用鲁米诺-过氧化氢-铜(Ⅱ)-考马斯亮蓝G250体系反相流动注射化学发光法测定铜(Ⅱ)

建立了一种Luminol-H2O2－Cu（Ⅱ）-考马斯亮蓝G250反相流动注射化学发光分析新方法,线性范围0．005－0．100mg/LCu（Ⅱ）,检出限为0．0015mg/LCu（Ⅱ）,对0．050mg／LCu（Ⅱ）溶液进行10次平行测定,其相对标准偏差为3．6％,干扰离子允许量大。该方法灵敏度、精密度和选择性好,直接用于江河水样中微量Cu（Ⅱ）的测定,取得了满意的结果。     

铜(Ⅱ)-三氮唑偶氮络合物与脱氧核糖核酸相互作用的电化学行为

运用电化学方法研究了铜（Ⅱ）－三氮唑偶氮（2－[2,3,5-三氮唑偶氮]-5－二甲氨基苯甲酸，TZAMB）络合物与脱氧核糖核酸（DAN）的相互作用。在pH2.5(0.05mol/L）邻苯二甲酸氢钾（PBS）缓冲溶液中，DNA与Cu(Ⅱ）－TZAMB络合物形成一种电惰性结合物，使Cu（Ⅱ）－TZAMB络合物的还原峰电流减小。通过循环伏安法、盐效应以及紫外－可见吸收谱证实了是由Cu(Ⅱ）－TZAMB络合物与DNA形成一种插入式的电惰性结合物而使其峰电流下降。根据这种峰电流下降可以测定DNA，测定结果令人满意。     

Cu(Ⅱ)为探针-分光光度法测定半胱氨酸

提出了以Cu（Ⅱ）为探针,分光光度法测定药物中半胱氨酸含量的方法。研究表明:在pH 4.0的乙酸盐缓冲溶液中,半胱氨酸中的巯基（—SH）能使Cu（Ⅱ）还原成Cu（Ⅰ）,生成的Cu（Ⅰ）与SCN^-反应生成CuSCN沉淀,所得Cu（Ⅱ）的量为定量生成CuSCN沉淀后留存的过量Cu（Ⅱ）的量,将此Cu（Ⅱ）的测定值间接换算成试样中半胱氨酸的含量。溶液的吸光度和半胱氨酸的质量浓度在0.20～9.0 mg·L^-1之间呈线性关系,表观摩尔吸光率为6.05×10⁴ L·mol^-1·cm^-1。方法用于模拟样品中半胱氨酸含量的测定,回收率在96.0%～103%之间,测定值的相对标准偏差（n=6）在0.67%～1.4%之间。     

新型含草酰胺桥基的[14]N_4大环的Cu(Ⅱ)-M(Ⅱ)(M=Cu,Ni)双核配合物合成与磁性

合成和表征了四个新的大环上含有草酰胺桥基的双核配合物[Cu(η-L1）ML22］(ClO4)2·nH2O,其中L1为2 ,3 －二羰基－5 ,6 ： 13, 14-二苯基-1 ,4 ,8 , 11－四氮杂十四环－7 , 11－二烯;L2 ＝乙二胺（en）,M=Cu(1),M=Ni（2）;L2 = 1 ,10－邻菲咯啉（phen）,M=Cu(3),M=Ni(4)。测定了配合物（3）和（4）的变温磁化率（4 ．2 －300K）,求得磁参数分别为（3）J＝－99．1 cm－1 和（4）J＝-47．0 cm-1,表明Cu（Ⅱ）、-Cu（Ⅱ）、Cu（Ⅱ）-Ni（Ⅱ）离子间存在反铁磁自旋交换相互作用。     

1,8-二羟基萘-3,6-二磺酸键合硅胶的制备、性质及其富集分离痕量元素的研究

本文介绍了1，8－二羟基萘－3，6－二碳酸键合硅胶（HNSA·SG）的合成方法，研究了HNSA·SG的性质及其对痕量元素的富集和分离行为。结果表明：HNSA·SG能在6mol／LHCl～pH8．0的溶液及常见有机溶剂中稳定存在；对Pd（Ⅱ）和Cu（Ⅱ）的最大吸附量分别为353μmol／g和197μmol／g；pH2．0时，可用HNSA·SG柱将痕量Pd（Ⅱ）与常见过渡金属离子分离；pH6．0时，HNSA·SG柱可将痕量Cu（Ⅱ）与性质相近的Pb（Ⅱ）、Cd（Ⅱ）、Mn（Ⅱ）、Co（Ⅱ）、Ni（Ⅱ）等金属离子分离。经柱富集后，可用分光光度法测定水样中痕量Cu（Ⅱ），测定下限可达ng／g级。     

