Distinct conformational properties determined by implicit and explicit representation of protein-solvent interactions. An analytical and computer simulation study

In the protein folding problem, solvent-mediated forces are commonly represented by intra-chain pairwise contact energy. Although this approximation has proven to be useful in several circumstances, it is limited in some other aspects of the problem. Here we show that it is possible to achieve two models to represent the chain-solvent system. one of them with implicit and other with explicit solvent, such that both reproduce the same thermodynamic results. Firstly, lattice models treated by analytical methods, were used to show that the implicit and explicitly representation of solvent effects can be energetically equivalent only if local solvent properties are time and spatially invariant. Following, applying the same reasoning Used for the lattice models, two inter-consistent Monte Carlo off-lattice models for implicit and explicit solvent are constructed, being that now in the latter the solvent properties are allowed to fluctuate. Then, it is shown that the chain configurational evolution as well as the globule equilibrium conformation are significantly distinct for implicit and explicit solvent systems. Actually, strongly contrasting with the implicit solvent version, the explicit solvent model predicts: (i) a malleable globule, in agreement with the estimated large protein-volume fluctuations; (ii) thermal conformational stability, resembling the conformational hear resistance of globular proteins, in which radii of gyration are practically insensitive to thermal effects over a relatively wide range of temperatures; and (iii) smaller radii of gyration at higher temperatures, indicating that the chain conformational entropy in the unfolded state is significantly smaller than that estimated from random coil configurations. Finally, we comment on the meaning of these results with respect to the understanding of the folding process. (C) 2009 Elsevier B.V. All rights reserved.

Titanium phosphate for Fuel Cell Proton Conduction Membranes

Environmental issues due to increases in emissions of air pollutants and greenhouse gases are driving the development of clean energy delivery technologies such as fuel cells. Low temperature Proton Exchange Membrane Fuel Cells (PEMFC) use hydrogen as a fuel and their only emission is water. While significant advances have been made in recent years, a major limitation of the current technology is the cost and materials limitations of the proton conduction membrane. The proton exchange membrane performs three critical functions in the PEMFC membrane electrode assembly (MEA): (i) conduction of protons with minimal resistance from the anode (where they are generated from hydrogen) to the cathode (where they combine with oxygen and electrons, from the external circuit or load), (ii) providing electrical insulation between the anode and cathode to prevent shorting, and (iii) providing a gas impermeable barrier to prevent mixing of the fuel (hydrogen) and oxidant. The PFSA (perfluorosulphonic acid) family of membranes is currently the best developed proton conduction membrane commercially available, but these materials are limited to operation below 100oC (typically 80oC, or lower) due to the thermochemical limitations of this polymer. For both mobile and stationary applications, fuel cell companies require more durable, cost effective membrane technologies capable of delivering enhanced performance at higher temperatures (typically 120oC, or higher. This is driving research into a wide range of novel organic and inorganic materials with the potential to be good proton conductors and form coherent membranes. There are several research efforts recently reported in the literature employing inorganic nanomaterials. These include functionalised silica phosphates [1,2], fullerene [3] titania phosphates [4], zirconium pyrophosphate [5]. This work addresses the functionalisation of titania particles with phosphoric acid. Proton conductivity measurements are given together with structural properties.

