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Determination of nicotine in tobacco by molecularly imprinted solid phase extraction with differential pulsed elution 分子印迹固相萃取-差分脉冲洗脱法测定烟草中的尼古丁
Pub Date : 1999-01-01 DOI: 10.1039/A902509J
W. Mullett, E. Lai, B. Sellergren
A molecularly imprinted solid phase extraction-differential pulsed elution (MISPE-DPE) method has been developed for the determination of nicotine in tobacco. Nicotine and a trace alkaloid myosmine were able to bind to the molecularly imprinted polymer (MIP) packed in a micro-column when acetonitrile was used as the mobile phase. However, over 95% of the bound myosmine could be desorbed and washed away by a 20 µl pulse of methanol, compared to only 43% of the bound nicotine. The remaining quantity of bound nicotine was desorbed by a 20 µl pulse of 1% trifluoroacetic acid in water, for direct UV detection at 254 nm. This MISPE-DPE method provided inherent selectivity for nicotine that allowed both a shorter analysis time (3 min) and a lower analysis cost than liquid chromatographic methods. A detection limit of 1.8 µg ml–1 and a linear dynamic range up to 1000 µg ml–1 were obtained. Preconcentration of 845 µl of a 10 ng ml–1 nicotine standard solution produced a detectable peak signal. These analytical figures of merit are superior to those reported previously for several nicotine–MIP-based methods.
建立了分子印迹固相萃取-差分脉冲洗脱(MISPE-DPE)测定烟草中尼古丁的方法。以乙腈为流动相时,尼古丁和微量生物碱肌胺能够与分子印迹聚合物(MIP)结合。然而,超过95%的结合肌氨酸可以被20µl的甲醇脉冲解吸和冲走,而只有43%的结合尼古丁。用1%三氟乙酸水溶液20µl脉冲解吸剩余的结合尼古丁,在254 nm处进行直接紫外检测。MISPE-DPE方法对尼古丁具有固有的选择性,与液相色谱方法相比,分析时间更短(3 min),分析成本更低。检测限为1.8µg ml-1,线性动态范围达1000µg ml-1。预浓缩845µl 10 ng ml-1尼古丁标准溶液产生可检测的峰值信号。这些优点的分析数字优于先前报道的几种基于尼古丁- mip的方法。
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引用次数: 70
The estimation of lanthanum by air-acetylene atomic absorption spectrophotometry using an indirect procedure 空气-乙炔原子吸收分光光度法间接测定镧
Pub Date : 1999-01-01 DOI: 10.1039/A900331B
S. J. Wilson, P. Marquis
A method for measuring the release of lanthanum from some ceramic dental materials was required using air–acetylene atomic absorption spectrophotometry (AA-AAS), and an analytical procedure was devised based on the release of calcium in the presence of phosphate by lanthanum addition. The extent of phosphate interference in the determination of calcium by AA-AAS was assessed, and it was shown that the absorbance of a 10 ppm Ca standard was reduced by 45% in the presence of 20 ppm or more of phosphate (as PO4). Analysis of standards containing 10 ppm Ca, 20 ppm PO4, and lanthanum added at concentrations up to 100 ppm showed rapid increase of calcium absorbances from 10 to 40 ppm La, after which absorbance increased slowly to a constant value at 90 ppm La. This corresponded to the value of a 10 ppm Ca standard solution containing no phosphate. Closer examination of solutions containing 10–40 ppm La revealed a quantitative relationship between lanthanum levels and calcium absorbances which deviated slightly from Beer’s law. Consequent analysis of solutions containing various amounts of lanthanum in the presence of 10 ppm Ca and 20 ppm PO4 followed by repeated analysis of standards demonstrated good precision and reproducibility. The relative standard deviation for repeated standard analyses was 4.2%, and the detection limit was 0.6 ppm La representing an increase of sensitivity of approximately 100 times over lanthanum determinations using nitrous oxide–acetylene techniques. The method indicates that similar procedures may be used to estimate elements which exercise similar release effects.
