光电直读光谱法测定高速工具钢中多元素

利用美国贝尔德公司生产的ＢＡＩＲＤＳＰＥＣＴＲＯＶＡＣ２０００（ＤＶ－５，ＨＲ－４００光源）光电直读光谱仪测定高速工具钢（Ｗ１８Ｃｒ４Ｖ）中硅，锰，磷，硫，铬，钒，镍，钨和钼，以铁元素做内标，对谱线进行基体和干扰校正，所得分析结果基本与标准值一致，其相对标准偏差为０．２％～５．６％。     

用反相高效液相色谱法分析测定Cd,Hg,Pb和Cu

用直接进样（Ｃ１８柱）反相高效液相色谱法研究了Ｍｅｎ＋－Ｄｚ（二硫腙）体系的色谱行为,建立了同时测定Ｃｄ,Ｈｇ,Ｐｂ和Ｃｕ的分析方法。方法的线性范围为０．０１～２．０ｍｇ／Ｌ,最低检出质量浓度为２．４～５．０μｇ／Ｌ,相对标准偏差为１．８％～９．７％,回收率为９４％～１０３％（Ｈｇ除外）。直接进样反相高效液相色谱法比萃取进样正相液相色谱法更快速,更简便,更容易操作,已用于人发测定。     

Dawson结构钨钒磷杂多化合物催化苯酚过氧化氢的羟化作用及其羟化机理

合成了系列Ｄａｗｓｏｎ结构钨钒磷杂多化合物（Ｃｐｙｒ）７＋ｎＰ２Ｗ１８－ｎＶｎＯ６２（ｎ＝１～３），并用ＩＲ，ＮＭＲ等手段对其结构进行了表征．考察了这类杂多化合物对苯酚过氧化氢的羟化活性，探讨了反应机理．     

二苯并18冠6及二苯并24冠8与六聚钼钨杂多酸超分子配合物的合成与晶体结构

报道了两种超分子配合物［Ｎａ（ＤＢ１８Ｃ６）（ＣＨ＿３ＯＨ）］＿２Ｗ＿４Ｍｏ＿２Ｏ＿（１９）·（ＤＢ１８Ｃ６）·（ＣＨ＿３ＯＨ）（Ⅰ）和［Ｎａ（ＤＢ２４Ｃ８）］＿２Ｗ＿１Ｍｏ＿５Ｏ＿（１９）（Ⅱ）的合成方式，用元素分析、电子能谱、ＩＲ和１ＨＮＭＲ等手段进行了表征，并用Ｘ射线测定了晶体结构。结构分析表明：配合物（Ⅰ）属单斜晶系，空间群为Ｐ２１／ｃ，晶胞参数：α＝１．８６９９（５）ｎｍ，ｂ＝１．９５４３（５）ｎｍ，ｃ＝２．２８０８（６）ｎｍ，β＝１１２．８７°，Ｚ＝４．冠醚与多酸根之间通过Ｎａ＋在ＤＢ１８Ｃ６空腔中的镶嵌和Ｏ—Ｎａ—Ｏ键的桥联结合在一起。超分子配合物（Ⅱ）则为Ｎａ＋与ＤＢ２４Ｃ８作用形成配位阳离子，然后与多酸阴离子静电吸引相结合。不同空腔孔径的冠醚与钼钨杂多酸配位时呈现出分子识别与选择性。     

同步荧光法同时测定强力霉素和土霉素

本文提出了表面活性剂增敏碱性降解同步荧光测定强力霉素（ＤＣ）和土霉素（ＯＴＣ）新法。土霉素和强力霉素在０．１ｍｏｌ／ＬＮａＯＨ溶液中反应，生成强荧光降解物，加入十六烷基三甲基溴化铵（ＣＴＭＡＢ）后，荧光强度分别增加４．２倍和１０．７倍。其同步荧光峰在△λ＝７０ｎｍ时基本分离，ＯＴＣ和ＤＣ浓度比在１＋４０～１０＋１范围内可同时测定ＯＴＣ和ＤＣ。本法测定尿液中ＯＴＣ和ＤＣ的回收率为９０％～１０４％。     