p-cresol as a reversible acylium ion scavenger in solid-phase peptide synthesis

In this work we have defined the nature of the p-cresol and p-thiocresol adducts generated from acylium ions during HF cleavage, following contemporary Boc/benzyl solid-phase peptide synthesis. Contrary to the results in previous reports, we found that both p-cresol and p-thiocresol predominantly form. aryl esters under typical cleavage conditions. Initially we investigated a number of small peptides containing either a single glutamate residue or a C-terminal long-chain amino acid which allowed us to unambiguously characterize the scavenged side products. Whereas, the p-cresol esters are stable at 0 degrees C they rearrange irreversibly at higher temperatures (5-20 degrees C) to form aryl ketones. By contrast, p-thiocresol esters do not undergo a Fries rearrangement but readily undergo further additions of p-thiocresol to form ketenebisthioacetals and trithio ortho esters, even at low temperatures. Importantly, we found by LC/MS and FT-ICR MS analysis that peptides containing p-cresol esters at glutamyl side chains are susceptible to amidation and fragmentation reactions at these sites during standard mild base workup procedures. The significance of these side reactions was further demonstrated in the synthesis of neutrophil immobilization factor, a 26-residue peptide, containing four glutamic acid residues. The side reactions were largely avoided by mild hydrogen peroxide-catalyzed hydrolysis which converted the p-cresol adducts to the free carboxylic acids in near quantitative yield. The choice of p-cresol as a reversible acylium ion scavenger when coupled with the simple workup conditions described is broadly applicable to Boc/benzyl peptide synthesis and will significantly enhance the quality of peptides produced.

VOC removal: Comparison of MCM-41 with hydrophobic zeolites and activated carbon

The recently discovered mesoporous molecular sieve MCM-41 was tested as an adsorbent for VOC removal. Its adsorption/desorption properties were evaluated and compared with other hydrophobic zeolites (silicalite-1 and zeolite Y) and a commercial activated carbon, BPL. The adsorption isotherms of some typical VOCs (benzene, carbon tetrachloride, and n-hexane) on MCM-41 are of type IV according to the IUPAC classification, drastically different from the other microporous adsorbents, indicating that VOCs, in the gas phase, have to be at high partial pressures in order to make the most of the new mesoporous material as an adsorbent for VOC removal. However, a proper modification of the pore openings of MCM-41 can change the isotherm types from type IV to type I without remarkable loss of the accessible pare volumes and, therefore, significantly enhance the adsorption performance at low partial pressures. Adsorption isotherms of water on these adsorbents are all of type V, demonstrating that they possess a similar hydrophobicity. Desorption of VOCs from MCM-41 could be achieved at lower temperatures (50-60 degrees C), while this had to be conducted at higher temperatures (100-120 degrees C) for microporous adsorbents, zeolites, and activated carbons.

Effect of temperature on the gamma-radiolysis of poly(tetrafluoroethylene-co-perfluoromethyl vinyl ether)

The effect of irradiation temperature on the polymer properties was investigated for the fluoroelastomer poly(tetrafluoroethylene-co-perfluoromethylvinyl ether) (TFE/PMVE). TFE/PMVE samples were gamma-irradiated to 150 kGy at temperatures ranging from 77 K to 373 K. Analysis of the sol/gel behaviour, tensile properties, and glass transition temperatures indicated that crosslinking commenced in the temperature range 195 to 263 K, for a dose of 150 kGy. The latter temperature was 13 K below the glass transition temperature. Crosslinking remained relatively constant to higher temperatures. Chain scission reactions were found to occur well below the glass transition temperature and increased at higher temperatures. The optimum temperature for the radiation crosslinking of TFE/PMVE, for the temperatures investigated, was 263 K. (C) 1998 Elsevier Science Ltd. All rights reserved.

Development of composite adsorbents of carbon and intercalated clay for N2 and O2 adsorption: A preliminary study

Composite adsorbents of carbon and alumina intercalated montmorillonite were prepared and characterized by adsorption of N-2 and O-2 at various temperatures. The effects of pyrolysis, temperature, heating rate, subsequent degassing, and doping of cations and anions were investigated. The adsorption capacities of the composite adsorbents developed at higher temperatures (0 and -79 degrees C) are found to be larger than those of normal alumina pillared clays. The experimental results showed that the framework of these adsorbents is made of alumina particles and clay sheets while the pyrolyzed carbon distributes in the space of interlayers and interpillars. The pores between the carbon particles, clay sheets, and alumina pillars are very narrow with very strong adsorption forces, leading to enhanced adsorption capacities at 0 and -79 degrees C. The composite adsorbents exhibit features similar to those of carbonaceous adsorbents. Their pore structures, adsorption capacities, and selectivities to oxygen can be tailored by a controlled degassing procedure. Meanwhile, ions can be doped into the adsorbents to modify their adsorption properties, as usually observed for oxide adsorbents like zeolite and pillared clays. Such flexibility in pore structure tailoring is a potential advantage of the composite adsorbents developed for their adsorption and separation applications. (C) 1999 Academic Press.

