低温等离子体剥蚀-电感耦合等离子体质谱联用对电路板镀层的深度分析

建立了基于低温等离子体(Low temperature plasma)剥蚀系统将固体样品直接引入电感耦合等离子体质谱(ICP-MS)并用于电路板镀层中Au,Ni和Cu的深度分析.此实验中采用介质阻挡放电(DBD)方式产生低温等离子体探针,逐层剥蚀样品表面,由ICPMS检测元素信号.对DBD所用放电气体种类、外加电场功率、放电气体流速和采样深度等实验条件进行优化.在优化条件下,应用LTP-ICPMS在30 s内完成电路板镀层(20 μm Au/10 μm Ni/Cu基底)的逐层剥蚀和深度分析,元素种类和分层顺序与X射线光电子能谱(XpS)相吻合,镀层的分辨率可拓展至微米水平,表明此技术可直接用于固体样品的深度分析.     

辉光放电光谱法分析镀锌钢板

介绍了利用辉光放电光谱法分析不同种类的热镀锌板和电镀锌板的镀层定量分析；在锌铁合金化热镀锌板上界面定量计算方法的设计；锌铁合金化热镀锌板表面问题的发现。试验结果表明，辉光放电光谱法是配合镀锌板产品质量控制、研究开发的一种有效的分析手段。     

辉光放电光谱法分析掺杂纳米硅薄膜的研究

介绍了利用辉光放电光谱法分析掺杂纳米硅薄膜,通过优化辉光光源激发参数、计算标准样品的溅射率,建立了掺杂纳米硅薄膜的定量表面分析方法。方法应用于实际掺杂纳米硅薄膜样品的分析,并将分析深度、剖析结果与表面形貌仪的结果进行了对照。试验结果表明,分析方法快速、准确,具有实际应用价值。     

CO3^2-对羟基乙叉二膦酸镀铜液的影响

研究羟基乙叉二膦酸（HEDPA）镀铜液中CO3^2-含量对电沉积时阴、阳极过程及镀层的择优取向的影响.通过分析阴、阳极的动电位极化曲线,发现镀液中逐渐加入的CO23-提高了阴极的极化,使电结晶晶粒细化,直至达到稳定;同时促进了铜阳极的溶解.而X射线衍射（XRD）结果表明,铜镀层的晶面择优取向从（222）逐渐向（111）转变.通过镀液中固体络合物的红外光谱分析表明,CO3^2-的加入以第二配体的方式进入该镀液的放电络合离子结构中,参与Cu2＋的络合,形成更稳定的络合物,从而导致铜沉积电位负移,镀层（111）晶面取向增强.     

材料组成特性的统计表征--原位统计分布分析

提出了原位统计分布分析的新概念，它以测试信息原位性、原始性、统计性为特征，旨在反映材料中较大尺度（cm^2）范围内不同组成的定量统计分布规律，系现有宏观平均含量分析及微观结构分析之外的另一种材料性能表征的技术。以火花光谱无预燃单次放电（SDA）、连续激发及高速采集解析技术为基础，研制了金属材料原位分析仪。火花光谱单次放电（SDA）研究指出，在无预燃的情况下，每一个火花单次放电的信号都与该材料对应位置及原始状态相关。当对材料在较大尺度范围内，实现无预燃激发时，则可以获得几万个、几十万、乃至几百万个单次放电的信号，它们分别与各自放电的原始位置厦原始状态相对应。在信号统计解析的基础上，提出了一些表征材料性状的新信息，如在材料中，各元素不同位置含量的统计定量分布；各元素偏析度的准确定量计算；元素不同含量在材料中所占的原位（置）权重比率（统计偏析度）；统计致密度；夹杂物及粒度的统计定量分布等．该技术成功地应用于连铸等冶金工艺、材料研究及生产的质量判据。     

高流速辉光放电质谱法测定纯镍中41种痕量元素

建立了高流速辉光放电质谱法（GDMS）测定纯镍中41种痕量元素含量的分析方法。使用有证标准物质IARM 190A校正其中29种元素的相对灵敏度因子（RSF）,其他12种元素采用标准RSF。在放电电流40 mA、放电电压1000 V、气体流速400 mL/min条件下,对样品预溅射20 min后进行测定。各元素的方法定量限在0.0000001%～0.000054%之间。应用该方法分析2个纯镍样品中的41种痕量元素,测定结果与高分辨电感耦合等离子体质谱法（HR-ICP-MS）、原子荧光光谱法（AFS）、高频感应炉燃烧红外吸收法测定结果一致,当待测元素含量大于0.0001%时,结果的相对标准偏差（RSD）为0.1%～13%;当待测元素含量在0.00001%～0.0001%之间时,测定结果的RSD为0.4%～46%;当待测元素含量小于0.00001%时,测定结果的RSD为7.4%～48%。     

辉光放电质谱技术应用进展

对辉光放电质谱(GDMS)在金属与半导体、非导体、薄层与深度分析、分子信息分析方面的应用和一些新装置、新方法进行了综述.着重介绍了近20年来我国学者在辉光放电质谱方面的成就,并结合国际上的报道对该领域的发展现状进行了总结.     

低磷化学镀镍层性能的研究

低磷镀层（ＬＰ）在碱性和中性盐水条件下的耐蚀性较高磷镀层好，当ＬＰ镀层在３５０℃下热处理１ｈ后，镀层在显微硬度从４５４Ｈｖ增加到８９０Ｈｖ。差热分析研究发现，在３４１．６℃和４０６．２℃有两个放热峰，分别对应于新相Ｎｉ５Ｐ２和Ｎｉ３Ｐ的形成，利用Ｘ射线衍射对镀层的结构进行分析，发现该镀层由非常细的微晶构成。     

MH—Ni电池封口化成及其性能

在硼氢化钾碱性溶液中对金属氢化物（ＭＨ）电极的表面进行化学还原处理，提高了ＭＨ电极的放电容量、活化性能和电催化活性．用其为负极组装的ＡＡ型ＭＨ－Ｎｉ电池进行了封口化成，电池放电容量达到１１５０ｍＡｈ，５Ｃ下电池的放电容量达到０．２Ｃ下容量的８０％以上，电池在１Ｃ１００％ＤＯＤ（放电深度）充放电条件下，循环寿命由原来的１００次左右提高到２００次以上     

辉光放电光谱法定量分析金属材料表面纳米级薄膜的研究

介绍了利用辉光放电光谱法分析金属材料表面的纳米级薄膜。通过优化辉光光源的放电参数，计算标准样品的溅射率。溅射率经校正后，建立各元素的标准工作曲线，从而形成了纳米级薄膜的定量表面分析方法。试验证明，此方法对膜厚的测定具有很好的准确度和精密度，可应用于多种金属材料表面纳米级薄膜的研究。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应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反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

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.