Self-association behaviour of atactic polymethacrylic acid in aqueous solution investigated by atomistic molecular dynamics simulations

The self-association behaviour of atactic poly(methacrylic acid) (a-PMA) in water was investigated by atomistic molecular dynamics (MD) simulations. Simulations show that interchain association of a-PMA occurs only in its un-neutralised form, by hydrogen bonding between –COOH groups, which is in agreement with the experimental observation. Chain conformations, dihedral angle distributions, hydration behaviour, scattering structure factor and enthalpy-of-hydration (i.e. aqueous solvation) were analysed as a function of concentration for un-neutralised PMA, across dilute to concentrated regimes. The average 〈R_g〉 of the chain remains unaffected in solution and also for amorphous undissolved a-PMA phase, confirming the occurrence of the approximate theta-solution condition for the first time, as revealed by simulations, in a polar hydrogen-bonding polymer aqueous solution. Chain hydration behaviour and scattering structure factor show significant changes in concentrated regime. Scattering intensity collapse occurs in concentrated PMA solution, due to the existence of the swollen regime captured for the first time by explicit-MD-simulations. The hydration of PMA is driven by H-bonding, specifically between H atoms of the COOH groups and O atoms of water molecules in the closest coordination shell. The enthalpy of hydration of PMA is dominated by PMA–water interactions (charges and H-bonding). The thermodynamic contributions of PMA–PMA and PMA–water interactions towards the electrostatics as well as the dispersion components of the total solvation-enthalpy become more favourable than water–water interactions.     

Fungicide control of Stenocarpella Maydis in the Nigerian Savanna

A survey of farmers' fields in the Savanna zone of Nigeria in 1999 indicated the presence of stalk and cob rots of maize at incidence rates of 15?–?43% and disease severity of 2.0?–?6.7. The causal organism was identified as Stenocarpella maydis (?=?Diplodia maydis). S. maydis was found to reduce seed germination by up to 29.2%. Laboratory and screen house experiments were used to evaluate the efficacy of six seed treatment fungicides indicated that Luxan (a local fungicide of unknown composition), benomyl (Benlate) and mancozeb (Dithane M-45) were more effective than metalaxyl?+?carboxin?+?furathiocarp (Apron-plus), carbendazin?+?maneb (Delsene M) and tetramethylthiuram disulphide?+?hexachlorobenzene (thiram?+?HCB) in controlling S. maydis. Stalk rot severity increased with increasing fertilization rates.     

Evaluation of neem seed powder for Fusarium wilt and Meloidogyne control on tomato

Fusarium wilt and root-knot are important diseases of tomato. The use of chemical is becoming less appealing because of the health implications. Also, the chemicals required are often not within the reach of farmers in most of the developing part of the world. This research is aimed at finding an alternative mode of control. Tomato variety Roma VF inoculated with Meloidogyne and Fusarium were treated with 2 g/kg soil neem seed powder in the screenhouse and 2 Mg ha ^{? 1} in the field. An untreated and Furadan treated plot in the field served as control. Neem seed powder significantly reduced the disease severity of Fusarium and root-knot in both screenhouse and field. Results suggest the possible use of neem seed powder for control of the root-knot nematodes - Fusarium wilt disease complex.     

Continued exploration of biphenylsulfonamide scaffold as a platform for aggrecanase-1 inhibition

Design, synthesis and structure-activity relationship of a series of biphenylsulfonamido-3-methylbutanoic acid based aggrecanase-1 inhibitors are described. In addition to robust aggrecanase-1 inhibition, these compounds also exhibit potent MMP-13 activity. In cell-based cartilage explants assay compound 48 produced 87% inhibition of proteoglycan degradation at 10 μg/mL. Good pharmacokinetic properties were demonstrated by 46 with a half-life of 6h and bioavailability of 23%.     

Directed evolution of enzymes and pathways for industrial biocatalysis

Directed evolution has become a powerful tool for developing enzyme and whole cell based biocatalysts. Significant recent advances include the creation of novel enzyme functions and the development of several new efficient directed evolution methods. The combination of directed evolution and rational design promises to accelerate the development of biocatalysts for applications in the pharmaceutical, chemical and food industries.     

