质谱法测定冰毒

采用直接进样化学电离（ＣＩ）质谱法，配合电子轰击（ＥＩ）及气相色谱－质谱联用（ＧＣ／ＭＳ）技术，测定了冰毒及其制备过程中的副产品与中间产物，为刑侦破案提供了依据。     

QUANTUM CHEMICAL STUDY ON THE MECHANISM OF PRODUCING OXYGENATES IN FISCHER－TROPSCH SYNTHESIS ON M／SiO＿2 （M＝Ni， Ru， Rh， Pd） CATALYSTS

ＱＵＡＮＴＵＭ　ＣＨＥＭＩＣＡＬ　ＳＴＵＤＹ　ＯＮ　ＴＨＥ　ＭＥＣＨＡＮＩＳＭ　ＯＦ　ＰＲＯＤＵＣＩＮＧ　ＯＸＹＧＥＮＡＴＥＳ　ＩＮ　ＦＩＳＣＨＥＲ－ＴＲＯＰＳＣＨ　ＳＹＮＴＨＥＳＩＳ　ＯＮ　Ｍ／ＳｉＯ＿２　（Ｍ＝Ｎｉ，　Ｒｕ，　Ｒｈ，　Ｐｄ）　ＣＡ...     

有机显微组分的二次离子质谱研究

采用二次离子质谱技术（ＳＩＭＳ）对煤及源岩中不同成熟度的镜质体、丝质体、沥青和笔石进行了详细研究。结果表明不同显微组分具有不同的ＳＩＭＳ谱图，反映出其化学组成和结构的差异性，且ＣＨ２＾＋／ＣＨ３＾＋参数变化趋势可以用来评价有机组分的热演化规律。同时说明ＳＩＭＳ技术是有机显微组分化学成分和结构研究的有效手段。     

MICROWAVE EFFECTS ON THE OXIDATIVE COUPLING OF MIETHANE OVER Li_2SO_4／BaCe_（0．93）La_（0．07）O_3

ＭＩＣＲＯＷＡＶＥＥＦＦＥＣＴＳＯＮＴＨＥＯＸＩＤＡＴＩＶＥＣＯＵＰＬＩＮＧＯＦＭＩＥＴＨＡＮＥＯＶＥＲＬｉ＿２ＳＯ＿４／ＢａＣｅ＿（０．９３）Ｌａ＿（０．０７）Ｏ＿３￥ＣｈａｎｇＬｉｎＣＨＥＮ；ＰｉｎＪｉｅＨＯＮＧ；ＳｈｕＳｈａｎＤＡＩ；Ｇｕａｎｇ...     

基体辅助激光解吸电离飞行时时质谱和热裂解色谱/质谱研究聚酯型聚氨酯链结构

聚酯型聚氨酯样品用基体辅助激光裂解离子化质谱（ＭＡＬＤＩ－ＴＯＦ／ＭＳ）和热裂解色谱质谱（ＰＹＧＣ／ＭＳ）方法进行了鉴定,ＰＹＧＣ／ＭＳ方法可检出ＰＵ的一些组成单元的化学结构,但ＰＹＧＣＩＭＳ中大多数的峰,无法从常规的标准化合物的质谱数据库中检索到,而ＭＡＬＤＩ－ＭＳ方法,可明确测出ＰＵ试样各种单元的组合、聚合度及ＰＵ长链的序列分布,质量数范围可达2300.     

基体辅助激光解吸电离飞行时间质谱和热裂解色谱／质谱研究聚酯 …

聚酯型聚氨酯样品用基体辅助激光裂解离子化质谱（ＭＡＬＤＩ－ＴＯＦ／ＭＳ）和热裂解色谱质谱（ＰＹＧＣ／ＭＳ）方法进行了鉴定,ＰＹＧＣ／ＭＳ方法可检出ＰＵ的一些组成单元的化学结构,但ＰＹＧＣ／ＭＳ中大多数的峰,无法从常规的标准化合物的质谱数据库中检索到,而ＭＡＬＤＩ－ＭＳ方法,可明确测出ＰＵ试样各种单元的组合、聚合度及ＰＵ长链的序列分布,质量数范围可达２３００。     

利用质谱—质谱法进行稠环芳烃化合物的结构解析

应用（ＥＩ）ＭＳ／ＭＳ法研究了吡啶并苯并蒽酮以及苯并苯并蒽酮类异构体的裂解方式及其与结构之间的相关性，探讨了不同异构体中由Ｍ＾ｉ＋产生的［Ｍ－Ｈ］＾＋、［Ｍ－ＨＣＮ］＾＋、［Ｍ－ＣＯＨ］＾＋、［Ｍ－ＣＯ］＾ｉ＋、［Ｍ－（ＣＯ＋２Ｈ）］＾ｉ＋以及［Ｍ－（ＣＯ＋ＨＣＮ）］＾ｉ＋（ｉ＝１，２）等１价及２价离子在ＭＳ／ＭＳ－ＣＩＤ谱上的强度差异和裂解方式，发现是否含有氮原子以及氮原子和苯环位置的差异，是支     

MICROCALORIMETRIC STUDIES OF SURFACE ACID/BASE PROPERTIES OF REDUCED IRON／MAGNESIUM CATALYSTS

ＭＩＣＲＯＣＡＬＯＲＩＭＥＴＲＩＣＳＴＵＤＩＥＳＯＦＳＵＲＦＡＣＥＡＣＩＤ／ＢＡＳＥＰＲＯＰＥＲＴＩＥＳＯＦＲＥＤＵＣＥＤＩＲＯＮ／ＭＡＧＮＥＳＩＵＭＣＡＴＡＬＹＳＴＳ＊ＴｕＭａｉ，ＳｈｅｎＪｉａｎｙｉ＊＊，ＣｈｅｎＹｉ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈ...     

溶剂甲醇过程的溶剂选择

溶剂甲醇过程的溶剂选择至关重要。本文筛选了三乙二醇二甲醚（ＴＲＩＧＬＹＭＥ）作为溶剂，测定了甲醇在溶剂中的溶解度及活度系数。在本文的研究条件下，甲醇的溶解特性符合亨利定律，以实验数据回归，亨利系数Ｈ＝０．３７４３ｅｘｐ（－３０１３．６／Ｔ）ＭＰａｍ＾３ｍｏｌ＾－１。通过与其他溶剂比较后可以得出：按甲醇在不同溶剂中的溶解度大小排序：ＴＧＩＧＬＹＭＥ〉ＴＥＧＤＭＥ〉Ｓｑｕａｌａｎｅ〉ＶｅｓｔｏｗａｘＳ     

SYNTHESIS,CRYSTAL STRUCTURE AND MAGNETISM OF THE COMPLEX:GdFe(CN)_64H_2O

ＳＹＮＴＨＥＳＩＳ，ＣＲＹＳＴＡＬ　ＳＴＲＵＣＴＵＲＥ　ＡＮＤ　ＭＡＧＮＥＴＩＳＭ　ＯＦ　ＴＨＥ　ＣＯＭＰＬＥＸ：ＧｄＦｅ（ＣＮ）_６４Ｈ_２ＯＳＹＮＴＨＥＳＩＳ，ＣＲＹＳＴＡＬＳＴＲＵＣＴＵＲＥＡＮＤＭＡＧＮＥＴＩＳＭＯＦＴＨＥＣＯＭＰＬＥＸ：ＧｄＦ...     

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%.     

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.     

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.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).