Separation of enantiomers of drugs by capillary electrophoresis with permethyl-gamma-cyclodextrin as chiral solvating agent

High-throughput screening is a promising new approach in analytical chemistry. Within the framework of an extended screening program (The German-Chinese Drug Screening Program), the enantioseparation of 86 drugs was investigated by capillary zone electrophoresis in the presence of the chiral solvating agent (CSA) octakis-(2,3,6-tri-O-methyl)-gamma-cyclodextrin (TM-gamma-CD). By this means, 15 drugs could be separated into enantiomeric pairs. Approximate measures for the degree of interaction (migration retardation factor, R-m) and for the degree of enantiomer recognition (migration separation factors, alpha(m)) revealed intriguing patterns that were compared with those found for native gamma-cyclodextrin (gamma-CD). Although there is a distinct influence of the analyte structure on the electrophoretic data, interpretation remains difficult. Most remarkably, permethylation of gamma-CD leads neither to a higher affinity nor to better chiral recognition, in contrast to the findings with alpha-CD.

Transient state of chiral recognition in a binary mixture of cyclodextrins in capillary electrophoresis

The transient state (as the defined point where no enantioseparation is obtained in a dual chiral selector system) of chiral recognition of aminoglutethimide in a binary mixture of neutral cyclodextrins (CDs) was studied by capillary electrophoresis (CE). The following three dual selector systems were used: alpha-cyclodextrin (alpha-CD) and beta-cyclodextrin (beta-CD); alpha-CD and heptakis(di-O-methyl-beta-cyclodextrin) (DM-beta-CD); alpha-CD and heptakis(tri-O-methyl-beta-cyclodextrin) (TM-beta-CD). The S-(-) enantiomer of the analyte was more strongly retained in the presence of either alpha-CD or TM-beta-CD at pH 2.5, 100 mM phosphate buffer, while the R-(+) enantiomer was more strongly retained in the presence of either P-CD or DM-P-CD. In the more simple case, the elution order is invariably kept if the enantiomers have the same elution order in either one of the two hosts of the binary mixture. In contrast, the elution order may be switched by varying the concentration ratio of two hosts that produce opposite elution order for this particular analyte. In such a dual selector system, the enantioselectivity will disappear at the transient state at a certain ratio of host,:host, Moreover, the migration times of the two enantiomers with host, alone (diluted in buffer) is approximately equal to the migration times at the corresponding concentration of host, alone (diluted in buffer), where the ratio of concentrations of host,:host, is the same as in the binary mixture at the transient state. As found by nuclear magnetic resonance experiments, the analyte is forming a 1:1 complex with either one of the CDs applied. From this finding, a theoretical model based on the mobility difference of the two enantiomers was derived that was used to simulate the transient state. (C) 2000 Elsevier Science B.V. All rights reserved.

Separation of drug enantiomers by capillary electrophoresis in the presence of neutral cyclodextrins

This is a selected review, highlighting our results obtained in an extended screening program ("The German-Chinese Drug Screening Program"), with a focus on a set of original data obtained with heptakis(2,3,6-tri-O-methyl)-beta-cyclodextrin(TM-beta-CD) as the chiral solvating agent (CSA). The enantioseparation of 86 drugs by capillary zone electrophoresis in the presence of this CSA was successful for 47 drugs. The migration separation factors (alpha(m)) and the migration retardation factors (R-m) were compared with those found for native beta-cyclodextrin (beta-CD). The patterns thus obtained were also compared with those observed for hexakis(2,3,6-tri-O-methyl)-alpha-CD (TM-alpha-CD) and octakis(2,3,6-tri-O-methyl)-gamma-CD (TM-gamma-CD), respectively. From the statistical data, it can be concluded that there is a remarkable influence of the analyte structure on the electrophoretic data. A substructure 4H was found in the analyte structure that has a significant influence on the analytes' behaviour. Thus, analytes bearing the substructure 4H do not only have a strong affinity to the CDs but also a high rate of success of chiral separation in all systems reviewed. In light of this, the different ring sizes of native cyclodextrins (alpha-, beta- and gamma-CD) readily explain their behaviour towards a limited test set of chiral drugs. Sterical considerations point to the significance of side-on-binding versus inclusion in the cavity of the host. In addition to the findings from the screening program, numerous references to the Literature are given. (C) 2000 Elsevier Science B.V. All rights reserved.

