二茂锆羧酸配合物的合成——二茂锆氢化物与α,β—不饱和酸或钠盐反应的研究

本文研究了Cp_2ZrH_2与丙烯酸和Cp_2Zr(H)Cl与丙烯酸钠、巴豆酸钠的反应。产物由IR 1~H和~(13)CNMR、ESR谱、气相色谱以及化学方法分析鉴定。产物水解得到与底物相应的饱和酸.用~1H NMR方法考察了Cp_2ZrH_2与丙烯酸的反应过程,用IR方法考察了Cp_2Zr(H)Cl与丙烯酸钠的反应过程。实验结果表明,上面两种反应首先消除H_2或NaCl,形成锆氧健,然后碳碳双键还原生成二茂锆羧酸盐配合物,其中羧酸根离子与二茂锆桥式双齿配位。     

氯氮平、去甲氯氮平及奥氮平的高效液相色谱电化学检测特性的研究

 采用高效液相色谱安培电化学检测法 ,考察了氯氮平、去甲氯氮平和奥氮平在不同 pH值流动相下的色谱分离情况及其色谱峰高与检测电压的关系。结果表明 ,氯氮平、去甲氯氮平和奥氮平的保留时间均随流动相 pH值的升高而延长 ;在pH值为 4 5 6和 5 5 6的流动相中 ,均可实现基线分离。 3种化合物的色谱峰高与检测电压之间呈典型的“S”型曲线 ,pH值升高时该曲线均左移。氯氮平、去甲氯氮平和奥氮平的检测电压必须大于产生最大氧化电流的最低电压才能得到稳定的检测电流。这种典型的“S”型伏安曲线对于化合物的定量和定性检测具有重要意义。     

衍生荧光法测定盐酸西布曲明

通过衍生反应，建立了用荧光光度法测定盐酸西布曲明的新方法。并对衍生体系、反应条件、产物稳定性等进行了研究。实验确定丙二酸和乙酸酐混合试剂与盐酸西布曲明在75℃的水浴中加热15min，所得产物发射强荧光，最大激发波长λcx=456nm，最大发射波长λem=496nm。在上述波长下，荧光强度与盐酸西布曲明的质量浓度在0．11～9．5μg／mL范围内呈良好的线性关系，检出限为13．4ng／mL，标准加入回收率在95．4％～104．2％。用于曲美胶囊中盐酸西布曲明的测定。     

Substituent effects on heats of formation, group interactions, and detonation properties of polyazidocubanes

We have calculated the heats of formation (HOFs) for a series of polyazidocubanes by using the density functional theory (DFT), Hartree-Fock, and MP2 methods with 6-31G* basis set as well as semiempirical methods. The cubane skeleton was chosen for a reference compound, that is, the cubane skeleton was not broken in the process of designing isodesmic reactions. There exists group additivity for the HOF with respect to the azido group. The semiempirical AM1 method also produced reliable results for the HOFs of the title compounds, but the semiempirical MINDO3 did not. The relationship between HOFs and molecular structures was discussed. It was found that the HOF increases 330-360 kJ/mol for each additional number of the azido group being added to the cubane skeleton. The distance between azido groups slightly influences the values of HOFs. The interacting energies of neighbor azido groups in polyazidocubanes are in the range of 2.3 approximately 6.6 kJ/mol, which are so small and less related to the substituent numbers. The average interaction energy between nearest neighbor --N3 groups in the most stable conformer of octaazidocubane is 2.29 kJ/mol at the B3LYP/6-31G* level. The relative stability related to the number of azido groups of the title compounds was assessed based on the calculated HOFs, the energy gaps between the frontier orbitals, and the bond orders of the C--N3 and C--C bonds. The predicted detonation velocity of hepta- and octa-derivatives is over 9 km/s, and the detonation pressure of them is ca. 40 GPa or over.     

Synthesis of （2R,4R）—2—N—tert—Butyloxycarbonyl Amino—4,5—epoxido—valeric Acid Methyl Ester

The stereoselective synthesis of (2R,4R)-2-N-tert-butyloxycarbonyl amino-4,5-epoxido-valeric acid methyl ester 8,which is the key intermediate for the synthesis of (2′S,2R)-3-trans-nitrocyclopropyl-alanine,was first accomplished.     

