DTPA—Eu^3＋螯合物在核酸杂交分析中的应用

报道了靶ＤＮＡ／生物素化λＤＮＡ探针／亲合素／Ｂｉｏ－ＢＳＡ（ＴＧ－Ｅｕ＾３＋体在核酸杂交分析中的应用，亲合素做为连结杂交体与ｉｏ－ＢＳＡ－ＤＴＰＡ－Ｅｕ＾３＋的桥，生物素和ＤＴＰＡ－Ｅｕ＾３＋均标记在载体蛋白（ＢＳＡ，ＴＧ）上，优化了分析条件，比较了己二胺，乙二胺转胺化探针及载体蛋白对杂交分析的影响，方法灵敏度高，重现性较好（ＲＳＤ－５．７％，ｎ＝６）。     

稀土离子与NAD^＋和NAD—LDH相互作用的伏安行为研究

报道了稀土离子与ＮＡＤ＾＋和ＮＡＤ－ＬＤＨ相互作用的伏安行为，研究结果表明，稀土离子能够与ＮＡＤ＾＋发生作用，使ＮＡＤ＾＋在－０．９４Ｖ处的还原峰分裂为２个还原峰；ＮＡＤ＾＋和ＬＤＨ在汞电极上可形成络合物，络合物的还原峰在－１．１６Ｖ处，加５μｍｏｌ／ＬＬａ＾３＋，Ｃｅ＾３＋，Ｐｒ＾３＋，Ｅｕ＾３＋，Ｇｄ＾３＋，Ｄｙ＾３＋，Ｙｂ＾３＋和Ｌｕ＾３＋离子，能增大ＮＡＤ－ＬＤＨ络合物的解离常数约４０％～     

DTPA－Eu~（3＋）螯合物在核酸杂交分析中的应用

报道了靶ＤＮＡ／生物素化λＤＮＡ探针／亲合素／Ｂｉｏ－ＢＳＡ（ＴＧ）－ＤＴＰＡ－Ｅｕ~（３＋）体系在核酸杂交分析中的应用。亲合素做为连结杂交体与Ｂｉｏ－ＢＳＡ－ＤＴＰＡ－Ｅｕ~（３＋）或Ｂｉｏ－ＴＧ－ＤＴＰＡ－Ｅｕ~（３＋）的桥，生物素和ＤＴＰＡ－Ｅｕ~（３＋）均标记在载体蛋白（ＢＳＡ，ＴＧ）上。优化了分析条件，比较了己二胺、乙二胺转胺化探针及载体蛋白对杂交分析的影响。方法灵敏度高（１ｐｇ／ｗｅｌｌ靶λＤＮＡ），重现性较好（ＲＳＤ＝５．７％，ｎ＝６）。     

金属离子与卟啉的嵌入反应动力学研究──Ⅶ．一元酸根催化Cu(Ⅱ)与溴化间－四(N－乙酸甲酯基－3－吡啶基)卟啉的配位反应

研究了在３５±０．１℃、离子强度０．５ｍｏｌ／Ｌ（ＫＣｌ）条件下，甲酸根、乙酸根、丙酸根和丁酸根分别催化Ｃｕ（Ⅱ）离子与四溴化间－四（Ｎ－乙酸甲酯基－３－吡啶基）卟啉（Ｈ２Ｔβ－Ｎ－ＡＣＭｓｐｙＰＢｒ４）的反应动力学及其机理，该类反应对卟啉和Ｃｕ（Ⅱ）离子均为一级反应，反应动力学方程为：ｄ［ＣｕＰ＾４＋］／ｄｔ＝ｋ｛１．０＋ｂ［Ａ＾－］）／（１．０＋Ｋ３，４．［Ｈ＾＋］＾２｝［Ｃｕ＾２＋］［Ｐ］Ｔ     

