A Novel Glutamate Transport System in Poly(γ-Glutamic Acid)-Producing Strain <Emphasis Type="Italic">Bacillus subtilis</Emphasis> CGMCC 0833

Bacillus subtilis CGMCC 0833 is a poly(γ-glutamic acid) (γ-PGA)-producing strain. It has the capacity to tolerate high concentration of extracellular glutamate and to utilize glutamate actively. Such a high uptake capacity was owing to an active transport system for glutamate. Therefore, a specific transport system for l-glutamate has been observed in this strain. It was a novel transport process in which glutamate was symported with at least two protons, and an inward-directed sodium gradient had no stimulatory effect on it. K _m and V _m for glutamate transport were estimated to be 67 μM and 152 nmol⁻¹ min⁻¹ mg⁻¹ of protein, respectively. The transport system showed structural specificity and stereospecificity and was strongly dependent on extracellular pH. Moreover, it could be stimulated by Mg²⁺, NH₄⁺, and Ca²⁺. In addition, the glutamate transporter in this strain was studied at the molecular level. As there was no important mutation of the transporter protein, it appeared that the differences of glutamate transporter properties between this strain and other B. subtilis strains were not due to the differences of the amino acid sequence and the structure of transporter protein. This is the first extensive report on the properties of glutamate transport system in γ-PGA-producing strain.     

Cation Transport across Bulk Liquid Organic Membranes with Oligomers of (R)-3-Hydroxybutanoic Acid

Several oligomeric derivatives 1–5 of (R)-3-hydroxybutanoic acid and a cyclic trimer of (R)-3-hydroxypentanoic acid ( 6 ) were used as ionophores to transport potassium picrate across a bulk liquid CH₂Cl₂ membrane. Using the cyclic trimer 1 and an oligomer mixture of (R)-3-hydroxybutanoic acid, 5 (ca. 28-mer), for the transport experiments, the alkali-metal ions from Li⁺ to Cs⁺ and the alkaline-earth-metal ions from Mg²⁺ to Ba²⁺ were also shown to be transported through the organic phase. Although a pronounced enhancement of the transport rates was observed in the presence of 3-hydroxyalkanoate oligomers, no special selectivity for one ion was detected. The ionophore properties of the investigated oligomers and oligolides derived from 3-hydroxybutanoic acid are compatible with the alleged role of oligo(3-hydroxybutanoate) (c-PHB; ca. 120-mer) as component of ion channels through cell membranes.     

Na<Superscript>+</Superscript>-stimulated ATPase of alkaliphilic halotolerant cyanobacterium <Emphasis Type="Italic">Aphanothece halophytica</Emphasis> translocates Na<Superscript>+</Superscript> into proteoliposomes via Na<Superscript>+</Superscript> uniport mechanism

Background  

When cells are exposed to high salinity conditions, they develop a mechanism to extrude excess Na⁺ from cells to maintain the cytoplasmic Na⁺ concentration. Until now, the ATPase involved in Na⁺ transport in cyanobacteria has not been characterized. Here, the characterization of ATPase and its role in Na⁺ transport of alkaliphilic halotolerant Aphanothece halophytica were investigated to understand the survival mechanism of A. halophytica under high salinity conditions.     

Terminal Redox‐Site Effect on the Long‐Range Electron Conduction of Fe(tpy)2 Oligomer Wires on a Gold Electrode