SDM－1型耐硫催化剂甲烷化反应动力学Ⅱ．宏观动力学模型

本文以工业应用为目的，采用内循环无梯度反应器，在５７３～６７３Ｋ，０．３０～１．２０ＭＰａ的条件下，原料气组成为Ｈ＿２５０～５４％，ＣＯ１１．７～２０．７％，ＣＨ＿４２．１～１４．３％，ＣＯ＿２６．４～１１．５％，Ｎ＿２１２．２～１８．１％范围内，研究了φ５×３ｍｍＳＤＭ－１型城市煤气耐硫甲烷化催化剂的宏观动力学方程。选择ＣＯ＋３Ｈ＿２＝ＣＨ＿４＋Ｈ＿２Ｏ（１）ＣＯ＋Ｈ＿２Ｏ＝ＣＯ＿２＋Ｈ＿２（２）为系统的独立反应，获得了可靠的动力学模型，井讨论了反应条件对甲烷化反应效率因子的影响。     

麦地霉素在玻碳电极上的阳极伏安法研究

用线性扫描伏安法（ＩＳＶ）、微分脉冲伏安法（ＤＰＶ）和循环伏安法（ＣＶ）在玻碳电极 （ＧＣＥ）上研究了麦地霉素（ＭＤ）在不同介质中的阳极伏安行为。发现在０．１ｍｏｌ／Ｌ Ｎａ_２ＨＰＯ_４溶 液中于０．７５Ｖ（υｓ． Ａｇ／ＡｇＣｌ）左右产生一个阳极氧化峰,峰高与ＭＤ浓度５ × １０~（－５）～１×１０~－１ｇ／Ｌ 范围内呈线性关系。用本法不需分离直接测定了药物制剂和加标尿样。ＲＳＤ为１．８％（ｎ＝ １０）。尿样中ＭＤ的回收率为９５％～１１５％。实验结果表明ＭＤ的电极氧化反应为不可逆过 程。     

高效液相色谱法测定细胞分裂素的方法研究

利用高效液相色谱法测定水稻愈伤组织和微生物发酵产品中的玉米素，二氢玉米素，核糖基玉米素和核糖基二氢玉米素。样品用抽提液抽提，经Ｂｉｏ－Ｒｅｘ７０弱阳离子交换柱和ＸＡＤ－７／Ｓｅｐ－ｐａｋＣ１８复合柱净化和富集后，直接用ＨＰＬＣ分析，方法回收率达９４％～８４％，相对标准偏差小于３．３％。最低检测限达２．０ｎｇ。     

Cu(Ⅱ)-DApCM-V(Ⅴ)体系阻抑光度法测定微量铜

在磷酸介质中,Ｃｕ（Ⅱ）能抑制二安替比林对氯苯基甲烷（ＤＡｐＣＭ）与钒（Ⅴ）的显色反应。研究了反应条件和动力学参数,建立了测定微量铜（Ⅱ）的新方法。其线性范围的质量浓度为０．０４～０．１８ｍｇ／Ｌ,检出限为０．０４ｍｇ／Ｌ。用于粗铅和铝合金样品中铜的测定,结果满意。     

气相色谱法分离和测定对甲硫基苯酚

采用气相色谱法分离和测定对甲硫苯酚。在Ф６ ×１ ．５ ×１ ５００ ｍ ｍ 玻璃柱内填充５ ％ Ｏ Ｖ１０１／ Ｃｈｒｏｍ ｏｓｏｒｂ Ｗ Ａ Ｗ Ｄ Ｍ Ｃ Ｓ 的色谱柱上,对甲硫基苯酚与内标物磷酸三丁酯及杂质之间具有较好的分离效果;而且以磷酸三丁酯为内标物时其重量校正因子相当稳定,即 ｆｗ ． Ａ ＝ ０ ．９４８ ±０ ．００５ ４（ｎ ＝ ９ ,α＝ ０ ．０５） 。该方法操作简便、快速、准确。对同一试样的８ 次平行独立测定其标准偏差为０ ．２５ ,变异系数为０ ．００７ ２ 。并且,该方法的３ 次加入法回收率达９８ ．１８ ％ ～９９ ．２２ ％ 。     

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.