Direct determination of nucleosides in the urine of patients with breast cancer using column-switching liquid chromatography-tandem mass spectrometry

We developed an analytical method for a simple, sensitive and simultaneous determination of oxidized nucleosides in urine using column-switching liquid chromatography-electrospray/tandem mass spectrometry (LC-ESI/MS/MS). We connected two columns through a six-way switching valve and effectively separated nucleosides in the urine from the interference by column-switching liquid chromatography. We monitored separated nucleosides using positive ionization tandem mass spectrometry in selective reaction monitoring (SRM) mode. The calibration ranges of nucleosides were 0.2-100 nmol/mL. The linearity of the method was 0.994-0.999, and the limits-of-detection (LOD) at a signal-to-noise (S/N) ratio of 3 were 0.1-0.2 nmol/mL. The coefficients of variation were in the range 2.28-11.74% for within-day variation and 4.36-11.15% for day-to-day variation, respectively. To explore the relationship between breast cancer and the nucleosides level in human urine, we measured the concentrations of nucleosides in female patients with breast cancer (n = 30) and in normal female subjects (n = 30). The concentration of nucleosides was significantly increased in patients with breast cancer when compared with the normal controls (1-methyladenosine; p < 0.005, N(2),N(2)-dimethylguanosine; p < 0.01, 5-hydroxymethyl-2'-deoxyuridine; p < 0.001, 8-hydroxy-2-deoxyguanosine; p < 0.001). Therefore, the elevated levels of nucleosides could be used as an important biomarker for breast-cancer research.     

In Situ Monitoring of Generation and Precipitation of Ferric Hydroxide Sol with a Piezoelectric Quartz Crystal Impedance Analyzer

The piezoelectric quartz crystal (PQC) impedance technique was applied to monitor in situ generation and precipitation of the ferric hydroxide sol in aqueous solutions at 90 degrees C. Equivalent circuit parameters and resonant frequencies as well as the half-peak width of the electroacoustic conductance spectrum deltaf(G1/2) for the PQC resonance were obtained and analyzed. Three stages, sol generation and simultaneous adsorption, adsorption equilibrium, and precipitation of ferric hydroxide sol could be identified in the process of adding the ferric nitrate solution into the hot water. A scheme of two consecutive reactions occurring at the electrode/solution interface was used to analyze the adsorption kinetics of ferric hydroxide sol onto the Au electrode. In addition, the electrolyte-induced precipitation of the colloid was monitored and discussed. Temperature effect on the PQC resonance behavior in liquid was also investigated. Since the PQC impedance technique provides multidimensional piezoelectric information in situ, it is highly recommended for studying the process of sol-gel generation and precipitation. Copyright 2001 Academic Press.     

预富集装置在QCM传感器检测芥子气中的运用

在化学战剂的诸种检测方法中, 质量型微传感器以其响应快速、使用简便等优点成为一种理想的检测手段. 但是这种传感器的使用往往受到检出限的限制, 对于低浓度的毒剂不能及时报警. 预富集技术的运用可以提高微传感器的检测限. 本文研制了一种预富集装置并对其进行了初步测试. 芥子气通过此预富集装置之后在QCM(石英晶体微天平)传感器上的检出限可以达到0.1 mg/m3.     

当归挥发性有机物的SPME/GC-MS分析

采用不同极性的SPME萃取吸附了当归的挥发性有机物,并用GC-MS定性和相对定量,比较了不同萃取时间和不同萃取温度下所获得的挥发性有机物的差异。结果表明:藁本内酯和α-蒎烯是其主要成分。随着萃取时间的延长,α-蒎烯含量逐渐减少,藁本内酯含量逐渐升高;随着萃取温度的升高,低沸点化合物含量逐渐减少,高沸点化合物含量逐渐增加。     

生物质能源的开发与利用

本文概述了生物质能源的特征以及发展生物质能源的意义,综述了国内外生物质能源开发与利用的现状,简介了中国石油天然气股份有限公司生物质能源的发展思路、部署及工作进展.中国石油天然气股份有限公司生物质能源发展策略重点放在发展生物柴油和燃料乙醇.本文结合公司生物质能源长期发展战略以及实际工作开展情况分别从生物柴油、燃料乙醇两个方面详细探讨了所面临的生物质能源化工关键技术的需求,并提出相关发展建议.     

