催化光度法同时测定铜和铁

利用具有Landolt效应的（NH4）2S2O8－KI－Na2S2O3体系催化光度法同时测定铜和铁（以淀粉为指示物）。可不经分离直接用于人发、大米及绿豆中痕量铜和铁的测定,结果满意。     

高分辨质谱解析委内瑞拉奥里常渣减黏反应杂原子化合物组成变化

运用电喷雾-傅里叶变换离子回旋共振质谱仪(ESI-FT-ICR MS),研究委内瑞拉奥里常渣减黏裂化反应前后杂原子组成及分布.常渣中O2类化合物的相对丰度最大,减黏裂化反应使O2、O1、N1O2、S1、O1S1、O2S1类化合物减少,甚至消失,而N1、N2、N2O1、N2S1、N3、N3O1、N1S2类化合物增多,减黏...     

锑湿法冶金浸取液中微量金属元素的光谱测定

本文制定了溶液干渣法定量测定锑湿法冶金浸出液中微量金属元素的分析方法,采用加入锑的方法,消除浸取液中锑含量变化对待测元素的影响。待测元素的测定下限为1.5×10~4—5×10~2克/升,所测定元素在不同浓度范围的变异系数小于20％。     

磷酸铵沉淀-DRC-ICP-MS法测定菜籽油中的微量硫

建立了磷酸铵沉淀-电感耦合等离子体质谱法测定菜籽油中微量S的检测方法。采用微波消解处理样品,选择48SO+作为观察信号,在动态反应池(DRC)内,O2作为反应气,与试样中的S元素生成48SO+,消除15N17O+,16O16O+等物质带来的质谱干扰;针对四级杆无法去除的48Ca+干扰(丰度:0.187%),通过加入磷酸铵生成沉淀去除,优化了沉淀所需磷酸铵用量及pH大小。方法的检出限为0.4 mg/kg,对精炼菜籽油和初榨菜籽油进行不同水平的添加,回收率为82.4%~112%,精密度为1.6%~3.9%(n=7)。方法可用于菜籽油中S元素的测定。     

聚4-(2-吡啶偶氮)间苯二酚膜修饰玻碳电极测定过氧化氢

利用循环伏安法（-0.5～2.2 V）将4-(2-吡啶偶氮)间苯二酚(PAR)电聚合修饰到玻碳电极表面,制备了聚PAR膜过氧化氢（H2O2）传感器。 并采用循环伏安法和计时安培法研究了修饰电极的电化学性质和对H2O2的响应特性。 结果表明,PAR膜修饰电极在低的电位下对H2O2具有优异的电催化还原效应。 在磷酸盐缓冲溶液中(pH=8.0)用计时安培法对H2O2进行了测定（工作电位0.45 V）,响应电流与其浓度在2×10-5～1.76×10-3 mol/L范围内呈良好的线性关系,线性相关系数r=-0.999 83,检测限(S/N=3)为3 μmol/L。该修饰电极灵敏度高、稳定性好、制备简单,在H2O2的测定中对抗坏血酸、尿酸和葡萄糖有较好的抗干扰性。     

氧瓶-离子色谱法测定树脂中的卤素和硫元素

含有卤素和硫元素的树脂样品经氧瓶法燃烧分解，用含H2O2的去离子水溶液吸收，离子色谱法分离测定．本法简便、快速，特别适于测定树脂中不活泼的卤族元素，且可同时测定。CI、S的相对标准偏差分别为0．22%,0．36％，最大绝对误差分别为0．43％和0．80％。树脂中CI、S的含量在0．28mmol/g～14mmol／g内可用此法准确测定，其最低检测限为0．05mmol／g。     

含Ce2O3炼钢精炼渣熔化及流动特性的研究

采用真空碳管炉制备得到含Ce2O3三元及四元炼钢精炼渣,分别利用X射线衍射仪、炉渣熔点测定仪和RTW-10型熔体物性仪对渣的物相、熔化温度及粘度进行检测分析.研究表明:Ce在精炼渣中以正三价的形式稳定存在;CaO-Al2O3-Ce2O3三元渣的熔化温度范围为1465～1516℃;CaO-Al2O3-Ce2O3-SiO2四元渣的熔化温度范围为1348～1361℃,1500℃时的粘度值范围为0.289～0.497 Pa·s,其中46%CaO-38%Al2O3-5%Ce2O3-10%SiO2(质量分数)精炼渣具有良好的熔化和流动特性.     

富锰渣冶炼烟尘的综合利用

本试验提出了一个从富锰渣冶炼烟尘中回收某些有价值元素的湿法冶炼工艺。首先烟尘直接用硫酸处理,然后通过控制适当的pH,锌锰被沉淀分离开来。最后,把它们转化为相应的硫酸盐和碳酸盐。在烟尘中的微量元素如镓、铟、铊等是通过萃取法分别提取的。试验表明,辛醇-(2)和N,N-二(1′-甲基庚基)乙酰胺是有效的萃取剂。     

过(氧)硫酸根中硫和氧及臭氧中氧的氧化数与相应的氧化还原电对

提出了氧族元素教学中有关S2O2-8(SO2-5)中硫和氧及O3中氧的氧化数、氧化性本质以及这两种物质与其还原产物所构成的电对的表示问题。对与S2O2-8和O3相关的元素电势图和氧化态-吉布斯自由能图的表示提出了建议,并建议将过二硫酸(以及过一硫酸)及其盐归属于氧系列,放在过氧化氢之后讨论。     

ICP-MS法测定菊花茶中砷镉铜铅锌

采用电感耦合等离子体质谱(ICP-MS)法,对菊花茶中微量元素砷、铅、镉、铜、锌进行了分析。用HNO3-H2O2消解样品,通过在线加入内标校正基体效应和接口效应,通过修正方程校正质量数干扰。测定元素校正曲线的相关系数都在0.999 5以上,各元素的检出限在0.020~0.14μg.L-1,样品分析结果的相对标准偏差为1.5%~4.3%(n=10),加标回收率在93.9%~101.6%之间。用此方法测定茶叶标准物质GBW 07605,结果与标准值基本一致。     

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.