金属卟啉－甲基紫精二连体配合物的合成及其光化学行为

本文合成了四（对－氯代甲基）苯基－甲基紫精卟啉及其Ｚｎ，Ｃｏ，Ｍｎ配合物，用元素分析、红外光谱和紫外可见光谱进行了表征。研究了它们的光化学性质。结果表明，在ＴＥＯＡ中光照使Ｍ。ＴＣＭＰＰ－ｍｖ＾２＋发生了分子内从卟啉到甲基紫精的电子迁移反应。在ＺｎＴＣＭＰＰ－ｍｖ＾２＋／ＴＥＯＡ／ＤＭＳＯ－Ｈ２Ｏ体系中可发生光敏化还原ｍｖ＾２＋反应，生成较稳定的ｍｖ＾＋。在Ｍｎ（Ⅲ）ＴＣＭＰＰ－ＭＶ＾２＋／ＣＨ３     

HYDROLYTIC CLEAVAGE OF ACMET-GLY PROMOTED BY CIS-[Pd(MET)(D_2O)_2](NO_3)_2

ＨＹＤＲＯＬＹＴＩＣＣＬＥＡＶＡＧＥＯＦＡＣＭＥＴ－ＧＬＹＰＲＯＭＯＴＥＤＢＹＣＩＳ－［Ｐｄ（ＭＥＴ）（Ｄ２Ｏ）２］（ＮＯ３）２￥ＸｉａｏＨｕａＣＨＥＮ；ＬｏｎｇＧｅｎＺＨＵ；Ｎ．Ｍ．Ｋｏｓｔｉｃ（ＣｏｏｒｄｉｎａｔｉｏｎＣｈｅｍｉｓｔｒｙＩｎｓｔｉ...     

β—型过渡元素三取代钨锗杂多配合物的合成,表征和催化活性

报道Ａ－β－Ｍ＇ｘＨｙ－［ＧｅＷＯＭ３（Ｈ２Ｏ）３Ｏ３７］．ｎＨ２Ｏ（Ｍ＝Ｃｒ＾３＾＋，Ｃｏ＾２＾＋，Ｎｉ＾２＾＋，Ｃｕ＾２＾＋；Ｍ＇＝Ｂｕ４Ｎ＾＋，Ｋ＾＋）的立体有择合成法制备及红外和远红外光谱，紫外和可见光谱和循环伏安，磁化率和磁矩，ＸＰＳ，ＥＳＲ以及催化活性等研究结果。     

PTFE—乙醚柱反相萃取层析连续分离和测定镓（Ⅲ）铟（Ⅲ）的研究

研究了在抗坏血酸存在下的６ｍｏｌ／Ｌ ＨＢｒ介质作流动相，以ＰＴＦＥ（聚四氟乙烯）负载的乙醚作固定相，反相萃取层析使微量Ｇａ（Ⅲ），Ｉｎ（Ⅲ）与Ｆｅ＾３＋、Ｔｌ＾３＋、Ｍｏ＾６＋、Ａｕ＾３＋、Ｔｉ＾４＋、Ｂｉ＾３＋、Ａｌ＾３＋、Ｍｇ＾２＋、Ｃａ＾２＋、Ｎｉ＾２＋、Ｃｏ＾２＋、Ｃｄ＾２＋、Ｚｎ＾２＋、Ｐｂ＾２＋、Ｃｕ＾２＋等多种离子分离。留于柱上的铟、镓分别用ＨＣｌ（４ｍｏｌ／Ｌ）－Ｈ２Ｏ２（３％）     

（η^2—C70）Pd（PPh3）2）配合物的合成和光电性能研究

在惰性气氛中由取代反应合成出（η＾２－Ｃ７０）Ｐｄ（ＰＰｈ３）２配合物，在光电化学电池中测定了（η２－Ｃ７０）Ｐｄ（ＰＰｈ３）２在ＧａＡｓ电极上形成的ｎ＋ｎ型异质结光伏效应，结果表明，在Ｉ２／Ｉ３电对介质中（η＾２－Ｃ７０）Ｐｄ（ＰＰｈ３）２有较大的光伏效应值；当（η＾２－Ｃ７０）Ｐｄ（ＰＰｈ３）２的薄膜厚度为１μｍ时光伏效应最大；（η＾２－Ｃ７０）Ｐｄ（ＰＰｈ３）２在ＧａＡｓ电极上的光电转换性能     

