N—BOC—8—氨甲基—2—萘甲酸的改进合成法

以２－萘甲酸为原料，经硝化，酯化，重氮化，选择性催化氢化，ＢＯＣ酸酐保护等六步反应，完成了Ｎ－ＢＯＣ－８氨甲基－２－萘甲酸（１ａ）的合成，为化合物１的合成提供了新的合成途径。     

桥联双（2—巯基—5—甲基—1,3,4—噻二唑）化合物及其配合物的合成和表征

通过２－巯基－５－甲基－１，３，４－噻二唑（１）与二溴乙烷（２ａ）或低聚乙二醇二溴化物（２ｂ￣２ｄ）反应，合成了四个新型非环中性离子配体低聚醚（３ａ￣３ｄ）及其与汞、钯形成的８个配合物。通过元素分析，ＵＶ，ＩＲ及＾Ｈ ＮＭＲ对它们的结构进行了表征。     

（＋）—1S,2R,5S—8—β—萘基薄荷醇的合成

以Ｒ－（＋）－Ｐｕｌｅｇｏｎｅ为起始原始经１，４－加成、溴代、水解、氧化等９步反应合成了手性辅助试剂（＋）－１Ｓ，２Ｒ，５Ｓ－８－β－萘基薄荷醇及其关向异构体（－）－１Ｒ，２Ｒ，５Ｓ－８－β萘基新薄荷醇，总收率分别为２４．０％和２２．６％。     

2—取代—1,7—二氧螺（4.4）壬—8—酮的合成研究

分别用Ｋ２ＣＯ３，１，５－二氮双环（４．３．０）壬－５－烯（ＤＢＮ）和四丁基氟化铵（ＴＢＡＦ）等碱催化３－（３－羟基丙基）－γ－丁烯酸内酯的分子内Ｍｉｃｈｅａｌ加成反应合成了２－取代－１，７－二氧螺（４．４）壬－８－酮     

2—[2‘—苯并噻唑偶氮]—1,8—二羟基萘—3,6—二磺酸的合成及与铝的显…

本合成了新的显色试剂２－［２＇－苯并噻唑偶氮］－１，８－二羟基萘－３，６－二磺酸，并研究了与铝的显色反应，在ＣＴＭＡＢ存在下，铝与试剂于ＰＨ７．０－８．０的缓冲溶液中的形成稳定的深紫红色络合物，组成为Ａｌ（Ⅲ）：Ｒ＝１：２，表观摩尔吸光系数为１．４６×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，铝浓度在０－５．０μｇ／２５ｍＬ范围内符合比尔定律。     

1—对甲苯磺酰基—2—氧代—2—苯氧基—3—芳基—1,4,2—二氮…

通过１－苯基本磺酰基硫脲（１）与亚磷酸三苯酯和取代苯甲醛在甲苯中进行的类Ｍａｎｎｉｃｈ反应合成１－对甲苯磺酰基－２－氧代－２－苯氧基－３－芳基－１，４，２－二氮磷杂环戊－５－硫酮（２）。本文对合成过程中所涉及到的副反应进行了初步探讨。     

新显色剂2—[2—（6—甲基—苯并噻唑）偶氮]—5—二甲氨基苯磺酸与钯（Ⅱ）…

合成了新试剂２－［２－（６－甲基－苯并噻唑）偶氮］－５－二氨基苯磺酸，并研究了其与钯（Ⅱ）的显色反应。实验表明，该试剂与钯（Ⅱ）反在生成１：１蓝色水溶性络合物，在阴离面活性剂十二烷基硫酸钠（ＳＤＳ）存在下可稳定２４ｈ，其最大吸收波长为６１５ｎｍ，表观摩尔吸光系数为７．９４×１０＾４．ｍｏｌ＾－＾１．ｃｍ＾－＾１。钯量在０－０．８μｇ／ｍｌ范围内符合比尔定律。本法是目前测定钯（Ⅱ）的高灵敏度显色反应     

