An Automated Approach to Luminescence Lifetime and Intensity Titrations

An apparatus is described for the automated collection of luminescence emission decay curves over a wide range of analyte concentrations. The decay curves allow for determination of the excited-state lifetime or calculated steady-state intensity of a luminophore as a function of the analyte concentration. The data presented here demonstrate the use of the apparatus for pH titrations.     

PAN-S作为一种新的金属指示剂络合滴定铜和锌

引言 1-(2-吡啶偶氮)2-萘酚(PAN)是一种难溶于水、稀酸、稀碱的金属指示剂和萃取显色剂,在一定的条件下,我们把PAN磺化就成为能溶于水的1-(2-吡啶偶氮)2-萘酚磺酸(简称PAN-S)(另文发表).它能与多种金属离子反应形成可溶于水的络合物.因此,作为指示剂和光度显色剂,PAN-S比PAN更为优越.它不象PAN,需加入有机溶剂和非离子表面活性剂,以保证无沉淀析出.对于2-(2-吡啶偶氮)-1-萘酚磺酸(α-PAN-S)已作了比较系统的研究,而对β-PAN-S作为金属指示剂尚未见报道.本文采用PAN-S作为指示剂,用EDTA滴定Cu~(2+)和Z_n~(2+),终点敏锐,测定精密度高,方法回收率满意.     

Nitroxide-mediated precipitation polymerization of styrene in supercritical carbon dioxide: Effects of monomer loading and nitroxide partitioning on control

Nitroxide-mediated solution and precipitation polymerizations of styrene in toluene and supercritical carbon dioxide (scCO₂), respectively, using the nitroxides N-tert-butyl-N-[1-diethylphosphono-(2,2-dimethylpropyl)]nitroxide (SG1) and 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide (TIPNO) are presented. Solution polymerizations are compared with simulations using PREDICI software, revealing that differences in the polymerization behaviours between the SG1- and TIPNO-mediated systems cannot be rationalized based on literature rate coefficients and the ideal mechanism for nitroxide-mediated polymerization. Nitroxide and monomer partitioning between the polymer particles and the continuous phase play important roles in the precipitation polymerizations in scCO₂. Loss of control (broader molecular weight distributions) as a result of nitroxide partitioning is accentuated at low monomer loading, and is significantly more pronounced for TIPNO than SG1. However, at higher monomer loading the level of control was superior in scCO₂ compared to in the corresponding solution polymerizations for both nitroxides, most likely caused by an increase in the number of activation-deactivation cycles experienced by any given chain during its growth.     

控制电位滴定法的误差分析

研究了影响控制电位滴定法测定结果准确度的因素,得到的结论是:第一,电位的控制误差及滴定剂体积的测定误差是影响控制电位滴定法测定结果准确度的主要因素.计算模型中的比例系数越大,滴定曲线的变化率越大,这种影响越小.第二,多组分体系的测定误差,与组分在计算模型中比例系数的相对大小有关.比例系数越大,测定误差越小.第三,不同浓度(或不同浓度比)待测溶液滴定曲线的差异越大,对控制电位滴定法的测定越有利.     

End-point detection in potentiometric titration by continuous wavelet transform

The aim of this work was construction of the new wavelet function and verification that a continuous wavelet transform with a specially defined dedicated mother wavelet is a useful tool for precise detection of end-point in a potentiometric titration. The proposed algorithm does not require any initial information about the nature or the type of analyte and/or the shape of the titration curve. The signal imperfection, as well as random noise or spikes has no influence on the operation of the procedure.The optimization of the new algorithm was done using simulated curves and next experimental data were considered. In the case of well-shaped and noise-free titration data, the proposed method gives the same accuracy and precision as commonly used algorithms. But, in the case of noisy or badly shaped curves, the presented approach works good (relative error mainly below 2% and coefficients of variability below 5%) while traditional procedures fail. Therefore, the proposed algorithm may be useful in interpretation of the experimental data and also in automation of the typical titration analysis, specially in the case when random noise interfere with analytical signal.     

Potentiometric and volumetric determination of 6-mercaptopurine

Three methods for the determination of 6-mercaptopurine in the pure state and in tablets are described. One method is based on the reaction of this compound with silver ions, whereby an equivalent amount of nitric acid is liberated, the latter being determined potentiometrically with sodium hydroxide. The other two methods involve titration with chloramine-T, with potentiometric and visual end-point-detection. All methods afford accurate and reproducible results and can be used for routine assay of 6-mercaptopurine in tablets.     

