运用含有偶氮苯的自组装单层膜在光化学条件下可逆地控制细胞黏附

细胞生物学研究的一个重要方向是动态地控制细胞在基底上的黏附。最近，随着表面化学的研究深入，尤其是对烷基硫醇在金基底上形成自组装单层膜（self-assembled monolayers, SAMs）这一体系的研究，使得人们能在分子水平的表面上控制细胞黏附。精氨酸-甘氨酸-天冬氨酸（arginine-glycine-aspartate, RGD）序列首先是从细胞外基质蛋白中分离出来的，能够识别并非共价结合细胞膜表面的整合素受体，从而促进细胞黏附。以前的一些工作已经证实，将含有RGD的肽链连接到SAMs表面之后，能够生物特异性地黏附动物细胞。已有的手段比如光照、电压、加热、微电极、微流控以及表面纳米形貌的梯度变化，都不能真正实现可逆地控制细胞黏附，原因是这些方法所用的化学有限；这些方法也不能得到完全抗拒细胞黏附的表面，原因是这些方法产生的表面缺陷等不完整。用两种不同波长的光（紫外光和可见光）照射偶氮苯，偶氮苯会发生可逆的光致异构变化，因此，偶氮苯的光致异构性质可以用来可逆地控制细胞在表面黏附。运用含有偶氮苯的混合SAMs，偶氮苯的末端连接GRGDS肽，混合SAMs中是以末端为六聚乙二醇的硫醇为背景，该SAMs修饰而成的表面能够黏附或者抗拒细胞黏附，其表面黏附性质取决于SAMs中偶氮苯的构象。该方法提供了一种在分子水平的表面上我们所了解到的唯一能可逆控制细胞黏附的方法，该方法需要用到的光源来自于标准荧光显微镜所配置的汞灯。 为了实现在金基底表面可逆的控制细胞黏附，我们合成了如下三个化合物： 由于化合物1的溶解性很差，几乎在所有溶剂里都不溶，所以不能直接用化合物1制备SAMs；化合物2能高效地抗拒细胞的黏附；化合物3的偶氮苯末端是活化酯，能够连接GRGDS肽，从而控制细胞黏附。 将化合物2和化合物3以一定的比例均匀混合在金基底表面形成SAMs，然后将GRGDS肽连接到偶氮苯(反式)的末端（通过GRGDS肽的甘氨酸上的伯胺基与偶氮苯末端的活化酯反应），从而得到细胞黏附的表面。用紫外光照射该细胞黏附表面5-10小时，随着偶氮苯的构象由反式变为顺式，偶氮苯末端的GRGDS肽淹没在化合物2的六聚乙二醇中，得到抗拒细胞黏附的惰性表面。再用可见光照射该惰性表面1个小时，随着偶氮苯的构象由顺式变为反式，原先埋没在六聚乙二醇中的GRGDS肽伸展至单层膜的末端，又得到了细胞黏附的表面。因此，该表面能完全可逆地控制细胞在金表面黏附。 An important area in cell biology is the dynamic control of cell adhesion on substrates. Recent advancements in surface chemistry, in particular, self-assembled monolayers (SAMs) of alkanethiols on gold substrates, have permitted unprecedented control of cell adhesion via molecularly defined surfaces. The tri-peptide sequence arginine-glycine-aspartate (RGD), initially isolated from the extracellular matrix (ECM) proteins, can recognize and non-covalently bind with integrin receptors on cell membranes to promote cell adhesion. Some previous work has demonstrated that RGD peptide grafted on SAMs can allow bio-specific adhesion of mammalian cells that mimic natural adhesion. Existing technologies such as light, voltage, heat, microelectrodes, microfluidic systems and surface gradient of nanotopography, either cannot realize fully reversible control of cell adhesion, due to the limitation in the chemistry used, or cannot yield a surface completely resistant against cell adhesion, due to the imperfection of surfaces. Azobenzenes undergo reversible photo-induced isomerization rapidly at two different wavelengths of light (UV and visible light), it therefore potentially allows the reversible control of cell adhesion on a surface. By using a mixed SAMs presenting azobenzene groups terminated in GRGDS peptides in a background of hexa(ethylene glycol) groups, the surface can either accommodate or resist cell adhesion depending on the conformation of the azobenzene embedded in SAMs. This method provides the only means we know to control cell adhesion reversibly on a molecularly well-defined surface by using light generated by a mercury lamp equipped on standard fluorescence microscopes. To realize the reversible control of cell adhesion on gold surface, we synthesized three kinds of compounds as following, We found that it was difficult to obtain SAMs directly from compound 1 because of its poor solubility in almost all kinds of solvents; compound 2 can resist cell adhesion efficiently; compound 3 presents an azobenzene terminated with NHS-activated ester, which can couple with a GRGDS peptide to control cell adhesion. After coating a gold surface with compound 2 and 3 in appropriate ratios to form a SAM followed by coupling the GRGDS peptides with NHS-activated esters at the end of azobenzene (E configuration) resulted in a cell-adhesive SAM. Irradiating this cell-adhesive SAM with UV light for 5-10 h converted the E configuration of azobenzene into the Z form, the GRGDS peptides becoming masked in the PEG, resulting in a cell-resistant surface. These SAM could again support cell adhesion as a result of the conformational switch of azobenzene from Z to E with the irradiation of visible light for 1 h. This surface, therefore, allows completely reversible control of cell adhesion on a gold surface.