Thermal acclimation of locomotor performance in tadpoles of the frog Limnodynastes peronii

Previous analyses of thermal acclimation of locomotor performance in amphibians have only examined the adult life history stage and indicate that the locomotor system is unable to undergo acclimatory changes to temperature. In this study, we examined the ability of tadpoles of the striped marsh frog (Limnodynastes peronii) to acclimate their locomotor system by exposing them to either 10 degrees C or 24 degrees C for 6 weeks and testing their burst swimming performance at 10, 24, and 34 degrees C. At the test temperature of 10 degrees C, maximum velocity (U-max) of the 10 degrees C-acclimated tadpoles was 47% greater and maximum acceleration (A(max)) 53% greater than the 24 degrees C-acclimated animals. At 24 degrees C, U-max was 16% greater in the 10 degrees C-acclimation group, while there was no significant difference in A(max) or the time taken to reach U-max (T-U-max). At 34 degrees C, there was no difference between the acclimation groups in either U-max or A(max), however T-U-max was 36% faster in the 24 degrees C-acclimation group. This is the first study to report an amphibian (larva or adult) possessing the capacity to compensate for cool temperatures by thermal acclimation of locomotor performance. To determine whether acclimation period affected the magnitude of the acclimatory response, we also acclimated tadpoles of L. peronii to 10 degrees C for 8 months and compared their swimming performance with tadpoles acclimated to 10 degrees C for 6 weeks. At the test temperatures of 24 degrees C and 34 degrees C, U-max and A(max) were significantly slower in the tadpoles acclimated to 10 degrees C for 8 months. At 10 degrees C, T-U-max was 40% faster in the 8-month group, while there were no differences in either U-max or A(max). Although locomotor performance was enhanced at 10 degrees C by a longer acclimation period, this was at the expense of performance at higher temperatures.

Catalytic conversion to N2O to N2 over potassium catalyst supported on activated carbon

Catalytic conversion of N2O to N-2 With potassium catalysts supported on activated carbon (K/AC) was investigated. Potassium proves to be much more active and stable than either copper or cobalt because potassium possesses strong abilities both for N2O chemisorption and oxygen transfer. Potassium redispersion is found to play a critical role in influencing the catalyst stability. A detailed study of the reaction mechanism was conducted based upon three different catalyst loadings. It was found that during temperature-programmed reaction (TPR), the negative oxygen balance at low temperatures (< 50 degrees C) is due to the oxidation of the external surface of potassium oxide particles, while the bulk oxidation accounts for the oxygen accumulation at higher temperatures (below ca. 270 degrees C). N2O is beneficial for the removal of carbon-oxygen complexes because of the formation of CO2 instead of CO and because of its role in making the chemisorption of produced CO2 on potassium oxide particles less stable. A conceptual three-zone model was proposed to clarify the reaction mechanism over K/AC catalysts. CO2 chemisorption at 250 degrees C proves to be an effective measurement of potassium dispersion. (C) 1999 Academic Press.

Thermal ecology and structural habitat use of two sympatric lizards (Carlia vivax and Lygisaurus foliorum) in subtropical Australia

The thermal ecology and structural habitat use of two closely related sympatric lizards, Carlia vivax (de Vis) and Lygisaurus foliorum de Vis, were examined in an open sclerophyll forest in subtropical Australia. Comparable mean body temperatures (T-b) and habitat temperatures (T-hab) at the point of capture were recorded for both species. However, sex- related differences in the thermal variables for C. vivax, with females displaying higher temperatures than males, resulted in some significant differences in T-b and T-hab between the species. Variation in T-b and T-hab within and between species was unrelated to time of capture. The difference in T-hab within C. vivax suggested that females were selecting warmer thermal environments than males. Both C. vivax and L. foliorum used most structural features of their habitat randomly as indicated by a similarity in canopy, shrub, ground, log and litter cover and litter depth between habitat surveys and random surveys. However, C. vivax displayed a preference for ground vegetation (height

