离子对高效液相色谱-分光光度法测定痕量铜、钴、锰和锌的研究

本文研究了TPPS_4为柱前衍生试剂,苄基三乙基氯化铵为离子对试剂,离子对高效液相色谱-光度法快速分离及测定铜、钴、锰、锌的新方法。络合物和试剂在12min内出峰完毕,于425nm处进行检测,最低检测限(×10~(-3)μg/ml)为Cu0.42、Co0.28、Mn0.23和Zn0.09。     

四—（对—三甲铵苯基）卟啉分光光度法测定食品中的微量铅

1 引言 应用四-(对-三甲铵苯基)卟啉(简称TAPP)及其衍生物TTPS_4、T(4-TMAP)P,TPPS_4等作为测定铅、镉、铜、锌等的显色反应得到了广泛的应用。但应用TAPP作为食品中的微量铅的测定,却未见报道。本试验拟定在同一个分液漏斗中,控制样液pH6～7条件下,采用酒石酸钾钠和氰化钾掩蔽分离干扰元素;用二乙基     

水溶性卟啉在分析中的应用 Ⅱ.meso-四-(对-磺基苯)卟啉(TPPS_4)与镉反应的分光光度研究

1978年五十岚淑郎等研究了TPPS_3与镉的反应。作为光度试剂,TPPS_4具有更优良的性质,因此我们研究了TPPS_4与镉的反应。实验部分镉标准溶液:纯金属镉溶于硝酸配制。 721型分光光度计。 Specord UV-VIS自记分光光度计。(二)实验步骤取含有0.5-2微克镉的溶液放入25毫升容量瓶中,加入0.5毫升TPPS_4,1毫升联吡啶溶液(10~-2M)及1毫升氢氧化钠(一)试剂及仪器 TPPS_4:10~-4M水溶液。     

微柱高效液相色谱法测定环境样品中的铁、钴、镍、铜、锌、锰

研究了用 2-(2-喹啉偶氮 )-间苯二酚 (QAR)为柱前衍生试剂 ,以WatersXterraTM RP18(1 .0×5 0mm ,2. 5 μm)微柱为固定相 ,60 %的甲醇 (内含 0 . 5 %的醋酸 )为流动相 ,高效液相色谱分离、二极管矩阵检测器测定铁、钴、镍、铜、锌和锰的方法。根据信噪比 (S N =3 )得各金属离子的检测限分别为 :铁3 μg L、钴 4μg L、镍 2 μg L、铜 4μg L、锌 5 μg L、锰 8μg L ,方法用于环境样品中痕量铁、钴、镍、铜、锌、锰的测定 ,相对标准偏差在 1 . 6%～ 3 . 5 %之间 ,标准回收率为 93 %～ 1 0 7%。     

Co2+、Zn2+、Cd2+的阴离子交换色谱法分离研究

本文对钴与锌、镉等金属离子的阴离子交换色谱法分离进行了研究．采用201×7型阴离子交换树脂经氧化铵溶液饱和后,在pH＝4．0时,使钴与其它金属离子分离,然后分别用0．02mol／L的盐酸溶液及蒸馏水将锌、镉等金属离子从阴离子交换树脂上洗脱．此法分离效果好,操作简单方便．     

高效液相色谱光度法测定痕量铜、锌、铁、锰的磺化四苯基卟啉配合物

本文用磺化四苯基卟啉作柱前衍生试剂,研究了试剂与铜(Ⅱ)、锌(Ⅱ)、铁(Ⅲ)及锰(Ⅱ)的络合反应。在ODS柱上,用乙腈-水(40:60,V/V)作流动相,溴化四丁基铵作离子对试剂,在420nm波长处进行光度检测。提出了离子对反相高效液相色谱快速分离及测定痕量铜、锌、铁及锰的新方法。检测下限为(×10^-3ppm):Mn 3.6、Fe 1.8 、Zn 0.93、Cu 0.70。应用于植物样品中痕量铜、锌、铁及锰的测定,分析结果与标准参考值相符。     

