Thermoplastic elastomers by hydrogen bonding

Summary Poly(butadienes) were modified by an ene-reaction using 4-phenyl-1, 2,4-triazoline-3,5-dione (1) 3-nitro-4-hydroxyphenyl-1, 2,4-triazoline-3,5-dione (2) and 4-hydroxyphenyl1, 2,4-triazoline-3,5-dione (3). The resulting hydrogen bond complexes between urazole groups act as thermoreversible crosslinks and alter the melt rheological behaviour. While dimeric chelate-like complexes are formed in polymers modified with 1 or 2, a three dimensional structure of hydrogen bond complexes is formed if 3 is used as the modifying agent. The thermorheologically complex behaviour of the latter material is interpreted by structural changes in the three dimensional structure with temperature.     

Provincial Hospital Graz-West, Graz, Austria

Domenig/Eisenk?ck/Gruber welcome daylight and fresh air into a public hospital with an upscale feel in a spectacular landscape.     

Quantitative structure-activity relationship studies for the prediction of antifungal activity of N-arylbenzenesulfonamides against Botrytis cinerea

The Botrytis cinerea is one of the most interesting fungal pathogens. It can infect almost every plant and plant part and cause early latent infections which damage the fruit before ripening. The QSAR is an alternative method for the research of new and better fungicides against B. cinerea. This paper describes the results of applying a topological sub-structural molecular design (TOPS-MODE) approach for predicting the antifungal activity of 28 N-arylbenzenesulfonamides. The model described 86.1% of the experimental variance, with a standard deviation of 0.223. Leave-one-out and leave-group-out cross validation was carried out with the aim of evaluating the predictive power of the model. The values of their respective squared correlations coefficients were 0.754 and 0.741. The TOPS-MODE approach was compared with three other predictive models, but none of these could explain more than 72.8% of the variance with the same number of variables. In addition, this approach enabled the assessment of the contribution of different bonds to antifungal activity, thereby making the relationships between structure and biological activity more transparent. It was found that the fungicidal activity of the chemicals analyzed was increased by the presence of a sulfonamide group bonded to two aromatics rings, making this group the most important of the molecule. The majority of the substituents present in the aromatic rings have an electron withdrawing effect and they contribute to a smaller degree than the sulfonamide group to the property under study. The aromatic moiety plays an important role in this activity; its contribution changes with different substituents. Generally, the nitro group has a positive and great contribution to the biological property but when this group is involved in some compounds in ortho effect with the SO2 moiety of the sulfonamide group a lower value of contribution is observed for both groups.     

Occupational exposure to hexabromocyclododecane at an industrial plant

Occupational exposure to hexabromocyclododecane (HBCD) among workers at an industrial plant producing expandable polystyrene (PS) added HBCD as flame retardant has been assessed in the present study. Airborne dust samples were collected near the breathing zone of 10 male workers during three 8-h work shifts. The HBCD concentrations in the airborne dust varied from 0.2 to 150 microg/m3 (mean 12.2 and median 2.1 microg/m3). Two serum samples were obtained from each of the workers. The mean serum concentration was 190 ng/g lipids; the median was 101 ng/g lipids (range 6 to 856 ng/g lipids). HBCD was not detected above 1 ng/g lipids (LOD) in any samples from persons in a reference group with no occupational exposure to HBCD. The contribution of gamma-HBCD to the total HBCD serum concentration was notably high (39%) compared to what has usually been observed in biological samples. There was no clear correlation of serum levels with average HBCD concentrations in the airborne dust samples collected near the subjects' breathing zone. The elevated exposure levels reported in this study compared to urban air and serum levels in general populations suggest that further and more detailed exposure assessment studies should be initiated in industries where HBCD is applied.     

Following the Kinetics of Barium Titanate Nanocrystal Formation in Benzyl Alcohol Under Near‐Ambient Conditions

In complex chemical syntheses (e.g., coprecipitation reactions), nucleation, growth, and coarsening often occur concurrently, obscuring the individual processes. Improved knowledge of these processes will help to better understand and optimize the reaction protocol. Here, a form‐free and model independent approach, based on a combination of time‐resolved small/wide‐angle X‐ray scattering, is employed to elucidate the effect of reaction parameters (such as precursor concentration, reactant stoichiometry, and temperature) on the nucleation, crystallization, and growth phenomena during the formation of nanocrystalline barium titanate. The strength of this approach is that it relies solely on the total scattered intensity (i.e., scattering invariant) of the investigated system, and no prior knowledge is required. As such, it can be widely applied to other synthesis protocols and material's systems. Through the scattering invariant, it is found that the amorphous‐to‐crystalline transformation of barium titanate is predominantly determined by the total amount of water released from the gel‐like barium hydroxide octahydrate precursor, and three rate‐limiting regimes are established. As a result of this improved understanding of the effect of varying reaction conditions, elementary boundary conditions can be set up for a better control of the barium titanate nanocrystal synthesis.     