Aspects of the biology of the yabby Trypea australiensis (Dana) (Decapoda : Thalassinidea) and the potential of burrow counts as an indirect measure of population density

The thalassinidean shrimp Trypea australiensis (the yabby) commonly occurs on intertidal sandflats and subtidal regions of sheltered embayments and estuaries along the east coast of Australia and is harvested commercially and recreationally for use as bait by anglers. The potential for counts of burrow openings to provide a reliable indirect estimate of the abundance of yabbies was examined on intertidal sandflats on North Stradbroke Island (Queensland, Australia). The relationship between the number of burrow openings and the abundance of yabbies was generally poor and also varied significantly through time, casting doubt on previous estimates of abundance for this species based on unvalidated hole counts. Spatial and temporal variation in population density, the size at maturity and the reproductive period of the yabby were also assessed. Except for an initial peak in abundance as a result of recruitment, the density of yabbies was constant throughout the study but considerably less than that estimated from a previous study in the same area. Ovigerous females were recorded at 3 mm carapace length (CL) which is smaller than previously recorded for this species and thalassinideans in general. Small ovigerous females were found throughout the study, including the summer months, which is unusual for thalassinideans in the intertidal zone. It was hypothesised that in the intertidal zone, small female yabbies may be able to balance the metabolic demands of reproduction and respiration at higher temperatures than can larger females allowing them to reproduce in the warmer months.

Maternal investment in egg production: environmental and population-specific effects on offspring performance in the snapping shrimp Alpheus nuttingi (Schmitt, 1924) (Decapoda, Alpheidae)

Among marine invertebrates, the overall biomass invested in egg production varies widely within populations, which can result from the interaction of endogenous and exogenous factors. Species that have constant reproduction throughout the year can be good models to study the influence of environmental factors on reproductive processes. We conducted a seasonal comparison of egg production in the intertidal snapping shrimp Alpheus nuttingi, which shows a continuous reproductive pattern, to examine the hypothesis that differences in egg production are driven by environmental conditions and population features. This population showed an uncommon strategy, characterized by females that produce eggs of varying sizes within their clutches, with reduced egg volume when the number of eggs is higher (Spring-Summer). In these seasons, higher temperatures and greater food availability may allow the production of more eggs compared to the Autumn-Winter seasons. Compared to other alpheid shrimps, this population produces small eggs, but in larger numbers. Despite the higher fecundity, the reproductive output is relatively low, this production being supported by the large size of females from the southern Atlantic region. Our findings showed that the egg production of A. nuttingi was greatly influenced by environmental factors. Therefore, this shrimp, and probably other decapods that possess continuous reproduction, adopt different reproductive strategies during the year. (C) Koninklijke Brill NV, Leiden, 2010.

Reproductive strategy of the snapping shrimp Alpheus armillatus H. Milne-Edwards, 1837 in the South Atlantic: fecundity, egg features, and reproductive output

The family Alpheidae, composed by shrimps of relatively small size, popularly known as snapping shrimps, is the one of the most diverse decapod groups. These shrimps are found worldwide and Occur in tropical and subtropical waters, from the intertidal zone to great depths. We investigated reproductive aspects of Alpheus armillatus, in order to gather information on egg production, aiming to enhance knowledge of its reproductive strategies in a population in an intertidal area of the South Atlantic. Ovigerous females were collected under rocks, in May and July 2006 (dry season) and in November 2006 and March 2007 (rainy season). Egg production and reproductive output were analyzed and compared seasonally and during the period of embryonic development. Females measured on average 11.28 mm CL with a mean of 763 eggs and 0.11 mm(3) egg volume. The egg volume of this population was smaller than previous estimates for other species of snapping shrimps, but the mean egg number was higher. The volume of eggs doubled during the incubation period, but despite this increase, no significant loss of eggs was observed. Alpheus armillatus invests oil average about 12% of body weight in reproduction. The proportional investment in egg production IS Significantly higher in the rainy season when compared with the dry season (17.9% vs 4.8%), correlated with higher temperatures and increased food availability at this time. Our results corroborated the hypothesis of a pattern of egg production influenced by environmental conditions and intraspecific variability among the family Alpheidae, as a function of the biogeographic region.