This article completes our comprehensive understanding of the electron transport properties of our original π‐conjugated redox‐active molecular wires comprising Fe bridged by p‐phenylene linkers (tpy=2,2′:6′,2′′‐terpyridine). The Fe(tpy)₂ oligomer wires comprise three types of tpy ligands: the anchor tpy ligand ( A series) makes a junction between the wire and electrode, the bridging bis‐tpy ligand ( L series) connects the Fe(tpy)₂ units, and the terminal tpy ligand ( T series) possesses a redox site as a probe for the long‐range electron transport ability. Taking advantage of the precise tunability of the composition of the Fe(tpy)₂ oligomer wires, thus far we investigated how A and L impacted on the electron‐transport ability. The excellent long‐range electron transport ability with ultrasmall attenuation constants (β^d, 0.002 Å^?1 as the minimum) depends on L significantly [Chem. Asian J. 2009 , 4, 1361], whereas A is unrelated to the β^d value, but influences the zero‐distance electron‐transfer rate constant, k_et⁰ [J. Am. Chem. Soc. 2010 , 132, 4524]. Herein we study the influence of terminal ligand T ^x (x=1–3). β^d is independent of T , however, T³ , with a cyclometallated Ru complex as the redox site, gives rise to a k_et⁰ value greater than T¹ and T² with ferrocene. This series of simple but definitive conclusions indicates that we have reached the stage of being able to precisely design molecular wires to attain desirable single‐molecule electron conduction.     

Study of Bulk Membrane Transport of Some Heavy Metal Cations Using Three Macrocyclic Ligands Containing Oxygen and Nitrogen Heteroatoms

The transport experiments of Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Ag⁺ and Pb²⁺ metal cations were carried out by dibenzo-18-crown-6 (DB18C6), dibenzyl-diaza-18-crown-6 (Dibenzyl-diaza-18C6) and di-tert-butyl-dibenzo-18-crown-6 (Di-tert-butyl-DB18C6) using chloroform (CHCl₃), 1,2-dichloroethane (1,2-DCE) and nitrobenzene (NB) organic solvents as liquid membranes. The source phase contained equimolar concentration of these metal cations and the source and receiving phases being buffered at pH=5 and pH=3, respectively. The obtained results show that the selectivity and the efficiency of transport for these heavy metal cations change with the nature of the ligand and also the organic solvents, which were used as liquid membranes in these experiments. A good selectivity was observed for silver (I) ion by dibenzyl-diaza-18C6 in all membrane systems. Dibenzo-18C6 and di-tert-butyl-DB18C6 showed the highest transport efficiency for cobalt (II) ion. The effect of stearic acid on transport efficiency was also investigated and the results show that the efficiency of transport of the heavy metal cations increases in the presence of this organic acid.     

Soil moisture effects on the carbon isotope composition of soil respiration

The carbon isotopic composition (δ¹³C) of recently assimilated plant carbon is known to depend on water‐stress, caused either by low soil moisture or by low atmospheric humidity. Air humidity has also been shown to correlate with the δ¹³C of soil respiration, which suggests indirectly that recently fixed photosynthates comprise a substantial component of substrates consumed by soil respiration. However, there are other reasons why the δ¹³CO₂ of soil efflux may change with moisture conditions, which have not received as much attention. Using a combination of greenhouse experiments and modeling, we examined whether moisture can cause changes in fractionation associated with (1) non‐steady‐state soil CO₂ transport, and (2) heterotrophic soil‐respired δ¹³CO₂. In a first experiment, we examined the effects of soil moisture on total respired δ¹³CO₂ by growing Douglas fir seedlings under high and low soil moisture conditions. The measured δ¹³C of soil respiration was 4.7‰ more enriched in the low‐moisture treatment; however, subsequent investigation with an isotopologue‐based gas diffusion model suggested that this result was probably influenced by gas transport effects. A second experiment examined the heterotrophic component of soil respiration by incubating plant‐free soils, and showed no change in microbial‐respired δ¹³CO₂ across a large moisture range. Our results do not rule out the potential influence of recent photosynthates on soil‐respired δ¹³CO₂, but they indicate that the expected impacts of photosynthetic discrimination may be similar in direction and magnitude to those from gas transport‐related fractionation. Gas transport‐related fractionation may operate as an alternative or an additional factor to photosynthetic discrimination to explain moisture‐related variation in soil‐respired δ¹³CO₂. Copyright © 2010 John Wiley & Sons, Ltd.     

