Atomistic insights into solvation dynamics and conformational transformation in thermo-sensitive and non-thermo-sensitive oligomers

Solvation dynamics and conformational transformation in oligomers with varying degree of temperature sensitivity is studied using molecular dynamics (MD) simulations. Conformational transformation in three model systems namely poly(N-isopropylacrylamide) (PNIPAM), poly(acrylamide) (PAA), and poly(ethylene glycol) (PEG) are compared and contrasted to understand the origin of a coil-to-globule transformations across the lower critical solution temperature (LCST) in thermo-sensitive oligomers. PNIPAM, PAA, and PEG are water-soluble oligomers. However, for the temperature range used in these simulations, PNIPAM shows an LCST whereas PAA and PEG are non-thermo-sensitive. Oligomers of PNIPAM, PAA, and PEG consisting of 30 monomer units (30-mer) each were simulated at 5 °C (278 K) and 37 °C (310 K). Conformational transformations in the oligomers are evaluated using structural and dynamical correlation functions such as radius of gyration, radial distribution function, residence time probabilities and hydrogen-bonding life-times. Our simulations suggest that the solubility, solvation dynamics, and conformation of the oligomers are dictated by two factors: (a) the local structure of proximal water and (b) the diffusion and exchange kinetics of proximal water with bulk water. In thermo-sensitive oligomer such as PNIPAM, we find that the coil-to-globule transition is closely related to the local ordering and solvation dynamics of PNIPAM. We have identified stable configurations of proximal water molecules for an oligomer undergoing conformational transition. The slow diffusional properties of proximal water molecules near PNIPAM oligomers suggests that water forms a stable network near hydrophilic groups of PNIPAM as compared to the hydrophilic groups of PAA and PEG. Thermal perturbation of this solvated structure results in significant reduction in local ordering of water, which contributes to the globular collapse and the reduced solubility of PNIPAM above its LCST. On the other hand, non-thermo-sensitive oligomers such as PAA and PEG are characterized by much faster diffusion and exchange kinetics of proximal water at the two simulated temperatures compared to PNIPAM. This faster exchange kinetics helps in maintaining higher hydration level of the oligomers and is responsible for the apparent hydrophilic character and thereby the observed solubility at the two simulated temperatures.     

Two‐Dimensional Molybdenum Trioxide and Dichalcogenides

In the quest to discover the properties of planar semiconductors, two‐dimensional molybdenum trioxide and dichalcogenides have recently attracted a large amount of interest. This family, which includes molybdenum trioxide (MoO₃), disulphide (MoS₂), diselenide (MoSe₂) and ditelluride (MoTe₂), possesses many unique properties that make its compounds appealing for a wide range of applications. These properties can be thickness dependent and may be manipulated via a large number of physical and chemical processes. In this Feature Article, a comprehensive review is delivered of the fundamental properties, synthesis techniques and applications of layered and planar MoO₃, MoS₂, MoSe₂, and MoTe₂ along with their future prospects.     

Effect of Bio-Lubricant and Biodiesel-Contaminated Lubricant on Tribological Behavior of Cylinder Liner–Piston Ring Combination

This article addresses the issue of friction and wear characteristics of diesel engine cylinder liner–piston ring combinations under different lubricating conditions using a pin-on-disc wear tribometer. The discs were made out of actual engine cylinder liner material using a casting process. Pins were made out of top compression ring material. The tests were conducted on a pin-on-disc tribometer for wear and friction characteristics of the cylinder liner and piston ring combination with diesel-contaminated rapeseed oil–based bio-lubricant, diesel-contaminated commercial synthetic lubrication oil (SAE 20W40), biodiesel-contaminated commercial synthetic lubrication oil (SAE 20W40), and used (150 h) commercial synthetic lubrication oil (SAE 20W40). Experimental results demonstrated that the rapeseed oil–based bio-lubricant and biodiesel-contaminated synthetic lubricant exhibited better performance in terms of wear, friction, and frictional force under similar operating conditions. Thus, usage of newly formulated bio-lubricant and biodiesel in the long run may have a positive impact on engine life.     

