N－乙酸基取代四氮杂大环及其镧系配合物的热力学研究

用ｐＨ电位滴定法分别在２５±０．１℃，４０±０．１℃和８０±０．１℃，０．５ｍｏｌ／ＬＫＮＯ３水溶液中测定了Ｈ_４Ｌ（５，７，１２，１４－四甲基－１，４，８，１１－四氮杂环十四烷－Ｎ＇，ｎ＂，Ｎ＂＇，Ｎ＂＂－四乙酸）的逐级质子化常数和焓值。又在４０±０．１℃和８０±０．１℃条件下测定了Ｈ４Ｌ与镧系金属离子（Ｌａ~（３＋），Ｎｄ~（３＋），ｐｒ~（３＋），Ｓｍ~（３＋），Ｅｕ~（３＋），Ｇｄ~（３＋），Ｄｙ~（３＋），Ｙｂ~（３＋））配合物的稳定常数。结果表明：配合物稳定性高。     

C2H3＋NO2反应速率常数的研究

利用激光光解C2H3Br产生C2H3自由基,在气相298 K, 总压2.66×103 Pa的条件下,研究C2H3与NO2的反应,用激光光解-激光诱导荧光（LP-LIF）检测中间产物OH自由基的相对浓度随着反应时间的变化关系,报导了双分子反应C2H3＋NO2的速率常数k(C2H3＋NO2)=(1.8±0.05)×10－11cm3•molec.－1•s－1,同时也得到OH＋NO2反应的速率常数k(OH＋NO2)=(2.1±0.15)×10－12 cm3•molec.－1•s－1.     

1，2－二甲氧基乙烷的真空紫外光电离和光解离

利用同步辐射真空紫外光对1，2－二甲氧基乙烷进行光电离解离研究，得到了 该分子的电离势为（9.33±0.04)eV，碎片离子CH_3OCH_2CH_3~+和CH_3OCH_2~+的 出现势分别为(9.83±0.05)eV, (9.99±0.05)eV，根据实验结果和B3LYP／6－31＋ G(d)理论计算的结果，分析了可能的解离通道，并得到了离子生成焓、键解离能这 些重要的热力学数据。     

2,2-二甲基-3-(2,2′-二氯乙烯基)-环丙烷羧酸-1-氰基-2-甲基-2-戊烯醇酯立体异构体的气相色谱分离

1引言毕富春等曾报道二氯菊酸－1－氰基－2－甲基－2－戊烯醇酯的气相色谱分离，但使用的样品是二氯菊酸－1－氰基－2－甲基－2－成烯醇酯的各个异构体的混合物，而且未加详细讨论。年文在合成光学活性二氯菊酯－（±）－1－氰基2－甲基－2－戊烯酸酯和（－）－1－氰基－2－甲基－2－戊烯醇的基础上，对它们的气相色谱行为进行了研究。其中顺式－（－）二组菊酸和顺式－（＋）－二氯菊酸的（±）－1－氰基－2－甲基－2－戊烯酸酯的两个异构体在两种固定液上都得到很好的分离。很难两个异构体的峰面积的比值可以求得手性氰醇的％e．e．值。2…     

CCl2自由基与H2O分子反应动力学研究

用213 nm激光光解CCl4产生CCl2自由基，用LP LIF技术测定了室温下基态CCl2自由基与H2O分子的反应速率常数为(5.45±0.95)×10－14 cm3•molecule－1•s－1.在G2MP2理论水平上计算了CCl2＋H2O反应的最低单重态势能面，揭示了插入与加成 消除两种反应机理，得到了三个可能的产物通道:HCl＋HClCO、HCl＋trans ClCOH以及HCl＋cis ClCOH.并用RRKM TST和传统过渡态理论计算了这三个通道的分支比及其温度效应.结果说明在低温下（273 K），插入机理的产物通道的分支比远大于加成 消除机理的产物通道， HCl＋HClCO是主要产物，分支比为77.4％，其次是HCl＋cis ClCOH，分支比为22.6％.而在高温下（3000 K），加成 消除机理的反应通道大于插入机理， HCl＋trans ClCOH分支比为82.3％.     