Electrochemical Elucidation of the Facilitated Ion Transport Across a Bilayer Lipid Membrane in the Presence of Neutral Carrier Compounds

The ion transport facilitated by neutral carrier compounds (valinomycin, nonactin) has been investigated by cyclic voltammetry in the several electrolyte solutions (KF, KCl, KBr, KNO₃, KSCN, KClO₄), and we demonstrated the effect of the counter anions on the facilitated transport of K⁺ from the viewpoint of electroneutrality. Voltammograms for the ion transport were generated at steady state and the current density between W1 and W2, j_W1–W2, increased with the absolute value of the applied membrane potential, E_W1–W2. Then, the magnitude of j_W1–W2 at a certain E_W1–W2 increased with the hydrophobicity of the counter anion. It was proved that the logarithm of |j_W1–W2|at a certain E_W1–W2 is almost proportional to the hydration energy of the counter anion. This indicates that not only K⁺ but also the counter anion distributes into the BLM. Therefore, the magnitude of j_W1–W2 at a certain E_W1–W2 increased with an increase of pH, because the hydroxide ion was served as a counter anion. Based on the variation of the zero‐current potential in case of various asymmetrical ionic compositions, it is found that the amount of cation transport is much larger than that of anion transport.     

Photoconductivity and hole transport in polymers of aromatic amine-containing methacrylates

Substantial hole transport can be achieved in organic polymers simply by incorporating aromatic amine groups into the monomer. Hole mobilities similar to or greater than those in poly(N-vinyl-carbazole) (PVK) were measured in a series of high molecular weight arylamine-substituted polymethacrylates. The hole transport in these polymers is electric-field-dependent as in PVK, varying between E and E² within a range of 4 × 10⁴ ? ～9 × 10⁵ V/cm. The polymers also exhibit carrier generation in ultraviolet (UV) light in the range of absorption. Synthesis of the monomers, their polymerization, and the general properties of these polymers are discussed.     

Alcohol‐Soluble Electron‐Transport Materials for Fully Solution‐Processed Green PhOLEDs

Two alcohol‐soluble electron‐transport materials (ETMs), diphenyl(4‐(1‐phenyl‐1H‐benzo[d]imidazol‐2‐yl)phenyl)phosphine oxide (pPBIPO) and (3,5‐bis(1‐phenyl‐1H‐benzo[d]imidazol‐2‐yl)phenyl)diphenylphosphine oxide (mBPBIPO), have been synthesized. The physical properties of these ETMs were investigated and they both exhibited high electron‐transport mobilities (1.67×10^?4 and 2.15×10^?4 cm² V^?1 s^?1), high glass‐transition temperatures (81 and 110 °C), and low LUMO energy levels (?2.87 and ?2.82 eV, respectively). The solubility of PBIPO in n‐butyl alcohol was more than 20 mg mL^?1, which meets the requirement for fully solution‐processed organic light‐emitting diodes (OLEDs). Fully solution‐processed green‐phosphorescent OLEDs were fabricated by using alcohol‐soluble PBIPO as electron‐transport layers (ETLs), and they exhibited high current efficiencies, power efficiencies, and external quantum efficiencies of up to 38.43 cd A^?1, 26.64 lm W^?1, and 10.87 %, respectively. Compared with devices that did not contain PBIPO as an ETM, the performance of these devices was much improved, which indicated the excellent electron‐transport properties of PBIPO.     

Thermocapillary Alignment of Gas Bubbles Induced by Convective Transport

The effect of a weak convective heat transfer on the thermocapillary interaction of two bubbles with an arbitrary orientation relative to an externally imposed temperature gradient is examined. Asymptotic analysis of the case of large separation distances, Z, suggests that the corrections to the bubbles' velocities are of (Pe/Z²), rather than (Pe²) previously found for an isolated bubble. Equal-sized bubbles are known to move with the same velocities, as if they were isolated, when heat conduction is the only transport mechanism. However, the convective transport results in a relative motion of the bubbles. The tendency of equal bubbles to line up in a plane perpendicular to the applied thermal gradient is shown analytically in the weakly nonlinear limit of small Pe numbers, and an interesting interaction behavior in the case of unequal bubbles is discussed.     

