Polymeric vesicle permeability: a facile chemical assay

We present a simple method to characterize vesicles and determine, at the same time, the membrane permeability to specific molecules. The method is based on encapsulating highly hydrophilic 3,3',3' '-phosphinidynetris-benzenesulfonic acid (PH) into vesicles and subsequently monitoring its reaction with 5,5'-dithiobis-2-nitrobenzoic acid (DTNB). We tested the method by measuring the membrane permeability of vesicles formed from a series of poly(ethylene oxide)-co-polybutylene oxide (EB) copolymers and egg yolk phosphatidylcholine. We found that the experimental data are in good agreement with calculations based on Fick's first law. We therefore quantified the DTNB permeability across vesicle membranes, finding that polymeric EB membranes have a more selective permeability toward polar molecules compared to phospholipids membranes.     

Effect of Sulfonation Degree on Performance of Proton Exchange Membranes for Direct Methanol Fuel Cells

A series of proton exchange membranes based on sulfonated polyarylene ether ketones(SPAEKs) was used to study the effect of sulfonation degree on proton conductivity, methanol permeation and performance of direct methanol fuel cells(DMFCs). Dependences of physical characteristics of the membranes, i. e., proton conductivity, water uptake, swelling ratio, methanol permeability and ion exchange capacity(IEC) were systematically studied. Both methanol permeability and proton conductivity of the SPAEK membrane grow rapidly as the increase in sulfonation degree since methanol molecules and protons share the same transfer channel. However,the methanol permeability plays more important role comparing to proton conductivity. As a result, the SPAEK membrane with a medium sulfonation degree(60%) was found to yield the best performance in a DMFC due to the acquirement of balanced conductivity and methanol permeability.     

利用荧光浓度指示剂fura-2研究稀土离子的跨膜行为

本文提出了利用fura-2测量细胞内游离稀土离子浓度的定量方法。实验结果表明, 在模拟细胞内离子组成的条件下, 稀土离子La^3^+和Y^3^+与fura-2形成1:1的配合物。其配合物的表观离解常数分别为161nmol.dm^-^3和404nmol.dm^-^3,pH7.05, 有未配对f电子的Nd^3^+, Ho^3^+, Sm^3^+, Dy^3^+,Ce^3^+, Yb^3^+等稀土离子对荧光起萃灭作用。此性质使我们能够定性鉴定它们是否进入了细胞。我们使用如上性质, 利用单细胞阳离子测试系统, 以小鼠骨髓瘤细胞为模式细胞, 研究了上游离稀土离子的跨膜行为及部分体内小分子对稀土离子跨膜行为的影响。实验结果支持游离稀土离子不能通过细胞膜的假设, 而且所研究的体内小分子在生理浓度下对稀土离子的跨膜也无明显作用。     

Gas phase hydrogen / deuterium exchange in electrospray ionization mass spectrometry as a practical tool for structure elucidation

Two methods for gas phase hydrogen/deuterium exchange have been developed for the analysis of small molecules. Hydrogen/deuterium exchange has been implemented by making simple modifications to the plumbing for the nebulizer and curtain gases on a nebulization-assisted electrospray ion source. The nebulizer gas exchange method has demonstrated deuterium exchange levels of 84–97% for a variety of molecules representing a wide range of structural classes containing up to 51 potentially exchangeable hydrogens; this allowed determination of the number of exchangeable hydrogens for all of the molecules studied containing ≤ 25 labile hydrogens (M _r ≤ 3000). ND₃ gas consumption is minimized in the nebulizer method by toggling the nebulizer from air to ND₃ for only a few scans of the total sample elution period. The curtain gas exchange method is more variable, yielding exchange levels of 32–98% for the same set of molecules; this was still sufficient to allow determination of > 70% of the molecules studied containing ≤ 25 labile hydrogens. Gas consumption is minimized in the curtain method by replacing ≤ 10% of the curtain gas flow with ND₃. Neither the nebulizer nor curtain exchange method requires the use of deuterated or aprotic solvents at typical 2 μL/min flow rates.     

Detecting phase transitions in phosphatidylcholine vesicles by Raman microscopy and self-modeling curve resolution

The study of phospholipid phase transitions is important for understanding drug- and protein-membrane interactions as well as other phenomena such as trans-membrane diffusion and vesicle fusion. A temperature-controlled stage on a confocal Raman microscope has allowed phase transitions in optically trapped phospholipid vesicles to be monitored. Raman spectra were acquired and analyzed using self-modeling curve resolution, a multivariate statistical analysis technique. This method revealed the subtle spectral changes indicative of sub- and pretransitions and main transitions in vesicles composed of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC). The Raman scattering results were compared to differential scanning calorimetry (DSC) experiments and found to be in good agreement. This method of observing lipid phase transition profiles requires little sample preparation and a minimal amount of lipid (相似文献   

Inclusion and fractionated release of nucleic acids using microcapsules made from plant cells.