NCO自由基与SO2、CS2反应的速率常数

利用波长为266 nm的激光光解CHBr3产生CH自由基,其与NO反应作为NCO自由基的来源.在298 K,总压2660 Pa的条件下,采用激光诱导荧光的方法,研究了NCO自由基与SO2、CS2的反应.得到了NCO自由基与SO2、CS2双分子反应速率常数分别为（1.8±0.3）×10－11和（3.1±0.4）×10－12 cm3•molecule－1•s－1.对这两个反应在B3LYP/6-31＋G(d)的水平上进行理论研究的结果表明,NCO自由基与SO2、CS2的反应是加成反应,其机理是NCO自由基中的N原子攻击反应物的中心原子,得到加成产物.     

光学活性二炔二醇类化合物的合成

报道了（Ｒ）－１，６－二（２－氯苯基）－１，６－二苯基－２，４－己二炔－１．６－二醇的全合成方法。提出了一种在Ｋ－ＤＭＳＯ－ＴＨＦ体系中二芳酮乙炔化的新方法。以比较温和的条件和较高收率地合成了（±）－炔醇，并进行了拆分，通过Ｇｌａｓｅｒ反应，将（＋）－炔醇偶联制得目的物。     

铜(Ⅱ)与苯基羧酸(HPCA)和2,2''''-联吡啶衍生物(dpx)混配配合物的合成和表征

合成了铜（Ⅱ）与苯基羧酸根［ＰＣＡ－＝苯甲酸根（Ｂｚ－），２－苯乙酸根（ＰＡｃ－），３－苯丙酸根（ＰＰｒ－），４－苯丁酸根［ＰＢｕ－）］和２，２′－联吡啶衍生物（ｄｐｘ：２，２′－联吡啶胺ｄｐａ、２，２′－联吡啶酮ｄｐｋ、２，２′－联吡啶甲烷ｄｐｍ）三大系列１２种新的三元配合物。用元素分析、摩尔电导、红外光谱、１Ｈ核磁共振、差热分析等实验方法表征了它们的组成和性质。确定该系列配合物化学组成为Ｃｕ（ＰＣＡ）２（ｄｐａ）、Ｃｕ（ＰＣＡ）２（ｄｐｍ）、Ｃｕ（ＰＣＡ）２（ｄｐｋ）·ｎＨ２Ｏ（ｎ＝２－４）。它们具有相似的组成和配位方式。它们的可能结构为：二个ＰＣＡ－与Ｃｕ（Ⅱ）单齿配位，一个ｄｐｘ与Ｃｕ（Ⅱ）Ｎ，Ｎ二齿螯合配位。ｄｐｋ的羰基在金属离子Ｃｕ２＋的存在下发生水化作用成ｄｐｋ·Ｈ２Ｏ。用１ＨＮＭＲ法研究了Ｃｕ（Ｂｚ）２（ｄｐｘ）·ｎＨ２Ｏ和Ｃｕ（ＰＡｃ）２（ｄｐｘ）·ｎＨ２Ｏ二个体系其分子内或分子间可能存在的非共价键作用。     

儿童发铅与智商关系的研究

为探讨环境中低浓度铅对儿童智商的影响，选择131名合肥市某小学四年级学生，以其发铅水平作为铅暴露指标，智商为效应指标。结果发现：131名儿童发铅值水平在0．05×10－6～8．35×10-6（均数上标准差为2．57×10－6±1．87±10-6，拟和智商（FIQ）水平在72～135（均数±标准差为105．27±12．68）。以3．5×10-6和1．5×10－6发铅值为分界线进行t检验，结果发现，发铅值在较低水平时（1．5×10－6）时，仍对智商有影响（P＜0．05）。控制11个对智商有影响的混杂因素后，经多元逐步回归分析，发铅值排在11个影响因素中的第2位。     