Cu(Ⅱ)-茜素红S-甲基紫-聚乙烯醇体系光度法测定痕量铜

提出了 Cu（Ⅱ）-茜素红 S-甲基紫-聚乙烯醇三元配合物体系光度法测定 Cu（Ⅱ）的新方法,在聚乙烯醇存在下,Cu（Ⅱ）-茜素红 S-甲基紫形成稳定的有色配合物,通过测定该化合物的吸光度而测定Cu（Ⅱ）含量。测定了天然水样。试验表明,方法有较好的灵敏度和选择性,精密度可靠,适用于水样中痕量Cu（Ⅱ）的测定。     

酰基吡唑啉酮配合物的合成、结构、量化计算及生物活性

在溶液中合成了1－苯基－3－甲基－4－苯甲酰基－吡唑啉酮－5（HPMBP）的Co(Ⅱ）、Ni（Ⅱ）、Cu（Ⅱ）、Zn（Ⅱ）配合物,对配合物进行了元素分析和红外光谱表征。用X射线衍射方法测定了Zn(Ⅱ）配合物的晶体结构,用密度泛函方法对Co(Ⅱ）及Zn（Ⅱ）配合物进行了量子化计算,生物活性实验表明四种配合物对大肠杆菌和金黄色葡萄球菌均有一定的抗菌作用。     

二氧化碳与丙烯直接合成甲基丙烯酸用CuPMo／TiO2催化剂的研究

 用溶胶－凝胶法以磷钼酸（MPA）的铜盐溶液水解钛酸四丁酯制备了CuPMo／TiO2催化剂，并用ICP，XRD，TG－DTA，IR，TPD－MS和微反技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化性能．结果表明：杂多钼酸盐与TiO2表面通过O2－桥发生键联．在623K下，杂多阴离子仍保持其原有的Keggin结构；CO2在Lewis酸位Cu（Ⅱ）和Lewis碱位Cu－O－Mo桥氧的协同作用下形成卧式吸附态Cu（Ⅱ）←O－（CO）←（O－－Cu）；丙烯以分子吸附态在催化剂上吸附；在空速1500h－1，压力1MPa和温度563K的反应条件下，丙烯的转化率为4．2％，甲基丙烯酸的选择性为96％．     

7,8—二甲基—10—（D—1—核糖醇基）—异咯嗪半合成中间体气相色谱分析

提出以三氟乙酸酐作为衍生化试剂,将核黄素半合成中间体Ｎ－（Ｄ）－脱氧核糖醇基－３,４－二甲苯胺（Ⅰ）及４,５－二甲基－Ｎ－（Ｄ）－脱氧核糖醇基－２－偶氮苯基苯胺（Ⅱ）转化为低沸点易汽化物质,采用以苯乙酮作为内标,测定中间体（Ⅰ）和（Ⅱ）纯度的气相色谱法。方法具有分析速度快、准确度高、重现性好等优点,方法回收率（Ⅰ）为９６．９％￣１０１．２％、（Ⅱ）为９９．４％￣１００．４％,相对标准偏差（Ⅰ）在４     

硫酸铵-锌试剂-Tween-80体系萃取分离铜(Ⅱ)、钴(Ⅱ)、镍(Ⅱ)、锌(Ⅱ)、镉(Ⅱ)、锰(Ⅱ)

研究了（NH4）2SO4－Zincon（锌试剂）－Tween-80体系萃取分离金属离子Cu（Ⅱ）、Co（Ⅱ）、Ni（Ⅱ）、Zn（Ⅱ）、Cd（Ⅱ）、Mn（Ⅱ）的行为。试验表明,Cu（Ⅱ）、Co（Ⅱ）、Ni（Ⅱ）在pH6～9范围内,与Zincon形成的螯合物可被Tween－80相完全萃取,而Zn（Ⅱ）、Cd（Ⅱ）、Mn（Ⅱ）基本不被萃取,进而实现了Cu（Ⅱ）、Co（Ⅱ）、Ni（Ⅱ）与Zn（Ⅱ）、Cd（Ⅱ）、Mn（Ⅱ）混合离子的定量萃取分离。     