Modification of properties of ion-exchange membranes. IV. Change of transport properties of cation-exchange membranes by various polyelectrolytes

A change in electrodialytic transport properties of various cation exchange membranes was observed after the membranes had been adsorbed or ion-exchanged with various cationic polyelectrolytes. Transport properties measured in this report were the relative transport number of calcium ion to sodium ion P^Ca_Na, the current efficiency of cations, and the electric resistance of the membrane during the electrodialysis. Weakly basic and strongly basic cationic polyelectrolytes of various molecular weights were used. Though P^Ca_Na of any cation exchange membrane decreased by the adsorption or ion exchange of any cationic polyelectrolyte, the degree of the decrease in P^Ca_Na changed with species and molecular weight of polyelectrolytes and species of cation-exchange membranes. Weakly basic polyelectrolytes and low molecular weight, strongly basic polyelectrolytes were effective in producing a marked decrease in P^Na_Ca of any cation exchange membrane. The effect of strongly basic polyelectrolytes of high molecular weight on P^Ca_Na was weak in most cases. However, if it was possible to make the polyelectrolyte adhere to the surface of the membrane to form a compact coiled structure, any cationic polyelectrolyte was effective in producing a remarkable decrease in P^Ca_Na of any cation-exchange membrane.     

Transport of Ca^2＋ Ion through a Bubbling Pseudo—emulsion Liquid Membrane with Calixarenes and Calixcrowns as Carriers

ＩｎｔｒｏｄｕｃｔｉｏｎＣａｌｉｘａｒｅｎｅｓｃｏｎｓｔｉｔｕｔｅａｖｅｒｓａｔｉｌｅｃｌａｓｓｏｆｍａｃｒｏｃｙｃｌｉｃｃｏｍｐｏｕｎｄｓｔｈａｔｃａｎｂｅｅａｓｉｌｙｆｕｎｃｔｉｏｎａｌｉｚｅｄ ,ｔｈｕｓａｆｆｏｒｄ ｉｎｇａｌａｒｇｅｖａｒｉｅｔｙｏｆｎｅｗｍｕｌｔｉｆｕｎｃｔｉｏｎａｌｒｅｃｅｐｔｏｒｓ .1Ｉｎｔｈｅｐａｓｔｔｗｏｄｅｃａｄｅｓ ,ｔｈｅｙｈａｖｅｐｌａｙｅｄａｎｉｍｐｏｒｔａｎｔｒｏｌｅｉｎｓｕｐｒａｍｏｌｅｃｕｌａｒｃｈｅｍｉｓｔｒｙａｓｕｓｅｆｕｌｂｕｉｌｄｉｎｇｂｌｏ…     

Oxygen-18 surface exchange and diffusion in Li2O-deficient single crystalline lithium niobate

¹⁸O/¹⁶O isotope exchange in combination with SIMS depth profiling was used to investigate oxygen transport in Li₂O-deficient single crystalline LiNbO₃ in the temperature range 983 ≤ T/K ≤ 1188 at 200 mbar oxygen. Within the limit of experimental error and for the investigated range of temperatures no significant differences between transport parallel and transport perpendicular to the c-axis were found. The following temperature dependencies were determined: for oxygen tracer diffusion D = 6.4 × 10⁻³exp[−333 kJ/mol/(RT)] m²/s; and for oxygen surface exchange k = 7.8 × 10²exp[−288 kJ mol⁻¹/(RT)] m/s. The activation enthalpy obtained for tracer diffusion can be interpreted as the enthalpy of migration of extrinsic oxygen vacancies induced by impurities with lower valency on niobium sites.     