一种高选择性固相萃取剂的合成及对汞(Ⅱ)的分离富集特性

制备了二甲酚橙键合硅胶(SGMXO)固相萃取剂,研究了它对常见重金属离子的分离富集行为,发现对水中痕量Hg2 有较好的选择性分离富集效果。系统考察了溶液的pH、过柱流速、洗脱液浓度及流速、柱始漏量及不同金属离子对Hg2 的定量回收的影响。在pH=1.0条件下,可在Cd2 、Pb2 、Cu2 、Mn2 等多种性质相近的金属离子存在时,对Hg2 进行选择性分离富集。所合成的固相萃取剂在使用50次后仍能重复出实验现象。该法用于对实际样品中Hg2 的分离富集,回收率在99%以上。     

动物尿液中盐酸克伦特罗的分子印迹固相萃取-气相色谱-质谱法研究

采用分子印迹聚合物(MIP)固相萃取小柱提取、净化并富集猪尿液中的盐酸克伦特罗分子,用N,O-双三甲基硅基三氟乙酰胺(BSTFA)衍生化,毛细管气相色谱-质谱联用(选择离子模式,选择离子为277、262、243和86)对衍生物分析。优化了MIP固相萃取柱的淋洗条件,考察了MIP固相萃取柱的净化效果和消除基体干扰能力,建立了对动物尿液中盐酸克伦特罗的定性、定量分析的方法。在优化条件下,本法检出限(LOD)为0.51μg/L,定量限(LOQ)为1.00μg/L;不同盐酸克伦特罗加入量的回收率为71.0%~89.3%;相对标准偏差为3.2%~9.7%。将该方法与农业行业标准方法比较,结果吻合较好。但该方法灵敏度和精密度高,操作更为简单、快捷。     

Studies on the Mass Spectra of N‐Aryl α,β‐Unsaturated γ‐Lactams

The mass spectra of a series of N‐aryl α,β‐unsaturated γ‐lactams were studied. Besides the molecular ion, the three characteristic fragments such as [M⁺‐29], [M⁺‐55], and [M⁺‐82] were commonly found in a series of N‐Aryl α,β‐unsaturated γ‐lactams in EI/MS. Further more the mechanism for the interpretation of these fragments is also de scribed.     

反相高效液相色谱柱前衍生荧光法测定肠粘膜中的谷氨酰胺

以邻苯二甲醛及３－巯基丙酸为衍生试剂,５０ｍｍｏｌ／Ｌ磷酸缓冲液（ｐＨ７．０）－乙腈（９４∶６,Ｖ／Ｖ）为流动相,在ＬｉｃｈｒｏｓｏｒｂＲＰ１８（１５０ｍｍ×４．６ｍｍｉ．ｄ．,５μｍ）柱上,研究并建立了测定动物肠粘膜中谷氨酰胺（Ｇｌｎ）的柱前衍生荧光ＲＰ－ＨＰＬＣ法。样品与衍生剂按４∶１进行衍生反应,Ｅｘ＝２３０ｎｍ,Ｅｍ＝３８９ｎｍ;流速为２．０ｍＬ／ｍｉｎ。Ｇｌｎ的保留时间为３．１５８ｍｉｎ,检测限为２５μｍｏｌ／Ｌ（Ｓ／Ｎ＝３．５）,线性范围为５０～３２００μｍｏｌ／Ｌ,ｒ＝０．９９９６。     

Soluble and easily crystallized anthracene derivatives: precursors of solution-processable semiconducting molecules

New soluble anthracene derivatives containing thiophene and phenylenevinylene derivatives were synthesized via well-known synthetic routes. TIPS derivatives were added at the 9,10-positions of anthracene for the solubility and crystallinity. Both of the molecules were found to be promising for high charge mobility and stable organic semiconductors. The soluble anthracene core (TIPSAnt) is a potential precursor for the synthesis of novel semiconducting materials.