5—（4‘—溴—2’—羧基苯偶氮）罗丹宁与铜（Ⅱ）的显色反应及其应用

本报道了新显色剂５－（４’－溴－２’－羧基苯偶氮）罗丹宁的合成及在水溶液中的离解常数Ｋ１和Ｋ２，研究了该显色剂与铜（Ⅱ）的显色反应，在弱酸性时，试剂与铜（Ⅱ）形成摩尔比２：１的络合物，摩尔吸光系数为８．９×１０＾４Ｌ．ｍｏｌ＾－１．ｃｍ＾－１。当铜的浓度在０～２．７ｍｇ／Ｌ的范围内符合比耳定律。用分光光度法测定了合金中铜的含量。     

2—[2‘—（6—溴—苯并噻唑）—偶氮]—1,8—二羟基萘—3,6—二磺酸的合成及…

本合成了一种新的苯并噻唑类显色试剂－－２－〔２′－（６－溴－苯并噻唑）－偶氮〕－１，８－二羟基萘－３，６－二磺酸（简称Ｂｒ－ＢＴＣＡ），并研究了其与钛的显色反应。在ＣＴＭＡＢ存在下，钛与试剂形成稳定的络合物，其ε６１６＝１．１５×１０＾５Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，组成为Ｔｉ（Ⅳ）：Ｒ：＝１：１，钛浓度在０－０．５ｍｇ／Ｌ范围内符合比尔定律，该方法灵敏度高，选择性好，并用于铝合金及硅铁试样中微     

用新试剂2[—5‘—氟—2’—砷酸基苯）偶氮]—1,8—二羟基—3,6—萘二磺酸荧光法

研究了试剂２－」５’－氟－２’－－砷酸基苯）偶氮「－１，８－二羟基－３，６－萘二磺酸与硼的荧光性能。硼与试剂形成１：２的强荧光配合物，其λｅｘ／λｅｍ＝２３４ｎｍ／３８０ｎｍ，Ｂ（Ⅲ）含量在０－３６０μｇ／Ｌ范围内呈良好线性关系，检测限为２．０６μｇ／Ｌ，据此建立了测定微量硼的新方法。     

Oriented Nickel Nanonetworks and Their Submicron Fibres as a Basis for a Transparent Electrically Conductive Coating

The paper demonstrates a technique for applying an oriented nickel network to a glass surface. The method is based on the chemical reduction of nickel salt. The shaping and orientation of the resulting system are carried out using a micellar template of a surfactant and a magnetic field. Submicron nickel fibres are used to impart unity to the plurality of individual-oriented nickel nanonetworks. The result is a single conductive coating on the surface of the glass, which has a transparency in the optical range. Investigations of the structure, chemical composition, morphology and electrical conductivity of the coating were performed.     

Development of Enzyme Conductometric Biosensor for Dopamine Determination in Aqueous Samples

Dopamine is a biologically active chemical that performs a number of vital functions as a hormone and neurotransmitter. Therefore, the determination of dopamine concentration in the human body is important for biomedical research. The content of dopamine in the blood varies depending on the age of a healthy person and can serve as a prognostic marker of many diseases. The aim of this work was to develop a new enzyme conductometric biosensor for the determination of dopamine in aqueous samples and to study the biosensor's analytical characteristics. The conductometric method of analysis with differential measurement mode was used in the work. Two pairs of gold interdigitated electrodes deposited on a sitall substrate were used as a conductometric transducer. The biorecognition element of the biosensor was based on laccase immobilized by glutaraldehyde cross-linking. The optimal conditions of laccase immobilization were selected. The influence of solution parameters (ionic strength, pH, buffer capacity) on the biosensor work was investigated. The biosensors demonstrated high sensitivity to dopamine (minimum limit of detection −7.8 μM) with the linear range up to 1 mM. The biosensor was highly selective and reusable. The proposed biosensor was tested regarding the possibility of its long-term storage under different conditions. The developed conductometric biosensor was proven to be suitable for measuring dopamine concentration in biological and pharmaceutical samples.     