The encapsulation and fractionated release of nucleic acids on vesicular packing (VP) materials have been investigated. The earlier described dependence of the permeation of nucleic acid molecules through the vesicle membranes on the salt concentration is a necessary precondition for both encapsulation and fractionation. Encapsulation is achieved by applying a suitable sample onto a VP column that has been equilibrated with a high-salt buffer. In that buffer the sample molecules are permeable. Immediately after sample application, elution is started with a low-salt buffer, from which the sample molecules are excluded. At the front between the two buffers the permeability changes, and some of the sample molecules distributed inside the vesicles cannot pass through the membranes. These encapsulated molecules can be released by increasing the salt concentration in the eluent. If the encapsulated nucleic acid sample is polydisperse, a stepwise or linear increase in the salt concentration leads to a fractionated release. The fractions obtained differ in their molecular size composition.     

Frequency‐dependent NMR relaxation of liquids confined inside porous media containing an increased amount of magnetic impurities

Frequency‐dependent NMR relaxation studies have been carried out on water (polar) and cyclohexane (nonpolar) molecules confined inside porous ceramics containing variable amounts of iron oxide (III). The porous ceramics were prepared by compression of powders mixed with iron oxide followed by thermal treatment. The pore size distribution was estimated using a technique based on diffusion in internal fields that exposed a narrow distribution of macropore sizes with an average pore dimension independent of iron oxide content. The relaxation dispersion curves were obtained at room temperature using a fast field cycling NMR instrument. They display an increase of the relaxation rate proportional to the iron oxide concentration. This behavior is more prominent at low Larmor frequencies and is independent of the polar character of the confined molecules. The results reported here can be fitted well with a relaxation model considering exchange between molecules in the close vicinity of the paramagnetic centers located in the surface and bulk‐like molecules inside the pores. This model allows the extraction of the transverse diffusional correlation time that can be related to the polar character of the confined molecules. Copyright © 2013 John Wiley & Sons, Ltd.     

First anionic micelle with unusually long lifetime: self-assembly of fluorocarbon-hydrocarbon hybrid surfactant

The exchange of a fluorocarbon-hydrocarbon hybrid surfactant between monomer and micelle states in deuterium oxide has been investigated through 19F NMR and 1H NMR experiments. The CF3 group in the surfactant gives two kinds of 19F NMR signals corresponding to the monomer and micelle states, indicating slow surfactant exchange on NMR time scale. The lifetime (taumic) of micelle, estimated by line shape analysis of the signals, is 2.0 ms at cmc, 102 to 103 times longer than that of general surfactant micelles. Pulsed-gradient spin-echo (PGSE) experiments show that the hybrid surfactant forms considerably small micelles with a hydrodynamic radius of 0.6 nm. In contrast, at a higher concentration where no slow surfactant exchange is observed, the micelle radius increases to 1.1 nm. The interdigitation between the surfactant molecules in the micelle will contribute to the unusually long lifetime, in other words, slow surfactant exchange on the NMR time scale.     

精氨酸插层氧化锰纳米结构材料的制备和表征

应用氧化法水热合成了Na型层状氧化锰[BirMO(Na)], 通过离子交换反应在0.1 mol/L HCl溶液中Na型层状氧化锰转化成H型层状氧化锰[BirMO(H)]. BirMO(H)在四甲基氢氧化铵[(CH3)4NOH]溶液中搅拌处理7 d后, 剥离生成了MnO2纳米层胶体分散液. 剥离的MnO2纳米层胶体分散液在pH＝4.0～11.0的精氨酸溶液中搅拌2 d, 得到了层间距为1.49 nm的精氨酸插层氧化锰纳米结构材料. 通过XRD, DSC-TGA, SEM, IR及元素分析对合成试样进行了分析表征. 结果表明精氨酸在氧化锰层间的插入量及插入形式与重组溶液的pH值密切相关, 其最大插入量为1.80 mmol/g.     

Fast grain boundary diffusion and surface exchange reactions at active surface sites of polycrystalline materials

Analytical solutions to the diffusion equations for fast grain boundary diffusion and surface exchange reactions at active surface sites are derived. The microstructure of the polycrystalline sample of finite thickness is modelled by parallel grain boundaries. The ratio between the surface exchange coefficient and the diffusion coefficient for the grain boundaries is assumed to be greater than or equal to that for the bulk. The analytical solutions allow the calculation of diffusion profiles for thin films. Special emphasis is laid on a detailed analysis of the time dependence of the total amount of diffusant exchanged between the constant diffusion source (e.g. gas phase) and the polycrystalline sample (e.g. oxide ceramics) which corresponds to relaxation curves obtained from, e.g., oxygen exchange measurements. The calculated relaxation curves refer to Harrison's type-A kinetics where homogeneous medium solutions are satisfactorily applicable, introducing effective kinetic parameters. Apart from expressions for the effective diffusion coefficient analogous relations for the effective surface exchange coefficient are proposed, depending on the microstructure of the polycrystalline material and the corresponding kinetic parameters of bulk and grain boundary regions, respectively.     