稀土元素荧光增强效应的研究──RE对Eu－2－（2－二苯乙酰基）－1，3－茚二酮－十六烷基三甲基溴化铵体系的荧光增强

研究了稀土元素Ｌａ~（３＋）、Ｇｄ~（３＋）、Ｙｂ~（３＋）、Ｌｕ~（３＋）、Ｙ~（３＋）及Ｓｃ~（３＋）对Ｅｕ－２－（２－二苯乙酰基）－１，３－茚二酮－阳离子表面活性剂体系的荧光增强效应，结果表明，在上述增强离子存在下，体系的荧光强度分别增加１０、１３０、３０、５０、５２和２０倍，利用标准加入法测定了混合稀土氧化物中的铕，铕浓度在１．０×１０~（－１０）～６．０×１０~（－７）ｍｏｌ／Ｌ范围内与荧光强度呈线性关系，最低检出限为６．０×１０~（－１２）ｍｏｌ／Ｌ。     

GC/MS and LC-MS/MS phytochemical evaluation of the essential oil and selected secondary metabolites of Ajuga orientalis from Jordan and its antioxidant activity

The current investigation aimed to shed light in the volatile and non-volatile secondary metabolites of Ajuga orientalis L. from Jordan. GC/MS and GC/FID analysis of the hydrodistilled essential oil obtained from aerial parts of the plant revealed tiglic acid (18.90 %) as main constituent. Each of the methanol and butanol fractions of A. orientalis were screened for their total phenol content (TPC), total flavonoid content (TFC), and antioxidant activity determined by DDPH and ABTS methods. The extracts were then analyzed by LC-ESI-MS/MS to unveil their chemical constituents, especially phenols and flavonoids. Results showed that the AO-B extract had the highest TPC (217.63 ± 2.65 mg gallic acid/g dry extract), TFC (944.41 ± 4.77 mg quercetin /g dry extract), highest DPPH and ABTS antioxidant activity ((4.00 ± 0.20) × 10^-2; (3.00 ± 0.20) × 10^-2 mg/mL, respectively) as compared to the AO-M extract. LC-ESI-MS/MS analysis of both extracts revealed the presence of several phenolics, flavonoids and nonphenolic acids.     

一种手性甲壳型液晶高分子的稀溶液行为及链刚性

用激光光散射和粘度法研究了一系列窄分子量分布的新的手性甲壳型液晶聚合物P1～P6的溶液行为及其链刚性.研究发现四氢呋喃是聚合物P1～P6的良溶剂.在四氢呋喃溶液中,聚合物P1～P6的特性粘数[η]和均方根旋转半径z12对重均分子量Mw的依赖关系分别是[η]=(2.75±0.05)×10-3Mw0.78±0.02和z12=(1.53±0.04)×10-2Mw0.60±0.01.按照YamakawaFujiiYoshizaki蠕虫状圆筒模型的粘度理论和BohdaneckyBushin表达式,求得聚合物的单位围长摩尔质量ML=(29.8±1.0)×102nm,构象保持长度q=(15.4±3.0)nm.q和MHS方程指数α的值说明这类在结构上属于侧链型液晶高分子的聚合物在良溶剂四氢呋喃中呈现比较伸展的刚性链构象,其链刚性与半刚性主链液晶高分子的相似.     

Solubility of thioindigo dopants in a smectic liquid crystal host evaluated by 2H NMR spectroscopy

