气相色谱法测定盐酸苯海索中环己醇杂质

目的:建立气相色谱法测定盐酸苯海索中环己醇的含量.方法:色谱柱为6％氰丙基苯-94％二甲基硅氧烷的毛细管柱(DB-624,30 m×0.53 mm),程序升温,初始温度为70℃,维持2 min,然后以每分钟2℃的速率升高温度,直至120℃,维持10 min.进样口160℃,检测器250℃(FID);2.0 mL/min...     

Nafion掺杂多壁碳纳米管固定Ru（bpy）32+的电致化学发光法检测壮观霉素的研究

利用Nafion掺杂多壁碳纳米管形成复合膜将Ru(bpy)32+固定于玻碳电极表面形成Ru(bpy)32+-N-C。基于壮观霉素对该电极电致化学发光信号的增强作用,建立了一种新的壮观霉素电致化学发光检测方法,方法的线性范围为1.0×10-5～2.0×10-4 mol.L-1,检测限为2.5×10-6 mol.L-1。该方法用于尿样中壮观霉素的测定,加标回收率在87.1%～120.2%之间。     

联吡啶钌体系电化学发光法测定盐酸曲马多的研究

盐酸曲马多是含苯环结构的叔胺类化合物,对联吡啶钌的电致化学发光具有显著的增强作用.本文采用循环伏安(CV)和电致化学发光(ECL)法,研究了该体系的电化学行为和电化学发光行为,首次将铅笔芯作为电极用于电致化学发光体系,建立了一种测定盐酸曲马多的电化学发光新方法.在0.1 mol/L的PBS(pH 8.50)缓冲溶液中,扫描速度为100mV/s时,该ECL的峰高与盐酸曲马多在3.0×10～5.0×10-8moL/L浓度范围内呈线性关系(r=0.999 4,n=14),其线性回归方程为,(counts)=33.802×106c 131.57,方法检出限为1.5 x 10-8 mol/L(S/N=3).连续测定2.0×10-5 mol/L的盐酸曲马多溶液10次,发光强度值的RSD为1.80%.对样品进行加标回收率试验,回收率为92.5%～101.4%.该方法具有较高的选择性和灵敏度,样品处理简单快速,用于盐酸曲马多片剂的测定,结果满意.     

联吡啶钌体系电致化学发光测定精胺的研究

基于精胺对Ru（bpy）32＋电化学发光的显著增强效应,利用池内停流技术,建立了精胺的电化学发光测定法。本方法具有灵敏度高,线性范围宽和分析速度快的特点。在最优条件下,相对电化学发光值与精胺浓度在5×10-8~5×10-5mol/L范围内呈现良好的线性关系,对5×10-8mol/L浓度的精胺进行11次平行测定,其相对标准偏差为3.03%,检出限为2.31×10-8mol/L。     

Nafion掺杂多壁碳纳米管固定Ru（bpy）3^2＋的电致化学发光法检测壮观霉素的研究

利用Nafion掺杂多壁碳纳米管形成复合膜将Ru（bpy）32＋固定于玻碳电极表面形成Ru（bpy）32＋-N-C。基于壮观霉素对该电极电致化学发光信号的增强作用,建立了一种新的壮观霉素电致化学发光检测方法,方法的线性范围为1.0×10-5～2.0×10-4 mol.L-1,检测限为2.5×10-6 mol.L-1。该方法用于尿样中壮观霉素的测定,加标回收率在87.1%～120.2%之间。     

齐墩果酸电致化学发光行为的研究

首次发现了齐墩果酸在中性介质中有较强的电致化学发光行为,其电致化学发光强度受电化学参数和发光条件的影响。详细考察了各种影响因素,确立了最佳发光条件,即+2.0V电压,1.0mol/lKCL体系,H2O2浓度为1.5×10-3mol/L。在这个条件下,齐墩果酸的电致化学发光强度与它的浓度在4.38×10-7￣4.38×10-5mol/L范围内呈现良好的线性关系,检出限达到2.0×10-7mol/L,从而提供了电致化学发光测定齐墩果酸含量的方法。     

柱前衍生高效液相色谱法测定盐酸苯海索中甲醛

目的:建立柱前衍生高效液相色谱法测定盐酸苯海索中甲醛的含量.方法:以2,4-二硝基苯肼作为衍生化试剂,以C18(4.6mm×150mm,5μm)为色谱柱,以磷酸溶液(取磷酸5.75g,加水稀释至1000ml,用氨水调pH值至2.85)-乙腈(50:50)为流动相;检测波长为336nm,进样量为20μl,流速为1.0ml...     