用超高灵敏度试剂四苯基卟啉反相高效液相色谱法同时测定微量铜、铅、锌和镉

〕本文研究了四苯基卟啉和一些金属离子的络合反应条件和反应速度;研究了铜、铅、锌及镉离子和四苯基卟啉所形成的络合物的稳定性,并测定了它们的组成;研究了这些络合物的吸收光谱及同时测定这些金属离子的合适波长,确定光度检测的条件;研究了络合物的色谱行为和可能的干扰,确定了反相色谱分离条件。在上述研究的基础上提出同时测定这些金属元素的反相液相色谱法。方法快速,精密度好,变异系数在0.62—3.5％之间。最低检出量为0.04ngCd,0.16ngPb,0.20ngCu和0.005ngZn。本文提出的方法已成功地应用于锡基合金及电镀废水中铜、铅、锌和镉的测定,准确度好。     

胶束增溶(增敏)络合体系的高效液相色谱研究 Ⅷ.七种重金属的离子色谱柱后衍生光度法

本文用单柱阳离子色谱法分离了铜、镍、锌、钻、锰、镉、铅等七种重金属离子,并首次提出用胶束增溶(增敏)络合物为柱后衍生手段。用5-Br-PADAP 为试剂,TritonX-100为增溶剂,建立了七种金属离子同时测定的离子色谱法。     

光度检测-低压离子色谱法同时分析水溶液中铜、锌

用吡啶-(2-偶氮-4-)雷琐辛(PAR)作柱后衍生剂,在优化的衍生和色谱条件下,使用可见光检测一低压离子色谱法同时测定了水溶液中铜和锌。在低压阳离子色谱柱上,用酒石酸．柠檬酸作流动相,在520nm处检测,得到线性良好的工作曲线,铜和锌的检出限均为0．05μg／mL。利用该法分析了环境水样中的铜和锌,其标准加入回收率分别为99％～102％,97％～104％。     

流动注射预富集-液相色谱联机测定痕量镍、铜、汞的研究

萃取－液相色谱用于同时测定痕量金属离子已引起广泛重视［１～３］，但操作方法繁琐，样品易玷污［４］．我们曾用固相萃取的方法使金属离子衍生为二乙基二硫代氨基甲酸盐（ＤＴＣ）配合物富集后，继以ＨＰＬＣ分离测定了钴、铜和汞［５］．本文研究了流动注射固相萃取预...     

Ion chromatography with the indirect ultraviolet detection of alkali metal ions and ammonium using imidazolium ionic liquid as ultraviolet absorption reagent and eluent

Indirect ultraviolet detection was conducted in ultraviolet‐absorption‐agent‐added mobile phase to complete the detection of the absence of ultraviolet absorption functional group in analytes. Compared with precolumn derivatization or postcolumn derivatization, this method can be widely used, has the advantages of simple operation and good linear relationship. Chromatographic separation of Li⁺, Na⁺, K⁺, and NH₄⁺ was performed on a carboxylic acid base cation exchange column using imidazolium ionic liquid/acid/organic solvent as the mobile phase, in which imidazolium ionic liquids acted as ultraviolet absorption reagent and eluting agent. The retention behaviors of four kinds of cations are discussed, and the mechanism of separation and detection are described. The main factors influencing the separation and detection were the background ultraviolet absorption reagent and the concentration of hydrogen ion in the ion chromatography‐indirect ultraviolet detection. The successful separation and detection of Li⁺, Na⁺, K⁺, and NH₄⁺ within 13 min was achieved using the selected chromatographic conditions, and the detection limits (S/N = 3) were 0.02, 0.11, 0.30, and 0.06 mg/L, respectively. A new separation and analysis method of alkali metal ions and ammonium by ion chromatography with indirect ultraviolet detection method was developed, and the application range of ionic liquid was expanded.     

高效液相色谱-激光诱导荧光-增强型电荷耦合器件检测氨基酸的研究

以3-对羟基苯甲酰喹啉-2-甲醛(CBQCA)为检测痕量氨基酸的柱前衍生试剂,利用高效液相色谱-激光诱导荧光-增强型电荷耦合器件检测器(HPLC-LIF-ICCD)系统,考察了氨基酸衍生和HPLC分离过程中多种因素的影响,建立了HPLC-LIF-ICCD分离检测痕量氨基酸的新方法,并应用于鼠脑微透析液的氨基酸检测.当信噪比为3时,对甘氨酸的质量检出限为5fmol.     

