Improving the gas barrier,mechanical and thermal properties of poly(vinyl alcohol) with molybdenum disulfide nanosheets

New multifunctional materials with both high structural and gas barrier performances are important for a range of applications. Herein we present a one‐step mechanochemical process to prepare molybdenum disulfide (MoS₂) nanosheets with hydroxy functional groups that can simultaneously improve mechanical strength, thermal conductivity, and gas permittivity of a polymer composite. By homogeneously incorporating these functionalized MoS₂ nanosheets at low loading of less than 1 vol %, a poly(vinyl alcohol) (PVA) polymer exhibits elongation at break of 154%, toughness of 82 MJ/m³, and in‐plane thermal conductivity of 2.31 W/m K. Furthermore, this composite exhibits significant gas barrier performance, reducing the permeability of helium by 95%. Under fire condition, the MoS₂ nanosheets form thermally stable char, thus enhancing the material's resistance to fire. Hydrogen bonding has been identified as the main interaction mechanism between the nanofillers and the polymer matrix. The present results suggest that the PVA composite reinforced with 2D layered nanomaterial offers great potentials in packaging and fire retardant applications. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 406–414     

Ocimum basilicum seed mucilage reinforced with montmorillonite for preparation of bionanocomposite film for food packaging applications

Use of nanocomposites is a well-established approach in enhancing the mechanical and barrier properties of bionanocomposite film for food packaging applications. The seed mucilage of Ocimum basilicum was employed for the preparation of bionanocomposite films with montmorillonite (MMT) as nanofiller. The films were prepared by solvent-casting method at varied solution pH (1, 3, 5 and 9) and MMT loading (1%, 3%, 5%, 10%, 15% and 20%). The films were characterized for physical, mechanical and barrier properties in addition to microstructure and X-ray diffraction pattern. XRD analysis revealed the exfoliated dispersion of MMT at pH 9, confirming its effective interaction with the bionanocomposite film. Maximum film tensile strength was achieved at a lower MMT load of 5%. Water vapour permeability reduced with increase in MMT loading up to 5%, followed by an increase at higher MMT loadings. Film formed at pH 9 showed tensile strength of 17.3 ± 0.33 MPa and reduced water vapour permeability (WVP) of 0.21 g mm.m⁻².hr⁻¹.kPa⁻¹.     

Chemoselective Hydrogenation of 6-Alkynyl-3-fluoro-2-pyridinaldoximes: Access to First-in-Class 6-Alkyl-3-Fluoro-2-pyridinaldoxime Scaffolds as New Reactivators of Sarin-Inhibited Human Acetylcholinesterase with Increased Blood–Brain Barrier Permeability

Novel 6-alkyl- and 6-alkenyl-3-fluoro-2-pyridinaldoximes have been synthesised by using a mild and efficient chemoselective hydrogenation of 6-alkynyl-3-fluoro-2-pyridinaldoxime scaffolds, without altering the reducible, unprotected, sensitive oxime functionality and the C−F bond. These novel 6-alkyl-3-fluoro-2-pyridinaldoximes may find medicinal application as antidotes to organophosphate poisoning. Indeed, one low-molecular-weight compound exhibited increased affinity for sarin-inhibited acetylcholinesterase (hAChE) and greater reactivation efficiency or resurrection for sarin-inhibited hAChE, compared with those of 2-pyridinaldoxime (2-PAM) and 1-({[4-(aminocarbonyl)pyridinio]methoxy}methyl)-2-[(hydroxyimino)methyl]pyridinium chloride (HI-6), two pyridinium salts currently used as antidote by several countries. In addition, the uncharged 3-fluorinated bifunctional hybrid showed increased in vitro blood–brain barrier permeability compared with those of 2-PAM, HI-6 and obidoxime. These promising features of novel low-molecular-weight alkylfluoropyridinaldoxime open up a new era for the design, synthesis and discovery of central non-quaternary broad spectrum reactivators for organophosphate-inhibited cholinesterases.     

Dynamic Docking and Undocking Processes Addressing Selectively the Outside and Inside of Polymersomes

Increasing complexity and diversity of polymersomes and their compartments is a key issue for mimicking cellular functions and protocells. Thus, new challenges arise in terms of achieving tunable membrane permeability and combining it with control over the membrane diffusion process, and thus enabling a localized and dynamic control of functionality and docking possibilities within or on the surface of polymeric compartments. This study reports the concept of polymersomes with pH‐tunable membrane permeability for controlling sequential docking and undocking processes of small molecules and nanometer‐sized protein mimics selectively on the inside and outside of the polymersome membrane as a further step toward the design of intelligent multifunctional compartments for use in synthetic biology and as protocells. Host–guest interactions between adamantane and β‐cyclodextrin as well as noncovalent interactions between poly(ethylene glycol) tails and β‐cyclodextrin are used to achieve selective and dynamic functionalization of the inner and outer spheres of the polymersome membrane.     

