flow and autonomous pipette liquid microjunction surface sampling probes, has recently been implemented as a liquid extraction surface analysis (LESA) mode on a commercially available chip‐based infusion nanoelectrospray ionization (nanoESI) system. In the present paper, the LESA mode was applied to the analysis of 96‐well format custom‐made solid‐phase extraction (SPE) cards, with each well consisting of either a 1 or a 2 mm diameter monolithic hydrophobic stationary phase. These substrate wells were conditioned, loaded with either single or multi‐component aqueous mixtures, and read out using the commercial nanoESI system coupled to a hybrid triple quadrupole/linear ion trap mass spectrometer or a linear ion trap mass spectrometer. The extraction conditions, including extraction/nanoESI solvent composition, volume, and dwell times, were optimized in the analysis of targeted compounds. Limit of detection and quantitation as well as analysis reproducibility figures of merit were measured. Calibration data was obtained for propranolol using a deuterated internal standard which demonstrated linearity and reproducibility. A 10× increase in signal and cleanup of micromolar angiotensin II from a concentrated salt solution was demonstrated. In addition, a multicomponent herbicide mixture at ppb concentration levels was analyzed using MS³ spectra for compound identification in the presence of isobaric interferences. Published in 2011 by John Wiley & Sons, Ltd.     

Engineering of an active animal fatty acid synthase dimer with only one competent subunit

Animal fatty acid synthases are large polypeptides containing seven functional domains that are active only in the dimeric form. Inactivity of the monomeric form has long been attributed to the obligatory participation of domains from both subunits in catalysis of substrate loading and condensation reactions. However, we have engineered a fatty acid synthase containing one wild-type subunit and one subunit compromised by mutations in all seven functional domains that is active in fatty acid synthesis. This finding indicates that a single subunit, in the context of a dimer, is able to catalyze the entire biosynthetic pathway and suggests that, in the natural complex, each of the two subunits forms a scaffold that optimizes the conformation of the companion subunit.     

Selected polymers on CW and pulsed THz investigations

The paper gives the results of refractive indexes for three plastic materials: polyethylene, polymethyl methacrylate and polyvinyl chloride, which are measured and compared in two arrangements - a CW THz photomixer and a pulsed THz spectrometer.     

Photoresistor based on ZnO nanorods grown on a p-type silicon substrate

In this work we discuss a method of preparation of a highly sensitive light detector based on ZnO nanorods. A photoresistor constructed by us is based on a heterojunction between high quality ZnO nanorods and high resistivity p-type Si used as a substrate for nanorods’ deposition. ZnO nanorods are grown by a modified version of a microwave assisted hydrothermal method which allows for growth of high quality ZnO nanorods in a few minutes. The obtained photoresistor responds to a wide spectral range of light starting from near infrared (IR) to ultraviolet (UV). Properties of the detector are evaluated. We propose the use of the detector as an optical switch.     

Effect of Ester Moiety on Structural Properties of Binary Mixed Monolayers of Alpha-Tocopherol Derivatives with DPPC

Phospholipid membranes are ubiquitous components of cells involved in physiological processes; thus, knowledge regarding their interactions with other molecules, including tocopherol ester derivatives, is of great importance. The surface pressure–area isotherms of pure α-tocopherol (Toc) and its derivatives (oxalate (OT), malonate (MT), succinate (ST), and carbo analog (CT)) were studied in Langmuir monolayers in order to evaluate phase formation, compressibility, packing, and ordering. The isotherms and compressibility results indicate that, under pressure, the ester derivatives and CT are able to form two-dimensional liquid-condensed (LC) ordered structures with collapse pressures ranging from 27 mN/m for CT to 44 mN/m for OT. Next, the effect of length of ester moiety on the surface behavior of DPPC/Toc derivatives’ binary monolayers at air–water interface was investigated. The average molecular area, elastic modulus, compressibility, and miscibility were calculated as a function of molar fraction of derivatives. Increasing the presence of Toc derivatives in DPPC monolayer induces expansion of isotherms, increased monolayer elasticity, interrupted packing, and lowered ordering in monolayer, leading to its fluidization. Decreasing collapse pressure with increasing molar ratio of derivatives indicates on the miscibility of Toc esters in DPPC monolayer. The interactions between components were analyzed using additivity rule and thermodynamic calculations of excess and total Gibbs energy of mixing. Calculated excess area and Gibbs energy indicated repulsion between components, confirming their partial mixing. In summary, the mechanism of the observed phenomena is mainly connected with interactions of ionized carboxyl groups of ester moieties with DPPC headgroup moieties where formed conformations perturb alignment of acyl chains, resulting in increasing mean area per molecule, leading to disordering and fluidization of mixed monolayer.     

Synthesis of nucleosides of 5-substituted-1,2,4-triazole-3-carboxamides

Nucleosides of 5-substituted-1,2,4-triazole-3-carboxamides were prepared by the acid-catalyzed fusion procedure and by glycosylation of the appropriate trimethylsilyl derivative. The following nucleosides were obtained in two steps starting from methyl 4-substituted-1,2,4-triazole-3-carboxylates: 5-chloro-1-β- D -ribofuranosyl-1,2,4-triazole-3-carboxamide ( 6 ), 3-chloro-1-β- D -ribofuranosyl-1,2,4-triazole-5-carboxamide ( 5 ), 3-nitro-1-β- D -ribofuranosyl-1,2,4-triazole-5-carboxamide ( 12 ), 3-amino-1-β- D -ribofuranosyl-1,2,4-triazole-5-carboxamide ( 13 ), 5-methyl-1-β- D -ribofuranosyl-1,2,4-triazole-3-carboxamide ( 15 ), and 3-methyl-1-β- D -ribofuranosyl-1,2,4-triazole-5-carboxamide ( 16 ). In addition, 5-amino-1-β- D -ribofuranosyl-1,2,4-triazole-3-carboxamide ( 7 ), and 1-β- D -ribofuranosyl-1,2,4-triazole-3-carboxamide-5-thiol ( 8 ) were prepared from 6 .     

Head-to-head coiled arrangement of the subunits of the animal fatty acid synthase

The role of the beta-ketoacyl synthase domains in dimerization of the 2505 residue subunits of the multifunctional animal FAS has been evaluated by a combination of crosslinking and characterization of several truncated forms of the protein. Polypeptides containing only the N-terminal 971 residues can form dimers, but polypeptides lacking only the N-terminal 422 residue beta-ketoacyl synthase domain cannot. FAS subunits can be crosslinked with spacer lengths as short as 6 A, via cysteine residues engineered near the N terminus of the full-length polypeptides. The proximity of the N-terminal beta-ketoacyl synthase domains and their essential role in dimerization is consistent with a revised model for the FAS in which a head-to-head arrangement of two coiled subunits facilitates functional interactions between the dimeric beta-ketoacyl synthase and the acyl carrier protein domains of either subunit.     

Exotic meson decay to omegapi0pi-

A partial-wave analysis of the mesons from the reaction pi(-)p --> pi(+)pi(-)pi(-)pi(0)pi(0)p has been performed. The data show b(1)pi decay of the spin-exotic states pi(1)(1600) and pi(1)(2000). Three isovector 2(-+) states were seen in the omegarho(-) decay channel. In addition to the well known pi(2)(1670), signals were also observed for pi(2)(1880) and pi(2)(1970).