Detailed Description of Pulse Isotopic Exchange Method for Analyzing Oxygen Surface Exchange Behavior on Oxide Ion Conductors

A novel pulse ¹⁸O-¹⁶O isotopic exchange (PIE) technique for measurement of the rate of oxygen surface exchange of oxide ion conductors was presented. The technique employs a continuous flow packed-bed micro-reactor loaded with the oxide powder. The isothermal response to an ¹⁸O-enriched pulse passing through the reactor, thereby maintaining chemical equilibrium, is measured by on-line mass spectrometry. Evaluation of the apparent exchange rate follows from the uptake of ¹⁸O by the oxide at given reactor residence time and surface area available for exchange. The developed PIE technique is rapid, simple and highly suitable for screening and systematic studies. No rapid heating/quenching steps are required to facilitate ¹⁸O tracer anneal or analysis, as in other commonly used techniques based upon oxygen isotopic exchange. Moreover, the relative distribution of the oxygen isotopologues ¹⁸O₂, ¹⁶O¹⁸O, and ¹⁶O₂ in the effluent pulse provides insight into the mechanism of the oxygen exchange reaction. The PIE technique has been demonstrated by measuring the exchange rate of selected oxides with enhanced oxide ionic conductivity in the range of 350?900 oC. Analysis of the experimental data in terms of a model with two consecutive, lumped steps for the isotopic exchange reaction shows that for mixed conductors Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ(BSCF) and La₂NiO_4+δ the reaction is limited by the apparent rate of dissociative adsorption of O₂ molecules at the oxide surface. For yttria-stabilized zirconia (YSZ), a change-over takes place, from rate-limitations by oxygen incorporation below ∽800 oC to rate-limitations by O₂ dissociative adsorption above this temperature. Good agreement is obtained with exchange rates reported for these materials in literature.     

Carrier gas flow arrangement based photoacoustic detection method for measuring gas permeability of polymer membranes

This paper describes a membrane permeability measuring set-up based on photoacoustic spectroscopy using continuous carrier gas flow to transport the permeated analyte molecules into a photoacoustic detection cell. The permeability parameters of the sample were determined from the measured permeation curves by using a numerical curve fitting algorithm. The method was applied to different membrane samples for determining methane and carbon-dioxide permeability at various carrier gas flow rates (CFRs). For each sample, a characteristic threshold flow rate (TFR) value can be identified below which a strong dependency of the determined permeation parameters on the CFR was found. For those cases when the CFR value cannot be set to be sufficiently high (i.e. above the TFR value), an extrapolation method was presented giving an accurate estimation of the permeation parameters.     

Partially Sulfonated Polystyrene and Poly(2,6‐dimethyl‐1,4‐phenylene oxide) Blend Membranes for Fuel Cells

Summary: Based on Flory–Huggins parameters (χ), the miscibility and the effect of morphological change on proton conductivity and methanol permeability of partially sulfonated polystyrene (SPS) and partially sulfonated poly(2,6‐dimethyl‐1,4‐phenylene oxide) (SPPO), having an identical ion exchange capacity, were investigated. When 50 wt.‐% of SPPO was blended, both the proton conductivity and methanol permeability had the highest values, which resulted from the change of amorphous domains and the hydrogen bonding between the two ionomers.

The proton conductivities, water uptake and methanol permeability for the SPPO/SPS blend membranes studied here. The membranes with 50 wt.‐% SPPO clearly showed the greatest increase in these properties.     

Capillary monolithic titania column for miniaturized liquid chromatography and extraction of organo-phosphorous compounds

A new sol?Cgel protocol was designed and optimized to produce titanium-dioxide-based columns within confined geometries such as monolithic capillary columns and porous-layer open-tubular columns. A surface pre-treatment of the capillary enabled an efficient anchorage of the monolith to the silica capillary wall during the synthesis. The monolith was further synthesized from a solution containing titanium n-propoxide, hydrochloric acid, N-methylformamide, water, and poly(ethylene oxide) as pore template. The chromatographic application of capillary titania-based columns was demonstrated with the separation of a set of phosphorylated nucleotides as probe molecules using aqueous normal-phase liquid chromatography conditions. Capillary titania monoliths offered a compromise between the high permeability and the important loading capacity needed to potentially achieve miniaturized sample preparations. The specificity of the miniaturized titania monolithic support is illustrated with the specific enrichment of 5??-adenosine mono-phosphate. The monolithic column offered a ten times higher loading capacity of 5??-adenosine mono-phosphate compared with that of the capillary titania porous-layer open-tubular geometry.     

