固相微萃取-脉冲火焰光度法测定大气及水中的路易氏剂

建立了固相微萃取（SPME）与气相色谱/脉冲火焰光度检测器（GC／PFPD）联用测定大气和水中路易氏剂及其水解产物的方法。探讨了影响SPME萃取效率的萃取头类型、萃取时间、解吸时间等因素。优化了PFPD的条件参数、衍生化试剂及衍生条件。在优化的条件下，路易氏剂衍生产物的响应值与浓度有良好的线性关系。本方法对水中路易氏剂及其水解产物的检出限为0．1μg/L；气体中路易氏剂的检出限为10ng／m^3；水样的加标回收率为96．7％-102．1％；气体样品的加标回收率为94．9％-103．0％；RSD为2．06％。     

微波辅助萃取-气相色谱-质谱法测定大气可吸入颗粒物中痕量多环芳烃

建立了微波辅助萃取－气相色谱－质谱联用测定大气可吸入颗粒物中痕量多环芳烃（PAHs）的分析方法，优化了萃取时间、溶剂用量、微波辐射功率等微波萃取条件，并与超声波萃取方法进行了对照研究。结果表明：除了苊、芴外，微波萃取方法的回收率在85％－130％之间；方法的检出限在0.002-0.016μg/m^3之间。通过实际样品中PAHs的分析表明，该法快速、溶剂用量小，满足痕量分析的要求。     

微波辅助萃取气相色谱-质谱联用测定蔬菜中的扑草净

研究了微波辅助萃取气相色谱．质谱联用测定植物样品中扑草净的方法，比较了几种不同溶剂的微波萃取效率，从而选取二氯甲烷为萃取溶剂，并采用三因素三水平的正交设计试验对溶剂体积、微波辐射时间、微波功率进行了优化。在优化的实验条件下分析了合成菠菜样品，对0．2μg/g和0．02μg/g的合成菠菜样品，回收率分别为99．5％和92．5％，相对标准偏差分别为5．0％和ll％，方法的线性范围为1．0—400ng／g，检出限为0．22ng／g。方法适合于分析植物样品中的扑草净。     

固相微萃取-气相色谱-质谱联用分析水中的痕量扑草净

研究了固相微萃取－气相色谱－质谱联用测定水中扑草净的方法，采用聚丙烯酸酯（PA）萃取头，对影响固相微萃取萃取效率的萃取时间、搅拌速度、pH值以及盐度等进行了优化。在优化实验条件下，方法线性范围在0．1mg/mL-1000ng/mL之间，检出限为1．5ng/L。用该法分析了合成井水、自来水和湖水样品，回收率在85．4％－89．1％之间，相对标准偏差在1．8％－5．2％之间。本方法适合于水中痕量扑草净的分析。     

顶空衍生固相微萃取-气相色谱质谱法测定聚碳酸酯树脂中的环境雌激素

建立了固相微萃取-气相色谱质谱联用测定聚碳酸酯树脂中环境雌激素4-枯基苯酚和双酚A的分析方法。优化了固相微萃取纤维、萃取温度和时间、解吸时间、搅拌速度、pH等萃取条件及衍生化温度和时间、衍生化方式等衍生化条件，并对样品浸泡时间、浸泡温度等进行了研究。方法的线性范围为0．05μg/L～1mg／L，4-枯基苯酚和双酚A的检出限分别为50ng／L和0．5ng／L，相对标准偏差（RSD，n=5）分别为5．2％和1．6％，平均回收率（n=3）在90．50％～107．3％之间，该方法简单、快速、灵敏。     