NOx storage-reduction over Pt/Mg-Al-O catalysts with different Mg/Al atomic ratios

A series of Pt/Mg-Al-O catalysts with different Mg/Al atomic ratios were prepared. The NOx storage capacities of these catalysts were measured by isothermal storage at 350 degreesC. It was found that the NOx storage capacity increased with increasing Mg/Al atomic ratios. The catalytic behaviors of Pt/Mg-Al-O and Pt/MgO were studied with storage-reduction cycles at 400 degreesC. Under oxidizing conditions, NOx concentration in the outlet gas gradually increased with time, which indicated the catalysts could store NOx effectively. After a switch from oxidizing conditions to reducing conditions, NOx desorption peak emerged immediately due to the incomplete reduction of stored NOx, which lowered the total NOx conversion. With increasing Mg/Al atomic ratio in the catalysts, NOx conversion increases. Pt/MgO has the highest NOx conversion because of its best activity in the reduction of NOx by C3H6. It seems that with an increasing amount of MgO in the catalysts, the self-poisoning of Pt-sites by adsorbed species during the reaction of NOx with C3H6 may be inhibited effectively.

过量Mg~(2+)对农作物种子萌发特性的影响(英文)

[Objective] The research aimed to reveal the effects of excessive Mg2+ on the germination characteristics of maize and soybean. [Method] Eleven concentration gradients of Mg2+ including 0,40,80,120,160,200,240,280,320,360 and 400 mmol/L were set up to study the effects of different treatments on such indices as the germination potential,germination rate,fresh weight,dry weight,root length,plant height and stem diameter of maize and soybean. [Result] With the increasing of Mg2+ concentration,the germination of maize delayed and the germination rate of soybean obviously decreased,reaching the significant difference at 0.05 level. When Mg2+ concentration increased,the fresh weight and dry weight of maize and soybean decreased,but maize and soybean showed some adaptability. The growth of radicles and seedlings in maize and soybean were obviously inhibited by Mg2+,and atrophy and dysplasia phenomena appeared. [Conclusion] Excessive Mg2+ stress has different effects on the germination potential and germination rate of different crops and has obvious poisoning effects on the root and stem growth of crops.