An investigation on characterization and thermal analysis of the Aughinish red mud

Summary Red mud is insoluble, fine-grained waste residue which is generated as a by product during the production of alumina from the Bayer process. In this article, the thermal behavior of Aughinish red mud was investigated using thermal gravimetric analysis (TG) and differential thermal analysis (DTA). For identification of oxide and mineral phases in the red mud sample, XRD method, scanning electron microscopy (SEM), EDAX were used. Iron (30.4%), aluminium (23.6%) and titanium (17.85%) oxides are major oxides in the sample. Two endothermic peaks were shown on DTA curve. The total mass loss in the red mud was found to be 10.1%, which was associated with moisture and water molecules in gibbsite and boehmite phases.     

Giant Water Uptake Enabled Ultrahigh Proton Conductivity of Graphdiyne Oxide

Proton conductors have attracted great attention in various fields, especially in energy production. Here, we find that graphdiyne oxide (GDYO), derived from graphdiyne (GDY), features the highest proton conductivity of 0.54 S cm⁻¹ (100 % RH, 348 K) among the oxidized carbon allotropes reported so far. The sp- and sp²-co-hybridized carbon skeleton of GDY enables GDYO with the giant water uptake, which is 2.4 times larger than that of graphene oxide (GO), resulting in ultrahigh proton conductivity by increasing the proton concentration and proton conduction pathways. This ultrahigh proton conductivity of GDYO is further proved in a methanol fuel cell by using GDYO membrane as proton exchange membrane. The GDYO membrane enables the cell with higher open circuit voltage, larger power density and lower methanol permeability, compared with commercial Nafion 117. Moreover, the GDYO membrane bears high ion exchange capacity, good acidic stability and low swelling ratio.     

Detecting high-potential conditions of asphaltene precipitation in oil reservoir

Crude oil contains a wide range of components with different chemical natures. Complex molecules consisting of associated groups of polyaromatic sheets and alkyl side chains are known as asphaltene. Asphaltenes are insoluble in solvents such as n-heptane and n-pentane and soluble in benzene and toluene. Asphaltene causes serious damages around the wellbore and the reservoir by reducing permeability and plugging the pores. This paper includes a natural depletion test, performed on the bottom-hole sample and on a carbonate-core sample. The main emphasis is to identify high potentially damaged conditions in the reservoir from the asphaltene precipitation point of view. Stability of asphaltene was investigated by Saturates-Asphaltenes-Resins-Aromatics (SARA) analysis; moreover, asphaltene composition, permeability reduction, and porosity reduction were measured using the natural depletion in 4500, 3000, 2500, and 1450 psig via both static and dynamic approaches. At the pressures above the bubble point, asphaltene precipitation decreases as pressure increases, and the solubility model becomes dominant; on the other hand, below the saturation pressure, decrease in the pressure would decreases asphaltene precipitation and let the colloidal model dominate. It can be concluded that the maximum amount of asphaltene precipitation occurs near the saturation pressure. Asphaltene precipitation was then investigated through the core sample, using a novel scaling equation.     

Nanoscale inhomogeneities in thermoresponsive triblock copolymers

We present continuous-wave (CW) electron paramagnetic resonance (EPR) spectroscopy data of the spin probe 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) in aqueous solutions of poly(ethylene oxide)/poly(propylene oxide)/poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers (Pluronic or Poloxamer). TEMPO is notably smaller than the spin probes conventionally used in the context of polymer science and reveals the early emergence of small hydrophobic cavities when PPO strands of several molecules aggregate and collapse upon temperature increase. The occurrence of hydrophobic cavities appears independent of the overall molecular weight of the Pluronics, but clearly depends on the relative PPO/PEO contents. In all the cases studied, the volume fraction of hydrophobic cavities increases in a broad temperature range of ≥40 °C. The appearance of the hydrophobic regions does not seem to be directly correlated to micellization of the polymers. A decrease of the relative PPO amount in the polymers not only hinders collapse of the PPO strands, it can also be described as a site exchange of the spin probes between hydrophobic cavities and the surrounding medium. On the other hand, in cases of high PPO contents, spin probe exchange could not be observed. This suggests that one may potentially control the diffusion of small molecules between the micellar cores and the surrounding medium by adjusting the PEO/PPO ratio of the used Pluronics.     

Water-protein interactions in microcrystalline crh measured by 1H-13C solid-state NMR spectroscopy

Using solid-state NMR carbon-proton dipolar correlation spectroscopy, we observed hydrogen exchange on the millisecond time scale between water molecules and protein protons in a solid sample. These interactions are shown to be related to important structural features of the protein such as hydrogen-bonding or salt-bridge networks.