Determination of 19-norandrosterone in CCQM-P68. NIST results using an isotope dilution liquid chromatography/tandem mass spectrometry method

The US National Institute of Standards and Technology (NIST) participated in an international interlaboratory study under the auspices of the Consultative Committee for Amount of Substance (CCQM) for the determination of 19-norandrosterone (19-NA) in urine, the principal metabolite of nandrolone and certain other synthetic testosterone substitutes banned for use by the World Antidoping Agency (WADA). Prior to this study, NIST developed a candidate reference measurement procedure based upon isotope dilution liquid chromatography/tandem mass spectrometry. This method was applied to a urine sample distributed to the participants in the study by the Australian National Measurement Institute, Pymble, Australia (NMIA). The NIST results were in very good agreement with those from the other participants, all of whom used methods based upon gas chromatography/mass spectrometry. All known significant sources of uncertainty were evaluated, resulting in a relative expanded uncertainty of less than 5% (coverage factor k = 2).     

硫杂蒽酮类稀土配合物的合成、表征及与DNA的作用(I)

合成了新的O-(硫杂蒽酮-[2]-基)-氧乙酸及其稀土配合物. 通过元素分析, IR, ¹H NMR, UV, DTA-TG和¹³C NMR谱对其结构进行了表征. 研究表明: 配体羧羰基脱质子后与金属离子配位, 2位氧原子也与金属离子配位, 配合物中含有一定量的配位水, 配合物为非电解质类型. 同时, 研究了O-(硫杂蒽酮-[2]-基)-氧乙酸稀土配合物对质粒DNA的切割作用. 结果表明: 铕的配合物对DNA的切割较明显, 且当配合物浓度增加时, 质粒DNA的超螺旋构型逐渐减少, 而缺刻、开环型构型逐渐增多. 在相同条件下, Eu(III)离子对质粒pBR322DNA几乎没有切割作用; 配体O-(硫杂蒽酮-[2]-基)-氧乙酸对质粒pBR322DNA也有切割作用, 但配合物EuL₃对质粒pBR322DNA的切割作用明显强于配体, 表明稀土离子Eu(III)与配体生成配合物后有较好的协同切割作用.     

N,N′‐Bis(2‐pyridylmeth­yl)ferrocene‐1,1′‐diyldicarboxamide and N,N′‐bis­(3‐pyridylmeth­yl)ferrocene‐1,1′‐diyldicarboxamide

The mol­ecules of N,N′‐bis­(2‐pyridylmeth­yl)ferrocene‐1,1′‐diyl­dicarboxamide, [Fe(C₁₂H₁₁N₂O)₂], contain intra­molecular N—H⋯N hydrogen bonds and are linked into sheets by three independent C—H⋯O hydrogen bonds. The mol­ecules of the isomeric compound N,N′‐bis­(3‐pyridylmeth­yl)ferrocene‐1,1′‐diyldicarboxamide lie across inversion centres, and the mol­ecules are linked into sheets by a combination of N—H⋯N hydrogen bonds and π–π stacking inter­actions between pyridyl groups.     

一种新型单体引发转移终止剂合成精细结构功能化的聚苯乙烯

自从1982年Ｏｔｓｕ[1]等提出引发转移终止剂(Ｉｎｉｆｅｒｔｅｒ)以来,这类化合物得到了广泛的研究和发展.使用引发转移终止剂的聚合反应是实现“活性”聚合的一个重要方法.引发转移终止剂又分为热引发转移终止剂和光引发转移终止剂两种.热引发转移终止剂除了三苯甲基偶氮苯外[2],均是六取代乙烷类化合物[3～7];而光引发转移终止剂则一般是一些含二硫代氨基甲酰氧基基团的化合物,如Ｎ,Ｎ二乙基二硫代氨基甲酸苄酯(ＢＤＣ)、双(Ｎ,Ｎ二乙基二硫代氨基甲酸)对苯二甲酯(ＸＤＣ)、Ｎ乙基二硫代氨基甲酸苄酯(ＢＥＤＣ)、双(Ｎ乙基二硫代氨基甲酸…