离子印迹传感器选择性检测甲基汞离子

以甲基汞离子为模板,8-巯基喹啉为荧光单体,4-乙烯基吡啶为功能单体,乙二醇二甲基丙烯酸酯为交联剂,偶氮二异丁腈为引发剂,在二甲基亚砜溶剂中,以聚偏氟乙烯(PVDF)膜为支撑介质,65℃热引发聚合得到甲基汞离子荧光印迹膜。该荧光印迹膜对甲基汞离子表现出良好的选择性,最佳吸附pH值为7.0,检出限为3.5×10-7mol/L。将其作为吸附材料,应用于河水中甲基汞离子的分离和富集,结果表明,该传感器对甲基汞离子具有良好的选择性和特异性吸附,回收率达93%～104%。     

Scanning electrochemical microscopy-development of instrumentation utilizing piezo-bimorph X-Y scanners

The development of the instrumentation of a scanning electrochemical microscopy (SECM) is presented. The core of the SECM sensing system is constructed based on piezobimorph scanners, a mechanical micropositioner of multi-dimensional adjustment and ultramicroelectrodes. The control of the electrochemical cell and the SECM system is realized by a battery powered bipoteniostat and analog control circuits respectively with the control of a microcomputer work station. The demonstrations of SECM experiments are given on both a standard IDA sample and a silver electrode. Discussions on the resolution and quality of SECM image are made.     

Titanium Anodes with Active Coatings Based on Iridium Oxides: A Sublayer between the Active Coating and Titanium

An optimum composition and a technique for applying a protecting sublayer on titanium are substantiated experimentally. The sublayer prevents the oxidation of titanium during the production and application of highly porous metal oxide anodes. The formation of such a sublayer involves several stages: (a) coating chemically polished and etched in 5-% hydrofluoric acid titanium with hexachloroiridic acid, (b) drying hexachloroiridic acid, (c) a two-step treatment of anodes in argon with a low concentration of oxygen at 350°C, and (d) a brief annealing of the anodes in air at 400°C. The application of such a sublayer makes sense especially in the case of an anode with a thin highly porous active coating. The remarkable protecting properties of the sublayer are due to the formation of a dense coating on titanium. The coating consists of metallic iridium, titanium, and an amount of oxides of these metals. The titanium substrate itself undergoes minimum oxidation.     

Determination of Glucose in Diluted Blood with a Thermal Flow Injection Analysis Biosensor

Abstract

The glucose concentration in diluted whole blood has been measured, using a miniaturized thermal biosensor based on the enzyme thermistor principle. The biosensor is a small flow injection system. A sample volume of 20μl is injected into a flow of 50μl/min. The heat produced when the sample passes the enzyme column is measured with a thermistor connected to a Wheatstone bridge. The enzyme column contains glucose oxidase and catalase co-immobilized on a solid support material. Samples of whole blood usually cause problems in flow-systems. The blood cells tend to block the enzyme column and the back pressure increases. We have tested a superporous agarose material as enzyme support material using tenfold diluted samples of whole human blood. The blood was collected from the finger-tip and diluted with buffer containing an anticoagulant and sodium fluoride. The number of samples possible to inject and the accuracy compared to the Boehringer Mannheim Reflolux have been determined. At least 100 ten-fold diluted blood samples could be injected on a micro-column of superporous agarose. The obtained glucose concentration correlated well with the one obtained with the reference instrument.     

A designed well-folded monomeric four-helix bundle protein prepared by Fmoc solid-phase peptide synthesis and native chemical ligation