镧系元素Dawson结构钨钒磷四元杂多配合物的合成,表征以…

合成了通式为Ｋ１５Ｈ３〔Ｃｅ（Ｐ２Ｗ１６ＶＯ６１）２〕．６１Ｈ２Ｏ、Ｋ１５Ｈ４〔Ｌｎ（Ｐ２Ｗ１６ＶＯ６１）２〕．ｘＨ２Ｏ（Ｌｎ＝Ｌａ＾３＋，Ｐｒ＾３＋，Ｎｄ＾３＋，Ｓｍ＾３＋，Ｅｕ＾３＋，Ｇｄ＾３＋，Ｄｙ＾３＋，Ｙｂ＾３＋）的９种镧系元素Ｄａｗｓｏｎ结构的钨钒磷四元杂多配合物，并用ＩＲ、ＵＶ、ＮＭＲ、ＥＳＲ、ＸＲＤ、ＴＧ－ＤＴＡ等对其结构和性质进行子研究。该类配合物具有与Ｋ１６〔Ｃｅ（Ｐ２Ｗ１７Ｏ     

ss-DNA在纳米金上固载和杂化的电化学传感研究

将2-氨乙基硫醇(AET)固载到玻碳电极(GCE)表面,进而化学吸附纳米金(NG),并在纳米金上固载ss-DNA得到ss-DNA/NG/AET/GCE,以Co(bpy)₃³⁺为电化学指示剂可以识别研究ss-DNA的杂化反应.结果表明,纳米金能使固载其上的ss-DNA发生部分变性而结合Co(bpy)₃³⁺,但用pH7.0的磷酸缓冲液浸泡可基本上避免这种变性,并明显提高杂化反应的识别能力.结合在ds-DNA/NG/AET/GCE上的Co(bpy)₃³⁺的峰电流与扫速的线性关系可保持到80mV/s.与电沉积法固载纳米金相比较,本电极更稳定和可靠.     

Electrochemical biosensor based on nanogold-modified poly-eriochrome black T film for BCR/ABL fusion gene assay by using hairpin LNA probe

A novel electrochemical biosensor is described for detection of breakpoint cluster region gene and a cellular abl (BCR/ABL) fusion gene in chronic myelogenous leukemia (CML) by using thiolated-hairpin locked nucleic acids (LNA) as the capture probe. The hairpin LNA probe was immobilized on the nanogold (NG)/poly-eriochrome black T (EBT) film-modified glassy carbon electrode (GCE). The immobilized LNA probe could selectively hybridize with its target DNA on LNA/NG/EBT/GCE surface. The immobilization and hybridization of the LNA probe were characterized with cyclic voltammetry and electrochemical impedance spectroscopy. The hybridization of the immobilized LNA probe with the target DNA was detected by differential pulse voltammetry with the electroactive methylene blue as an indicator. The results indicated this new method has excellent specificity for single-base mismatch and complementary after hybridization, and a high sensitivity. This novel electrochemical biosensor has been used for assay of PCR real sample with satisfactory result.     

碳纳米管负载铂修饰玻碳电极用于电化学发光的研究及其对富马酸酮替芬的测定

在玻碳电极上制备了碳纳米管负载纳米铂修饰电极(Pt-MWCNTs/GCE)。考察了联吡啶钌和富马酸酮替芬在3个不同电极上的电化学及其发光行为,并对其进行了对比。结果表明,在Pt-MWCNTs/GCE上富马酸酮替芬对联吡啶钌的电化学发光强度有明显的增敏作用,其增敏效果约为MWCNTs/GCE电极的2倍,约为裸玻碳电极的3.5倍,据此,建立了一种Pt-MWCNTs/GCE电极上电化学发光法检测富马酸酮替芬的新方法。在优化实验条件下,富马酸酮替芬的浓度在1.0×10-7～1.0×10-4mol/L范围内与其相对发光强度呈线性关系,线性回归方程为I=48.805×106c+221.03(r=0.9969),检出限为2.4×10-9mol/L,连续平行测定1.0×10-5mol/L的富马酸酮替芬溶液5次,发光强度的RSD为3.3%。对样品进行回收率实验,回收率为99%～104%,RSD为2.1%。     

