电感耦合等离子体原子发射光谱分析中易电离元素的基体干扰及其抑制的研究

选取铝、铜、镁、钙、铁、锰和锌等7种元素的9条谱线,研究电感耦合等离子体原子发射光谱法对其测定时易电离元素钾、钠的基体干扰。结果表明:易电离元素对待测元素具有较明显的干扰作用,而增大射频发射功率及降低雾化器压力可有效地抑制易电离元素对待测元素的干扰。     

低功率微波等离子体炬（MPT）光源基本性质的初步研究

对低功率微波等离子体炬(MPT)光源基本性质进行了初步研究,采用“双线法”测定了有、无样品引入时光源中激发温度随观测高度的变化;测定了Zn、Cd、Mg的原子线和离子线发射强度随观测高度的变化;还研究了一些实验参数对等离子体激发温度的影响。     

微波等离子体炬耦合方式的研究

采用气动雾化连续进样、端视观测法,考察了微波等离子体炬原子发射光谱法中等离子体Ar线的背景发射以及Al,Mg,V等元素的信号发射强度随天线耦合连接点位置的不同而发生的变化.结果表明,当天线位于炬管顶端,即天线距离活塞3λ/4和λ/4时均能获得较好的等离子体,λ/4略好,信号发射强度和信背也较大,只是精密度略差一些.初步探讨了MPT炬管的电磁场结构.     

高钙基体在DCP光源中的分析特性

一般认为三电极DCP光源的基体成分的影响较小,但一些研究指出,存在易电离元素会引起其它元素发射强度的增强。碱土金属如钙由于在等离子体光源中强烈发射对一些测定元素有严重的背景干扰。本工作对高钙基体在DCP光源中的分析特性:激发温度轴向分布,对测定元素谱线强度的增强效应、背景干扰及校正方法以及谱线选择等进行了研究,同时还对高钙基体的测定重现性进行了探讨,并提出了改善办法。     

植物中多元素测定的微波消解前处理技术

植物中多元素同时测定的前处理采用微波消解技术 ,利用原子吸收法和单频直流等离子体原子发射法测定茶叶和中药中的Ba、Ca、Cu、Fe、K、Mg、Mn、Na、Sr、Ti和Zn。用四种国家标准参考样品进行考察 ,结果表明这是一项安全可靠且快速无污染的技术     

电感耦合高频等离子体光源中谱线激发特性的研究

本文测量并比较了遵守局部热平衡的交流电弧光源和非热平衡的Ar ICP与N_2/Ar ICP光源的激发温度、多元素离子线/原子线的强度比,实验指出在ICP光源中,(激发电位+电离电位)与亚稳态氩原子的能量相近的离子谱线发射显著增强,表明亚稳态氩和潘宁电离在该光源的激发过程中所起的特殊作用。     

MPT-AES测定奶粉中的Ca和Fe

用微波等离子体(MPT)为激发光源,氩气为等离子体工作气体,用气动雾化进样,采用标准曲线法研究了微波等离子体炬原子发射光谱法(MPT-AES)测定奶粉中Ca、Fe的方法。详细考察了溶液中HCl浓度、HNO3浓度、微波前向功率、载气流量、工作气流量等实验参数对测定的影响,同时考察了共存元素钠、镁、锌对钙和铁发射强度的影响。     

ICP-AES锂内标法测定水中钾钠

钾、钠原子的第一电离能小于 6 .1eV ,属于易电离易激发元素[1] ,它们的谱线标准温度 ,钾原子线 76 6 .4nm为 2 870K、钠原子线 5 88.9nm为3470K[2 ] ,相对于其他元素较低 ,而ICP等离子体温度很高 ,在 6 0 0 0～ 10 0 0 0K ,中心温度 80 0 0K[1] ,这对于钾、钠温度过高 ,电离度很大[1] ,在ICP中测定结果不理想 ,而使用加内标方法 ,钾、钠电离度受到抑制 ,可使准确度提高。另外 ,铷和铯的电离电位比钾、钠小 ,锂则大于钾、钠 ,所以铷和铯作内标要比锂理想。本文通过对锂不同浓度的试验 ,发现合适的内标元素浓度 ,可以得到满意的结果。1…     

覆氧或氧离子轰击下固体表面二次正离子发射的研究

通过对离子轰击下固体表面电离过程重新考虑认为，在固体表面覆氧或氧离子轰击下除表面原子的直接电离外，激发态双原子间电子交换和断键亦起重要作用。在此基础上修正了局部热力学平衡模型，得到了一个包含各类离子内配分函数、电离能、金属－氧原子键断键能以及表面金属原子与氧原子结合份数等参数决定的新电离几率分析表达式。应用该分析表达式解释了金属表面覆氧、氧离子轰击金属、化合物半导体表面二次离子发射中氧增强效应、充氧量对二次离子发射的影响及其基体效应等实验现象。并由此得到了元素相对灵敏度因子的分析表达式，对化合物半导体及一些陶瓷材料表面二次离子质谱分析中元素灵敏度因子随元素电离能变化曲线给予了相应的物理解释。     

磷酸三丁酯-煤油-硝酸铀酰体系的等离子体光谱研究

研究了磷酸三丁酯-煤油试样的等离子体光谱的发射特性，测试了C2、CN、Ar、N2、OH、NH、U、Ca等分子和原子的发射强度的垂直分布，讨论了氰带抑制问题，增加Ar等离子体气的流量有助于降低氰带强度，元素分析线的强度则不发生明显变化。讨论了有机标准溶液的制备问题。     

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%.     

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.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

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.