Microstructural Changes of Aramid Fiber Due to Reaction with Toluene 2,4-diisocyanate under Tension in scCO2

High modulus aramid fiber, such as Kevlar 49, is conventionally prepared by the heat annealing of high strength aramid fiber under a suitable tension at high temperature, especially higher than 500 °C. This enables the mobility of a rigid molecule chain to be rearranged into a more perfect crystalline or orientation structure under tension. However, annealing decreases the tensile strength, since the thermal degradation of the molecular chain at high temperature cannot be avoided. Kevlar 49 fibers treated in supercritical carbon dioxide (scCO2) under tension could improve their mechanical properties at a low temperature. The effects of the tension on the mechanical properties and structure of the Kevlar 49 fibers were studied by mechanical testing, wide-angle and small-angle X-ray scattering (WAXS, SAXS), and scanning electron microscopy (SEM). The results show that the mechanical properties, crystallinity and orientation of the fiber can be improved when the tension is less than 0.6 cN/dtex, which may be due to the increasing of the mobility of a rigid segment with the help of the plasticization of scCO2 and re-arrangement of macromolecular chain into crystalline and orientation structure under tension. What’s more, the amorphous region also was enhanced by crosslinking reaction of toluene 2,4-diisocyanate (TDI) with the chain end groups of the macromolecules in the amorphous regions. However, a decrease of tenacity was found when the tension was higher than 0.6 cN/dtex, which is because the tension was so high that the microfibril was broken. The results indicated that treating the Kevlar 49 fiber in scCO2 under a suitable tension with TDI as a crosslink agent can simultaneously improve both the tenacity and modulus of the fiber.

Физически корректные конфигурационные пространства в описании внутренней динамики жесткой молекулы

A family of configuration spaces in the description of the internal dynamics of a rigid molecule has been considered. It has been shown that the requirement of the physical correctness of the description leads to serious restrictions for such spaces. In particular, only spaces satisfying the Eckart condition are allowed for a nonlinear rigid molecule.

Hand-twistable plastically deformable crystals of a rigid small organic molecule

The crystals of the small rigid molecule 4-bromobenzonitrile exhibit highly flexible plastic bending behaviour that occurs on two perpendicular faces of the crystal, a rare situation, leading to the formation of helical/twisted and curled crystals.

Neutral Sphingomyelinase Behaviour in Hippocampus Neuroinflammation of MPTP-Induced Mouse Model of Parkinson’s Disease and in Embryonic Hippocampal Cells

Neutral sphingomyelinase is known to be implicated in growth arrest, differentiation, proliferation, and apoptosis. Although previous studies have reported the involvement of neutral sphingomyelinase in hippocampus physiopathology, its behavior in the hippocampus during Parkinson’s disease remains undetected. In this study, we show an upregulation of inducible nitric oxide synthase and a downregulation of neutral sphingomyelinase in the hippocampus of 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine- (MPTP-) induced mouse model of Parkinson’s disease. Moreover, the stimulation of neutral sphingomyelinase activity with vitamin 1,25-dihydroxyvitamin D3 reduces specifically saturated fatty acid sphingomyelin by making sphingomyelin a less rigid molecule that might influence neurite plasticity. The possible biological relevance of the increase of neutral sphingomyelinase in Parkinson’s disease is discussed.

Crystal structure prediction of rigid molecules

A non-polarizable force field based on atomic multipoles fit to reproduce experimental crystal properties andab initiogas-phase dimers is described. The Ewald method is used to calculate both long-range electrostatic and 1/r6dispersion energies of crystals. The dispersion energy of a crystal calculated by a cutoff method is shown to converge slowly to the exact Ewald result. A method for constraining space-group symmetry during unit-cell optimization is derived. Results for locally optimizing 4427 unit cells including volume, cell parameters, unit-cell r.m.s.d. and CPU timings are given for both flexible and rigid molecule optimization. An algorithm for randomly generating rigid molecule crystals is described. Using the correct experimentally determined space group, the average and maximum number of random crystals needed to find the correct experimental structure is given for 2440 rigid single component crystals. The force field energy rank of the correct experimental structure is presented for the same set of 2440 rigid single component crystals assuming the correct space group. A complete crystal prediction is performed for two rigid molecules by searching over the 32 most probable space groups.