Synthesis of N,N-diethyldithiocarbamate functionalized 1,4-polyisoprene, from natural rubber and synthetic 1,4-polyisoprene

N,N-Diethyldithiocarbamate functionnalized 1,4-polyisoprenes were prepared from 1,4-polyisoprenes (natural or synthetic). The syntheses were performed by nucleophilic addition of N,N-diethyldithiocarbamate salts upon oxirane rings of epoxidized units according to a SN2 mechanism with ring opening. Studies on model molecules of epoxidized 1,4-polyisoprene units (1,2-epoxy-1-methylcyclohexane and 4,5-epoxy-4-methyloctane) were previously achieved to develop the procedure. The best yields were obtained at low temperature in polar medium, and more especially in water with sodium N,N-diethyldithiocarbamate (DEDT-Na) as reagent. A diastereospecific addition was noted when reaction was performed in water with DEDT-Na. Afterwards, the developed procedure was successfully generalized to epoxidized synthetic polyisoprenes and epoxidized natural rubber (in THF, then in latex medium). Excellent results were obtained in latex medium with epoxidized natural rubber (ENR) latices. As with the models, a diastereospecific addition of sodium N,N-diethyldithiocarbamate trihydrate onto epoxidized 1,4-polyisoprene units of ENR was observed at the condition to bring the latex medium to pH 8 before introduction of DEDT-Na. Influence of temperature, drc, and DEDT-Na concentration were successively examined to determine the best conditions of the addition on ENR latices.     

Research on 1-azabicyclic compounds

1-(2-Furyl)-3-amino-4,4-dimethylpentane was used to obtain 3-tert-butyl-1,2-dihydropyrrolizine, the catalytic hydrogenation of which over Rh/Al₂O₃ at room temperature gives a mixture of cis- and trans-3,8-H-3-ter-butylpyrrolizidines with predominance of the cis isomer, whereas hydrogenation at 90–100 °C gives a mixture containing the trans isomer as the principal component. The three-dimensional structures of the isomers follow from data on the catalytic hydrogenation and isomerization and the IR, Raman, and PME spectra. A considerable percentage of the trans-fused form is characteristic for cis-3,8-H-3-tert-butylpyrrolizidine.     

Diffusion of additives and plasticizers in poly(vinyl chloride)—II: The self-diffusion of the stabilizers dibutyltin dilaurate and dibutyltin bismonobutylmaleate in plasticized poly(vinyl chloride)

The self-diffusion coefficient, D, of dibutyltin dilaurate and dibutyltin bismonobutylmaleate have been obtained at 35, 45 and 55° in samples of poly(vinyl chloride) plasticized with 34, 60 and 100 phr of di(2-ethylhexyl)phthalate. D at 2 phr of the laurate is 3–5 times larger than for the smaller maleate molecule. In all cases, D increases with increasing plasticizer concentration, an effect interpreted in terms of the free volume theory of diffusion. D for the laurate increases by a factor of about 2.7 when the laurate diffusant concentration is increased from 0 to 4 phr. The activation energies for diffusion, E_D, lie between 50 and 90 kJ mol^?1. They increase with increasing plasticizer concentration but become constant at higher plasticizer concentrations (60–100 phr). It is impossible to correlate all the known data on diffusion in plasticized PVC with an equation of the form log D₀ = C₁ + C₂ E_D/RT     

α-CGRP disrupts amylin fibrillization and regulates insulin secretion: implications on diabetes and migraine