The design and total chemical synthesis of a monomeric native-like four-helix bundle protein is presented. The designed protein, GTD-Lig, consists of 90 amino acids and is based on the dimeric structure of the de novo designed helix-loop-helix GTD-43. GTD-Lig was prepared by the native chemical ligation strategy and the fragments (45 residues long) were synthesized by applying standard fluorenylmethoxycarbonyl (Fmoc) chemistry. The required peptide-thioester fragment was prepared by anchoring the free gamma-carboxy group of Fmoc-Glu-allyl to the solid phase. After chain elongation the allyl moiety was orthogonally removed and the resulting carboxy group was functionalized with a glycine-thioester followed by standard trifluoroacetic acid (TFA) cleavage to produce the unprotected peptide-thioester. The structure of the synthetic protein was examined by far- and near-UV circular dichroism (CD), sedimentation equilibrium ultracentrifugation, and NMR and fluorescence spectroscopy. The spectroscopic methods show a highly helical and native-like monomeric protein consistent with the design. Heat-induced unfolding was studied by tryptophan absorbance and far-UV CD. The thermal unfolding of GTD-Lig occurs in two steps; a cooperative transition from the native state to an intermediate state and thereafter by noncooperative melting to the unfolded state. The intermediate exhibits the properties of a molten globule such as a retained native secondary structure and a compact hydrophobic core. The thermodynamics of GuHCl-induced unfolding were evaluated by far-UV CD monitoring and the unfolding exhibited a cooperative transition that is well-fitted by a two-state mechanism from the native to the unfolded state. GTD-Lig clearly shows the characteristics of a native protein with a well-defined structure and typical unfolding transitions. The design and synthesis presented herein is of general applicability for the construction of large monomeric proteins.     

Thermoresponsive hydrogel of poly(glycidyl methacrylate‐co‐N‐isopropylacrylamide) as a nanoreactor of gold nanoparticles

The synthesis of a thermoresponsive hydrogel of poly(glycidyl methacrylate‐co‐N‐isopropylacrylamide) (PGMA‐co‐PNIPAM) and its application as a nanoreactor of gold nanoparticles are studied. The thermoresponsive copolymer of PGMA‐co‐PNIPAM is first synthesized by the copolymerization of glycidyl methacrylate and N‐isopropylacrylamide using 2,2′‐azobis(isobutyronitrile) as an initiator in tetrahydrofuran at 70 °C and then crosslinked with diethylenetriamine to form a thermoresponsive hydrogel. The lower critical solution temperature (LCST) of the thermoresponsive hydrogel is about 50 °C. The hydrogel exists as 280‐nm spheres below the LCST. The diameter of the spherical hydrogel gradually decreases to a minimum constant of 113 nm when the temperature increases to 75 °C. The hydrogel can act as a nanoreactor of gold nanoparticles because of the coordination of nitrogen atoms of the crosslinker with gold ions, on which a hydrogel/gold nanocomposite is synthesized. The LCST of the resultant hydrogel/gold nanocomposite is similar to that of the hydrogel. The size of the resultant gold nanoparticles is about 15 nm. The hydrogel/gold nanocomposite can act as a smart and recyclable catalyst. At a temperature below the LCST, the thermoresponsive nanocomposite is a homogeneous and efficient catalyst, whereas at a temperature above the LCST, it becomes a heterogeneous one, and its catalytic activity greatly decreases. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2812–2819, 2007     

C60笼内内陷粒子的运动

研究C60笼内内陷粒子的量力力学运动, 导出运动能量与波函数, 以内陷CO分子为例做了计算, 解释了分子对微波的吸收现象。     

Measurement of bubble size distribution in protein foam fractionation column using capillary probe with photoelectric sensors

Bubble size is a key variable for predicting the ability to separate and concentrate proteins in a foam fraction ation process. It is used to characterize not only the bubble-specific interfacial a rea but also coalescence of bubbles in the foam phase. This article describes the development of a photoelectric method for measuring the bubble size distribution in both bubble and foam columns for concentrating proteins. The method uses a vacuum to withdraw a stream of gas-liquid dispersion from the bubble or foam column through a capillary tube with a funnel-shaped inlet. The resulting sample bubble cylinders are detected, and their lengths are calculated by using two pairs of infrared photoelectric sensors that are connected with a high-speed data acquisition system controlled by a microcomputer. The bubble size distributions in the bubble column 12 and 1 cm below the interface and in the foam phase 1 cm above the interface are obtained in a continuous foam fractionation process for concentrating ovalbumin. The effects of certain operating conditions such as the feed protein concentration, superficial gas velocity, liquid flow rate, and solution pH are investigated. The results may prove to be helpful in understanding the mechanisms controlling the foam fractionation of proteins.