QuEChERS-超高效液相色谱-三重四极杆质谱测定野生食用菌中尼古丁

云南省拥有大量的野生食用菌资源，其中内源性的尼古丁近年来受到了广泛的关注。该研究以野生食用菌为研究对象，将QuEChERS方法进行改进，优化了提取溶剂、净化条件等，并针对尼古丁在超高效液相色谱不同流动相条件下的色谱行为进行优化，结合三重四极杆质谱仪，建立了测定野生食用菌中尼古丁的高效、快速、高灵敏的方法。结果表明，氨水-乙腈（6：94，v/v）混合溶液能够较好地提取野生食用菌中的尼古丁，提取溶液经石墨化碳黑（GCB）和N-丙基乙二胺（PSA）混合填料净化后，利用0.1%（体积分数）氨水溶液和乙腈作为流动相，正离子多反应监测（MRM）模式下，得到的尼古丁色谱峰形较好，响应较高。尼古丁在0.05~50.0 μg/L范围内线性关系良好，相关系数（r²）为0.9999，定量限为0.2 μg/kg，检出限为0.05 μg/kg。3个加标浓度下的平均回收率为86.3%~96.4%，相对标准偏差为4.4%~6.3%。该方法的灵敏度和回收率均符合食用菌产业中尼古丁的快速测定要求。     

Validation and application of a method for the determination of nicotine and five major metabolites in smokers' urine by solid-phase extraction and liquid chromatography-tandem mass spectrometry

An SPE-LC-MS/MS method was developed, validated and applied to the determination of nicotine and five major metabolites in human urine: cotinine, trans-3'-hydroxycotinine, nicotine-N-glucuronide, cotinine-N-glucuronide and trans-3'-hydroxycotinine-O-glucuronide. A 500 microL urine sample was pH-adjusted with phosphate buffer (1.5 mL) containing nicotine-methyl-d3, cotinine-methyl-d3 and trans-3'-hydroxycotinine-methyl-d3 internal standards. For the unconjugated metabolites, an aliquot (800 microL) of the buffered solution was applied to a 30 mg Oasis HLB-SPE column, rinsed with 2% NH4OH/H2O (3.0 mL) and H2O (3.0 mL) and eluted with methanol (500 microL). The eluate was analyzed isocratically (100% methanol) by LC-MS/MS on a diol column (50 x 2.1 mm). For the total metabolites, a beta-glucuronidase/buffer preparation (100 microL) was added to the remaining buffered solution and incubated at 37 degrees C (20 h). An aliquot (800 microL) of the enzymatically treated buffered solution was extracted and analyzed in the same manner. The conjugated metabolites were determined indirectly by subtraction. The quantitation range of the method (ng/mL) was 14-10,320 for nicotine, 15-9800 for cotinine and 32-19,220 for trans-3'-hydroxycotinine. The validated method was used to observe diurnal variations from a smoker's spot urine samples, elimination half-lives from a smoker's 24 h urine samples and metabolite distribution profiles in the spot and 24 h urine samples.     

Determination of Nicotine in Cartridge-Based Electronic Cigarettes

Electronic cigarettes are a relatively new form of nicotine delivery and their popularity is increasing rapidly. One concern regarding the safety of electronic cigarette is quality control during their manufacture, including whether the nicotine concentration matches the labelling. An assay was developed to evaluate the concentration of nicotine in electronic cigarette cartridges. For nicotine extraction, the pad was removed from the cartridge. Deuterated nicotine solution (1 µg), used as the external standard, was added to the pad and allowed to penetrate into the matrix. The pad was treated with 50 mL of 50% (v/v) methanol/deionized water in an ultrasonic bath for fifteen minutes at ambient temperature. After sonication, the extract was further diluted with deionized water and then analyzed by ultra-high performance liquid chromatography–tandem mass spectrometry. The recovery of nicotine-d₄ was 81.5 ± 3.7%. Based on the recovery, the nicotine concentration in the electronic cigarette cartridges was 11.9 ± 1.3 mg, which was lower than the labelled concentration (16 mg). The nicotine concentration did not vary significantly between cartridges within one pack or between packs. The nicotine concentration in the electronic cigarette cartridges was determined by this assay. Differences between labelled and actual nicotine concentrations may affect clinical trials.     