Despite being relatively benign and not an indicative signature of toxicity, fibril formation and fibrillar structures continue to be key factors in assessing the structure–function relationship in protein aggregation diseases. The inability to capture molecular cross-talk among key players at the tissue level before fibril formation greatly accounts for the missing link toward the development of an efficacious therapeutic intervention for Type II diabetes mellitus (T2DM). We show that human α-calcitonin gene-related peptide (α-CGRP) remodeled amylin fibrillization. Furthermore, while CGRP and/or amylin monomers reduce the secretion of both mouse Ins1 and Ins2 proteins, CGRP oligomers have a reverse effect on Ins1. Genetically reduced Ins2, the orthologous version of human insulin, has been shown to enhance insulin sensitivity and extend the life-span in old female mice. Beyond the mechanistic insights, our data suggest that CGRP regulates insulin secretion and lowers the risk of T2DM. Our result rationalizes how migraine might be protective against T2DM. We envision the new paradigm of CGRP : amylin interactions as a pivotal aspect for T2DM diagnostics and therapeutics. Maintaining a low level of amylin while increasing the level of CGRP could become a viable approach toward T2DM prevention and treatment.

CGRP concentration is elevated in migraine conditions. The protective effect of migraine against type 2 diabetes is attributed to the ability of CGRP to remodel human amylin aggregation and to suppress the secretion of mouse insulin 2 (the orthologue of human insulin).     

Coupled reference interaction site model/simulation approach for thermochemistry of solvation: theory and prospects

We present a new methodology for computing solvation free energy, which is based upon the reference interaction site model (RISM)/hypernetted chain (HNC) solvation free energy expression, but which substitutes radial distribution functions taken from simulations for those calculated by simultaneous solution of the RISM and HNC equations. Consequently, solvation free energy can be obtained from a single molecular dynamics or Monte Carlo simulation. Here we describe in detail the coupled RISM/simulation approach, and offer some error analysis. Finally we give the results of its application to a set of small test molecules in aqueous solution. The success shown in some of our results demonstrates that the coupled RISM/simulation approach is worth considering further as a potentially useful tool in studies of solvated systems, such as aqueous molecular biosystems.     

Inhomogeneity in Distribution and Conformation of Bovine Serum Albumin in Sol–Gel: A Closer Look with a Near-Infrared Multispectral Imaging Technique

Concentration distributions and conformations of bovine serum albumin (BSA) entrapped in sol–gels were successfully determined for the first time by use of the recently developed NIR multispectral imaging instrument. It was found that BSA molecules were inhomogeneously distributed within the sol–gel matrix, independent of its concentration. At relatively high concentration (366 mg/mL) the encapsulation process does not seem to produce any observable changes in the conformation of BSA. However, when the concentration of BSA was decreased to 220 mg/mL, pronounced changes in the spectra of the protein were observed as a function of (sol–gel reaction) time. The observed inhomogenity might be traced to both a non-uniform concentration distribution of BSA and changes in protein native conformation resulting from interactions between the charged protein and the silicate anions. Results obtained seem to suggest that the protein molecules might adapt themselves to accommodate evolving geometry and sites of the silica network.     

Synthesis of cation-exchanged laponite suspensions by laser ablation of microsized-metal particles in liquid

Laser ablation in the liquid technique has been used to synthesize cation-exchanged laponite suspensions. In summary, laser ablation of the microsize-metal powder (Co, Al, and Cu) dispersed in an aqueous solution containing deionized water laponite crystals was carried out using laser beam generated by a single-mode, Q-switched Nd-Yag laser operating at 532 nm with a pulse duration of 5.5 ns and 10 Hz repetition rate. Laser fluence was 0.265 J/cm² for all tests. For all samples, the mass fraction of laponite was 1%. General observations of the prepared samples indicated that an aqueous suspension of 1 wt% laponite retained its free flowing liquid phase characteristics even after aging for several weeks. When bivalent cationic metals (Cu, Co, Al) were ablated in it for about 1 h, even with a small amount of the metal (0.025% and 0.050%) were generated, the suspension became highly viscous and behaved as a shear-thinning and thixotropic material. That is, the suspension gelled strongly when it was allowed to rest. The gels, however, could easily be reverted to a low viscosity liquid with simple shaking. Information from TEM and XRD analysis indicated that such a sol-gel transformation might be due to the charge exchange between the cationic species produced during the laser ablation and the sodium ions in the interlayers of the clay sheets.