The solubility of two partially deuterated thioindigo dopants in a smectic liquid crystal host was evaluated by variable temperature ²H NMR spectroscopy and polarized microscopy. 2H NMR spectra showed that the dopant (±)-6,6'-bis(2-octyloxy)-5,5-dinitrothioindigo-d ₆ forms a homogeneous solution with the smectic phases of the liquid crystal host (±)-4-(4-methylhexyloxy)phenyl 4-decyloxybenzoate (PhB) up to its saturation point of 3 mol %. These results are consistent with polarized microscopy observations of the dopant crystallizing out of solution upon reaching a concentration of 3 mol %. On the other hand, ²H NMR spectra of (±)-5,5'-dichloro-6,6'-bis(2-octyloxy)thioindigo-d ₆ dissolved in PhB showed evidence of a partitioning of the solution between smectic and isotropic microdomains, which increases with increasing dopant concentration—from 1.2 to 9.1 mol %. To a large extent, this smectic/isotropic microphase separation could not be detected by polarized microscopy. These results suggest that ²H NMR spectroscopy can provide a more accurate determination of the occurrence and extent of microphase separation in doped liquid crystal samples.     

Darstellung und Kristallstruktur von Barium-Cadmium-Thiostannat (iv) BaCdSnS4

Preparation and Crystal Structure of Barium-Cadmium-Thiostannate (IV) BaCdSnS₄ BaCdSnS₄ was prepared for the first time and the crystal structure determined by single crystal X-ray investigations. Lattice constants: a = 2186 ± 2; b = 2169 ± 1; c = 1318 ± 0.5 pm. Space group: C–Fdd2. There are pairs of edge-sharing tetrahedrons linked together characteristically to form twodimensional endless nets. The crystal structure is described and discussed.     

Crystal and molecular structures of (3Z)-(±)-4-(2′-hydroxypropyl)amino-and (3Z)-4-(2′-hydroxyethyl)amino-pent-3-en-2-ones

An X-ray study of (3Z)-(±)-4-(2′-hydroxypropyl)amino-and (3Z)-4-(2′-hydroxyethyl)amino-pent-3-en-2-ones is reported. The bond lengths inside the H ring are equalized due to the classical N-H...O hydrogen bond between the carbonyl oxygen and the amino group. In the 4-(2′-hydroxyethyl)amino-pent-3-en-2-one crystal, due to the classical N-H...O bonds, infinite zigzag chains are formed along the 0b axis and arranged into a layered structure due to the weak C-H...O interactions. In (±)-4-(2′-hydroxypropyl)aminopent-3-en-2-one crystal, however, centrosymmetric dimers are formed, which are then linked by weak C-H...O intermolecular interactions to form a layered structure along the a0b plane.     

Solid state of a new COX-2 inhibitor CG100649

CG100649 [4-(3-(3-Fluorophenyl)-5,5-dimethyl-4-oxo-4,5-dihydrofuran-2-yl)-benzenesulfonamide, polmacoxib, Acelex™] is a new NSAID used to treat osteoarthritis. It inhibits the enzymes carbonic anhydrase and COX-2. The objective of this work was to investigate the existence of polymorphs of CG100649 and the solubility of different crystal forms of CG100649. Four crystal forms of CG100649 (Forms 1–4) have been isolated by recrystallization and characterized by differential scanning calorimetry and powder X-ray diffractometry. In dissolution studies in pH 6.8 ± 0.05 buffer at 37 ± 0.5 °C, the solubility of Form 1 was the highest, and the dissolution rate at 30 min in water decreased in rank order: Form 3 > Form 2 > Form 4. After storage for one month at 2 °C and 24% relative humidity, all crystal forms were not transformed.

     

Synthesis of 1,2,5-Thiadiazolidin-3-one 1,1-Dioxide Derivatives and Evaluation of Their Affinity for MHC Class-II Proteins