Exploring the conformational changes of the ATP binding site of gyrase B from Escherichia coli complexed with different established inhibitors by using molecular dynamics simulation: protein-ligand interactions in the light of the alanine scanning and free energy decomposition methods

Currently, bacterial diseases cause a death toll around 2 million people a year encouraging the search for new antimicrobial agents. DNA gyrase is a well-established antibacterial target consisting of two subunits, GyrA and GyrB, in a heterodimer A(2)B(2). GyrA is involved in DNA breakage and reunion and GyrB catalyzes the hydrolysis of ATP. The GyrB subunit from Escherichia coli has been investigated, namely the ATP binding pocket both considering the protein without ligands and bound with the inhibitors clorobiocin, novobiocin and 5'-adenylyl-β-γ-imidodiphosphate. The stability of the systems was studied by molecular dynamics simulation with the further analysis of the time dependent root-mean-square coordinate deviation (RMSD) from the initial structure, and temperature factors. Moreover, exploration of the conformational space of the systems during the MD simulation was carried out by a clustering data mining technique using the average-linkage algorithm. Recognizing the key residues in the binding site of the enzyme that are involved in the binding mode with the aforementioned inhibitors was investigated by using two techniques: free energy decomposition and computational alanine scanning. The results from these simulations highlight the important residues in the ATP binding site and can be useful in the design process of potential new inhibitors.     

Ultrathin Films from Fluorine Containing Polymers: Fabrication and Characterization

Monolayers and ultrathin films of some fluorine containing polymers were prepared by the Langmuir‐Blodgett (LB) technique. The polymers were obtained using two main synthetic approaches: firstly, polyamide (PA‐1) and polyimide (PI‐1) were prepared from direct polycondensation of 4,4′‐hexafluoroisopropylidenediphthalic anhydride and 4,4′‐hexafluoroisopropylidenedianiline in N‐methyl‐2‐pyrrolidone (NMP). The thermogravimetric analysis (TGA) for PI‐1 yielded 580°C by 1% weight loss. They formed stable monolayers with a collapse pressure of 62 mN/m and a collapse area of 0.20 nm² per repeat unit (R.U.) in the case of PA‐1, for PI‐1 the collapse pressure was 60 mN/m associated with a collapse area of 0.23 nm² per R.U. Secondly, poly[(maleic acid perfluorooctylamide‐imide)‐co‐ethylene] (PAPE) with fluorinated side chains was synthesized from poly[(maleic anhydride)‐co‐ethylene]. They formed stable monolayers too. Multilayer depositions onto various substrates were possible for all the synthesized polymers. LB films were characterized by ultra‐violet/visible spectroscopy (UV‐Vis), surface plasmon resonance (SPR), dielectric spectroscopy and atomic force microscopy (AFM). Gas phase polymerization of tetrafluoropropyl methacrylate (TFPM) was carried out in the presence of macroinitiator, poly[octadecene‐co‐(maleic anhydride)] modified with tert‐butyl hydroperoxide. Film thickness could be controlled on different hydrophobic substrates varying the reaction time.     

Predicting union attitudes in student part-time workers.

Examined the predictors of general union attitudes in a sample of 84 high school and 42 first year university students (aged 15–21 yrs) who were employed part-time. In addition to two aspects of family socialization towards unions (parents' perceived union attitudes and perceived union activities), Ss' job quality and satisfaction with both co-workers and supervisors were also assessed as predictors of their own general union attitudes. Results show that only Ss' perception of their parents' general union attitudes was significantly associated with their own general union attitudes. Thus, family socialization contributed the greatest amount of variance to general union attitudes. Neither job quality, nor supervisory or co-worker satisfaction were associated with Ss' union attitudes. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Characterization of metal-cyanobacteria sorption reactions: a combined macroscopic and infrared spectroscopic investigation

In this study, we conducted synchrotron radiation Fourier transform infrared (IR) spectroscopy, potentiometric titration, and metal sorption experiments to characterize metal-cyanobacteria sorption reactions. Infrared spectra were collected with samples in solution for intact cyanobacterial filaments and separated exopolymeric sheath material to examine the deprotonation reactions of cell surface functional groups. The infrared spectra of intact cells sequentially titrated from pH 3.2 to 6.5 display an increase in peak intensity and area at 1400 cm(-1) corresponding to vibrational COO- frequencies from the formation of deprotonated carboxyl surface sites. Similarly, bulk acid-base titration of cyanobacterial filaments and sheath material indicates that the concentration of proton-active surface sites is higher on the cell wall compared to the overlying sheath. A three-site model provides an excellent fit to the titration curves of both intact cells and sheath material with corresponding pKa values of 4.7 +/- 0.4, 6.6 +/- 0.2, 9.2 +/- 0.3 and 4.8 +/- 0.3, 6.5 +/- 0.1, 8.7 +/- 0.2, respectively. Finally, Cu2+, Cd2+, and Pb2+ sorption experiments were conducted as a function of pH, and a site-specific surface complexation model was used to describe the metal sorption data. The modeling indicates that metal ions are partitioned between the exopolymer sheath and cell wall and that the carboxyl groups on the cyanobacterial cell wall are the dominant sink for metals at near neutral pH. These results demonstrate that the cyanobacterial surfaces are complex structures which contain distinct surface layers, each with unique molecular functional groups and metal binding properties.     

New Semifluorinated Siloxane‐Grafted Copolyimides: Synthesis and Comparison with Their Linear Analogs

A siloxane‐grafted new diamino monomer DBPDMS has been prepared and used as a co‐monomer in combination with the fluorinated diamine monomer TFBB to prepare siloxane‐grafted polyimides. The polymers have been characterized by means of GPC, IR, and NMR. Their thermal, mechanical, and surface properties have been evaluated and compared with the homopolyimide and with polyimides where polysiloxane is incorporated in the main chain. DSC revealed melting of the grafted siloxane chain at sub‐ambient temperature and a glass transition corresponding to the main polymer chain at high temperature. Isothermal gravimetric analysis at 350 °C indicated that grafted siloxane moiety can be removed thermally from the polymer chain without affecting the polymer backbone.