用Benson基团加和法预测气相色谱保留值

应用Ｂａｎｓｏｎ基团加和法，对氯代苯，脂肪醇两类化合物分子结构与气相色谱保留值间的关系进行了研究。对部分化合物的保留值做了预测，结果表明这两类化合敢相色谱保留值具有基团加和性，预测值与实验值吻合很好。     

双柱气相色谱法测定有机物的正辛醇/水分配系数

通过对烷烃，醇类等有机物在五种不同极性固定相上的气相色谱保留值的测定，提出了从有机物气相色谱保留值测定其正辛醇/分配系数的公式，研究了从不同极性固定相上测得的保留值来测定其分配系数的准确性，得出烷烃类在所有柱上测得的保留值与其分配系数间均具有很好的关联，烷烃醇类在极性相异柱上的保留值之比值与其分配系数间也有很好的相关性，从而为烷烃及醇类等有机物分配系数的测定提供了一种简单、可靠，易行的新方法。     

用非极性固定相分离不同极性化合物时色谱峰峰形的EMG参数及计算机拟合

对用非极性固定相分离不同极性的化合物时色谱峰的峰形与保留值的关系进行了研究使用非极性固定相分离不同极性的化合物时,不同极性化合物的色谱峰的EMG参数σ、τ与组分的保留值不存在线性关系：建立了使用非极性固定相分离极性化合物时色谱峰峰形的计算机模拟方法该法作为《开放式气相色谱仿真软件》中的模拟方法之一,效果较好。     

氮杂冠醚聚硅氧烷固定液的色谱保留机理

氨杂冠醚聚硅氧烷是一类呈中等极性的新颖气相色谱固定液．本文通过测定醇、酯、卤代烃和苯系列化合物的色谱保留值和相应势力学参数，研究它对上述不同化合物的保留机理及其分子识别的热力学性质     

应用基团贡献法关联抗生素的高效液相色谱的保留值

应用ＵＮＩＦＡＣ基团贡献模型计算了４种头孢菌素在ＯＤＳ柱上及不同配比甲醇－水体系中的活度系数，采用多元线性回归法关联了头孢菌素－甲醇－水体系的反相高效液相色谱的保留值，可预测不同配比流动相下的容量因子，经验证实验值与计算值的对误差小于１０％。     

单酮类有机物气相色谱保留值与结构参数的相关性

应用半经验量子化学AM1方法和分子图形学技术获得了42种单酮类有机物分子的电子结构和几何结构参数，并将这些参数与它们在非极性固定相(SE-30柱)上的气相色谱保留值相关联，采用逐步回归分析方法，成功地建立了拟合度高、物理意义明确、预测能力强的气相色谱保留值一结构参数定量关系方程，找出了影响气相色谱保留值的主要结构因素．     

色谱与色谱/质谱法相结合分析热裂解汽油C9馏分

采用毛细管气相色谱-氢火焰离子化检测器（CGC-FID）和气相色谱-质谱法(GC/MS)分析了热裂解汽油C9 馏分的组成。实验使用PONA毛细管气相色谱柱(100 m×0.25 mm i.d.×0.5 μm),根据烃类化合物在PONA柱上的保留规律,以正构烷烃标样保留值作为碳数分布依据,定量分析了裂解汽油C9 馏分中烃类化合物的碳数分布和单体烃含量;用GC/MS联用技术和CGC保留值定性法相结合对裂解汽油C9 馏分中相对含量大于0.2%的39种化合物进行了定性。     

湖泊水体中土霉味化合物2-甲基异莰醇的合成与测定

利用甲基格氏试剂和天然樟脑反应，合成土霉味化合物２－甲基异醇，并用色谱，质谱和红外光谱对其进行鉴定，然后以合成ＭＩＢ作标样，测定ＭＩＢ的气相色谱保留值及其在东湖水体中浓度随季节变化规律，研究结果表明，东湖水体产生土霉味的主要成分为ＭＩＢ，在１９９５－１９９６年期间，１月、４月和９月为武汉东湖水体中ＭＩＢ浓度的高峰期，经测量定东湖水中ＭＩＩＢ的ＧＣ保留值与合成的ＭＩＢ的ＧＣ保留值完全一致。     

气相色谱与液相色谱保留值的换算方法

根据色谱热力学理论,在色谱保留值公式统一形式的基础上导出了气相色谱保留系数（I）与反相液相色谱保留公式参数a,c之间的关系式,证明结构类似化合物的a,c值与保留指数呈线性关系,同时存在氢键作用能、偶极矩作用的影响,从而提出了色相色谱与反相液相色谱保留值换算的方法;该理论为氯代芳烃的文献数据所证实。     

从信息论指标预测氯代羟基苯甲醛的气相色谱保留值

分子结构与其保留值规律的研究是色谱热力学研究的主要内容。几十年来,许多色谱工作者为探索分子结构与色谱保留值之间的关系作了不懈努力。用分子的拓扑结构指标来关联化合物的气相色谱行为,是十分引人注目的一个方法。到目前为止,已经提出了多种拓扑结构指标。本文试图定义一种信息论指标,     

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.     

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.     

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.