Molecular transport of some industrial solvents through a polyurethane membrane

Sorption and transport studies of several industrial solvents have been investigated through a Uralite 3142 polyurethane. Diffusion coefficients have been measured for the preswollen and fully swollen polyurethanes. For majority of solvents, non-Fickian transport mode was observed and these results have been interpreted in terms of polymer-penetrant interactions. Temperature-dependent diffusion parameters followed the Arrhenius relation from which energy of activation have been obtained. The Flory–Rehner equation, in spite of its limitations, has been found to be useful to estimate the molar mass between crosslinks of the network polyurethane.     

Molecular transport characteristics of a chlorosulfonated polyethylene geomembrane in the presence of aromatic esters

Results of a study on sorption and diffusion of chlorosulfonated polyethylene geomembrane with methyl benzoate, ethyl benzoate, methyl salicylate, iso-butyl salicylate, phenyl acetate, and diethyl phthalate in the temperature range 25–60°C are presented. A gravimetric sorption method is used to calculate the diffusion and permeation coefficients from the Fickian relationship. The diffusion results are dependent on penetrant–membrane interactions, temperature, and on penetrant concentration. The values of diffusion coefficients range from 0·02 × 10^?7 cm² s^?1 for diethyl phthalate at 25°C to 1·81 × 10^?7 cm² s^?1 for ethyl benzoate at 60°C. The activation energies for diffusion range from 21 to 50 kJ mol^?1. The values of heat of sorption ranged between 2·2 and 6·4 kJ mol^?1. Sorption results are also analyzed using a first-order sorption kinetic equation. Experimental results and calculated parameters are used to discuss the transport behavior. None of the esters used have shown any chemical attack toward the geomembrane.     

Technological and kinetic aspects of sublethal acid toxicity in microbial gum production

Chemostat culture of Xanthomonas campestris were obtained at a dilution rate of 0·05 h⁻¹ and the normal feed then supplemented with 0·58 and 1·74 mmol dm⁻³ isobutyric acid (IBA). Data revealed that the organism responded to sublethal acid stress by overproducing xanthan. The acid additions led to transient zones in the continuous cultivation profiles. By adding feed containing 1·74 mmol dm⁻³ IBA, volumetric growth rate immediately decreased from 0·059 to 0·026 g dm⁻³ h⁻¹ whereas the specific xanthan formation rate increased from 0·23 g g⁻¹ biomass h⁻¹ to a maximum 0·65 g g⁻¹ biomass h⁻¹ (with 1·0 mmol dm⁻³ IBA addition), before decreasing as the concentration of acid attained that of the feed. By monitoring the outlet CO₂ in parallel with biomass and polysaccharide levels in the IBA fermentation a 10% diversion of the total carbon flux from biomass synthesis to xanthan biosynthesis was detected. A consistent pattern of variation in activity was detected in enzymes of intermediary metabolism, suggesting an action at the regulatory level. Enhanced activities of carbon catabolism and xanthan anabolic reactions (phosphomannose isomerase) were observed in the presence of the acid. Batch experiments carried out in the pres-ence of IBA gave results which correlated with the undissociated acid form con-centration. An undissociated acid fraction of 6·5×10⁻³ mmol dm⁻³ was calculated in a set of flasks under the same conditions and a statistically vali-dated 12% increase in xanthan production was found. The maximum activation was determined to be below 1·1×10⁻² mmol dm⁻³ when a 58% specific xanthan production rate increase occurred in parallel with a 35% decrease in biomass concentration.     

Molecular electronics--resonant transport through single molecules

The mechanically controllable break-junction technique (MCBJ) enables us to investigate charge transport through an individually contacted and addressed molecule in ultra-high vacuum (UHV) environment at variable temperature ranging from room temperature down to 4 K. Using a statistical measurement and analysis approach, we acquire current-voltage (I-V) characteristics during the repeated formation, manipulation, and breaking of a molecular junction. At low temperatures, voltages accessing the first molecular orbitals in resonance can be applied, providing spectroscopic information about the junction's energy landscape, in particular about the molecular level alignment in respect to the Fermi energy of the electrodes. Thereby, we can investigate the non-linear transport properties of various types of functional molecules and explore their potential use as functional building blocks for future nano-electronics. An example will be given by the reversible and controllable switching between two distinct conductive states of a single molecule. As a proof-of-principle for functional molecular devices, a single-molecule memory element will be demonstrated.     

Molecular transport of organic esters and ketones into fluoropolymer membranes

The effect of different fluorine contents of DuPont VITON fluoropolymers and their transport characteristics in the presence of phenyl acetate, diethyl oxalate, diethyl malonate, diethyl succinate, acetone, methyl ethyl ketone and methyl iso-butyl ketone has been investigated over the temperature interval of 25?60°C. The average values of diffusion coefficients are obtained from the Fickian relation and the molecular transport is found to follow an anomalous behavior. Kinetic rate constants and pentration velocities are also calculated. The experimental results and the calculated quantities are studied in terms of polymer-solvent interactions.     