Use of biopartitioning micellar chromatography and RP-HPLC for the determination of blood–brain barrier penetration of α-adrenergic/imidazoline receptor ligands,and QSPR analysis

For this study, 31 compounds, including 16 imidazoline/α-adrenergic receptor (IRs/α-ARs) ligands and 15 central nervous system (CNS) drugs, were characterized in terms of the retention factors (k) obtained using biopartitioning micellar and classical reversed phase chromatography (log k_BMC and log k_wRP, respectively). Based on the retention factor (log k_wRP) and slope of the linear curve (S) the isocratic parameter (φ₀) was calculated. Obtained retention factors were correlated with experimental log BB values for the group of examined compounds. High correlations were obtained between logarithm of biopartitioning micellar chromatography (BMC) retention factor and effective permeability (r(log k_BMC/log BB): 0.77), while for RP-HPLC system the correlations were lower (r(log k_wRP/log BB): 0.58; r(S/log BB): –0.50; r(φ₀/P_e): 0.61). Based on the log k_BMC retention data and calculated molecular parameters of the examined compounds, quantitative structure–permeability relationship (QSPR) models were developed using partial least squares, stepwise multiple linear regression, support vector machine and artificial neural network methodologies. A high degree of structural diversity of the analysed IRs/α-ARs ligands and CNS drugs provides wide applicability domain of the QSPR models for estimation of blood–brain barrier penetration of the related compounds.     

Multi-Stage Upscaling: Selection of Suitable Methods

Reservoirs are often composed of an assortment of rock types giving rise to permeability heterogeneities at a variety of length-scales. To predict fluid flow at the full-field scale, it is necessary to be aware of these different types of heterogeneity, to recognise which are likely to have important effects on fluid flow, and to capture them by upscaling. In fact, we may require a series of stages of upscaling to go from small-scales (mm or cm) to a full-field model. When there are two (or more) phases present, we also need to know how these heterogeneities interact with fluid forces (capillary, viscous and gravity). We discuss how these effects may be taken into account by upscaling. This study focusses on the effects of steady-state upscaling for viscous-dominated floods and tests carried out on a range of 2D models are described. Upscaling errors are shown to be reduced slightly by the increase in numerical dispersion at the coarse scale. We select a combination of three different upscaling methods, and apply this approach to a model of a North Sea oil reservoir in a deep marine environment. Six different genetic units (rock types) were identified, including channel sandstone and inter-bedded sandstone and mudstone. These units were modelled using different approaches, depending on the nature of the heterogeneities. Our results show that the importance of small-scale heterogeneity depends on the large-scale distribution of the rock types. Upscaling may not be worthwhile in sparsely distributed genetic units. However, it is important in the dominant rock type, especially if there is good connectivity through the unit between the injector wells (or aquifer) and the producer wells.This revised version was published online in May 2005. In the previous version one of the authors name was missing.     

Fractal porous media II: Geometry of porous geological structures

Some geological structures are analysed and found to be fractal. An interesting feature is the very large range of scales involved; the spreading dimension is also measured for some of them. The consequences of these measurements on the analysis of transport processes in porous media are presented - the existence of fractal structures multiplies the variety of actual porous media.     

定量开采条件下径向渗流的液固耦合问题

考虑到多孔介质渗透率随孔隙度变化的特点，建立了力学模型，研究定量抽放问题；对于广义平面应力状态下的非线性渗流耦合问题，提出了解的构造方法和解耦方法；求出了耦合条件下的孔隙压力，多孔介质总应力、总应变和总位移的解析解；进行了实例计算，并与Biot理论进行了对比，结果表明两种理论的差别很大。因此在渗透系数有较明显变化的场舍下不能采用Biot理论进行分析。     

Self-similar approximants of the permeability in heterogeneous porous media from moment equation expansions

We use a mathematical technique, the self-similar functional renormalization, to construct formulas for the average conductivity that apply for large heterogeneity, based on perturbative expansions in powers of a small parameter, usually the log-variance of the local conductivity. Using perturbation expansions up to third order and fourth order in obtained from the moment equation approach, we construct the general functional dependence of the scalar hydraulic conductivity in the regime where is of order 1 and larger than 1. Comparison with available numerical simulations show that the proposed method provides reasonable improvements over available expansions.