Separation of a New Antidiabetic Agent,N-(Trans-4-Isopropylcyclohexylcarbonyl)-D-Phenylalanine,and its Isomers by Chiral High-Performance Liquid Chromatography

Abstract

N-(trans-4-Isopropylcyclohexylcarbonyl)-D-phenylalanine (A4166) is a new oral antidiabetic agent. In order to determine the purity of chemical samples of A4166, a high-performance liquid chromatographic method for the separation of A4166 and synthetic by-products (an L-enantiomer and a cis-iosmer of A4166) has been developed. A chiral stationary phase column packed with 5 μm N-(tert-butylaminocarbonyl)-L-valylaminopropyl silica gel was used for the direct separation of A4166 and its isomers after derivatization with a non-chiral reagent.     

Continuous on-line derivatization and selective separation of D-aspartic acid by a capillary electrophoresis system with a continuous sample introduction interface

A rapid and selective method is described for the separation of D-aspartic acid (D-Asp) using a continuous on-line derivatization system coupled to capillary electrophoresis (CE). D-Asp was derivatized using o-phthaldialdehyde/N-acetyl-L-cysteine (OPA/NAC). By on-line derivatization, amino acid enantiomers were automatically and reproducibly converted to the UV-absorbing diastereomer derivatives which were separated by capillary zone electrophoresis (CZE) in the presence of 10 mmol/L beta-cyclodextrin (beta-CD). Under the investigated separation conditions, D-Asp is resolved from L-aspartic acid (L-Asp) and other amino acids in a standard mixture of amino acids. The separation could be achieved within 4 min and the sample throughput rate can reach up to 16 h(-1). The repeatability (defined as relative standard deviation, RSD) was 3.21%, 3.58% with peak area evaluation and 3.72%, 4.03% with peak height evaluation for L-Asp and D-Asp.     

柱前衍生高效液相色谱法测定四氢噻唑-2-硫酮-4-羧酸的光学纯度

用苯胺对四氢噻唑-2-硫酮-4-羧酸(TTCA)进行柱前衍生,将其衍生物在手性固定相上拆分,通过二极管阵列紫外检测器和在线旋光检测仪对其衍生物进行检测,建立了一种拆分TTCA消旋体、测定TTCA光学纯度的新方法。以正己烷和乙醇或异丙醇为流动相,在DNB-Leucine手性固定相上对TTCA衍生物进行了拆分,并考察了流动相组成和柱温对其衍生物分离的影响,获得较优分析条件,分离因子大于1.2。非手性试剂苯胺柱前衍生化法测定(R)-TTCA的光学纯度与旋光度方法比较,结果一致,相对偏差小于1.34%。     

Ion-chromatographic trace analysis of mercury, cadmium and zinc by post-column derivatisation with a water-soluble porphyrin

Summary A post-column derivatisation system with mesotetra (4-sulfonatophenyl)-porphyrin (TPPS₄) and PAR as accelerating agent in a borate buffer pH 11.5 in the presence of tartrate and NaCl is proposed. The complexes of Cd, Zn and Hg have maximum absorption at 430 nm. The separation system consists of silica-gel chemically bonded cation exchanger as stationary phase and a tartrate-NaCl solution as mobile phase. The separation can be finished within 10 min. The calibration curves of these metal ions with the peak area of the chromatogram were found to be linear in the range of 0.002–0.8, 0.1–8.0 and 0.05–20.0 mg/l for Cd, Hg and Zn. The detection limits for Cd, Hg and Zn are 0.05, 5 and 1 ng. This new method was applied to the analysis of waste water, silicates and corn with satisfying results.

