Functionalized inorganic-organic composite material derivated by sol-gel for construction of mediated amperometric hydrogen peroxide biosensor

A novel functionalized inorganic-organic hybrid material with cation exchange property was prepared by sol-gel method. The H2O2 biosensor was fabricated by simply dipping the horseradish peroxidase-containing functionalized membrane modified electrode into Meldola's blue (MDB) solution. MDB was adsorbed and firmly immobilized within the membrane. The electrochemical behavior of MDB incorporated in the membrane was more reversible compared with that of the solution species and suitable as mediator for the horseradish peroxidase. The response time was less than 25 s. Linear range is up to 0.6 mM (COH. coeff. 0.9998) with detection Limit of 9 x 10(-7) M. High sensitivity of 75 nA mu M cm(-2) was obtained due to high MDB-loading. The biosensor exhibited a good stability. (C) 1999 Elsevier Science B.V. All rights reserved.

Sodium sulfonate-functionalized poly(ether ether ketone)s

A new monomer, sodium 5,5'-carbonylbis(2-fluorobenzenesulfonate) (1), was synthesized by sulfonation of 4,4'-difluorobenzophenone (2) with fuming sulfuric acid. Poly(ether ether ketone)s containing sodium sulfonate groups were synthesized directly via aromatic nucleophilic substitution from the sodium sulfonate-functionalized monomer 1 and Bisphenol A (3) in the presence of potassium carbonate in dimethyl sulfoxide. The polycondensation proceeds without any side reactions. The differential scanning calorimetry measurement indicated that the polymers are amorphous and the glass transition temperatures increase with the content of sodium sulfonate groups in the polymer chain. The degree of substitution with sodium sulfonate groups has strong influence on their thermal stability and solubility.

Ac voltammetric and square wave voltammetric study of the self-assembled monolayers of thiol-functionalized viologen derivative

Electroactive self-assembled monolayers (SAMs) containing viologen group are formed through the adsorption of thiol-functionalized viologen compound CH3(CH2)(9)V2+(CH2)(8)SH, where V2+ is N,N'-dialkylbipyridinium (i.e. a viologen group), onto gold electrodes from methanol/water solution and its electrochemical behavior is investigated ty Ac voltammetry and square wave voltammetry, which have the high sensitivity against background charging. The viologen SAM formed is a sub-monolayer and the normal potentials corresponding to the two successive one-electron transfer processes of the active centers (viologen) are -360 mV and -750 mV (vs. Ag/AgCl) in 0.1 mol/L phosphate buffer solutions (pH 6.96) respectively, and the standard electron transfer rate constant is 9.0 s(-1). The electrochemical behavior of this SAM in various solutions has been preliminarily discussed.

FRACTIONATED CRYSTALLIZATION IN POLYOLEFINS-NYLON-6 BLENDS

The crystallization behavior of polyolefins-nylon 6 polymer blends was studied by differential scanning calorimetry (DSC) measurements. In these blends, the crystallization of the minor component often starts with distinctly deeper supercooling than that

Structural relation properties of hydrothermally stable functionalized mesoporous organosilicas and catalysis

The surfactant assistant syntheses of sulfonic acid functionalized periodic mesoporous organosilicas with large pores are reported. A one-step condensation of tetramethoxysilane (TMOS) with 1,2-bis(trimethoxysilyi)ethane (BTME) and 3-mercaptopropyltrimethoxysilane (MPTMS) in highly acidic medium was performed in the presence of triblock copolymer Pluronic P123 and inorganic salt as additive. During the condensation process, thiol (-SH) group was in situ oxidized to sulfonic acid (-SO3H) by hydrogen peroxide (30 wt % H2O2). X-ray diffraction studies along with nitrogen and water sorption analyses reveal the formation of stable, highly hydrophobic, and well-ordered hexagonal mesoscopic structures in a wide range of -CH2CH2-concentrations in the mesoporous framework. The resultant materials were also investigated by Si-29 MAS and C-13 CP MAS NMR, thermogravimetric analyses, UV-Raman spectroscopy, and FT-IR spectroscopy. The role of the bridged organic group on the hydrothermal stability of the mesoporous materials was established, which revealed an enhancement in hydrothermal stability of the materials with incorporation of the bridged organic groups in the network. The catalytic performance of -SO3H functionalized mesoporous materials was investigated in the esterification of ethanol with acetic acid, and the results demonstrate that the ethane groups incorporated in the mesoporous framework have a positive influence on the catalytic behavior of the materials.

