FT-IR study of gamma-radiation induced degradation of polyvinyl alcohol (PVA) and PVA/humic acids blends

Samples of pure polyvinyl alcohol (PVA) and PVA doped with humic acids were exposed to gamma radiation. Gamma rays induced the degradation of the pure polymer. Degradation changes were observed using ATR FT-IR equipment. Dehydration, double bond creation, and their subsequent oxidation (surrounding atmosphere was air) were found out. Also, other degradation reactions (e.g. chain scission, cyclization) occur simultaneously. Formation of C=C and C=O bonds is apparent from FT-IR spectra. In contrast the presence of humic acids in the PVA sample showed stabilizing effect on PVA structure within the concentration range 0.5–10%.     

Tunable THz metamaterials based on an array of paraelectric SrTiO<Subscript>3</Subscript> rods

This work presents theoretical and experimental investigations of a tunable metamaterial which exhibits negative permeability in the THz frequency range. The tunability is obtained by temperature changes, and the sample consists of an array of high-permittivity SrTiO₃ (STO) rods micromachined by a femtosecond laser. Structures exhibiting a negative permeability on multiple frequency bands are also investigated and a proper choice of the dimensions of the pattern allows us to achieve a substantial broadening of the frequency band with negative μ.     

Synthesis and characterization of cyclopentadithiophene‐based low bandgap copolymers containing electron‐deficient benzoselenadiazole derivatives for photovoltaic devices

We have synthesized two cyclopentadithiophene (CDT)‐based low bandgap copolymers, poly[(4,4‐bis(2‐ethyl‐hexyl)‐4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene‐2,6‐diyl)‐alt‐(benzo[c][1,2,5]selenadiazole‐4,7‐diyl)] (PCBSe) and poly[(4,4‐bis(2‐ethyl‐hexyl)‐4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene‐2,6‐diyl)‐alt‐(4,7‐dithiophen‐2‐yl‐benzo[c][1,2,5]selenadiazole‐5,5′‐diyl)] (PCT2BSe), for use in photovoltaic applications. Through the internal charge transfer interaction between the electron‐donating CDT unit and the electron‐accepting benzoselenadiazole, we realized exceedingly low bandgap polymers with bandgaps of 1.37–1.46 eV. The UV–vis absorption maxima of PCT2BSe were subjected to larger hypsochromic shifts than those of PCBSe, because of the distorted electron donor–acceptor (D–A) structures of the PCT2BSe backbone. These results were supported by the calculations of the D–A complex using the ab initio Hartree‐Fock method with a split‐valence 6‐31G* basis set. However, PCT2BSe exhibited a better molar absorption coefficient in the visible region, which can lead to more efficient absorption of sunlight. As a result, PCT2BSe blended with [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) exhibited a better photovoltaic performance than PCBSe because of the larger spectral overlap integral with respect to the solar spectrum. Furthermore, when the polymers were blended with PC₇₁BM, PCT2BSe showed the best performance, with an open circuit voltage of 0.55 V, a short‐circuit current of 6.63 mA/cm², and a power conversion efficiency of 1.34% under air mass 1.5 global illumination conditions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1423–1432, 2010     

Predicting melting temperature directly from protein sequences

Proteins of both hyperthermophilic and mesophilic microorganisms generally constitute from the same 20 amino acids; however, the extent of thermal tolerance of any given protein is an inherent property of its amino acid sequence. The present study is the first to report a rapid method for predicting Tm (melting temperature), the temperature at which 50% of the protein is unfolded, directly from protein sequences (the Tm Index program is available at http://tm.life.nthu.edu.tw/). We examined 75 complete microbial genomes using the Tm Index, and the analysis clearly differentiated hyperthermophilic from mesophilic microorganisms on this global genomic basis. These results are consistent with the previous hypothesis that hyperthermophiles express a greater number of high Tm proteins compared with mesophiles. The Tm Index will be valuable for modifying existing proteins (enzymes, protein drugs and vaccines) or designing novel proteins having a desired melting temperature.     

Spectroscopic and Computational Insight into the Intermolecular Interactions between Zwitter‐Type Ionic Liquids and Water Molecules