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Ionen-chromatographische Spurenanalyse von Hg, Cd und Zn durch Nachsäulen-Derivatisierung mit einem wasserlöslichen Porphyrin

     

Chromatographic resolution of racemic amines,carboxylic acids,and alcohols by a new homochiral reagent derived fromendo-borneol

Summary Chromatographic separation of racemic amines, carboxylic acids and alcohols can be achieved with excellent resolution as measured in terms of the chromatographic separation factor by derivatization with a homochiral oxazolidin-2-one easily prepared in three steps fromendo-borneol. The resolved materials can be isolated in excellent yields by cleavage of the resultant diastereomers using conventional methods, which also allow recovery of the chiral resolving agent for re-use.     

Fast turnaround bioanalysis in discovery and early clinical development

Summary The difect and indirect separation of enantiomers of secondary amino acids was studied by high-performance liquid chromatography. Direct separation was by using a macrocyclic glycopeptide, teicoplanin or ristocetin A, as chiral stationary phase. Indirect separation was via pre-column derivatization with (S)-N-(4-nitrophenoxycarbonyl)phenylalanine methoxyethyl ester [(S)-NIFE] as a new chiral derivatizing agent. Both direct and indirect separations were performed by means of reversed-phase HPLC. Conditions for separations were optimized. The methods described offer good enantioselectivity for synthetic chiral imino acids. Presented at Balaton Symposium '01 on High-Performance Separation Methods, Siófok, Hungary, September 2–4, 2001     

Proline-coated column for the capillary electrochromatographic separation of amino acids by in-column derivatization

With 3-trimethoxysilylpropyl chloride as the spacer, a proline-coated capillary column was prepared for the capillary electrochromatographic (CEC) separation of amino acids by in-column derivatization. Nine standard mixtures, including aspartic acid, glutamic acid, valine, phenylalanine, alanine, isoleucine, leucine, tyrosine, and tryptophan, were injected. o-Phthalaldehyde (OPA), OPA/2-mercaptoethanol (2-ME) and OPA/N-acetylcysteine (NAC) in borate buffer were tested as the derivatizing agent. Among them, OPA (50 mM) in borate buffer (pH 9.5, 50 mM) gave the best performance. The formation of isoindole could be detected by UV detection. The sandwich-type injection was carried out in hydrostatic mode (10 cm) with the program R(10 s)S(10 s) R(10 s)W(10 min) with R, S, and W being the reagent, sample, and waiting times. Mesityl oxide, benzyl alcohol, and acetone showed some interaction with the column. A current monitoring method was used instead of the determination of the electroosmotic flow (EOF). The direction of EOF was from anode to cathode even under acidic condition lower than the pI value (6.31) of the bonded group due to some unreacted silanol groups. Some parameters including pH, nature, and concentration of the mobile phase and the effect of organic modifier with regard to the CEC separation were investigated. With the proline-coated column (75 (50) cm x 75 microm ID) the best separation was performed in phosphate buffer (pH 4.00, 100 mM) with an applied voltage of -15 kV. The established method was also compared with those precolumn derivatized prior to the separation with proline-coated column as well as with in-capillary derivatization and separation with a bare fused-silica column.     

基于在线富集与原位衍生技术的植物组织中内源性油菜素甾醇的超高效液相色谱-串联质谱分析方法

油菜素甾醇是一类重要的植物激素,对植物的生长发育过程起显著调节作用。已报道的油菜素甾醇分析方法存在样品前处理过程复杂和灵敏度低等问题。本研究采用C18 PEEK管填充柱为富集柱,以4-N,N-二甲氨基苯硼酸为衍生试剂,搭建了基于双泵-双六通阀的在线管内固相微萃取-超高效液相色谱-串联质谱（UPLC-MS/MS）联用系统,对油菜素甾醇进行在线富集和原位衍生,实现植物组织中内源性油菜素甾醇的自动化分析。该系统程序化地控制了油菜素甾醇的进样、萃取、衍生、分离和检测过程,有效简化前处理过程,节省人力;在线富集步骤实现了样品溶液大体积进样,提高样品利用率;原位衍生改善了油菜素甾醇电喷雾的离子化效率,使油菜素甾醇的电喷雾质谱检出限降低至pg/mL。该系统可在300 mg鲜重植物组织中检测到内源性油菜素甾醇,已成功用于水稻、油菜中多种油菜素甾醇的定量分析。