燃料电池电极制作方法的研究

对燃料电池,性能良好的催化剂至关重要,它决定着大电流密度放电时的性能、成本和运行寿命［１］．但因电极上的反应是气、液、固三相反应,所以必须制备出高效的、结构合理的气体电极［２～３］,减小气相、液相传质阻力,提高三相接触性能,降低电极极化．Ｋ．Ｍｕｎｄ等［４～５］所制作的电极,气体扩散距离长,溶解气体的扩散电阻大．Ｒ．Ｐ．Ｉｃｚｋｏｗｓｋｉ等人［６］用ＰＴＦＥ（ｐｏｌｙｔｅｔｒａｆｌｕｏｒｏｅｔｈｙｌｅｎｅ,聚四氟乙烯）作疏水剂,在整个气体反应层制成气体扩散通道,改善了电极性能．后来,Ｓ．Ｍｏｔ…     

Permeation of complexed metal ions through a hydrophobic membrane

Selective concentration of a heavy metal complex with acetylacetone (acac) through a hydrophobic polystyrene membrane was carried out under a pressure gradient. A chelate forming heavy metal was selectively concentrated about 2 fold by this method. When using a coating membrane with a high water flux, the permeabilities increased with increasing complex fraction in the aqueous solution, while using a membrane with a low water flux, a bulky complex was not highly concentrated because of steric hindrance. The complex partitioned on the membrane surface was transported and concentrated under a pressure gradient and a linear relationship was found to exist between permeabilities and partition coefficients. It will be possible to concentrate hydrophobic organic solutes by this method, for acac was concentrated when the Cu—acac complex was formed. As the permeabilities increased with decreasing pressure and membrane compaction was strong for a coating membrane, it seems effective to permeate at a low pressure.     

Flow of an Anisotropic Dielectric Liquid in a Diverging Channel in a Strong Transverse Electric Field

A steady plane flow of an anisotropically polarizable liquid in a channel with nonparallel walls was considered. One of the walls was grounded, and the other was under a high electric potential. The polarization anisotropy was described in terms of a unit vector whose direction was determined by a relaxation equation. The dependence of the polarization of the liquid on the strength of the electric field and the anisotropy vector was specified using an equilibrium relation. Such a model can describe, for example, a suspension of anisotropically polarizable particles in a highly insulating liquid. The velocity, pressure, polarization, anisotropy vector, and electric field distributions in the liquid were determined and investigated. It was shown that, at some critical Reynolds number, backflows are initiated near the channel walls. The dependence of the critical Reynolds number on the diverging angle of the channel and on the properties of a liquid in a strong electric field was determined. The applied electric field increases the critical Reynolds number, which provides a means of controlling the regime of the considered flow using electrical methods.     

Purification method for recombinant proteins based on a fusion between the target protein and the C-terminus of calmodulin

Calmodulin (CaM) was used as an affinity tail to facilitate the purification of the green fluorescent protein (GFP), which was used as a model target protein. The protein GFP was fused to the C-terminus of CaM, and a factor Xa cleavage site was introduced between the two proteins. A CaM-GFP fusion protein was expressed in E. coli and purified on a phenothiazine-derivatized silica column. CaM binds to the phenothiazine on the column in a Ca(2+)-dependent fashion and it was, therefore, used as an affinity tail for the purification of GFP. The fusion protein bound to the affinity column was then subjected to a proteolytic digestion with factor Xa. Pure GFP was eluted with a Ca(2+)-containing buffer, while CaM was eluted later with a buffer containing the Ca(2+)-chelating agent EGTA. The purity of the isolated GFP was verified by SDS-PAGE, and the fluorescence properties of the purified GFP were characterized.     

Flow injection analysis of DPPH radical based on electron spin resonance

In order to construct a rapid and selective determination system of free radicals, we developed an FIA system using an electron spin resonance (ESR) spectrophotometer (flow injection spin analysis) equipped with a flow-through flat cell. In the present investigation, 1,1-diphenyl-2-picrylhydrazyl (DPPH) was used as a model free radical. Using a single line flow system, 0.5 mM DPPH was repetitively injected. When the magnetic field was fixed at 335.3 mT, the largest change in the ESR signal was observed and obtained peak height was proportional to the concentration of DPPH radical. A double line flow system was constructed in which a carrier stream containing 0.15 mM DPPH was fed into the flat cell after confluence with a sample stream. When ascorbic acid was injected as a typical DPPH radical scavenger, a negative peak appeared in proportional to the concentration. Lower detection limit of ascorbic acid was 0.01 mM (S/N=4), sampling frequency was 13 samples per h, and a satisfactory reproducibility (CV=3.2%, 0.1 mM, n=5) was obtained. The present system was also applied to estimate the DPPH radical-scavenging activity of other substances and food samples.     