Protein A immobilized monolithic capillary column for affinity chromatography

Monolithic capillary columns for affinity chromatography were prepared by an in situ polymerization procedure using glycidyl methacrylate (GMA) as a monomer and trimethylolpropane trimethacrylate (TRIM) and ethylene dimethacrylate (EDMA) as cross-linkers, respectively. Scanning electron microscopy was applied to characterize the morphology of the end of monolithic capillary and mercury intrusion porosimetry to characterize the polymer rod prepared within the confines of a stainless steel column with 50 mm x 4.6 mm i.d. under the same polymerization condition. Obvious differences in the porous properties between the TRIM- and EDMA-based monoliths could be observed. Moreover, the mechanical stability of these two monolithic capillary columns was compared by testing the reproducibility of the column performance. The rod prepared with GMA and TRIM proved to be mechanically more stable than that prepared with GMA and EDMA. Protein A was immobilized on the monolithic rod for affinity chromatography and the experiments were performed on a capillary electrophoresis instrument, using its pressure system as the driving force. Non-specific adsorption was not observed on the TRIM-based affinity column, as proved with bovine serum albumin (BSA) as a test protein. The affinity column prepared with GMA and TRIM was then applied to determine the hIgG concentration in human serum. The correlative coefficient of the calibration curve reached 0.9942. The amount of adsorbed hIgG was unaffected by the flow rate of the loading buffer, which makes this method suitable for fast determination of biomacromolecules in microliter samples. (C) 2002 Elsevier Science B.V All rights reserved.

Automated voltammetric system for shipboard determination of metal speciation in sea water

An automated and semi-intelligent voltammetric system is described for trace metal analysis. The system consists of a voltammeter interfaced with a personal computer, a sample changer, 2 peristaltic pumps, a motor burette and a hanging mercury drop electrode. The system carries out fully automatically approximately 5 metal determinations per hour (including at least 3 repetitive scans and calibration by standard addition) at trace levels encountered in clean sea water. The computer program decides what level of standard addition to use and evaluates the data prior to switching to the next sample. Alternatively, the system can be used to carry out complexing ligand titration with copper whilst recording the labile copper concentration; in this mode up to 8 full titrations are carried out per day. Depth profiles for chromium speciation in the Mediterranean Sea and a profile for copper complexing ligand concentrations in the North Atlantic Ocean measured on board-ship with the system are presented. The chromium speciation was determined using a new method to differentiate between Cr(III) and Cr(VI) utilizing adsorption of Cr(III) on silica particles.

Nontoxic electrodes of solid amalgams

This is a review of electrodes based on nontoxic solid amalgams (MeSAE) (prepared by amalgamation of soft metal powders) in connection with some other kinds of voltammetric electrodes is given. Information is summarized on various types of MeSAEs (esp. AgSAE, CuSAE, AuSAE), pretreatment of their surfaces, their hydrogen overvoltage in aqueous solutions, conditions for their testing, electroanalytical parameters and use, in compared with the hanging mercury drop electrode (HMDE). Although the solid amalgam electrodes do not reach the quality of the HMDE, in many cases they represent its possible alternative. The broad range of voltammetric applications of the MeSAEs, especially of the AgSAEs, their good mechanical stability, simple handling, and new aspects of their use in electrochemical techniques are documented by numerous examples.

Stripping voltammetric determination of Pb(II) and Cd(II) based on the multiwalled carbon nanotubes-Nafion-bismuth modified glassy carbon electrodes

In this work, a new method for the simultaneous determination of Pb(II) and Cd(II) on the multiwalled carbon nanotubes (MWNT)-Nafion-bismuth modified glassy carbon electrode (GCE) using square-wave anodic stripping voltammetry has been studied. Scanning electron microscopy was used to investigate the characteristics of the MWNT-Nafion-bismuth modified GCE.

Bluish-white emission from radical carbonyl impurities in amorphous Al2O3 prepared via the Pechini-type sol-gel process

Many efforts have been devoted to exploring novel luminescent materials that do not contain expensive or toxic elements, or do not need mercury vapor plasma as the excitation source. In this paper, amorphous Al2O3 powder samples were prepared via the Pechini-type sol-gel process. The resulting samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FESEM), photoluminescence (PL) excitation and emission spectra, kinetic decay, and electron paramagnetic resonance (EPR).