采用空气-乙炔原子吸收分光光度法(AA-AAS)测定了某些牙科陶瓷材料中镧的释放量,并设计了一种以镧在磷酸盐存在下钙释放量为基础的分析方法。对AA-AAS法测定钙的磷酸盐干扰程度进行了评估,结果表明,在20 ppm或更多的磷酸盐(如PO4)存在下,10 ppm Ca标准的吸光度降低了45%。对含有10 ppm Ca、20 ppm PO4和浓度高达100 ppm镧的标准物的分析显示,钙的吸光度从10 ppm La迅速增加到40 ppm La,之后吸光度缓慢增加到90 ppm La时的恒定值。这相当于不含磷酸盐的10 ppm Ca标准溶液的值。对含有10-40 ppm La的溶液进行更仔细的检查,揭示了镧水平和钙吸光度之间的定量关系,这与比尔定律略有偏离。随后对含有不同数量镧的溶液在10 ppm Ca和20 ppm PO4的存在下进行分析,然后对标准品进行重复分析,证明了良好的精度和再现性。重复标准分析的相对标准偏差为4.2%,检出限为0.6 ppm La,灵敏度比使用氧化亚氮-乙炔技术的镧测定提高了约100倍。该方法表明,可以采用类似的方法来估计具有相似释放效应的元素。
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引用次数: 2
A photoelectric method for analyzing cell-free apoptosis induced by dATP dATP诱导细胞游离凋亡的光电分析方法
Pub Date : 1999-01-01 DOI: 10.1039/A900317G
Y. Ci, Chun-yang Zhang, Jun Feng, Ai-dong Lang, Chun‐hui Huang, Zhengfan Jiang
A new photoelectric method for analyzing cell-free apoptosis had been developed with ITO (a transparent electrode of indium–tin oxide coated borosilicate) technology. The C5710 mice liver nuclei responded with a negative photoelectric current pulse to white light (200–800nm). During the apoptosis of liver nuclei induced by dATP (deoxyadenosine-5-triphosphate), the photoelectric current showed a dynamic decrease, which was in accordance with the results of fluorescence microscopy and agarose gel electrophoresis. This photoelectric analytical method might provide a rapid and sensitive way to evaluate apoptosis quickly and in a continuous fashion.
利用ITO(一种氧化铟锡包覆硼硅酸盐的透明电极)技术,建立了一种新的分析细胞游离凋亡的光电方法。C5710小鼠肝核对白光(200-800nm)有负电电流脉冲响应。在dATP(脱氧腺苷-5-三磷酸)诱导的肝核凋亡过程中,光电流呈动态下降,这与荧光显微镜和琼脂糖凝胶电泳结果一致。这种光电分析方法为快速、连续地评价细胞凋亡提供了一种快速、灵敏的方法。
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引用次数: 2
At-line coupling of surface-enhanced resonance Raman spectroscopy and reversed-phase ion-pair chromatography 表面增强共振拉曼光谱与反相离子对色谱的联机耦合
Pub Date : 1999-01-01 DOI: 10.1039/A903254A
R. M. Seifar, R. J. Dijkstra, U. Brinkman, C. Gooijer
At-line coupling of surface-enhanced resonance Raman spectroscopy (SERRS) and reversed-phase ion-pair chromatography with an excitation wavelength of 514.5 nm was applied for the isocratic separation and identification of four representative basic dyes (basic fuchsin, nile blue, crystal violet and ethyl violet). The effluent from a chromatographic column was deposited on a thin layer chromatography (TLC) plate by means of a spray-jet interface and analysed by Raman spectroscopy. The presence of non-volatile ion-pair reagents (1-heptanesulfonic acid sodium salt, sodium perchlorate) did not interfere with the deposition process and also not with the SERRS experiments. In fact higher SERRS intensities were observed in the presence of the ion-pair reagents. Reliable spectra could be recorded down to 90 pg of dyes deposited on the TLC plate.