聚苯胺的图形化沉积

自1976年发现第一个有机聚合物聚乙炔掺杂后具有类似金属的导电性以来，先后发现了聚吡咯、聚噻吩和聚苯胺(PAn)等导电聚合物，其中聚苯胺以其合成方法简单、稳定性好、较高的电导率及良好的电化学性能等被预言为是最有应用前景的导电高分子材料之一。近年来，随着导电聚合物研究的广泛开展和不断深入，     

Miniature liquid flow sensor and feedback control of electroosmotic and pneumatic flows for a micro gas analysis system.

Accurate liquid flow control is important in most chemical analyses. In this work, the measurement of liquid flow in microliters per minute was performed, and feedback control of the flow rate was examined. The flow sensor was arranged on a channel made in a polydimethylsiloxane (PDMS) block. The center of the channel was cooled by a miniature Peltier device, and the change in temperature balance along the channel formed by the flow was measured by two temperature sensors. Using this flow sensor, feedback flow control was examined with two pumping methods. One was the electroosmotic flow method, made by applying a high voltage (HV) between the reagent and waste reservoirs; the other was the piezo valve method, in which a micro-valve-seat was fabricated in a PDMS cavity with a silicone diaphragm. The latter was adopted for a micro gas analysis system (microGAS) for measuring atmospheric H2S and SO2. The obtained baselines were stable, and better limits of detection were obtained.     

Bioanalysis of diclofenac as its fluorescent carbazole acetic acid derivative by a post-column photoderivatization high-performance liquid chromatographic method

A sensitive and selective bioanalytical liquid chromatographic method for diclofenac is described. The drug was detected as a flourescent derivative, which was demonstrated by 1H NMR and mass spectrometric studies to be carbazole acetic acid. Diclofenac was derivatized by UV irradiation of the substance performed as a post-column photoreaction. The reactor was a PTFE capillary wound around a 254-nm UV lamp. Diclofenac was isolated from the plasma samples by precipitation of the proteins with acetonitrile. A 50-microliters volume of the supernatant was injected onto a Nucleosil C18 column. The mobile phase was 32% acetonitrile in pH 6.6 buffer. Carbazole acetic acid was detected by a fluorescence detector using an excitation wavelength of 288 nm and an emission wavelength of 360 nm. The recovery was 92%, the standard curve was linear in the range 10-5500 ng diclofenac per ml plasma, and the relative standard deviation at 10 and 5000 ng of diclofenac per ml plasma was 9.0% and 3.3%, respectively. The limit of detection was 6 ng/ml at an injection volume of 50 microliters. Chromatograms of human and rat plasma containing diclofenac are shown.     

高温非平衡条件下氟原子亲电动力学的激波管研究

To study electron affinity kinetics, a shock tube method was applied, in which the test gas was ionized by a reflected shock wave and subsequently quenched by a strong rarefaction wave. As the quenching speed of 106 K/s was reached, a nonequilibrium ionization recombination process occurred, which was dominated by ion recombination with electrons. A Langmuir electrostatic probe was used to monitor variation in the ion number density at the reflection shock region. The working state of the probe was analyzed, and a correction was introduced for reduction of the probe current due to elastic scattering in the probe sheath. The three body electron affinity rate coefficient of the fluorine atom over the temperature range 1200 to 2200 K in an ambiance of argon gas was directly determined. The temperature dependence of electron affinity rate coefficient was discussed.     

Microchip-based enzyme-linked immunosorbent assay (microELISA) system with thermal lens detection

A microchip-based enzyme-linked immunosorbent assay (microELISA) system was developed and interferon-gamma was successfully determined. The system was composed of a microchip with a Y-shaped microchannel and a dam structure, polystyrene microbeads, and a thermal lens microscope (TLM). All reactions required for the immunoassay were done in the microchannel by successive introduction of a sample and regents. The enzyme reaction product, in a liquid phase, was detected downstream in the channel using the TLM as substrate solution was injected. The antigen-antibody reaction time was shortened by the microchip integration. The limit of the determination was improved by adopting the enzyme label. Moreover, detection procedures were greatly simplified and required time for the detection was significantly cut. The system has good potential to be developed as a small and automated high throughput analyzer.     

Automatic positioning of a microinjector in mouse ES cells and rice protoplasts

A 2-channel (2C) microinjector was prepared by pulling a glass capillary with a theta-shaped cross section. One channel was used as a potential measuring electrode (MeaE) and the other was used as an electrophoretic introduction electrode (IntE). The 2C microinjector was propelled by an oil pressure manipulator driven by a pulse motor, while the MeaE output was recorded continuously. When the 2C microinjector penetrated the cell membrane of a mouse ES cell or a rice protoplast, the output potential changed sharply. The differential of this potential change was used as a stop signal for the pulse motor. Thus, the microinjector was correctly positioned in the cell without losing cell viability. Its success rate was 73% and 84% for ES cells and rice protoplasts, respectively. After the positioning of the microinjector in the cell, Lucifer yellow (LY) was introduced via IntE. Under these conditions, the rate of viable cells was 16% and 62% for ES cells and rice protoplasts, respectively.     