Palladium-catalyzed asymmetric hydrogenation of functionalized ketones

A novel catalytic system for asymmetric hydrogenation of functionalized ketones has been developed using a Pd/bisphosphine complex as the catalyst in 2,2,2-trifluoroethanol. The reaction exhibits high enantioselectivity, and up to 92.2% ee was obtained.

Biological application of multi-component nanowires in hybrid devices powered by F-1-ATPase motors

In this paper, construction of hybrid device by integrating nanowires with F1-ATPase motors is described. The nickel nanowires and multi-segment nanowires, including gold and nickel, were fabricated by electrochemical deposition in nanoporous templates. The nickel nanowires functionalized by biotinylated peptide can be assembled directly onto F1-ATPase motors to act as the propellers. If the multicomponent nanowires, including gold and nickel, were selectively functionalized by the thiol group modified ssDNA and the synthetic peptide, respectively, the biotinylated F1- ATPase motors can be attached to the biotinylated peptide on nickel segment of the nanowires. Then, the multi-component nanowires can also be used as the propellers, and one may observe the rotations of the multi-component nanowires driven by F1-ATPase motors. Therefore, introduction of multiple segments along the length of a nanowire can lead to a variety of multiple chemical functionalities, which can be selectively bound to cells and special biomolecules. This method provides an insight for the construction of other hybrid devices with its controlling arrangement of different biomolecule on designed nanometer scale structures.

Applying the Electrochemical Deposition Technology to Construct the Hybrid Devices

Nanowires functionalized by special molecules can be used to as the candidates for biological application in many areas. In this paper, nickel nanowires, which were fabricated by electrochemical deposition and functionalized by biotinylated peptide, were applied to constructing the hybrid device powered by F-1-ATPase motors.

基于功能化磁性纳米材料的高灵敏聚离子选择性电极

聚离子如肝素和鱼精蛋白等在临床医学领域有着广泛的应用。快速准确地检测其浓度 对安全有效地使用聚离子具有指导意义。然而现有的检测手段已经不能满足人们的需要， 开发新的能够直接检测聚离子的传感器已成为迫切的需要。 聚离子电极的出现使人们找到了一种能够快速简便地检测聚离子的手段。利用掺杂了 合适的离子交换剂的聚合物膜，电极能够对聚离子产生明显的电位响应。这种响应的机理 是聚离子通过萃取从样品溶液进入有机相，与有机相中的离子交换剂形成离子对，从而导 致膜电位的变化。理论表明，通过加快萃取过程，电极的灵敏度能够得到显著提高。实验 证明，利用旋转圆盘电极可以有效降低扩散层厚度并增强传质，从而使电极的灵敏度得到 提高。然而旋转圆盘电极的装置比较复杂且容易产生信号噪音。 功能化的纳米粒子能够均匀分散在样品溶液中从而促进纳米粒子上功能基团与样品 分析物之间的反应，这是因为其粒径较小能够降低扩散层厚度增强传质。在众多的纳米粒 子中，磁性纳米粒子具有磁响应的特性，在许多方面具有潜在的应用价值。本文中我们报 道一种利用磁性纳米粒子快速灵敏检测聚离子的电位型分析方法。 实验中采用共沉淀法合成了磁性纳米粒子，并采用油酸钠作为分散剂。功能化磁性纳 米粒子通过蒸发溶剂，利用长链分子的非共价结合力修饰。透射电镜照片显示磁性纳米粒 子粒径均匀，平均粒径约为25 nm。X 射线衍射证明磁性纳米粒子为四氧化三铁，且无其 它杂质存在，用德拜-休克尔公式计算得纳米粒子粒径约为25 nm，与透射电镜表征的结果 相符。红外光谱的结果表明，磁性纳米粒子表面成功地包覆了油酸分子以及离子交换剂与 增塑剂，从而使磁性纳米粒子表面功能化。最后通过对离子交换剂用量的考察，得到了最 佳的功能化磁性四氧化三铁纳米粒子。 将功能化磁性纳米粒子与聚合物膜电极结合，开发了一种新的聚离子电极，并在 0.05-50 μg mL-1 的浓度范围内检测鱼精蛋白。考察了聚合物敏感膜组成与反应时间的影响， 得到了最优的检测条件。使用最大电位变化速率对鱼精蛋白浓度的对数作图，得到了在 0.05-5 μg mL-1 的浓度范围内的线性关系，建立了标准工作曲线，其检出限为0.033 μg mL-1。 控制实验说明，只有在磁场与功能化磁性纳米粒子都存在的条件下，电极才会产生明显的 电位变化。利用此电