Application of isotachophoretic and conductometric methods for neomycin trisulphate determination

Determination of neomycin trisulphate (NMS) in a dosage form (Neox and Neosol) was carried out by capillary isotachophoresis (cITP) with conductometric detection. The following electrolytes: leading: 10 mmol dm⁻³ sodium acetate + 0.08 % hydroxyethylcelulose (HEC) and acetic acid to pH = 5.5, and terminating: 10 mmol dm⁻³ β-alanine were tested for isotachophoretic separation of NMS. The calibration curve was linear over the range of 10.00 mg dm⁻³ to 100.00 mg dm⁻³ with LOD = 5.69 mg dm⁻³ and LOQ = 18.96 mg dm⁻³. The results were compared to the conductometric determination of NMS with: ammonium molybdate (VI), silver nitrate (V) and Reinecke salt. Good accuracy was obtained from conductometric titration of NMS with Reinecke salt, the recoveries being as follows: 100 % (RSD = 1.99 %); 96.17 % (RSD = 2.10 %) and 95.22 % (RSD = 1.55 %) for NMS in pure form, Neosol and Neox, respectively.     

A Facile Synthesis of Cu NPs and Ag NPs Coated by PS with Core–Shell Structure by Precipitation Polymerization

Copper nanoparticles (Cu NPs ) coated with polystyrene (PS ) (Cu NPs @PS ) were prepared by precipitation polymerization. First, Cu NPs were prepared by chemical reduction using cupric acetate as precursor, sodium polyacrylate (PAANa ) as stabilizer, and hydrazine hydrate as reducing agent. Then Cu NPs were coated by precipitation polymerization using styrene as monomer, 3‐(trimethoxysilyl) propyl acrylate as co‐monomer, and 2, 2‐azobisisobutyronitrile (AIBN ) as initiator. Ultraviolet–visible (UV –vis) spectroscopy and transmission electron microscopy (TEM ) results showed that stable composite particles could be synthesized by precipitation polymerization. The amount of PAANa had a significant effect on the size of Cu NPs . The addition of more PAANa resulted in smaller Cu NPs . The spherical Cu NPs became nanowires when increasing the stirring rate from 350 to 700 rpm during precipitation polymerization. Ag NPs @PS with core–shell structure were also prepared by this method, which appears to be universal.     

聚脲多孔材料的简单制备及在酶固定和手性拆分中的应用

以甲苯二异氰酸酯(TDI)为单体,在水与丙酮混合溶剂中通过沉淀聚合一步法制备了富含胺基的聚脲多孔材料(PPU),通过扫描电镜和压汞法对其表面形貌和孔结构进行了表征.PPU经戊二醛(GA)活化后用于荧光假单胞菌脂肪酶(PFL)的固定,考察了GA活化过程中GA浓度对酶固定量及固定酶活性的影响.结果表明,PPU是一种粒子尺寸分布在30~50μm范围的形状不规则的多孔粒子,孔径在2 nm~100μm之间呈连续分布.在pH=8.0的缓冲溶液中用0.17 mol/L的GA对PPU进行改性,将改性后的PPU用于PFL的固定,当酶溶液浓度为2.56 mg/m L时,得到酶的最大固定量为95.2 mg/g,固定酶的活性为375 U/mg,相对活性为76%.将此固定酶作为催化剂,用于1-苯乙醇外消旋化合物的手性拆分,并与游离酶催化的结果相比较.结果表明,固定酶的反应活性和立体选择性都明显优于游离酶.通过沉淀聚合制备的聚脲多孔材料在酶固定及手性分子拆分方面具有应用前景.     

海螺状碳酸钙的可控合成与荧光性能

采用液相沉淀法,以硝酸铋[Bi(NO_3)_3]为添加剂来调控碳酸钙晶体的形状与大小,制备了海螺状碳酸钙粒子.通过扫描电子显微镜(SEM)、X射线衍射仪(XRD)、热重分析仪(TGA)、原子荧光光谱仪(AFS)等对产物的结构和性能进行了表征.结果表明,在60℃条件下,添加20 mL浓度为2 g/L的Bi(NO_3)_3溶液可得到海螺状球霰石型碳酸钙粒子,且其荧光性明显增强.在碳酸钙的成核过程中,Bi~(3+)的加入起到了显著的调控作用.