Ba1.03Ce0.8 Ho0.2O3-α固体电解质的制备和电性能

采用高温固相反应法制备了非化学计量组成的Ba1.03Ce0.8 Ho0.2O3-α 固体电解质,用XRD和SEM对其相组成和表面及断面形貌进行了表征。用气体浓差电池方法测定了材料在600～1000 ℃温度范围内,干燥空气、湿润空气和湿润氢气气氛中的离子迁移数;用交流阻抗谱技术测定了它们在各实验气氛中的电导率。研究了材料的离子导电特性,并与BaCe0.8Ho0.2O3-α 和Ba0.97Ce0.8Ho0.2O3-α 的性能进行了比较。结果表明：该材料为单相钙钛矿型斜方晶结构。在600～1000 ℃温度范围内、干燥空气中,是氧离子与电子空穴的混合导体,氧离子迁移数为0.10～0.36;在湿润空气中,是质子、氧离子与电子空穴的混合导体,质子迁移数为0.11～0.01,氧离子迁移数为0.34～0.30;在湿润氢气气氛中,是纯质子导体,质子迁移数为1。在600～1000 ℃温度范围内,干燥空气、湿润空气和湿润氢气气氛中,非化学计量组成材料(x = 1.03,0.97)的电导率高于化学计量组成材料(x = 1)的电导率,其中,Ba1.03Ce0.8 Ho0.2O3-α的电导率最高 (1000 ℃时、在干燥空气气氛中：3.92×10-2 S·cm-1;在湿润空气气氛中：3.46×10-2 S·cm-1;在湿润氢气气氛中：2.10×10-2 S·cm-1)。Ba1.03Ce0.8 Ho0.2O3-α材料的离子导电性优于BaCe0.8Ho0.2O3-α 和Ba0.97Ce0.8Ho0.2O3-α。     

Proportionality of intrinsic heat of transport to standard entropy of hydration for aqueous ions

Intrinsic ionic heats of transport q _o ^* (ion) and ionic heats of transport Q _o ^* (ion) have been evaluated for 53 aqueous ions at infinite dilution at 25°C using the reduction rule proposed by the authors and the limiting laws of Agar, and of Helfand and Kirkwood without electrophoretic terms. q _o ^* (ion) have been found to correlate linearly with the standard ionic entropies of hydration for the 38 ions investigated. The correlation yields three distinctive proportionality constants indicating that the ions may be divided into three distinctive groups. Although the sign of Q _o ^* (ion) is not definite, all values of q _o ^* (ion) are positive. For 17 ions Q _o ^* (ion) are in good agreement with TS _o ^* (ion). Here, S _o ^* (ion) is the absolute standard ionic entropy of transport which can be obtained from potentiometric measurements on cells. The values of S _o ^* (ion) were determined by Agar, and recently by Lin and coworkers.     

A study of solvent diffusion in thin polyimide films using laser interferometry

Using laser interferometry, we have determined in situ the thickness increase with time of thin supported polyimide films (4–8 μm in initial thickness) immersed in n-methyl-2-pyrrolidone (NMP) as a function of NMP temperature (22–120°C). Similar experiments were also performed in dimethyl sulfoxide (DMSO) at 22°C with polyimide films of 4.1 μm in thickness. For NMP, the equilibrium fractional thickness increase (about 20%) is independent of initial polyimide thickness and temperature. The time scale for reaching equilibrium sharply decreases with temperature from 2–3 days at 22°C to 30–60 min at 120°C. Compared with NMP, the rate of DMSO sorption is considerably faster, reaching equilibrium swelling of about 28% in about 5 h at 22°C. To describe the transport process, we applied a phenomenological model proposed by Astarita and Sarti¹ but reformulated in polymer fixed frame to enable straightforward comparison with the thickness data. Our analysis indicated that the transport of NMP is best described as anomalous, that is, intermediate between diffusion controlled and case II transport. The effective diffusion coefficient D_eff and the front velocity U₀ at 22°C were found to be 3–6 × 10^?12 cm²/s and 8 × 10^?9 cm/s, respectively. Our front velocity is in good accord with the value of 6 × 10^?9 cm/s obtained for a similar polyimide based on gravimetric measurements.² Both D_eff and U₀ show an activation energy of ～56 kJ/mol. For DMSO, however, the transport is clearly case II. The front velocity at 22°C was found to be about 6 × 10^?8 cm/s, which is about four times that obtained by Rutherford back-scattering spectrometry.³     