Recent progress in adsorbed stationary phases for capillary electrochromatography

This review surveys the recent progress in the adsorbed stationary phases for capillary electrochromatography (CEC). Adsorption-based methods for preparation of stationary phase are novel approaches in CEC, which allow rapid and facile preparing stationary phases with desirable selectivity onto an open-tubular fused-silica capillary, a baresilica or ion-exchange packed column or a monolithic silica or polymer column. A variety of adsorbing agents have been developed as adsorbed stationary phases, including ionic long-chain surfactant, protein, peptide, amino acid, charged cyclodextrin (CD), basic compound, aliphatic ionene, and ion-exchange latex particle. The adsorbed stationary phases have been applied to separation of neutral, basic and acidic organic compounds, inorganic anions and enantiomers. They have also been applied to on-line sample concentration, fast separation and study of the competitive binding of enantiomers with protein.

Analytical intercomparison results from the 1990 Intergovernmental Oceanographic Commission open-ocean baseline survey for trace metals: Atlantic Ocean

“Dissolved” (< 0.4 μm filtered) and “total dissolvable” (unfiltered) trace element samples were collected using “clean” sampling techniques from four vertical profiles in the eastern Atlantic Ocean on the first IOC Trace Metals Baseline expedition. The analytical results obtained by 9 participating laboratories for Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, and Se on samples from station 4 in the northeast Atlantic have been evaluated with respect to accuracy and precision (intercomparability). The data variability among the reporting laboratories was expressed as 2 × SD for a given element and depth, and was comparable to the 95% confidence interval reported for the NASS seawater reference standards (representing analytical variability only). The discrepancies between reporting laboratories appear to be due to inaccuracies in standardization (analytical calibration), blank correction, and/or extraction efficiency corrections.Several of the sampling bottles used at this station were not adequately pre-cleaned (anomalous Pb results). The sample filtration process did not appear to have been a source of contamination for either dissolved or particulate trace elements. The trace metal profiles agree in general with previously reported profiles from the Atlantic Ocean. We conclude that the sampling and analytical methods we have employed for this effort, while still in need of improvement, are sufficient for obtaining accurate concentration data on most trace metals in the major water masses of the oceans, and to enable some evaluation of the biogeochemical cycling of the metals.

Interference effects in the extraction of trace metals from estuarine waters

We have found that a commonly used complexation and solvent extraction technique (using mixed dithiocarbamates/Freon/HNO3) does not always extract Cd, Co, Cu and Ni from estuarine samples with the same efficiency as from Milli-Q water. For samples collected from the Derwent Estuary (Australia), the reduced extraction efficiency only occurred for unfiltered samples, but low extraction efficiencies were also observed for a (filtered) riverine certified reference material (SLRS-3) suggesting that the effect may be widespread. We have not been able to identify the reason for the low extraction efficiency and, although it is strongly correlated with the presence of high concentrations of suspended solids, dissolved organic matter and particulate iron, we have no experimental evidence to directly link any of these parameters to the effect. It is possible that similar effects may occur in other techniques which rely on a preconcentration step prior to analysis and that some literature values of heavy metals in estuarine waters may be low. We propose a modification of the standard complexation/solvent extraction method which overcomes these difficulties without adding significantly to the time taken for analyses.