Determination of tobacco alkaloids in single plant cells by capillary electrophoresis

A new capillary electrophoresis system with direct UV detection for the analysis of the tobacco alkaloids nicotine, nornicotine and anabasine in plant microsamples was developed. An electrolyte containing a high concentration of citric acid to provide good buffer capacity at pH 3.6 was found to be most suitable in terms of sensitivity and separation efficiency. At this low pH the tobacco alkaloids are present in cationic form, showing high mobility and increased UV absorption. This system was used for the analysis of nicotine in single epidermal leaf cells of tobacco plants. Only vacuolar concentrations of nicotine were determined, as the vacuole occupies >95% of the entire volume in epidermal cells. The procedure of sample acquisition and preparation for nicotine analysis of vacuolar samples in the pl range is shown. The results indicate a gradient of nicotine from the leaf base to the tip with higher concentrations present in the cells at the tip. Compared to simultaneously measured bulk leaf samples containing all types of cells, tissues and compartments, the concentrations in epidermal cells are much higher. As nicotine is the major defence substance against insects in tobacco and the epidermis is the most exposed leaf tissue this result is physiologically plausible.     

阳极改性对微生物燃料电池处理秸秆水解物性能影响

以玉米秸秆稀酸水解液为阳极底物,用污水处理厂活性污泥为产电微生物菌源构建双室微生物燃料电池(MFC),采用三种不同方法改性阳极碳毡,并对其MFC产电性能进行研究。结果表明,以未改性碳毡(CC)、HNO_3酸解CC(HNO_3/CC)、壳聚糖改性CC(chitosan/CC)、PDADMAC/α-Fe_2O_3层层自组装改性碳毡(PDADMAC/α-Fe_2O_3/CC)的MFC的最大产电量分别为248、315、452和522 mV,最大功率密度分别为54.6、92.7、203.8和248.1 mW/m~2,COD的去除率分别为82.21%、81.46%、82.53%和86.44%。循环伏安曲线显示,PDADMAC/α-Fe_2O_3层层自组装改性的阳极碳毡具有较高的氧化还原电位。电化学阻抗谱图表明,PDADMAC/α-Fe_2O_3层层自组装改性碳毡的极化内阻最小,为7Ω。几种改性材料为阳极的MFC性能依次为PDADMAC/α-Fe_2O_3/CC壳聚糖/CCHNO_3/CC空白CC。     

Occurrence,fate and determination of tobacco (nicotine) and alcohol (ethanol) residues in waste- and environmental waters

This review includes one hundred and two peer reviewed papers that focus on metabolic residues of the two most used licit drugs globally, nicotine (nicotine, cotinine, trans-3’-hydroxycotinine – HCOT) and alcohol (ethyl sulphate and ethyl glucuronide), in waste- and environmental waters. Sampling strategies and analytical methods are also summarised and discussed. Although grab sampling is the most widely applied method for collecting environmental samples (74% cases), wastewater samples are typically composite samples collected automatically at the wastewater treatment plants (66% cases). Sample preparation and analysis usually include solid-phase extraction (SPE) followed by reverse-phased liquid chromatography with tandem mass spectrometry detection (RP-LC-MS/MS) for nicotine residues. In contrast, alcohol residues are commonly determined via direct injection onto the LC-MS/MS using an ion-pair reagent to improve retention, leaving room for method improvement, e.g., introducing a suitable extraction procedure to achieve lower detection limits and quantification. In comparison to alcohol residues, more studies look into nicotine residues (85% of the studies). Concentration ranges for nicotine, cotinine, HCOT and ethyl sulphate were < 424,000, < 42,300, 50–52,000 and 500–33,000 ng/L in wastewater influents and 15–32,000, < 18,000, 15–1,552 and < 500 ng/L in effluents, while nicotine (12.6–947 ng/L) and cotinine (17–62 ng/L) were detected in reclaimed waters. Among environmental waters, the highest concentrations of nicotine residues were measured in surface waters (nicotine: < 9,340 ng/L, cotinine: < 6,582 ng/L and HCOT: 14–777 ng/L), while their concentrations in groundwater and drinking water were generally in the low ng/L range. This review also reveals the discrepancy between the number of studies in developed countries (90%) compared to developing countries and the need for more studies in the former, where most wastewater flows untreated into the environment.     