Elevation in cardiovascular disease risk in South Asians is mediated by differences in visceral adipose tissue

South Asians have a higher risk for cardiovascular disease (CVD) that remains largely unexplained. We hypothesized that the increased CVD risk in South Asians compared to Europeans is mediated through higher levels of visceral adipose tissue (VAT) in South Asians compared to total body fat and subcutaneous abdominal adipose tissue (SAT). South Asians (207) and Europeans (201) underwent assessment for demographics, body fat, and risk factors. Linear regression models were created by sex for each risk factor to explore mediation effects of total body fat, SAT, and VAT adjusted for age, income, smoking, and BMI (menopausal status for women). Mediation was based on changes in the ethnicity β coefficient due to additional adjustment for our adipose variable of interest and the Sobel test for mediation. South Asians had worse lipid, glucose, insulin, and C-reactive protein (CRP) levels than Europeans after adjusting for confounders. Most of these differences remained even after further adjustment by either total body fat or SAT. In contrast, VAT attenuated the ethnic differences in risk factors by 16%-52%. After adjusting for VAT, there were no longer ethnic differences in total cholesterol (TC), LDL-C, TC/HDL-C, glucose, and diastolic blood pressure (BP) in men, and in HDL-C, triglycerides (TG), TC/HDL-C, and homeostasis model (HOMA) in women, and VAT was a significant mediator for these risk factors. Higher levels of risk factors for CVD in South Asians are predominantly because of the unique phenotype of South Asians having greater VAT than Europeans even at the same BMI.     

Micronuclei as a marker for medical screening of subjects continuously occupationally exposed to low doses of ionizing radiation

Context: Genotoxicity assays are widely employed in human biomonitoring studies to assess genetic damage inflicted by genotoxic agents.

Objective: Evaluation of micronuclei (MN) as a screening marker of occupational ionizing radiation (IR) exposure.

Materials and methods: Using micronucleus test, peripheral blood lymphocytes (PBL) of 402 control and exposed subjects were screened for genetic damage.

Results: The mean frequencies of micronucleus test parameters were significantly higher in exposed persons. Increase of micronucleus yield with duration of exposure (DOE) by 0.303MN/year was revealed.

Discussion and conclusion: The obtained data encourage us to consider MN as valuable markers for preventive medical screening of occupationally exposed groups.     

Molecular dynamic simulations study of the effect of salt valency on structure and thermodynamic solvation behaviour of anionic polyacrylate PAA in aqueous solutions

The effect of salt concentration and valency on intermolecular structure and solvation thermodynamic properties of aqueous solution containing polyacrylicacid (PAA) chains and multi-valent salts calcium chloride (CaCl₂) and aluminium chloride (AlCl₃) as a function of charge density was investigated using atomistic molecular dynamic simulations with explicit solvent. Salt-free solution favours the self-association of uncharged (acidic form) PAA chains facilitated by inter-chain hydrogen bonds. The ionised (charged) PAA chains are not associated in salt-free aqueous solutions and undergo self-association in the salt solutions due to bridging effect induced by condensed salt ions in agreement with scattering investigations available in literature. The collapse behaviour of PAA in presence of CaCl₂ and re-expansion behaviour of PAA chains in case of AlCl₃ salt solutions are observed. The rigidity of PAA chains decrease with increase in salt concentration, in agreement with experimental results available in literature. The trivalent salt favours relatively the greater extent of shrinking of PAA chains as well as inter-chain interactions as compared to divalent salts as evident from radius-of-gyration, H-bond and pair-wise solvation enthalpy data. The conformation and hydration behaviour of the acid form of PAA chains are not significantly altered by added salt ions. The hydration behaviour of ionised PAA chains is significantly reduced by added salts due to screening effect of the condensed salt ions. The pair correlation functions of solutions species such as Ca²⁺, Al³⁺, Na⁺ and Cl^? with respect to PAA oxygen show the greater affinity of PAA units with the higher valency Al³⁺ ions over Ca²⁺ and Na⁺ in solution. With increase in concentration of AlCl₃ and CaCl₂ salts, a decrease in effective charge density of ionised PAA chains is observed from the existence of unfavourable PAA–water, PAA–Ca²⁺ and PAA–Al³⁺ interactions.