Thermal analysis, nuclear magnetic resonance spectroscopy, and impedance spectroscopy of N,N-dimethyl-pyrrolidinium iodide: An ionic solid exhibiting rotator phases

N,N-dimethyl-pyrrolidinium iodide has been investigated using differential scanning calorimetry, nuclear magnetic resonance (NMR) spectroscopy, second moment calculations, and impedance spectroscopy. This pyrrolidinium salt exhibits two solid-solid phase transitions, one at 373 K having an entropy change, Delta S, of 38 J mol(-1) K-1 and one at 478 K having Delta S of 5.7 J mol(-1) K-1. The second moment calculations relate the lower temperature transition to a homogenization of the sample in terms of the mobility of the cations, while the high temperature phase transition is within the temperature region of isotropic tumbling of the cations. At higher temperatures a further decrease in the H-1 NMR linewidth is observed which is suggested to be due to diffusion of the cations. (C) 2005 American Institute of Physics.

The chemistry of novolac resins .3. C-13 and N-15 nmr studies of curing with hexamethylenetetramine

The reactions between novolac resins and hexamethylenetetramine (HMTA) which occur on curing have been studied by C-13 and N-15 high-resolution n.m.r. in both solution and the solid state. Strong evidence for the existence of many curing intermediates is obtained. New curing intermediates are reported along with experimental data to support previously postulated intermediates. The initial curing reactions between novolac and HMTA produce various substituted benzoxazines and benzylamines. Thermal decomposition/oxidation and further reactions of these initial intermediates generate methylene linkages between phenolic rings for chain extension and cross-linking. Among the three kinds of methylene linkages, the para-para methylene linkages are formed at relatively lower temperatures. Various imine, amide and imide side-products also concurrently appear during the process. The initial amount of HMTA plays a critical role in the curing reactivity and chemical structures of the cured resins. The lower the amount of HMTA, the lower the temperature at which curing occurs, and the lower the amount of the nitrogen-containing side-products in the finally cured resins. The ortho-linked intermediates are relatively stable, and can remain in the cured resins up to higher temperatures. The study provides an extensive description of the curing reactions of novolac resins. (C) 1997 Elsevier Science Ltd.

Effects of adhesive temperature on the early and 6-month dentin bonding

Objectives: The aim of this study was to test the effect of adhesive temperature on the bond strength to dentin (mu TBS) and silver nitrate uptake (SNU) of an ethanol/water (Adper Single Bond 2 [SB]) and an acetone-based (Prime&Bond 2.1 [PB]) etch-and-rinse adhesive system. Methods: The bottles of each adhesive were kept in various temperatures (5 degrees C, 20 degrees C, 37 degrees C and 50 degrees C) for 1 h previously to its application in the occlusal demineralized dentin of 40 molars. Bonded sticks (0.8 mm(2)) were tested in tension (0.5 mm/min) immediately (IM) or after 6 months (6 M) of water storage. Two bonded sticks from each hemi-tooth were immersed in silver nitrate and analyzed by SEM. Data were analyzed by two-way repeated measures ANOVA and Tukey`s test (alpha = 0.05). Results: No significant difference in mu TBS was detected for both adhesives at 5 degrees C and 20 degrees C. The highest bond strength for PB was observed in the 37 degrees C group while for SB it was in the 50 degrees C. Significant reductions of bond strengths were observed for PB at 37 degrees C and SB at 50 degrees C after 6 M of water storage. Silver nitrate deposition was seen in all hybrid layers, irrespective of the group. Lower silver nitrate deposition (water trees) in the adhesive layer was seen for PB and SB at higher temperatures. Conclusions: The heating or refrigeration of the adhesives did not improve their resin-dentin bond resistance to water degradation over time. (C) 2009 Elsevier Ltd. All rights reserved.