两种螯合剂施用对污染土壤中叶用叶叶叶Cd富集的影响

为探讨螯合剂对植物吸收重金属的影响,采用盆栽试验,研究了螯合剂乙二胺四乙酸(EDTA)和柠檬酸(CA)对土壤重金属Cd的的的态的及的用的的的(Beta vulgaris var.cicla L)富集Cd能力的影响。结果表明:EDTA的添加比柠檬酸更显著增加了土壤重金属镉的的的态含量,同时提高了的用的的的茎的的富集系数和转运能力;施用螯合剂促进了Cd从的用的的的茎的菜部菜茎的的菜菜,的用的的的茎的含Cd量显著增加,EDTA的作用是柠檬酸的2~3倍。

黄土高原不同土壤中Cd形态分级及其生物有效性研究

研究黄土高原主要农田土壤重金属Cd的形态与生物有效性的关系,为评价本区土壤重金属Cd污染程度及其生物有效性提供一定的理论与数据依据。【方法】以黄土高原自北向南采集的12个0~20 cm耕层土壤为供试土样,通过室内分析和盆栽试验,研究了黄土高原石灰性土壤中不同形态Cd的分布特征及其生物有效性。【结果】黄土高原农田土壤Cd各形态总体分布特征为:有机结合态Cd、铁锰氧化物结合态Cd>碳酸盐结合态Cd>交换态Cd>残渣态Cd,自北向南各形态Cd含量均呈不同程度的增加趋势。各土壤类型间铁锰氧化物结合态Cd及碳酸盐结合态Cd平均含量均表现为:干润砂质新成土<黄土正常新成土<简育干润均腐土<土垫旱耕人为土,自北向南依次增加。碳酸盐结合态Cd和全Cd含量主要受到全氮、有效磷和砂粒含量的影响,且全氮和有效磷含量对其的影响为正效应。铁锰氧化物结合态Cd含量主要受全氮、有效磷、砂粒和粉砂粒含量的影响,且全氮、有效磷和粉砂粒含量对其的影响为正效应。土壤中各形态Cd含量与有机质、C/N、pH、CaCO3、粘粒含量的相关性均不显著,其中与C/N、pH、粘粒含量呈负相关。Cd在小麦茎叶层的含量小于根系;而作物不同部位Cd累积量表现...

平菇菌丝体对Cd、Pb及其复合污染的生长与富集响应

在PDA平板培养条件下,研究Cd、Pb及其复合污染对平菇菌丝体生长的影响以及平菇菌丝体对生长基质中Cd、Pb的生物富集作用.结果表明,在实验浓度范围内,菌丝生长势、菌落直径和菌丝体干重等均随着重金属浓度的增大而减弱(小)或降低.平菇菌丝体对Cd、Pb均具有生物富集作用,并且随着重金属浓度的增大菌丝体中重金属含量逐渐增大.Cd、Pb复合污染能促进平菇菌丝体对Pb的吸收,而抑制对Cd的吸收.

球果蔊菜脯氨酸的积累及与Cd耐性的关系

采用盆栽方法,以风花菜(Rorippa islandica)为对照植物,研究Cd超积累植物球果蔊菜[Rorippa globosa(Turcz.)Thell.]脯氨酸的积累、丙二醛含量、生物量及叶绿素含量的变化,及其与Cd生物积累的关系.结果显示,Cd处理能明显促进2种植物体内脯氨酸的积累,当土壤中Cd浓度≤25μg/g时,球果蔊菜叶片脯氨酸的积累效应尤为显著;此时叶片生物量、叶绿素及丙二醛含量与对照相比均无显著差异,表明其叶片脯氨酸的积累在一定程度上可缓解Cd胁迫造成的氧化损伤.相关分析表明,球果蔊菜根系脯氨酸可指示球果蔊菜根系中Cd的积累.

土壤有效态Pb和Cd与大蒜吸收Pb和Cd的关系

通过对大蒜的重金属添加土培试验,采用DTPA(二乙基胺五乙酸)为有效态铅、镉提取剂,对受试土壤进行浸提检测,分析Pb和Cd在大蒜不同部位的吸收、积累及其与土壤中有效态含量的相关性。根据GB 2762-2005《食品中污染物限量标准》中对食品中Pb、Cd的限量要求,初步确定了本试验条件下,土壤中重金属Pb、Cd有效态的临界值,并以此临界点评价该种土壤中Pb、Cd对大蒜的潜在污染。