TiO_2自水溶液中对钌(Ⅲ)离子及其配合物的吸附

研究了锐钛矿型TiO2对Ru3+离子的吸附,测定了吸附速率曲线,研究了浓度、温度、pH值、配体对吸附的影响。结果表明:Ru3+离子的吸附符合一级Lagergen动力学方程,吸附活化能为35.66kJ/mol;Ru3+离子在锐钛矿型TiO2上的吸附为熵驱动的自发吸热过程, G0<0, H0>0, S0>0;在较低浓度时,吸附符合吸附Langmuir等温式;溶液pH值对吸附有显著影响,pH=1.5～4呈现吸附突跃;可溶性配合物的形成完全抑制Ru(OH)3沉淀生成,使吸附操作的pH范围由无配体时的pH≤4扩大到下列范围:硫脲pH<8,草酸pH<12,吡啶pH<9,1,10邻菲口罗啉pH<9。     

磁性/量子点纳米复合材料的制备与电致化学发光性能

利用共沉淀法制备了磁性Fe_3O_4纳米粒子,多巴胺(DA)在其表面自动氧化聚合形成核/壳结构纳米粒子(Fe_3O_4@PDA);通过红外光谱(IR)和扫描电子显微镜(SEM)对其结构和形貌进行表征;采用水相合成法合成了CdSe量子点,并由L-半胱氨酸修饰其表面;由制备的核/壳结构纳米粒子与CdSe量子点通过静电吸引力结合在一起形成兼具有磁性和电致化学发光(ECL)的纳米复合材料。Fe~(3+)、Cu~(2+)、Cd~(2+)对复合材料ECL强度增强或猝灭的性质,在一定浓度范围内,离子浓度与发光强度呈线性关系,利用此性质检测这些离子的浓度,结果表明效果较好。     

基于Ru(bpy)32+ECL的生物传感器的原理及应用

对Ru(bpy)32 ECL的机理和特点进行了分析和描述;对基于Ru(bpy)32 ECL的酶传感器、免疫传感器和DNA探针的检测原理及应用作了综述。     

Ru(bpy)3-doped silica nanoparticle DNA probe for the electrogenerated chemiluminescence detection of DNA hybridization

A sensitive electrogenerated chemiluminescence (ECL) detection of DNA hybridization, based on tris(2,2′-bipyridyl)ruthenium(II)-doped silica nanoparticles (Ru(bpy)₃²⁺-doped SNPs) as DNA tags, is described. In this protocol, Ru(bpy)₃²⁺-doped SNPs was used for DNA labeling with trimethoxysilylpropydiethylenetriamine(DETA) and glutaraldehyde as linking agents. The Ru(bpy)₃²⁺-doped SNPs labeled DNA probe was hybridized with target DNA immobilized on the surface of polypyrrole (PPy) modified Pt electrode. The hybridization events were evaluated by ECL measurements and only the complementary sequence could form a double-stranded DNA (dsDNA) with DNA probe and give strong ECL signals. A three-base mismatch sequence and a non-complementary sequence had almost negligible responses. Due to the large number of Ru(bpy)₃²⁺ molecules inside SNPs, the assay allows detection at levels as low as 1.0 × 10⁻¹³ mol l⁻¹ of the target DNA. The intensity of ECL was linearly related to the concentration of the complementary sequence in the range of 2.0 × 10⁻¹³ to 2.0 × 10⁻⁹ mol l⁻¹.     

DNA分子光开关钌配合物[Ru(phen)2(dppz)]2+的研究进展

综述了近20年来典型的DNA-分子光开关钌(Ⅱ)多吡啶类配合物[Ru(phen)2(dppz)]2+在实验和理论上的研究进展与应用.阐明了该配合物的结构特征及其与DNA的作用机理、作用模式以及在一些相关热点问题上的争议,同时还介绍了该配合物在DNA-结构识别及定量分析等方面的重要应用.基于此,还对DNA-分子光开关钌配合物的开发作了展望.     

Influence of nature, concentration and pH of buffer acid-base system on rate determining step of the electrochemiluminescence of Ru(bpy)3 with tertiary aliphatic amines