Simultaneous detection of aflatoxin b1 and ochratoxin a in olive oil

A screening method has been developed for simultaneous determina-tion of aflatoxin B₁ and ochratoxin A in olive oil. The technique includes extraction of both mycotoxins with aqueous methanol, clean-up using lead acetate, partitioning in chloroform, and thin layer chromatography. The detection limits achieved are, respec-tively: 4 μg aflatoxin B₁ and 40 μg ochratoxin A/kg. 60 samples of crude farm olive oil were analyzed using this method: three of them contained traces of ochratoxin A while none was contaminated with aflatoxin B₁.     

Molecular electronics: insight from first-principles transport simulations

Conduction properties of nanoscale contacts can be studied using first-principles simulations. Such calculations give insight into details behind the conductance that is not readily available in experiments. For example, we may learn how the bonding conditions of a molecule to the electrodes affect the electronic transport. Here we describe key computational ingredients and discuss these in relation to simulations for scanning tunneling microscopy (STM) experiments with C60 molecules where the experimental geometry is well characterized. We then show how molecular dynamics simulations may be combined with transport calculations to study more irregular situations, such as the evolution of a nanoscale contact with the mechanically controllable break-junction technique. Finally we discuss calculations of inelastic electron tunnelling spectroscopy as a characterization technique that reveals information about the atomic arrangement and transport channels.     

含硅聚合物中小分子扩散行为的分子模拟

选择PCFF和COMPASS分子力场对橡胶态聚合物PDMS 和玻璃态聚合物PS1体系进行模拟。COMPASS力场模拟得到的体系密度,O2和N2在PDMS与PS1中扩散系数更接近实验值。在模型大小一定时,Group-based求和法中截断距离越长,耗用机时越长,但对计算结果改进不大;截断距离为1.3 nm时计算结果最好。Ewald方法耗时多而对计算结果却无明显改进。体系大小对扩散系数的计算值影响甚微。体积越小的分子,在聚合物中运动的范围越大,扩散系数越大。氧气和氮气分子在PDMS与PS1中运动轨迹不同,在PS1中氧气运动范围远大于氮气,而在PDMS中氧气运动范围稍大于氮气。小分子运动轨迹基本与聚合物自由体积分布对应,自由体积分数大,扩散系数也大。     

Molecular simulations of gas transport in nitrile rubber and styrene butadiene rubber

Nitrile rubber (NBR, 39:61 wt% of acrylonitrile:butadiene) and styrene butadiene rubber (SBR, 50:50 wt% of styrene:butadiene) matrices have been equilibrated by molecular dynamics (MD) simulations. Transition-state approach is used to calculate the diffusion and solubility coefficients of small penetrants in these matrices, indicating quite low values in NBR and reasonable agreement with experimental results. MD simulations have been performed to analyze water diffusion in these matrices. Aggregation of water molecules is observed in the hydrophobic matrix SBR. MD simulations with fictitious nonpolar water molecules inhibit aggregation and lead to enhanced diffusion in SBR. In NBR there is a slight increase in diffusion for fictitious water molecules. The lower diffusion constants in NBR result from slower local relaxation of the matrix due to tighter intermolecular packing and higher cohesive energy density. The free volume distribution that affects solubility coefficients is not a major determining factor for the diffusion coefficients in these matrices.     

Molecular transport of benzene and methyl-substituted benzenes into filled natural rubber sheets

Sorption and diffusion of benzene and methyl-substituted benzenes were investigated through natural rubber reinforced with four types of carbon black: superbrasion furnace, intermediate superabrasion furnace, high-abrasion furnace, and semireinforcing furnace. The rubber loaded with superabrasion furnace took the lowest amount of solvents among all the samples. It was observed that the mechanism of transport deviates from the normal Fickian trend with a decrease in particle size of the fillers. The diffusion coefficients were determined considering the changes in thickness as well as the diameter of the natural rubber samples. From the temperature dependence of diffusivity, the activation energy for the diffusion process was computed. The sorption data were used to estimate the rubber-solvent interaction parameter, enthalpy, and entropy of the sorption process. © 1996 John Wiley & Sons, Inc.     

分子模拟研究壳聚糖-氮化硼纳米管封装及输运阿霉素

壳聚糖-BNNTs复合载体在药物输运领域存在潜在的应用前景。通过分子动力学方法,以抗癌药物阿霉素DOX为药物模型,研究利用壳聚糖-BNNTs复合载体材料封装及跨膜输运抗癌药物的过程。结果表明,非质子化壳聚糖能吸附且调整DOX以合适的构象进入管中。细胞膜磷脂分子能自发嵌入到BNNT (14,14)管中,将管中壳聚糖挤出并使DOX在管中快速上升。该研究可以为实验提高药物封装效率,并提高癌细胞表面药物浓度提供设计思路。     

Molecular transport of aromatic hydrocarbons through crosslinked styrene-butadiene rubber membranes

Molecular transport of aromatic hydrocarbons through crosslinked SBR has been carried out in the temperature range (25–65°C). SBR has been vulcanized by four different vulcanizing techniques viz., conventional, efficient, dicumyl peroxide and a mixture consisting of sulfur and peroxide. SBR vulcanized with EV system showed highest solvent uptake tendency and that vulcanized with peroxide showed the lowest. The influence of penetrant size on sorption behaviour of SBR has been examined. The thermodynamic constants such as standard entropy, standard enthalpy and first-order kinetic rate constant have been evaluated. A correlation between theoretical and experimental sorption results was evaluated. The polymer—solvent interaction parameter (χ) was also computed from the diffusion data.