Volume and Enthalpy Changes upon Photoexcitation of Bovine Rhodopsin Derived from Optoacoustic Studies by Using an Equilibrium between Bathorhodopsin and Blue-Shifted Intermediate

A complex multistep model including an equilibrium was used for the first time to analyze data obtained by laser-induced optoacoustic spectroscopy (LIOAS) with bovine rhodopsin in washed membranes (T = 5–32°C). The thermal equilibrium was between bathorhodopsin, batho, and the blue-shifted intermediate (BSI), i.e., batho ⇄ BSI. This analysis considers a 14-ns intermediate detected by LIOAS at 25°C (with similar decay activation parameters as those reported for BSI in solubilized rhodopsin). The energy content of lumirhodopsin (lumi) and the structural volume difference between lumi and rhodopsin were essentially the same (E_lumi. = 80 kJ/mol and ΔV_lumi–rho = 40 mL/mol) for both a model based on a simple batho → BSI → lumi sequence and one including the batho ⇄; BSI equilibrium. However, the structural volume changes for the individual steps batho → BSI and BSI → lumi were markedly changed by the introduction of the equilibrium. With the rate constant for the forward reaction batho → BSI for solubilized rhodopsin determined by Hug et al. (Hug, S.J.; Lewis, W.J.; Einterz, C.M.; Thorgeirsson, T.E.; Kliger, D.S. Biochemistry, 1990 , 29, 1475–1485) the structural volume changes obtained with the equilibrium model are ΔV_BSI-batho = 79 mL/mol and ΔV_lumi-BSI = −44 mL/mol. The resulting batho → BSI expansion is larger than with the sequential model, and ΔV_lumi-BSI is now a contraction instead of an expansion. A small expansion of 5 mL/mol is derived for the formation of batho with both models. The estimated energy content of BSI is clearly higher than the value of lumi. The structural volume changes between batho, BSI, and lumi derived from the equilibrium model correlate better than those from the simple sequential model with the chromophore transition dipole moment changes determined in the literature using linear dichroism measurements. The structural volume changes are discussed in terms of the variations upon transformation of the chromophore–protein interactions.     

Specific interactions in ternary system quaternized polysulfone/mixed solvent

Theoretical and experimental aspects on the specific interactions developed via electrostatic interactions and hydrogen‐bonding in a ternary system formed of a proton‐donor solvent (N,N‐dimethylformamide or methanol), a proton‐acceptor solvent (water), and a quaternized polysulfone with various contents of ionic chlorine, which indicates a proton‐acceptor character, are investigated. Thus, the interactions of the ternary systems are corrected on the basis of the association phenomena defined through association constants. Numerical values for these constants were evaluated as a function of the system composition, by mathematical simulations for an accurate adjustment of preferential adsorption, determined by the Flory–Huggins–Pouchly theoretical approach applied to the experimental data. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

Study of different nanostructured carbon supports for fuel cell catalysts

Pt clusters were deposited by an impregnation process on three carbon supports: multi-wall carbon nanotubes (MWNT), single-wall carbon nanohorns (SWNH), and Vulcan XC-72 carbon black to investigate the effect of the carbon support structure on the possibility of reducing Pt loading on electrodes for direct methanol (DMFC) fuel cells without impairing performance. MWNT and SWNH were in-house synthesised by a DC and an AC arc discharge process between pure graphite electrodes, respectively. UV-vis spectrophotometry, scanning and transmission electron microscopy, X-ray diffraction, and cyclic voltammetry measurements were used to characterize the Pt particles deposited on the three carbon supports. A differential yield for Pt deposition, not strictly related to the surface area of the carbon support, was observed. SWNH showed the highest surface chemical activity toward Pt deposition. Pt deposited in different forms depending on the carbon support. Electrochemical characterizations showed that the Pt nanostructures deposited on MWNT are particularly efficient in the methanol oxidation reaction.     

Preexposure and extinction effects of lithium chloride induced taste-potentiated aversions for spatially contiguous auditory food cues in rats.

[Correction Notice: An erratum for this article was reported in Vol 101(6) of Behavioral Neuroscience (see record 2008-10703-001). The aforementioned article contains errors in the last paragraph of the Results section, none of which change the results of the experiment. The corrected paragraph sections are provided in the erratum.] Taste potentiated illness-induced aversions for noisy food were studied in Sprague-Dawley rats. The rats ate from receptacles containing salty food and a contiguous tone produced by speakers under the food followed by lithium chloride injections. In preference tests, the rats then avoided noisy food in favor of quiet food followed by extinction and spontaneous recovery of the auditory aversion over repeated nonreinforced trials. Other rats were given either 4 or 10 days of exposure to the noisy food prior to taste-toxicosis treatment. None of these rats subsequently avoided noisy food. The importance of spatial contiguity and methodological variation in associating nongustatory food cues with illness is discussed. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Simultaneous degradation of atrazine and simazine by a binary culture of Stenotrophomonas maltophilia and Arthrobacter sp. in a two‐stage biofilm reactor