Electrodeposition of platinum nanoclusters on type I collagen modified electrode and its electrocatalytic activity for methanol oxidation

We firstly reported a novel polymer matrix fabricated by type I collagen and polymers, and this matrix can be used as nanoreactors for electrodepositing platinum nanoclusters (PNCs). The type I collagen film has a significant effect on the growth of PNCs. The size of the platinum nanoparticles could be readily tuned by adjusting deposition time, potential and the concentration of electrolyte, which have been verified by field-emitted scanning electron microscopy (FE-SEM). Furthermore, cyclic voltammetry (CV) has demonstrated that the as-prepared PNCs can catalyze methanol directly with higher activity than that prepared on PSS/PDDA film, and with better tolerance to poisoning than the commercial E-TEK catalyst. The collagen-polymer matrix can be used as a general reactor to electrodeposit other metal nanostructures.

Highly efficient electrocatalytic oxidation of formic acid by electrospun carbon nanofiber-supported PtxAu100-x bimetallic electrocatalyst

Electrospun carbon nanofiber-supported bimetallic PtxAu100-x electrocatalysts (PtxAu100-x/CNF) were prepared by electrochemical codeposition method. The composition of PtAu bimetallic nanoparticles could be controlled by varying the ratio of H2PtCl6 and HAuCl4. Scanning electron microscopy images showed that bimetallic nanoparticles had coarse surface morphology with high electrochemically active surface areas. X-ray diffraction analysis testified the formation of PtAu alloys. PtxAu100-x/CNF electrocatalysts exhibited improved electrocatalytic activities towards formic acid oxidation by providing the selectivity of the reaction via dehydrogenation pathway and suppressing the formation/adsorption of poisoning CO intermediate, indicating that PtxAu100-x/CNF is promising electrocatalyst in direct formic acid fuel cells.

Structural and Bluish-White Luminescent Properties of Li+-Doped BPO4 as a Potential Environmentally Friendly Phosphor Material

Many efforts have been devoted to exploring novel luminescent materials that not contain expensive or toxic elements, or do not need a mercury vapor plasma source. In this paper, BPO4 and Li+-doped BPO4 powder samples were prepared by the Pechini-type sol-gel (PSG) process. The structure and optical properties of the resulting samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FESEM), photoluminescence (PL) excitation and emission spectra, kinetic decay, and X-ray photoelectron spectra (XPS), respectively. It was found that PSG -derived Li+-doped BPO4 annealed at 960 degrees C exhibited bright bluish-white emission centered at 416 nm. The luminescence decay curves analysis indicates that each sample has two kinds of lifetimes (5.9 ns and 0.529 ms) and two types of kinetic decay behaviors which can be fitted into a single-exponential function and a double-exponential function, respectively.

Sensitive and Selective Sensor for Biothiols in the Cell Based on the Recovered Fluorescence of the CdTe Quantum Dots-Hg(II) System

Herein, a sensitive and selective sensor for biothiols based on the recovered fluorescence of the CdTe quantum dots (QDs)-Hg(II) system is reported. Fluorescence of QDs could be quenched greatly by Hg(II). In the presence of biothiols, such as glutathione (GSH), homocysteine (Hcy), and cysteine (Cys), however, Hg(H) preferred to react with them to form the Hg(II)-S bond because of the strong affinity with the thiols of biothiols rather than quenching the fluorescence of the QDs. Thus, the fluorescence of CdTe QDs was recovered. The restoration ability followed the order GSH > Hcy > Cys due to the decreased steric hindrance effect. A good linear relationship was obtained from 0.6 to 20.0 mu mol L-1 for GSH and from 2.0 to 20.0 mu mol L-1 for Cys, respectively. The detection limits of GSH and Cys were 0.1 and 0.6 mu mol L-1, respectively. In addition, the method showed a high selectivity for Cys among the other 19 amino acids. Furthermore, it succeeded in detecting biothiols in the Hela cell.