固相萃取-气相色谱-质谱法测定猪组织中沙丁胺醇残留量

建立了动物组织中沙丁胺醇残留量固相萃取-气相色谱-质谱分析方法。动物组织样品经过葡萄糖醛甙酶酶解后调节pH至9．5，然后用异丙醇／乙酸乙酯混合溶剂液液分配去除杂质，旋转浓缩后用乙酸铵缓冲溶液溶解经SCX固相萃取（SPE）柱净化，洗脱液经氮气吹干后用双三甲基硅基三氟乙酰氨（BSTFA）衍生，采用选择离子模式（86、350、369、440）进行测定，外标法定量。检出限为0．10μg/kg。在添加浓度0．5～5．0μg/kg范围内，平均添加回收率在66．4％～82．4％，相对标准偏差（批内）（CV）在3．5％～5．9％之间；批间（CV）在2．2％～4．8％之间。衍生物的峰面积与样品浓度在0．002～0．50mg／L范围内呈良好的线性关系，线性回归系数大于0．999。     

顶空固相微萃取-气相色谱-质谱联用分析纺织品中挥发性有机物

建立了顶空固相微萃取（HSSPME）-气相色谱（GC）-质谱（MS）联用测定纺织品中甲苯、4-乙烯基环己烯、苯乙烯、萘和1-苯基环己烯5种挥发性有机物（VOCs）的分析方法。选择聚二甲基硅氧烷（PDMS）作为萃取涂层，优化了SPME的萃取条件，包括平衡时间、萃取时间、萃取温度、顶空体积、离子强度、搅拌速度、解吸温度和时间以及GC—MS仪器条件。对于甲苯、4-乙烯基环己烯、苯乙烯、萘和1-苯基环己烯方法线性范围分别为0．087～870、3．32～3320、2．28～2280、0．015～150和0．050～50．0ng／g；检出限分别为0．005、0．042、0．670、0．008和0．011ng／g。实际样品加标回收率在80．1％～122％之间，RSD在0．8％～8．6％之间。方法符合纺织品中痕量VOCs的快速分析要求。     

土壤中痕量水胺硫磷的微波辅助萃取-固相微萃取-GC-MS法测定

研究了微波辅助萃取(MAE)-固相微萃取(SPME)联合萃取、气相色谱-质谱法(GC-MS)测定土壤中水胺硫磷的分析方法；采用正交设计试验优化了微波升温程序、萃取温度、萃取时间、萃取溶剂体积等MAE条件；研究了SPME萃取涂层、萃取时间、解吸温度等对萃取效率的影响；方法的线性范围在1．O～20μg/L之间，检出限为O．49ng/g；测定25、100ng/g加标土壤样品，回收率分别为79％和107％。RSD分别为2．6％和6．5％；方法综合了MAE快速高效和SPME富集浓缩的优点，以水为萃取溶剂，特别适合于固体样品中痕量有机物的分析。     

海水中雪松醇的SPME-GC-MS测定及其与赤潮关系

建立了用固相微萃取-气相色谱-质谱联用测定海水中雪松醇的分析方法；优化了萃取涂层、萃取时间、萃取温度、搅拌速度、介质离子强度、解吸温度和时间等实验条件；方法的线性范围为0.020-10μg/L，检出限为0.008μg/L，相对标准偏差在6.8％-8.5％之间，回收率在90％-94％之间；分析海水样品发现赤潮海水中雪松醇的质量浓度是非赤潮海水的1-3倍，通过对海水中雪松醇质量浓度变化的监测，可能对赤潮的预报和防治提供依据；该法简便、快速、灵敏度高，满足海洋赤潮监测快速化要求。     

固相萃取-气相色谱-质谱联用法测定人尿中11种蛋白同化激素

建立了固相萃取（SPE）-气相色谱-质谱联用（GC-MS）同时测定尿样中11种蛋白同化激素的分析方法,并将该方法用于关雄酮（MADE）阳性尿的分析。尿样前处理采用含500mg填料的C18 SPE柱净化浓缩,然后进行酶解,最后由液-液萃取获得待测样品。为了提高灵敏度,待测样品采用硅烷化衍生后进行GC-MS分析。在选择离子监测（SIM）模式下,采用甲睾酮（MT）为内标进行定量分析,方法检出限为0．1～2．0μg·L^-1;分析加标实际样品,回收率在70．5％～121％,相对标准偏差为1．1％～13．9％。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.