Geometric and conformational changes of zwitter‐type ionic liquids (ZILs) due to hydrogen‐bonding interactions with water molecules are investigated by density functional theory (DFT), two‐dimensional IR correlation spectroscopy (2D IR COS), and pulsed‐gradient spin‐echo NMR (PGSE NMR). Simulation results indicate that molecular structures in the optimized states are strongly influenced by hydrogen bonding of water molecules with the sulfonate group or imidazolium and pyrrolidinium rings of 3‐(1‐methyl‐3‐imidazolio)propanesulfonate ( 1 ) and 3‐(1‐methyl‐1‐pyrrolidinio)propanesulfonate ( 2 ), respectively. Concentration‐dependent 2D IR COS reveals kinetic conformational changes of the two ZIL–H₂O systems attributable to intermolecular interactions, as well as the interactions of sulfonate groups and imidazolium or pyrrolidinium rings with water molecules. The dramatic changes in the ¹H self‐diffusion coefficients elucidate the formation of proton‐conduction pathways consisting of ZIL networks. In ZIL domains, protons are transferred by a Grotthuss‐type mechanism through formation, breaking, and restructuring of bonds between ZILs and H₂O, leading to an energetically favorable state. The simulation and experimental investigations delineated herein provide a perspective to understanding the interactions with water from an academic point of view as well as to designing ILs with desired properties from the viewpoint of applications.     

Biodegradation of tobacco waste by composting: Genetic identification of nicotine-degrading bacteria and kinetic analysis of transformations in leachate

The tobacco industry produces large quantities of solid and liquid waste. This waste poses a significant environmental problem, as some major components are harmful and toxic. The aim of this work is to isolate and identify the nicotine-degrading microorganisms in the composting of tobacco waste. The bioremediation process for the detoxification of waste was carried out in a column reactor at an airflow-rate of 0.4 L min^?1 kg^?1. The concentrations of nicotine and number of CFU in the samples taken from reactor were monitored over nineteen days. After nineteen days, 89.8 % of nicotine conversion was obtained. A nicotine-degrading bacterium, strain FN, was isolated from the composting mass and identified as Pseudomonas aeruginosa on the basis of morphology, 16S rDNA sequence, and the phylogenetic characteristics. To confirm that the isolated Pseudomonas aeruginosa FN is the actual nicotine degrader, batch experiments were performed using tobacco leachate. It was confirmed that the strain FN possesses a considerable capacity to degrade nicotine with simultaneous COD removal. The Monod kinetic model for single substrate was applied to obtain the substrate degradation rate and half saturation constant.     

Situations in traffic — how quickly they change

Spatio-temporal correlations of traffic intensity are analyzed employing data collected for the motorway M-30 around Madrid during one week in January 2009. We found that the lifetime of these correlations is the shortest in the evening between 6:00 p.m. and 8:00 p.m. This lifetime represents a new indicator for the amount of attention that is demanded by drivers in given traffic conditions.     

Spectrochemical properties and solvatochromism of bis(salicylidene-2-amino-3-methylpyridine)copper(II)

The title complex, denoted as [Cu(Msap)₂], is a deep brown solid soluble in common solvents like chloroform, toluene, benzene, dioxane, acetone, methanol, ethanol, 2-propanol, dimethylformamide, dimethyl sulfoxide, and acetonitrile that is a necessary condition for solvatochromism observation. The complex has been characterized by elemental analysis, molar conductivity, ultraviolet, and visible spectroscopy. The available X-ray data for similar compounds show that copper atom adopts planar coordination geometry. The molar conductivities indicate their non-electrolytic properties. The electronic spectra have been used to study the coordination properties of donor atoms and their bonding abilities, as well as solvatochromism. The results obtained show that the interactions of metal with donors depend on solvent polarity and the color changes are subtle.     

Structural studies on aryl‐substituted enaminoketones and their thio analogues. Part I. Analysis of high‐resolution 1H, 13C NMR and 13C CP MAS spectra combined with GIAO‐DFT calculations

A series of aryl‐substituted enaminoketones and their thio analogues in CDCl₃ solution and in the solid state were studied by the use of high‐resolution ¹H and ¹³C as well as ¹³C cross polarization magic angle spinning (CP MAS) NMR spectra in combination with gauge including atomic orbitals‐density functional theory (GIAO‐DFT) calculations performed at the B3PW91/6–311 + + G(d,p) level of theory using the B3PW91/6‐311 + + G(d,p)‐optimized geometries. The analysis of the ¹³C NMR spectra in solution was done by using the Incredible Natural Abundance DoublE QUAntum Transfer Experiment (INADEQUATE) technique, whereas trends observed in the ¹³C shielding constants, calculated for the compounds studied, were a great help in assigning most of the signals in the ¹³C CP MAS NMR spectra. It was established on the basis of the experimental and theoretical NMR data that both groups of compounds exist in the form of Z‐s‐Z‐s‐E isomers in CDCl₃ solution as well as in the solid state, with the NH hydrogen atom involved in intramolecular hydrogen bonding. This conclusion is in agreement with the fact that some of the compounds studied reveal liquid‐crystalline properties. Three‐bond H, H and C, H coupling constants measured in solution played a crucial role in the structure elucidation. Copyright © 2009 John Wiley & Sons, Ltd.