Duplication and independent selection of cell-wall invertase genes GIF1 and OsCIN1 during rice evolution and domestication

Background: Various evolutionary models have been proposed to interpret the fate of paralogous duplicates, which provides substrates on which evolution selection could act. In particular, domestication, as a special selection, has played important role in crop cultivation with divergence of many genes controlling important agronomic traits. Recent studies have indicated that a pair of duplicate genes was often sub-functionalized from their ancestral functions held by the parental genes. We previously demonstrated that the rice cell-wall invertase (CWI) gene GIF1 that plays an important role in the grain-filling process was most likely subjected to domestication selection in the promoter region. Here, we report that GIF1 and another CWI gene OsCIN1 constitute a pair of duplicate genes with differentiated expression and function through independent selection. Results: Through synteny analysis, we show that GIF1 and another cell-wall invertase gene OsCIN1 were paralogues derived from a segmental duplication originated during genome duplication of grasses. Results based on analyses of population genetics and gene phylogenetic tree of 25 cultivars and 25 wild rice sequences demonstrated that OsCIN1 was also artificially selected during rice domestication with a fixed mutation in the coding region, in contrast to GIF1 that was selected in the promoter region. GIF1 and OsCIN1 have evolved into different expression patterns and probable different kinetics parameters of enzymatic activity with the latter displaying less enzymatic activity. Overexpression of GIF1 and OsCIN1 also resulted in different phenotypes, suggesting that OsCIN1 might regulate other unrecognized biological process. Conclusion: How gene duplication and divergence contribute to genetic novelty and morphological adaptation has been an interesting issue to geneticists and biologists. Our discovery that the duplicated pair of GIF1 and OsCIN1 has experiencedsub-functionalization implies that selection could act independently on each duplicate towards different functional specificity, which provides a vivid example for evolution of genetic novelties in a model crop. Our results also further support the established hypothesis that gene duplication with sub-functionalization could be one solution for genetic adaptive conflict.