Ionizing radiation and genetic risks. VI. Chronic multifactorial diseases: a review of epidemiological and genetical aspects of coronary heart disease, essential hypertension and diabetes mellitus

This paper provides a broad overview of the epidemiological and genetical aspects of common multifactorial diseases in man with focus on three well-studied ones, namely, coronary heart disease (CHD), essential hypertension (EHYT) and diabetes mellitus (DM). In contrast to mendelian diseases, for which a mutant gene either in the heterozygous or homozygous condition is generally sufficient to cause disease, for most multifactorial diseases, the concepts of genetic susceptibility' and risk factors' are more appropriate. For these diseases, genetic susceptibility is heterogeneous. The well-studied diseases such as CHD permit one to conceptualize the complex relationships between genotype and phenotype for chronic multifactorial diseases in general, namely that allelic variations in genes, through their products interacting with environmental factors, contribute to the quantitative variability of biological risk factor traits and thus ultimately to disease outcome. Two types of such allelic variations can be distinguished, namely those in genes whose mutant alleles have (i) small to moderate effects on the risk factor trait, are common in the population (polymorphic alleles) and therefore contribute substantially to the variability of biological risk factor traits and (ii) profound effects, are rare in the population and therefore contribute far less to the variability of biological risk factor traits. For all the three diseases considered in this review, a positive family history is a strong risk factor. CHD is one of the major contributors to mortality in most industrialized countries. Evidence from epidemiological studies, clinical correlations, genetic hyperlipidaemias etc., indicate that lipids play a key role in the pathogenesis of CHD. The known lipid-related risk factors include: high levels of low density lipoprotein cholesterol, low levels of high density lipoprotein cholesterol, high apoB levels (the major protein fraction of the low density lipoprotein particles) and elevated levels of Lp(a) lipoprotein. Among the risk factors which are not related to lipids are: high levels of homocysteine, low activity of paraoxonase and possibly also elevated plasma fibrinogen levels. In addition to the above, hypertension, diabetes and obesity (which themselves have genetic determinants) are important risk factors for CHD. Among the environmental risk factors are: high dietary fat intake, smoking, stress, lack of exercise etc. About 60% of the variability of the plasma cholesterol is genetic in origin. While a few genes have been identified whose mutant alleles have large effects on this trait (e.g., LDLR, familial defective apoB-100), variability in cholesterol levels among individuals in most families is influenced by allelic variation in many genes (polymorphisms) as well as environmental exposures. A proportion of this variation can be accounted for by two alleles of the apoE locus that increase (ε4) and decrease (ε2) cholesterol levels, respectively. A polymorphism at the apoB gene (XbaI) also has similar effects, but is probably not mediated through lipids. High density lipoprotein cholesterol levels are genetically influenced and are related to apoA1 and hepatic lipase (LIPC) gene functions. Mutations in the apoA1 gene are rare and there are data which suggest a role of allelic variation at or linked LIPC gene in high density lipoprotein cholesterol levels. Polymorphism at the apoA1--C3 loci is often associated with hypertriglyceridemia. The apo(a) gene which codes for Lp(a) is highly polymorphic, each allele determining a specific number of multiple tandem repeats of a unique coding sequence known as Kringle 4. The size of the gene correlates with the size of the Lp(a) protein. The smaller the size of the Lp(a) protein, the higher are the Lp(a) levels. (ABSTRACT TRUNCATED)     

Isolation of ethylenediamine from industrial solution of ethylenediamine hydrochloride by electrodialysis