采用激发波长为514.5 nm的表面增强共振拉曼光谱(SERRS)和反相离子对色谱的在线耦合对4种代表性碱性染料(碱性紫红、尼罗蓝、结晶紫和乙基紫)进行了等密度分离和鉴定。采用喷雾-喷射界面法将色谱柱流出液沉积在薄层色谱板上,用拉曼光谱对其进行分析。非挥发性离子对试剂(1-庚烷磺酸钠盐、高氯酸钠)的存在不影响沉积过程,也不影响SERRS实验。事实上,在离子对试剂的存在下观察到更高的SERRS强度。在薄层色谱板上沉积的染料可记录到90pg的可靠光谱。
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引用次数: 14
An approach to the identification of selenium species in yeast extracts using pneumatically-assisted electrospray tandem mass spectrometry 利用气动辅助电喷雾串联质谱法鉴定酵母提取物中硒的种类
Pub Date : 1999-01-01 DOI: 10.1039/A900319C
C. Casiot, V. Vacchina, H. Chassaigne, J. Szpunar, M. Potin-Gautier, R. Łobiński
An approach to the identification of unknown signals in selenium speciation analysis of yeast by reversed-phase chromatography with ICP-MS detection is described. The analytical strategy was based on: (i), heart-cutting of a Se-containing fraction in the reversed-phase chromatographic eluate followed by its lyophilization; (ii), pneumatically-assisted electrospray (ESI) MS and ESI tandem MS of the lyophilizate; and (iii) confirmation of the fragmentation pattern obtained using the sulfur analogue of the seleno compound that was expected to have been identified. The approach developed allowed the identification of Se–adenosylhomocysteine as the major selenium species in an extract of a selenized yeast sample.
介绍了一种利用ICP-MS反相色谱法识别酵母硒形态分析中未知信号的方法。分析策略是基于:(i)反相色谱洗脱液中含硒部分的心脏切割,然后将其冻干;(ii)气助电喷雾(ESI)质谱法和ESI串联质谱法;(iii)确认使用预期已经确定的硒化合物的硫类似物获得的破碎模式。所开发的方法允许鉴定硒腺苷型同型半胱氨酸作为硒化酵母样品提取物中的主要硒种。
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引用次数: 100
Study on fluorescence of the Tb(III)–enoxacin system and the determination of enoxacin Tb(III) -依诺沙星体系的荧光研究及依诺沙星的测定
Pub Date : 1999-01-01 DOI: 10.1039/A902452B
Y. Fangtian, J. Linpei, Z. Huichun
A very simple, rapid and highly sensitive fluorimetric method for the determination of enoxacin (ENX) is described. The method is based on the formation of Tb(III)–ENX complex in the aqueous solution, which fluoresces intensely with an emission maximum at 545 nm (Tb3+∶5D4 → 7F5) when excited at 335 nm. Optimum conditions for the determination were investigated. A linear relationship was obtained between the fluorescence intensity and ENX concentration in the range 8.0 × 10–9–6.0 × 10–6 M. The limit of detection was 5.9 × 10–10 M. Analytical recoveries from untreated urine samples spiked with ENX were in the range 95–102.5%.