Selective enrichment of anti-inflammatory drugs from river water samples by solid-phase extraction with a molecularly imprinted polymer

A molecularly imprinted polymer (MIP) is synthesised by a noncovalent protocol in which ibuprofen was used as a template molecule. The polymer was evaluated chromatographically and it was seen that the MIP showed cross-reactivity. Subsequently, when this polymer was used as sorbent in SPE it was possible to selectively extract a mixture of nonsteroidal anti-inflammatory drugs from aqueous samples when a cleanup step with dichloromethane was performed. The performance of the MIP was evaluated with river water and water from a wastewater treatment plant, and compared with the performance of a commercial Isolute ENV+ sorbent.     

Extraction and separation of cationic surfactants from river sediments: application to a spectrophotometric determination of cationic surfactant in an aquatic environment using membrane filters.

The quantitative extraction of cationic surfactant (CS+) in river sediments was studied. Further, the developed method was applied to the spectrophotometric determination of CS+ in urban river sediment samples by solid-phase extraction with membranes. A mixture of methanol and hydrochloric acid was proposed as an eluent. Dried sediment was digested in the eluent under ultrasonic irradiation. After elution, the eluent was evaporated to almost dryness. The residue was dissolved in a small volume of methanol and diluted to a certain volume with water. The pH of the solution was adjusted to 4-5 to separate iron and some other metals as precipitates of hydroxides. The solution was passed through two-piled membranes: first glass-fiber and then polytetrafluoroethylene (PTFE) membranes. A small volume of methanol was passed through the membranes to elute any CS+ retaining on the membranes. After passing the methanol solution through a cationic exchange resin column, the retained CS+ was eluted with methanol containing a high concentration of sodium chloride. Water, Bromophenol Blue (BPB) and hydrochloric acid were added to the solution. The solution was passed through a mixed cellulose ester membrane filter to retain an ion associate of CS+.BPB-. The retained ion associate was dissolved in a small volume of N,N-dimethylformamide together with the membrane filter, followed by the addition of triethanolamine to make the solution alkaline. The absorbance due to BPB2- was measured at 603 nm against a reagent blank. This method was applied to the determination of CS+ in river water and sediment. A cationic surfactant in sediments at 10(-5) mol kg-1 levels was detected with satisfactory precision. It was found that CS+ was about 500-fold enriched in the sediment from water at the place where domestic wastewater was discharged.     

Microencapsulation of oil with poly(styrene-N,N-dimethylaminoethyl methacrylate) by SPG emulsification technique: effects of conversion and composition of oil phase

Microcapsules with narrow size distribution, in which hexadecane (HD) was used as a oily core and poly(styrene-co-N,N-dimethylaminoethyl methacrylate) [P(St-DMAEMA)] as a wall, were prepared by a Shirasu porous glass (SPG) emulsification technique and a subsequent suspension polymerization process. That is, a mixture of St monomer, DMAEMA monomer, HD, and N,N'-azobis(2,4-dimethylvaleronitrile) initiator was permeated through the uniform pores of an SPG membrane into a continuous phase containing a poly(vinylpyrrolidone), sodium lauryl sulfate, and sodium nitrite water-soluble inhibitor by applying a pressure, to form uniform droplets. Then, the droplets were polymerized at 70 degrees C. It was found that HD was encapsulated completely only when conversion was quite high, irrespective of whether a DMAEMA hydrophilic monomer was incorporated into the polymer. As the amount of HD increased, HD was more easily encapsulated by the polymer. In order to clarify the reason for such unique behavior, a simulation was carried out, taking the St monomer partition in the HD phase and PSt wall phase into the consideration. It was found that the main reason HD could not be encapsulated completely by PSt when conversion was lower was that the interfacial tension of the HD phase with water and the PSt phase with water got closer. As a result, both HD and PSt can come in contact with the water phase.     