An industrial solution of ethylenediamine hydrochloride which contains about 18% chloride and 12% amine was electrodialysed in a five‐compartment cell to obtain pure ethylenediamine. Different parameters such as alkali concentration and current density were studied to optimise conditions of maximum current efficiency for amine recovery and chloride removal from the feed solution. The Suitabilities of different ion‐exchange membranes for electrodialysis were compared. Variation in current efficiency for amine recovery with increases in the concentration of amine during electrodialysis was also studied. Current efficiency for amine recovery and chloride removal is about 78% and 91% respectively under optimum conditions. The amount of electrical energy consumed is 12.1 kWh kg^?1 for ethylenediamine recovery and 8.6 kWh kg^?1 for chloride removal. The concentration of pure amine obtained after the electrodialysis was around 20%. The results are encouraging for industrial applications whereby ethylenediamines free from chlorides can be isolated. Copyright © 2003 Society of Chemical Industry     

The influence of Al2O3 particulate reinforcement on cyclic stress response and fracture behavior of 6061 aluminum alloy

The cyclic stress response characteristics and cyclic fracture behavior of aluminum alloy 6061 discontinuously reinforced with particulates of Al₂O₃ are presented and discussed. The 6061/Al₂O₃ composite specimens and the unreinforced 6061 aluminum alloy were cyclically deformed using tension-compression loading under constant total strain amplitude control. Both the composite and the unreinforced alloy exhibited softening to failure from the onset of cyclic deformation. The degree of softening was observed to increase at the elevated test temperature for both the composite and the unreinforced counterpart. The intrisic micromechanisms controlling the stress response characteristics during fully-reversed cyclic straining are highlighted and rationale for the observed behavior is discussed. The cyclic fracture behavior of the composite is discussed in terms of the competing influences of intrinsic microstructural effects, deformation characteristics arising from a combination of mechanical and microstructural contributions, cyclic stress response, and test temperature.     

Category learning and change: Differences in sensitivity to information that enhances or reduces intercategory distinctions.

We examined the amenability of abstractions of categories to new and relevant information. In Experiment 1, Ss formed impressions of 2 sets of numbers by periodically estimating the cumulative means of each set. During the 1st half of the procedure, the 2 means were mathematically stable. During the 2nd half of the procedure, the mean of 1 set was modified and the mean of the other set remained unchanged. We predicted and found that the resultant estimates for the modified category changed more when the mean difference between the 2 categories was enhanced than when it was reduced. Experiment 2 suggested that the accentuation effect results from a 2-stage process of category learning (Stage 1) and category change (Stage 2). Experiment 3 replicated the effect with person categories. The relevance of category accentuation is discussed with respect to the modifiability of social beliefs. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Development and Validation of a Drug Release Rate Method for a Water Soluble Drug in a Liposome Preparation

An in vitro method was developed to determine the rate of drug release from a liposome preparation. Three batches of liposomes containing orciprenaline sulphate were evaluated for release of drug over a 24 hour period in an end-over-end tumbler device. Intra and inter day precision studies indicate good reproducibility for this test method. This method is easy to use in drug development and quality control laboratories to evaluate drug release from liposome formulations.     

Global variations in cancer survival. Study Group on Cancer Survival in Developing Countries

Population-based cancer registries from Algeria, China, Costa Rica, Cuba, India, the Philippines, and Thailand are collaborating with the International Agency for Research on Cancer in a study of cancer survival in developing countries. Comparisons with the SEER program results of the National Cancer Institute in the United States, and the EUROCARE study of survival in European countries revealed considerable differences in the survival of patients with certain tumors associated with intensive chemotherapeutic treatment regimes (Hodgkin's disease and testicular tumors), more modest differences in the survival of patients with tumors for which early diagnosis and treatment confer an improved prognosis (carcinomas of the large bowel, breast, and cervix), and only slight differences for tumors associated with poor prognosis (carcinomas of the stomach, pancreas, and lung). With limited resources to meet the challenge of the increasing incidence of cancer expected in the next few decades, health authorities in developing countries should be aware of the importance of investing in a range of cancer control activities, including primary prevention and early detection programs as well as treatment.