外源Cd~(2+)在土壤各级微团聚体中的含量和形态分布

采用室内培养和室内分析相结合的方法,研究了外源Cd2+进入土壤30d后,在土壤各级微团聚体中的含量富集和形态赋存情况。研究结果表明:外源水溶性镉进入土壤30d后,100%转化成了颗粒态,其中58.5%转化为了可交换态,0.98%转化成了碳酸盐结合态,1.26%转化成了铁锰氧化物结合态,7.68%转化成了有机结合态,31.5%转化成了残渣态,这基本与其中各粒级微团聚体中的赋存形态的情况一致。在土壤中赋存的镉主要分布在各级微团聚体中,在各粒级微团聚体中的含量分布顺序为<10μm微团聚体>10～50μm微团聚体>50～250μm微团聚体;外源镉向小粒级微团聚体的富集倾向明显高于向大粒级微团聚体的富集倾向,其中在<10μm微团聚体中富集系数为1.43,在50～250μm微团聚体中的富集系数只有0.60。

卧龙泉河流域土壤重金属污染的模糊评价

运用模糊评价模型对卧龙泉河流域土壤-植物重金属污染现状进行了评价,结果表明,卧龙泉河上游和中游地区土壤-植物重金属污染严重。其中,卧龙泉河上游土壤污染因子为Cu、Pb,水稻和玉米分别为Pb、Cu、C r、A s和Pb、C r、Hg;王家崴子地区土壤的污染因子主要为A s、Pb、Cd、Zn,水稻和玉米分别为Pb、Cu、Cd、C r、A s和Pb、C r、A s、Hg;氰化厂旱田土和靠山屯林地土为轻污染,污染因子分别为Pb、Zn、Cu、Hg和Hg、Pb;卧龙泉河下游万福旱田土和王家崴子西山坡林地土无污染。王家崴子和万福地区的韭菜Pb、Zn、Hg污染严重。同一地区不同植物的污染因子不同,不同地区水稻或玉米的的污染因子也不同。

细河流域土壤中Hg、Cd、Pb和Zn含量的空间分布特征

利用地统计学方法研究了沈阳市细河流域表层土壤中Hg、Cd、Pb和Zn含量的空间结构及其分布特征。结果表明,土壤中Hg、Cd、Pb和Zn的平均含量均高于其背景值;土壤Cd和Zn含量属中等程度的空间相关,Hg和Pb属于空间弱相关,其空间变异均为随机性因素和结构性因素共同作用的结果,但Cd和Zn含量主要受结构性因素影响,而Hg和Pb主要受随机性因素影响。土壤中Hg、Cd、Pb和Zn空间分布特征表明,4种重金属含量在上游较高,顺流而下含量明显下降;土壤中Hg和Pb含量最大值在四方台地区,Cd和Zn含量最大值分布在甘官和富官一带。细河流域土壤Hg、Cd、Pb和Zn含量空间分异是污水灌溉、固体废弃物堆放、农业生产及交通尾气等因素综合作用的结果。

新型TCAS吸附树脂对水中Cd~(2+)的吸附去除研究

通过静态吸附试验,研究一种由超分子受体化合物磺化硫杂杯芳烃(TCAS)与树脂结合的产物——新型TCAS吸附树脂对重金属Cd2+的吸附去除性能,并初步探讨了吸附机理。试验研究结果表明,TCAS吸附树脂对Cd2+的饱和吸附量为14.45 mg/g。当温度为20℃,0.5 g TCAS吸附树脂对10 mL浓度为5 mg/L的Cd2+溶液吸附60 min时,Cd2+的去除率可达到99%以上。pH值是影响TCAS吸附树脂吸附效果的重要因素,在pH=5~9时,Cd2+的去除率随着pH值的升高而增大。在试验范围内,TCAS吸附树脂对Cd2+吸附符合Freundlich方程。吸附在TCAS吸附树脂上的Cd2+可洗脱回收,TCAS吸附树脂也可再生利用。TCAS吸附树脂对重金属Cd2+的吸附机理主要归因于TCAS对Cd2+的络合作用。