石墨电极固载DNA的一种新修饰方法

首次报道通过充石蜡石墨电极电化学氧化腐蚀制备的微孔穴电极,成功地用于 ss-DNA的固载和杂化反应,证明了这种微孔穴石墨充石蜡电极可以固载较多量的 ss-DNA（包括解链的小牛胸腺DNA和15-mer ss-DNA）,可以成为性能良好的DNA杂 化探针。用Co(phen)_3~(3+)电化学指示剂和循环伏安方法,讨论了电极预氧化腐 蚀的时间和ss-DNA固载时间的影响,提出了DNA探针在微孔穴三维结构中固载的可 能机理。     

Cuprous Oxide/Nitrogen-doped Graphene Nanocomposites as Electrochemical Sensors for Ofloxacin Determination

Cu₂O/nitrogen-doped grapheme(NG) nanocomposite material was prepared via a facile one step chemical reduction and characterized by means of X-ray diffraction(XRD) and scanning electron microscopy(SEM). A new electrochemical sensor was then fabricated by coating Cu₂O/nitrogen-doped graphene nanocomposite with Nafion on glassy carbon electrode(Cu₂O/NG/Nafion/GCE). The electrochemical response of this modified electrode toward ofloxacin was examined by cyclic voltammetry. The results indicate that Cu₂O/NG/Nafion composite-modified electrode exhibits higher catalytic activity in the electrochemical oxidation of ofloxacin compared with glassy carbon electrode(GCE), Cu₂O/Nafion modified electrode(Cu₂O/Nafion/GCE), and N-doped graphene/Nafion modified electrode(NG/Nafion/GCE). Under optimal conditions, the peak current was found to be linearly proportional to the concentration of ofloxacin in the 0.5-27.5 μmol/L and 27.5-280 μmol/L ranges with a lower detection limit of 0.34 μmol/L, higher sensitivity of 39.32 μA·L·mmol^-1 and a shorter reaction time of less than 2 s. In addition, Nafion can enhance the stability of the modified electrode and prevent some negative species. Thus the modified electrode exhibits good selectivity and a long working life. The Cu₂O/NG/Nafion composite modified electrode shows promising application in electrochemical sensors, biosensors, and other related fields because of its excellent properties.     

Reduced Graphene Oxide Supported Cobalt Bipyridyl Complex for Sensitive Detection of Methyl Parathion in Fruits and Vegetables

Herein, we are described a green route to prepare reduced graphene oxide supported cobalt inorganic complex nanocomposite (GRGO/[Co(bpy)₃]) (bpy=2,2′‐bipyridine) through facile and wet chemical approach. The formation of the nanocomposite was confirmed through suitable physical and chemical characterization techniques. The GRGO/[Co(bpy)₃] nanocomposite was coated on the pretreated glassy carbon electrode (GCE). The GCE/GRGO/[Co(bpy)₃] modified electrode has excellent electrocatalytic ability towards methyl parathion reduction, while the overpotential drops drastically to –0.18 V (vs. Ag/AgCl). Moreover, the effect of concentration, scan rate and electrolyte pH were detail studied. Besides, the linear response range was 0.05‐1700 μM and the detection limit was 0.0029 μM (S/N=3) and the sensitivity was 1.8197 μA μM⁻¹ cm⁻². Moreover, the fabricated electrode has high level of selectivity, which delivers satisfactory repeatability, reproducibility and stability. The sensing method was successfully demonstrated in real samples such as, tomato and apple samples.     