An improved headspace solid-phase microextraction method for the analysis of free-base nicotine in particulate phase of mainstream cigarette smoke

The content of free-base nicotine in cigarette smoke is a controversial subject, partly due to methodological issues. In this investigation, an improved method to measure free-base nicotine in cigarette smoke using headspace solid-phase microextraction (HS-SPME) combined with GC/MS analysis, was developed and validated for this purpose. Cigarette smoke particulate phase (PP) was collected onto a 44 mm glass fiber filter pad. The pad was cut in halves with one half used to determine the concentrations of total nicotine and water. The remaining half was analyzed by HS-SPME for free-base nicotine. The following factors were found to have a significant impact on the responses of free-base nicotine: SPME fiber type, pre-equilibrium time before HS-SPME, extraction time and temperature, PP water content, and the solvent used for the preparation of standards. It was also found that the impact of PP water content on the determination of free-base nicotine from smoke sample could be corrected by a water correction factor calculated based on an experimentally determined reciprocal model. The precision of the method was evaluated with smoke samples of reference cigarettes: Canadian flue-cured monitor and Kentucky reference 2R4F. The RSD values obtained were in the 12.8-16.8% range.     

High-throughput dynamic microwave-assisted extraction on-line coupled with solid-phase extraction for analysis of nicotine in mushroom

A simple and low-cost high-throughput dynamic microwave-assisted extraction (HTDMAE) device was firstly assembled and validated by the extraction of nicotine in mushroom samples. In this device, a household microwave oven was applied to provide the microwave energy; a vacuum pump was used to deliver the solvent. Compared with traditional dynamic microwave-assisted extraction method, the sample throughput and microwave energy utilization were improved by the HTDMAE, up to 20 samples could be treated simultaneously in 9 min. Taking extraction of nicotine in mushroom sample as an example, a method was established with extraction, separation and enrichment of nicotine in a single step by the device on-line coupled with solid-phase extraction (SPE). Nicotine was first extracted from the mushroom samples with water under the action of microwave energy, and then directly introduced into the SPE column which was packed with cation-exchange resins. Subsequently, the nicotine trapped on the resins was eluted with methanol-ammonia (95:5, v/v) and determined by high-performance liquid chromatography. The limit of detection of nicotine obtained is 5.6 μg kg(-1) in fresh mushroom sample. The recovery of nicotine in mushroom samples is in the range of 87.4-104.0%. The proposed method which significantly reduced the overall analysis time and increased sample throughput should be favored for routine analyse of complex solid sample.     

原子发射光谱法间接测定烟碱的研究

本文提出了测定烟碱的间接原子发射光谱分析新方法。根据在盐酸介质中，烟碱被质子化后能与雷氏铵盐定量形成难溶化合物的性质，将沉淀溶解后，用原子发射光谱法测定铬来间接测定烟碱的含是。实验中研究了沉淀反应的最佳酸度、雷氏铵盐用量及放置时间等条件，选择了最佳的沉淀溶解剂，考查了共存离子的影响及方法的回收率和精密度。用本法测定了烟叶和香烟样品中的烟碱的含量，结果与光度法比较一致。方法的相对标准偏差为３．１６％     

Potentiometric determination of nicotine in tobacco products with a nicotine-sensitive liquid membrane electrode

A simple potentiometric method with standard additions is described for the rapid determination of nicotine in tobacco products. A nicotine-sensitive electrode with a liquid membrane of nicotine hydrogen tetra(m-chlorophenyl)borate dissolved in o-nitrotoluene is used. The electrode exhibits near-Nernstian response to monoprotonated nicotine cation activity from 0.08 to 10^-5 M, in the pH range 4–7. Nicotine down to 2 mg per g of sample can be determined with a standard deviation of about 0.5 mg of nicotine. Comparison with an official method gave satisfactory results.