Ion Transport in a Three-Layered Ion-Exchange Membrane: A Mathematical Model

An ion transport model is considered. The model is based on the Nernst–Planck equations, the elements of nonequilibrium thermodynamics, the principle of local equilibrium, and the concept of a virtual solution. The model is applied to an ion-exchange membrane with two diffusion layers for the cases of electrotransport of two and three types of ions. To determine transfer coefficients L ^* _j in the Nernst–Planck equations, two approaches are used. In the phenomenological approach, L ^* _j are found from experimental data on the electroconductivity and transport numbers. In the modeling approach, values of L ^* _j are sought for from a model of a microheterogeneous membrane. The obtained boundary-value problem is solved using a numerical method of parallel shooting developed earlier, which perfectly fits specific features of the problem formulation (utilizing the Nernst–Planck equations in all the three layers and the concept of a virtual solution).     

Charge dynamics of a methane adsorption storage system: Intraparticle diffusional effects

The charge of natural gas adsorption storage systems is studied numerically, With emphasis given to the impact on its dynamics of intraparticle diffusional resistances to mass transport. Besides adsorption kinetics and thermal effects, the simulation model takes into account both mass transport inside the adsorbent and hydrodynamics of flow through the packed bed. Numerical results are presented for change with methane of a 50 liter cylindrical reservoir, filled with hypothetical adsorbents with diffusional time constants in the range 10^–3 s¹ D/R _p ² . and with the adsorption equilibrium curve of a commercially available activated carbon with a good adsorptive storage capacity. An attempt is made to assemble the charge histories for different values ofD/R _p ² , in a single cure by using a modilied time scale.     

Technetium-99m extraction and transport across tri-n-octylamine-xylene based supported liquid membranes

The nuclear properties of^99mTc radionuclide are ideal for organ imaging. Study of the technetium transport across supported liquid membranes has been performed to get data for its separation from other elements. Tri-n-octylamine diluted in xylene was used to constitute the liquid membranes, supported in polypropylene microporous films. Stripping on the product solution side was performed with dilute NaOH solutions. The effect of sulphuric acid, nitric acid and hydrochloric acid in the feed on transport of^99mTc as TcO ₄ ^– ions has been studied. The permeability of the given ions determined from kinetic activity data has been found to be in the order of PH₂SO₄>PHCl>PHNO₃. The flux values have been calculated based on this permeability data. The increase in carrier concentration has shown an increase in flux and permeability values to a given optimum concentration. The increase in temperature has been found to reduce the transport of Tc ions. The optimum conditions for transport of^99mTc for the given acid concentration have been determined. Mechanism of Tc ion transport has also been provided based on chemical reactions involved at the membrane interfaces and uptake of Tc ions by the membrane. MoO ₄ ^2– ions do not permeate through membrane under optimum conditions of transport for TcO ₄ ^2– ions from H₂SO₄ solution.     

Mass-transfer in pertraction of butyric acid by phosphonium ionic liquids and dodecane

Transport of butyric acid (BA) through a supported liquid membrane (SLM) containing phosphonium ionic liquid (IL) Cyphos IL-104 and dodecane occurs by two mechanisms. The first is related to the physical solubility of undissociated acid in dodecane in the form of a monomer or dimer and the second to the reactive extraction of acid by IL. Although the model of pertraction indicates that increasing the mean concentration of acid in the feed, c _F,lmv, increases the participation of pertraction based on the physical solubility; in the tested range of c _F,lmv from 0 kmol m⁻³ to 0.45 kmol m⁻³ it does not play an important role and at the highest c _F,lmv value, less than 10 % of the overall BA transport were achieved. The presence of IL in SLM considerably increases the value of the overall mass transfer coefficient in pertraction at low BA concentrations. However, at c _F,lmv > 0.4 kmol m⁻³ its values are similar for SLMs with and without IL. Compared to lactic acid, the pertraction of BA through the same SLM is about five times faster. Reactive transport of BA is connected with the back transport of water via reverse micelles decomposition and formation on the extraction and stripping interfaces.