The electrogenerated chemiluminescence (ECL) of Ru(bpy)₃²⁺ (bpy = 2,2′-bipyridyl) with tertiary aliphatic amines as co-reactants, was theoretically and experimentally studied as a function of the pre-equilibria involved in the ammonium proton lost and in relation to the nature of the rate determining step. Transient potential steps were used with a 3-mm glassy carbon disk electrode or carbon fiber ultramicroelectrodes array to investigate emission behavior in a variety of aqueous solution types, containing phosphate, tartrate and phthalate acid-base systems at differing pH values. The emission of Ru(bpy)₃²⁺ resulting from the reaction with n-tripropylamine (TPrA), tri-isobutylamine (TisoBuA), n-tributylamine (TBuA), methyl-di-n-propylamine (MeDPrA) and triethylamine (TEtA) in varying acid-base media was interpreted on the basis of the quoted pre-equilibria, ammonium pK_a being known. The nature of the rate determining steps changes depending on pH. Above pH ≈ 5 the amine neutral radical formation is the rate determining step and, is independent of pH with rate constant close to 10³ s⁻¹; below pH ≈ 5 the rate determining step becomes the deprotonation of the ammonium ion, operated by different bases present in solution. Different amines in the same acid-base system showed analogous ECL behavior, conditioned by the chosen acid base system. A single amine in different acid-base systems showed different kinetic behaviors, due to the dissociation constants of the chosen buffers. The concentration of the acid-base system also played an important role and influenced emission intensity and shape. ECL emission were simulated by finite difference methods, implementing a previously proposed mechanism by including the relevant pre-equilibria. Simulation may also give estimates of the pK_a values of the ammonium ions. An ion pair formation between R₃N⁺ and the mostly charged species present in solution is hypothesized to explain the contradictory experimental results concerning the reaction mechanism of the proton lost of the radical cation.     

Use of Ru(bpy)32+/tertiary aliphatic amine system fast potential pulses electrochemiluminescence at ultramicroelectrodes coupled to electrochemical data for evaluating E° of amine redox couples

The electrochemiluminescent (ECL) reaction mechanism of the tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)₃²⁺) with six tertiary aliphatic amines, namely, tri-n-butylamine (TBuA), tri-iso-butylamine (TisoBuA), tri-n-propylamine (TPrA), methyl-di-n-propylamine (MeDPrA), tri-ethylamine (TEtA) and tri-methylamine (TMeA) in aqueous solution was examined using fast potential pulses at carbon fiber microelectrodes and with simulation techniques with the aim to obtain information on the E° value of the amine redox couples. Pulse time was chosen so as emission occurred after the potential pulse end. The experimental approach to estimate the E° values of the amine redox couples consisted in combining electrochemical and ECL data under the assumptions that at least one amine E° value is available and that the proposed reaction mechanism well represents the experiment. TPrA was used as reference compound (E° = 0.88 V versus SCE) and from this, 1.05 ± 0.04 V (TMeA), 0.92 ± 0.04 V (TEtA), 0.91 ± 0.03 V (MeDPrA), 0.79 ± 0.03 V (TBuA) and 0.72 ± 0.03 V (TisoBuA) were the estimated E° values of the other amines. The TEtA E° value (also known from the literature) is equal within the indicated experimental errors and gives information on the accuracy of the proposed method. Moreover, was possible to confirm the already proposed order of magnitude of the rate determining step of the ECL process through the evaluation of two experimental parameters, A% (number of photons percent recorded at the inversion time, t_inv) and T_r (relative position of the peak emission with respect to t_inv). The k_sh value of the considered amines was estimated close to 10^−3.5 cm s⁻¹ comparing emissions at Pt ultramicroelectrode.     

氮在钌单晶表面Ru(0001)上的吸附

钌系氨合成催化剂作为第二代氨合成催化剂,近年来日益受到重视。研究氮分子在钌表面上的离解吸附对提高钌催化剂的催化性能有着十分重要的意义。综述了氮分子在Ru(0001)单晶表面吸附的研究进展，并指出钌催化剂的发展方向。     

Study of [Fe(bpy)3] complex encapsulated in zeolite Y

Tris complex of Fe^II with 2,2′ bipyridine (bpy) ligand, has been encapsulated in the supercages of zeolite Y and characterized by powder X-ray diffraction, Infrared spectroscopy, ⁵⁷Fe Mössbauer, effect measurements and multinuclear NMR spectroscopy. The complex was prepared in the supercages of Zeolite Y by exchanging the cations of zeolite Y with Fe^II and its subsequent complexing with bpy ligand. Based on the comparison of the results obtained for [Fe^II(bpy)₃](ClO₄)₂ and the [Fe(bpy)₃]Y complexes, it has been inferred that there is significant structural distortion for the encapsulated complex and all Fe is present as Fe^II in low spin state, which is characterized by isomer shift, δ = 0.37 mm s⁻¹ and quadrupole splitting, ΔE_q = 0.81 mm s⁻¹ as revealed by ⁵⁷Fe Mössbauer spectroscopic measurements.     

[Cu（en）3]^2＋发生Jahn-Teller畸变吗

就大一学生对[Cu（en）3]^2＋是否发生Jahn-Teller畸变的作答情况,引发的关于规律的总结、知识的连续性、阶段性及教材处理方面的思考。