1,2,5-Thiadiazolidin-3-one 1,1-dioxide derivatives (±)- 1a – d and (±)- 2 were designed by molecular modeling as MHC (major histocompatibility complex) class-II inhibitors. They were prepared from the unsymmetrically N,N′-disubstituted acyclic sulfamides (±)- 4a – d (Scheme 1) and (±)- 11 (Scheme 2). These N-alkyl-N′-arylsulfamide precursors were synthesized by nucleophilic substitution of either a sulfamoyl-chloride or a N-sulfamoyloxazolidinone. Extension of base-induced cyclization methods from aliphatic to aromatic sulfamides gave access to the desired target molecules. The N-alkyl-1,2,5-thiadiazolidin-3-one 1,1-dioxide derivatives (±)- 3a – c were also prepared by the oxazolidinone route (Scheme 4) for coupling to a tetrapeptide fragment. The X-ray crystal structure of 1,2,5-thiadiazolidin-3-one 1,1-dioxide (±)- 21a was solved, and the directionality of the H-bond donor (N−H) and acceptor (SO₂) groups of the cyclic scaffold determined (Figs. 1 and 2). The pK_a value of the N−H group in (±)- 21a was determined by ¹H-NMR titration as 11.9 (Fig. 3). Compounds (±)- 1a – d were shown to inhibit competition peptide binding to HLA-DR4 molecules in the single-digit millimolar concentration range.     

Molecular conformation of the racemic indan derivative (±)-1-trans-3-(3,4-dichlorophenyl)-2,3-dihydro-1H-indene-1-carboxamide

This paper presents the structural characterization of the indan derivative (±)-1-trans-3-(3,4-dichlorophenyl)-2,3-dihydro-1H-indene-1-carboxamide, which was unambiguously determined by X-ray diffraction (XRD) to be a racemate (R/S: 50/50) crystallizing in an achiral crystal structure (P2₁/c, a = 9.3180(1) Å, b = 7.9070(2) Å, c = 19.7550(4) Å, β = 103.250(1)°, V = 1416.75(5) Å³ and Z = 4). The diastereomers are related by the inversion symmetry and linked by H bond forming a dimer. The crystal packing is stabilized by hydrogen bonds, including the classical one responsible for the formation of centrosymmetric dimers, and non-classical ones involving C–H···O and C–H···π-aryl interactions. The intra and intermolecular geometry of the title compound is compared to the (±)-1-trans-3-(3,4-dichlorophenyl)-2,3-dihydro-1H-indene-1-carboxylic acid one, which also present an achiral crystal structure from racemates (R/S: 50/50). The two indan derivatives crystallize in a very similar unit cell.     

Crystal and molecular structure of 6-(p-bromobenzoyl)-6-azabicyclo[3.1.0]hexane

The molecular structure of 6-(p-bromobenzoyl)-6-azabicyclo[3.1.0]hexane has been determined by a single crystal, three-dimensional x-ray study. The compound crystallizes in the monoclinic space group (P) with four molecules in a unit cell of dimensions a = 8.83, b = 10.15, c = 12.63 ± 0.02Å and β = 94°55′ ± 5′. The aziridine ring is eis fused to the cyclopentane ring with the two rings together in a boat conformation. The fusion angle of the two rings is 110.8°. The aziridine ring has all angles of 60 ±1° and all bond distances of 1.48 ± 0.03Å. The cyclopentane ring has alternately long (1.61 ± 0.04Å) and short (1.52 ± 0.02Å) distances. Non-fusion angles in the cyclopentane ring are 106.0 ± 0.5°. Other molecular parameters are as anticipated. The 844 independent reflections obtained were refined to a final value of R = 0.11₆ using full-matrix least squares techniques.     

Refinement of β-LiIO3 crystal structure by use of zeeman effect on the NQR line and ir-reflection spectra

The NQR Zeeman effect of ¹²⁷I quadrupole resonance (±$\text{1}\text{2}$ ↓ ±$\text{3}\text{2}$ transition) and the polarized IR spectra of a single crystal of β-LiIO₃ have been studied. The z-axes of the EFG orientation in the unit cell were determined; the EFG asymmetry parameter for the ¹²⁷I nuclei was refined giving η = 0.027 ± 0.003 at 300 K for β-LiIO₃. The dichroic ratio in the (100) crystal plane over the I-O stretching vibration region has been measured from polarized spectra and calculated on the basis of an “oriented gas” model by the use of refined structural data. Comparison of some spectral, structural and quantum-chemical characteristics of both β- and α-modifications of LiIO₃ crystal has been made.