Problems on the Evaluation of the Critical Wavelength of Sunscreens for “Broad Spectrum” Approval Brought on by Viscous Fingering During Sunscreen Application

When a viscous liquid is applied to a solid substrate, a patterned liquid layer is usually formed by the phenomenon called viscous fingering, since the moving liquid surface is in far‐from‐equilibrium conditions to let the morphological fluctuation to grow. Pseudosunscreen solutions were prepared and applied on a flat quartz plate. A spatially periodic stripe pattern was formed on the pseudosunscreen layer when a block applicator was used, whereas a flat surface layer was formed when a four‐sided applicator was used. UV absorbance of the patterned layer was lower than that of the flat layer having the same average thickness. In addition, a larger decrease in the UV absorbance by the pattern formation was observed at wavelengths at which the UV absorbance of the flat layer was large, which was consistent with theoretical simulations. In 2011, US FDA introduced a new rule using the term “Broad Spectrum” for labeling the sunscreens. The different decrease in the UV absorbance at each wavelength was found to change the critical wavelength, which is a criterion for sunscreens to be labeled as “Broad Spectrum” protection. The result of this study makes the problem on the evaluation of the critical wavelength come to the surface.     

HPLC study of tissue distribution of loganin in rats

A rapid, sensitive and selective high performance liquid chromatography (HPLC) method was developed and validated for determination of loganin in rat tissues. Samples were prepared based on a simple protein precipitation. Separation of loganin was achieved on a reversed-phase C(18) column (250 x 4.6 mm, 5 microm) with a mobile phase consisting of acetonitrile and water (16:84, v/v) at a flow rate of 1.0 mL/min. The detection wavelength was set at 236 nm and the temperature of the column was kept at 30 degrees C. The method was applied to study tissue distribution of loganin in rats after a single administration of loganin at a dose of 20 mg/kg. The highest level was observed in kidney, then in stomach, lung and small intestine. The lowest level was found in brain. The peak levels were attained at 90 min in most tissues. It was indicated that kidney was the major distribution tissue of loganin in rats, and that loganin had difficulty in crossing the blood-brain barrier. It was also found there was no long-term accumulation of loganin in rat tissues.     

Studies on Surface Properties and Cell Adhesion Properties of BSA Modified DBM Scaffold

As a scaffold material for bone tissue engineering, demineralized bone matrix(DBM) has such a limited ability to load cells and growth factors that the surface of the DBM scaffold was modified with bovine serum albumin(BSA) with different concentrations to improve the protein stmcture and physicochemical properties of the scaffold surface so as to enhance the adhesion of the cells. And the appropriate BSA concentration was explored. Compared with DBM, the scaffold with BSA coating had a smaller pore size and a lower porosity, also, the degradation rate was accelerated and the hydrophilic property was improved. Cells adhesion was observed inside the DBM seaffold before and after it had been modified, and the BSA modified scaffold had a good cell compatibility. Wlien the concentration of BSA was 20 mg/mL, the adhesion ability of the cells to modified scaffold was significantly increased, and the cell proliferation was facilitated.     

番红花红T与表面活性剂的作用及其在标记DNA中的应用

对阳离子染料番红花红Ｔ（ＳＴ）在阴离子表面活性剂存在时的溶液状态的吸收光谱和荧光光谱进行了研究。结果表明，低浓度阴离子表面活性剂与ＳＴ形成缔合物，导致ＳＴ的吸收与荧光强度降低；增大表面活性剂的浓度，其分子胶束前预聚集促使染料形成非荧光二聚体，导致荧光急剧猝灭，吸收光谱出现新的特征吸收峰；当表面活性剂浓度大于临界胶束浓度（ＣＭＣ）时，染料二聚体离解，ＳＴ单体增溶于胶团中形成新的高量子产率荧光体。本文     

Reflective thermal lens detection device

A reflective thermal lens detection device was developed for realizing a portable and sensitive detector for a microsystem. An aluminum mirror was formed on the main plate of a microchip, and a reflected probe beam was detected with a single pick-up unit. The background signal due to light absorption of the aluminum mirror was 60 times reduced when the microchannel and the mirror were separated with an interval of 600 microm. The tilt angle of the microchip significantly affected the precision of the measurement. Then a quadrant photodiode was used to detect the center of gravity of the reflected probe beam to regulate the tilt angle within +/-0.05 degrees , and this value was enough to achieve 1% CV (coefficient of variance) precision in the measurements. The limit of detection (LOD) was 60 nM for xylene cyanol solution, and the absorbance was 9.4 x 10(-6) AU. About 40 times higher sensitivity was obtained in comparison with a spectrophotometer.     

Investigation of thermal properties of high-temperature (1000–4000 K) systems by an arc spectroscopic method

An arc spectroscopic method was developed on the analogy of thermogravimetry. Using spectrographic recording, line intensity vs. arcing time relations were determined and transformed to weight loss vs. time curves for the components evaporated from a carbon electrode cavity. The temperature of a spot 3 mm below the bottom of the cavity was followed with a thermocouple and temperature of the bottom was calculated. As a first attempt the decomposition of tricalcium phosphate was investigated. It was estimated that in the reductive surroundings of the cavity the temperature at which the rate of decomposition was maximum, was about 2000°.