预反应微波密封消解催化光度法测定尿碘研究

提出尿碘的预反应微波密封消解催化光度法，该法解决了微波密封消解尿样过程中有机物反应产生气体造成内压过大的关键问题，将消解时间由传统的1h缩短至10min左右，可同时消解上百个样，将该法用于质控样测定，结果符合要求。实际尿样测定RSD≤1．1％，回收率90．1％－110．4％，该法有较好的实用性，可作为常规法测尿碘的等效或取代方法。     

微波密封消解催化光度法测定尿中碘

１引言 本文首次提出微波密封消解尿样，很好地解决了微波密封消解尿样过程中有机物产生降密气体造成密封管内压力过大的问题，建立了微波密封消解催化光度法快速测定尿中碘的新方法，本文摒弃了昂贵的聚四氯乙烯高压罐，采用普通 １０ ｍＬ比色管，同时消解上百个样品，将消解时间由标准法的 １ｈ缩短至约 １０ ｍｉｎ。本法节时省电，快速准确，操作简便，成本低廉，有较好的实用性，可作为常规法测定尿中碘的等效或取代方法。２实验部分２．１仪器及主要试剂ＷＰ９００格兰仕家用微波炉（广东顺德格兰仕电器有限公司），７２２光栅分光光…     

微波消解ICP-AES法测量铁锰结壳中的砷

借助微波密闭消解技术和电感耦合等离子体原子发射光谱(ICP-AES)方法,研究试样溶解和仪器测定的最佳工作条件,建立了快速测定海底铁锰结壳中微量砷的方法.结果表明,微波密闭消解法处理铁锰结壳,效率高、损失少、空白低.微波密闭消解和ICP-AES相结合,分析操作简单,结果准确,并能多元素同时测定.该方法相对标准偏差小于5% (n=5),砷的回收率在102%～107%之间,检出限为5.55 μg/L,适合铁、锰含量高的海底结壳样品中砷的定量分析.     

微波消解ICP-MS法测定广西北部湾海鸭蛋中硒和锗的含量

以硝酸-过氧化氢（体积比为5：3）混合溶液为消解剂,微波消解法处理海鸭蛋样品,采用电感耦合等离子体质谱法测定样品溶液中的硒和锗的含量。选择适合的同位素元素,运用碰撞室技术（CCT）降低多原子离子对元素硒、锗的干扰,用钇作为在线内标。硒、锗工作曲线的线性范围均为0．0-100．0ng／mL,相关系数r=0．9996;硒、锗的检出限分别为1．1,0．15ng／mL,测定结果的相对标准偏差分别为4．78％,5．70％（n=6）,加标回收率为92．2％-104．0％。用该法测定国家标准物质黄鱼（GBW08573）中硒的含量,测定值在标称值范围内。     

微波消解技术在难溶贵金属(铂)化合物分析中的应用

本文提出了微波密闭消解处理难溶贵金属化合物Pt（NH3）4Cl2、Pt（NH3）2Cl2、Pt（NH3）2（NO2）2和K2PtCl4的方法；对比了它们的微波密闭消解和传统分解条件；分析了消解后Pt的含量。结果表明：上述各类化合物对应消解时间分别为传统分解法的1／15、1／13和1／11；分析手段随之简化且总分析流程大大缩短；两种方法测得的Pt含量吻合。     

微波消解-氢化物发生原子荧光光谱法测定头发样品中的微量汞

对微波消解-氢化物发生原子荧光光谱法测定头发样品中微量汞的方法进行了研究。采用HNO3和H2O2作消解剂，在最佳微波消解条件和测定条件下，线性回归线方程为Y=259．7c 155.4，相关系数r=0.9996，检出限为0．01ng／mL，线性范围为0-20ng／mL。测定结果的相对标准偏差为0，4％～2．8％，回收率为94，0％-102．0％。     

非完全消化-分光光度法测定环烷酸钴中钴

用非完全消化法处理环烷酸钴样品，即先用(1 3)HClO4-HNO3混合酸及H2O2消解破坏样品，使Co^2 游离出来，再用乳化剂Triton X-100溶解残存的环烷酸根而配制成透明的样品溶液。采用Co^2 -5-Br-PADAP-OP显色体系测定钴，在硫磷混合酸介质中共存元素与5-Br-PADAP形成的有色络合物被分解破坏，从而达到消除干扰的目的。建立了非完全消化-分光光度法测定环烷酸钴中钴的分析方法。对测定条件、线性范围进行了考察。测定结果与灰化法-分光光度法一致，相对标准偏差小于0．7％，加标回收率97．4％～103．0％。     

石墨炉原子吸收光谱法测定红薯粉丝中的痕量铅含量

为建立对红薯粉丝中有害元素铅含量的测定方法,采用微波消解法处理红薯粉丝样品,加入2％NH4H2PO4和0．2％Mg（NO3）：混合液作为基体改进剂,用石墨炉原子吸收分光光度法测定了红薯粉丝中铅含量。结果表明,红薯粉丝样品中铅在2．0—40．0ng／mL的范围内吸光度与含量呈良好的线性关系（r=0．9956）,平均回收率为98．06％,RSD=1．67％（n=5）。可见该法简单、准确,可作为检测红薯粉丝中铅含量的方法。     

石墨炉原子吸收光谱法测定中药口服液中的铬铅镉

利用石墨炉原子吸收光谱法测定,采用常温消解和密闭微波消解等方式处理口服液样品,并进行比较。结果表明,采用HNO3 HClO4 H2O2作为消解试剂用常温消解方式进行消解后,可不加基体改进剂直接进行测定,在此基础上研究了石墨炉原子吸收测定的最佳条件。应用这种方法测定了双黄连、清开灵、生脉饮和抗病毒口服液中痕量镉、铬和铅,RSD小于5．0％,回收率在83．4％～113％。     

微波消解-分光光度法测定石油焦中的钒

研究了用微波消解分光光度法测定石油焦中的钒。在石油焦样品处理中采用了常规溶样及微波消解两种方法。重点研究了微波消解石油焦样品的方法，详细考察了微波消解时样品的最佳用量、消解压力、功率、时间，建立了最佳微波消解程序。结果表明两种方法测定结果基本吻合。样品测定的RSD小于4、02％，加标回收率均在98．6％～102．7％之间，但微波消解法的溶样速度是常规法的10倍。钒的线性范围为0～8．0g／L。结果表明，微波消解分光光度法测定石油焦中的钒是一种快速、准确且无环境污染的方法。     

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.