介绍了一种简便、快速、高灵敏度的测定依诺沙星(ENX)的荧光法。该方法基于在水溶液中形成Tb(III) -ENX配合物,在335 nm激发时,该配合物发出强烈荧光,在545 nm处发射最大值为(Tb3+∶5D4→7F5)。考察了测定的最佳条件。荧光强度与ENX浓度在8.0 × 10 - 9 ~ 6.0 × 10-6 m范围内呈线性关系,检出限为5.9 × 10-10 m,加标ENX未经处理的尿液样品的分析回收率为95 ~ 102.5%。
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引用次数: 16
Direct measurement of atmospheric formaldehyde using gas chromatography-pulsed discharge ionisation detection 气相色谱-脉冲放电电离检测法直接测定大气中甲醛
Pub Date : 1999-01-01 DOI: 10.1039/A809762C
M. Hunter, K. Bartle, P. Seakins, A. Lewis
A gas chromatographic system has been developed for the direct analysis of atmospheric formaldehyde and other oxygenated hydrocarbons. This method utilises the trapping of analytes in a loop cooled with liquid nitrogen, separation by gas chromatography and then subsequent detection using a pulsed discharge helium ionisation detector (pdHID). The detection limit of this instrument is estimated to be 32 parts per trillion by volume (pptv) for 0.2 l of gas sampled at a flow rate of 30 ml min–1 (S/N at 4:1). A number of other compounds have been monitored simultaneously using this method, including higher molecular weight aldehydes and acetone. Continuous measurement of formaldehyde can be performed with a time resolution of 15 min, with longer analysis times required for inclusion of other species. Calibrations were performed using a permeation tube instrument for both formaldehyde and acetone. A linear response has been observed for formaldehyde sample volumes of 60–200 ml of a 272 ppbv sample (20–68 ng). For acetone a linear response was observed from 175–360 ml of a 30 ppbv standard (12–26 ng). A flame ionisation detector (FID) was also utilised during system development to confirm separation of formaldehyde from atmospheric hydrocarbons.
建立了一种气相色谱系统,用于直接分析大气中的甲醛和其他含氧烃。该方法利用将分析物捕获在液氮冷却的循环中,通过气相色谱分离,然后使用脉冲放电氦电离检测器(pdHID)进行后续检测。该仪器的检出限估计为体积的万亿分之32 (pptv),对0.2升气体取样,流速为30 ml min-1 (S/N为4:1)。许多其他化合物已被同时监测使用这种方法,包括高分子量醛和丙酮。甲醛的连续测量可以进行15分钟的时间分辨率,与较长的分析时间需要包含其他物种。使用渗透管仪器对甲醛和丙酮进行校准。在272 ppbv样品(20-68 ng)中,甲醛样品体积为60-200 ml时,观察到线性响应。对于丙酮,在30 ppbv标准溶液(12-26 ng)中,175-360 ml呈线性响应。在系统开发过程中,还使用了火焰电离检测器(FID)来确认甲醛与大气碳氢化合物的分离。
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引用次数: 33
A new sandwich-type assay of estrogen using piezoelectric biosensor immobilized with estrogen response element 用雌激素反应元件固定压电生物传感器的新型三明治式雌激素检测方法
Pub Date : 1999-01-01 DOI: 10.1039/A902872B
Mo Zhihong, Long Xiaohui, F. Weiling
A new methodology, sandwich-type monitoring assay system using an estrogen response element (ERE)-immobilized piezoelectric biosensor in combination with flow injection technique, has been developed for analysis of estrogen (E). The principle of the assay is that the estrogen receptor (ER) captures estrogen and then the complex is bound with ERE immobilized on the sensor. It was confirmed that initial binding of the ERE with ER is significantly accelerated by the formation of an E–ER complex. This kinetic difference was monitored by real-time measurement of the resonance frequency of the ERE piezoelectric biosensor and applied to detect 17β-estradiol. The calibration graph was linear in the range 10–100 nmol l–1 with a detection limit of 7.8 nmol l–1, an RSD of 5.9% for 50 nmol l–1 (6 replicates), and one run time of 4 min. Gradient flow injection on-line connection to an array of ERE piezoelectric biosensors is in progress for the simultaneous determination of endogenous and synthetic estrogens in drinking water and urine. In comparison with present chromatographic methods coupled with MS, the proposed technique is simple, flexible and cheap and has great potential in applications such as field and on-site monitoring and screen testing of endocrine disruptors.