功能化聚丙烯及其与聚对苯二甲酸丁二醇酯共混物的制备及结构性能研究

本工作通过电子束预辐照处理和反应挤出方法，制备了丙烯酸功能化预辐照聚丙烯rPP-g-AA，采用化学滴定和红外光谱方法均证明接枝共聚物的存在，同时确定了预辐照剂量和单体浓度对接枝率的影响：（1）当单体浓度一定时，接枝率随预辐照剂量的增加而增加并逐渐达到平台值；（2）当预辐照剂量固定时，单体浓度在0～4.0wt%范围内，接枝率几乎呈线性增加。研究发现，丙烯酸(AA)接枝链能起到异相成核作用而促进预辐照聚丙烯(rPP)的结晶过程，但却不改变结晶晶型；虽然接枝反应可以部分抑制降解反应，但相对于原料聚丙烯(PP)，接枝产物的力学性能仍大大下降；因此提出的反应机理认为接枝反应主要是通过链断裂降解反应形成的端自由基引发的，从而形成了以端基接枝为主的产物。 为了控制PP接枝过程中的严重降解，本工作首次提出了均相和异相引发接枝反应的原理，即采用部分rPP和预辐照聚乙烯(rPE)分别作为PP接枝反应的均相和异相“引发剂”，经反应挤出制备丙烯酸功能化聚丙烯PP-g-AA。对于均相引发体系：（1）当rPP用量为20phr时，PP-g-AA的接枝率已经达到rPP-g-AA的水平，而且降解反应得到有效控制；（2）和PP/rPP-g-AA共混物的对比研究证明，均相引发接枝产物不但接枝率明显提高，而且接枝分布非常均匀；（3）由此提出均相引发主要是发生rPP和PP分子间夺氢反应并形成以基体PP接枝为主的产物，而rPP分子内夺氢反应形成的接枝产物rPP-g-AA只占较少比例。对于异相引发体系： （1）通过红外光谱表征及接枝率计算得出异相引发接枝产物的接枝率比相应的PP/ rPE-g-AA共混物略高；（2）由于rPE及rPE-g-AA对基体PP的结晶没有影响，通过异相引发接枝产物中PP的结晶温度升高直接验证了异相引发接枝反应的实现；（3）提出的机理认为异相引发主要发生在rPE的分子内夺氢并形成rPE-g-AA，造成rPE引发的PP分子间夺氢反应形成PP-g-AA产物的比例下降。 本工作还详细研究了rPP预辐照剂量、rPP用量和单体浓度对均相引发反应的影响。得到的结果如下：（1）高预辐照剂量导致了接枝率下降的“假相”是由于形成的微凝胶造成的；（2）rPP用量的增大在提高接枝率的同时也导致降解反应的逐渐增强；（3）单体浓度的增加导致接枝率的逐步提高并最终达到最大值，而且可能导致部分微凝胶的产生；（4）接枝没有破坏PP-g-AA结晶的完善性和晶型，却能促进了晶体在（040）晶面的生长并可能产生部分横晶形态；（5）PP-g-AA和金属能形成良好的粘接作用。 以上述制备的rPP-g-AA和PP-g-AA增容PP/聚对苯二甲酸丁二醇酯(PBT)共混体系，发现高分子量的PP-g-AA比低分子量的rPP-g-AA的增容效果要好，因此认为PP-g-AA和PBT通过酯化反应形成的长链接枝共聚物PP-g-PBT对PBT相的分散和界面作用增强更加有效。而随着增容剂PP-g-AA比例的增加，原位反应生成的PP-g-PBT逐渐增加，使得PBT相分散和界面增强效果更加显著，因此共混物的力学性能也更佳；DSC研究发现，随着PBT相尺寸减小到1μm以下，PBT出现了结晶受限行为。 将引发剂rPP和单体AA加入到PP/PBT共混体系中实现了一步法反应增容，得到共混物的扭矩、相形态、力学性能都和分步法增容共混物的结果几乎相同，这说明一步法共混能使PBT产生良好分散并得到性能较佳的产物，从而为高分子合金材料制备提供了一种简单有效的方法。 采用该方法对AA、马来酸酐(MAH)和甲基丙烯酸甘油酯(GMA)三种单体的接枝和增容反应对比研究证明，AA的效果最好，MAH次之，而GMA的效果最差，分析认为，AA和MAH通过接枝反应形成PP-g-AA和PP-g-MAH，随后再和PBT发生酯化增容反应形成PP-g-MAH-PBT共聚产物，而GMA首先和PBT反应形成PBT-GMA，而后由长链PBT-GMA发生接枝反应生成PP-g-GMA-g-PBT，但是这种接枝反应的效率很低，由此造成增容效果较差。