Fabrication of Nanocomposite Containing Naphthoquinone and Nanogold Supported on Poly(2,6‐pyridinedicarboxylic acid) Film for Voltammetric Determination of N‐Acetyl‐L‐Cysteine

A modified electrode was fabricated by grafting of poly (2,6‐pyridinedicarboxylic acid) film (PDC) by electropolymerization of 2,6‐pyridinedicarboxylic acid on the glassy carbon electrode (GCE). Then, gold nanoparticles (NG) and 1,2‐naphthoquinone‐4‐sulfonic acid sodium (Nq) were immobilized on the PDC/GCE to prepare Nq/NG/PDC/GCE by immersing electrode into NG and Nq solution, respectively. The Nq species on NG/PDC/GCE could catalyze electrooxidation of N‐acetyl‐L ‐cysteine (NAC) with lowering the over potential by about 600 mV. This method used for detection of NAC in dynamic range from 4.0×10^?6 M to 1.30×10^?4 M with a detection of limit (2σ) 8.0×10^?7 M.     

One pot synthesis of Ru(bpy)_3~(2+) doped graphene oxide-silica composite film for constructing high performance solid-state electrochemiluminescent sensor

The Ru(bpy)_3~(2+) doped graphene oxide-silica composite film(Ru/GO-SiCF) was synthesized by one pot hydrolysis and condensation of tetraethylorthosilicate(TEOS) in the water-alcohol solution of graphene oxide and Ru(bpy)_3~(2+) at room temperature.The prepared Ru/GO-SiCF modified glassy carbon electrode(GCE) showed excellent electrochemiluminescence(ECL) behavior for the determination of tripropylamine(TPA) with high sensitivity and good stability.We expected this simple and novel material will find further application in construction of other targets sensors.     

以乙二胺为手臂分子制备的DNA修饰电极及其伏安性能

Carboxyl was formed on the surface of glassy carbon electrode(GCE) by electrochemical oxidation. Ethylenediamine(En) was used as the arm molecule to link carboxyl with dsDNA using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDC) and N- hydroxysuccinimide (NHS) as the activators to prepare dsDNA modified electrode(dsDNA/En/GCE). It was shown that dsDNA couM be covalently immobilized on the surface of GCE. ssDNA modified electrode(ssDNA/En/GCE) was obtained via the thermal denaturation of dsDNA/En/GCE. The dsDNA/En/GCE and ssDNA/En/GCE were characterized by voltammetry with methylene blue(MB) as the indicator. The results indicated that the currents of the redox peaks of MB at ssDNA/En/GCE were larger than those at dsDNA/En/GCE, and the currents of the redox peaks at En/GCE were the smallest. The peak-currents of MB at the DNA modified electrode had good reproducibility after multi-denaturation and hybridization cycles.     

基于包被包膜糖蛋白抗体纳米金磁性微粒的无试剂安培免疫传感器

在玻碳电极(GCE)表面固定对H2O2有催化还原活性的富马酸二甲酯联吡啶铜(GCE|CuL);再在GCE|CuL表面修饰一层金磁微粒-壳聚糖复合膜(nano Au/Fe3O4/Chit), 进而固定艾滋病毒(HIV)诊断标志物--包膜糖蛋白(gp160)抗体(anti gp160), 由此构建了一类快速检测 gp160的无试剂安培免疫传感器.当该传感器在含gp160溶液中37 ℃下温育30 min后, 传感器表面生成的免疫复合物随gp160浓度的增大而增加, 导致CuL 对H2O2 电催化还原效果降低, 催化电流呈现下降趋势.在PBS溶液(pH 7.0)和-300 mV下, 催化电流的降低值ΔIo与gp160浓度在1～400 μg/L 呈线性关系; 检出限为0.5 μg/L(3σ).研制的免疫传感器检测gp160时, 一步免疫反应即可得结果, 较相同条件下包被gp160抗体的纳米金单分子层修饰电极灵敏度更高, 检测范围更宽, 有望用于艾滋病人血清标志物gp160快速筛测.