本文提出了一种将雌激素反应元件(estrogen response element, ERE)固定化压电生物传感器与流动注射技术相结合的新型检测方法——三明治式检测系统。该检测方法的原理是雌激素受体(estrogen receptor, ER)捕获雌激素,然后将复合物与固定化在传感器上的ERE结合。经证实,E-ER复合物的形成显著加速了ERE与ER的初始结合。通过实时测量ERE压电生物传感器的共振频率来监测这种动力学差异,并将其用于检测17β-雌二醇。校准图在10-100 nmol - 1范围内呈线性,检出限为7.8 nmol - 1, 50 nmol - 1(6个重复)的RSD为5.9%,运行时间为4 min。梯度流动注射在线连接ERE压电生物传感器阵列,用于同时检测饮用水和尿液中的内源性和合成雌激素。与现有的色谱联用质谱技术相比,该技术简单、灵活、廉价,在内分泌干扰物的现场和现场监测和筛选检测等方面具有很大的应用潜力。
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引用次数: 39
Depth profiling of a Co-implanted silicon wafer by total-reflection X-ray fluorescence analysis after repeated oxidation and HF-etching 重复氧化和hf刻蚀后共植入硅片的全反射x射线荧光分析
Pub Date : 1999-01-01 DOI: 10.1039/A809804B
R. Klockenkämper, A. Bohlen
A new method of depth profiling has been developed and applied to a Co-implanted Si-wafer. A square section of only some cm2 was chosen, a thin near-surface sublayer oxidized by an oxygen plasma and the oxidized sublayer precisely etched by a solution of hydrofluoric acid. The mass of Si within the sublayer was determined via differential weighing of the wafer piece and the mass of Co determined by TXRF (total reflection X-ray fluorescence) of the loaded acidic solution. These steps were repeated time and again in order to record a total depth profile showing the relative concentration of Co dependent on the depth within the wafer. The integration of this profile gave a total dose of 1.13 × 1017 ions cm–2 with high accuracy. The depth resolution of the new method might be in the order of a few nm, the detection limit about 0.01% or 5 × 1018 atoms cm–3 of Co.
提出了一种新的深度剖面方法,并将其应用于共注入硅片。选择一个只有几平方厘米的正方形截面,用氧等离子体氧化一个薄的近表面亚层,并用氢氟酸溶液精确地蚀刻氧化亚层。子层内Si的质量通过硅片的差分称重来测定,Co的质量通过负载酸性溶液的TXRF(全反射x射线荧光)来测定。这些步骤一次又一次地重复,以记录总深度剖面,显示Co的相对浓度取决于晶圆片内的深度。综合得到的总剂量为1.13 × 1017离子cm-2,精度较高。新方法的深度分辨率可能在几nm左右,检测限约为Co的0.01%或5 × 1018个原子cm-3。
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引用次数: 13
An acrylamide-based molecularly imprinted polymer for the efficient recognition of optical amino acid hydantoins 一种基于丙烯酰胺的分子印迹聚合物,用于光学氨基酸醛酸的高效识别
Pub Date : 1999-01-01 DOI: 10.1039/A902025J
Jie Zhou, Xiwen He, Yijun Li
Using acrylamide as a hydrogen bonding functional monomer and (5R)-5-benzylhydantoin as a template, a molecularly imprinted polymer was prepared in a polar solvent, which exhibited good enantiomeric recognition properties. The binding selectivity of the polymer was evaluated by batch methods. Scatchard analyses showed that two classes of binding sites were produced in the imprinted polymer and their dissociation constants were estimated to be (4.6 ± 0.8) × 10–5 and (1.3 ± 0.2) × 10–4 mol L–1, respectively. This was in agreement with the prediction of the binding characteristics of the polymer by a spectrophotometric method. Study of the effect of water on the separation factor of the polymer further proved that the hydrogen bonding interactions played an important role in the recognition of acrylamide-based molecularly imprinted polymers.
以丙烯酰胺为氢键功能单体,以(5R)-5-苄基海因为模板,在极性溶剂中制备了具有良好对映体识别性能的分子印迹聚合物。用批处理法评价了聚合物的结合选择性。Scatchard分析表明,印迹聚合物中产生了两类结合位点,其解离常数分别为(4.6±0.8)× 10-5和(1.3±0.2)× 10-4 mol L-1。这与分光光度法对聚合物结合特性的预测一致。水对聚合物分离因子影响的研究进一步证明了氢键相互作用对丙烯酰胺基分子印迹聚合物的识别起着重要作用。
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引用次数: 14
期刊
Analytical Communications
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