BACKGROUND: The impact of mixtures of chloro‐triazinic herbicides, such as atrazine and simazine, on aquatic ecosystems is of environmental concern. To study their biodegradation under various operational conditions, a binary community comprising Stenotrophomonas maltophilia and Arthrobacter sp. attached to the porous support of a packed bed reactor, was evaluated. RESULTS: The genetic analysis of the two atrazine‐degrading strains revealed that genes atzA, atzB, atzC are present in both bacteria, but only S. maltophilia possess atzD. Thus, by cultivating Arthrobacter sp. on these herbicides, cyanuric acid accumulation was observed. When the binary community was cultivated in the biofilm reactor, at all the loading rates probed, both herbicides were entirely removed. However, complete biodegradation of cyanuric acid was not achieved. CONCLUSIONS: Even with a two‐stage reactor, cyanuric acid was only partially removed. This fact could be attributed to the absence, in the second stage, of an easily degradable energy source, required by S. maltophilia for the uptake and cometabolic degradation of the recalcitrant heterocyclic ring. Responding to differences in nutritional conditions prevailing at each reactor stage, local differences in species' predominance were clearly detected by microbiological and molecular biology methods. Copyright © 2010 Society of Chemical Industry     

Secondary production and biomass of Cladocera in marginal lakes after the recovery of their hydrologic connectivity in a river–reservoir transition zone

Secondary production and biomass of Cladoceran populations were studied in two marginal lakes whose connections to a tropical river were re‐established after a prolonged drought period. This study investigates the process of the recovery of the cladoceran populations after the hydrologic reconnection with the river was established. It also compares the energetic dynamic of Cladoceran populations in two lakes, one with a wide and another with a narrow connection to the river. Samples were collected every 48 h for 1 month, immediately after the river water inflow to the lakes, and 7 months after the reconnection with the river during a period of hydrologic stability of the lakes. Secondary production and biomass were compared between lakes and periods, to identify the main controlling factors for the observed variations in Cladoceran productivity. Cladocerans were more productive during the rainy period, immediately after the increased water volume, when high water temperatures were recorded in the two lacustrine systems. Secondary production and biomass values were higher in the more eutrophic lake, wherein the water chemical and physical characteristics presented slow alterations during the rainy period. Although the lake with large spatial heterogeneity and linkages with the river exhibited high Cladoceran richness, the secondary production and biomass were low. Variations in water volumes and temperatures and changes in trophic status affected the secondary production and biomass of the main Cladoceran species in the two studied lakes.     

Liquid-crystallization induced reactions. Microstructure and morphology of copolyesters synthesized by transesterification of PET with some LCP monomers

The transesterification of poly(ethylene terephthalate) (PET) with a mixture of sebacic acid (S), 4,4′-diacetoxybiphenyl (B) and 4-acetoxybenzoic acid (H), carried out under conditions expectedly favoring the formation of a p(ET-SBH) random copolyester, produces biphasic materials with an isotropic matrix and a highly fibrous, liquid-crystalline dispersed phase. Spectroscopic, calorimetric, microscopic and diffractometric characterization of the fractions separated by solvent extraction has shown that the two phases consist of practically random copolyesters having different average composition. Interestingly, the degree of aromaticity of the matrix is even lower than that of PET, whereas that of the minor phase is appreciably higher than that calculated for the SBH copolyester that would be produced from the monomer mixture in the absence of PET. This unexpected result is interpreted on the basis of an enthalpy-driven progressive diffusion of aromatic-rich material toward the mesophase which segregates at an early stage of the polycondensation within the isotropic mixture of low molar mass oligomers initially produced by the PET acidolysis. Thus, an increasing differentiation, rather than an equilibration, of the composition of the two phases takes place. It is noteworthy that, despite the strong compositional difference, the two phases of these products show fairly good compatibility and interfacial adhesion.     

Automation of a spectrophotometric method for measuring L -carnitine in human blood serum

A spectrometric method for the determination of L-carnitine has been developed based on the reaction of the 5,5^′ dithiobis-(2-nitrobenzoic) acid (DTNB) and adapted to a Technicon RA-2000 automatic analyser Química Farmacéutica Bayer, S.A.). The detection limit of the method is 13.2 μmol/l, with a measurement interval ranging from 30 to 320 μmoll1. Imprecision and accuracy are good even at levels close to the detection limit (coeffcient of variation of 5.4% for within-run imprecision for a concentration of 35 μmol/l). A good correlation was observed between the method studied and the radiometric method. The method evaluated has suffcient analytical sensitivity to diagnose carnitine deficiencies. The short time period required for sample processing (30 samples in 40min), the simple methodology and apparatus, the ease of personnel training and the low cost of the reagents make this method a good alternative to the classical radiometric method for evaluating serum L-carnitine in clinical laboratories without radioactive installations.