用"一锅法"合成取代吲哚衍生物

利用取代苯肼盐酸盐与丙酮酸、1,3-二苯基-1,3-丙二酮反应合成了3种取代吲哚衍生物.采用"一锅法"对酯化反应进行了改进,以盐酸酸化的乙醇作溶剂,苯磺酸催化,一步得到取代的吲哚酸酯.本文对吲哚环化的反应机理、合成条件进行了探讨,发现反应温度不同所得产物也不同.合成产物用IR, 1H NMR和MS进行了分析表征.     

通过三组分串联反应构建硫醚化吲哚衍生物

为了优化硫醚化试剂与吲哚类化合物构建碳-硫键的反应,以对甲苯磺酰氯、吲哚和水合肼为底物,以碘为催化剂,采用三组分串联法合成吲哚芳基硫醚,并对反应条件进行优化.在此基础上,选用连有不同取代基团的吲哚和苯磺酰氯,在最优反应条件下进行串联反应合成硫醚化的吲哚类化合物.在最优条件下吲哚芳基硫醚的产率为68%.利用连有不同取代基团的苯磺酰氯和吲哚合成了14种硫醚化吲哚衍生物,产率为41%~86%.这些结果表明,三组分串联反应是合成硫醚化吲哚的一个简洁有效的方法.     

交叉脱氢偶联反应研究进展

交叉脱氢偶联(CDC反应)是在氧化条件下直接通过两分子反应底物C—H键的断裂而形成C—C键的一种高效率、高原子经济性的直线合成方法.本文按照以下分类,含有胺N原子α-C—H键底物的CDC反应;含有醚O原子α-C—H键底物的CDC反应;烯丙基和苄基底物进行的CDC反应;烷烃的CDC反应,详细综述了近年来该领域的一些研究进展.     

1-苄基-3-(2-H-吡唑-3-酮基)-3'-(2-H-1,2-二乙氧甲酰肼基)-二取代氧化吲哚的合成

以3-(3-羟基吡唑基)氧化吲哚作为氨化反应的前体,偶氮二甲酸二乙酯作为氨化试剂,在四氢呋喃溶剂中,一步合成3,3'-二取代的氧化吲哚衍生物。该方法通过C-H活化构建了CN键,同时优化了反应条件,探讨了温度、催化剂,溶剂对反应产率的影响。该合成反应具有操作简便、高收率(95%)和产物易纯化等特点。     

1-Boc-吲哚-2-硼酸衍生物的合成

1-Boc-吲哚-2-硼酸衍生物是一类重要的有机中间体,广泛用于卤代芳烃参与的Suzuki-Miyaura偶联反应,从而构建复杂吲哚化合物.为了合成这类吲哚硼酸衍生物,以邻甲基硝基苯的衍生物(1a~1g)为起始原料,通过与DMFDMA、THP进行反应并进行浓缩结晶合成对应的烯胺;烯胺与还原剂进行还原关环得到吲哚衍生物;吲哚衍生物与二碳酸二叔丁酯反应完成对吲哚的保护; Boc保护的吲哚衍生物在低温无水无氧条件下与硼酸三异丙酯、LDA反应引入硼酸基团共4步反应,成功合成了包括6-苄氧基-1-Boc-吲哚-2-硼酸在内的共计7种吲哚硼酸衍生物(5a~5g),其结构经~1H NMR、~(13)C NMR、IR和MS表征.     

吲哚里西啶生物碱5-epi-167B的合成研究

报道一种简洁、高效的吲哚里西啶生物碱5-epi-167B的合成方法.该方法经过Michael加成反应、烯丙基三甲基硅烷参与的Schmidt重排反应，构建分子核心骨架，共6步反应，以12%总收率完成生物碱5-epi-167B高级中间体的合成.该方法在吲哚里西啶类生物碱的合成及其生物活性研究方面具有重要价值，可为相关研究提供参考.     

钴催化C—H键烯基化反应构建吲哚骨架荧光化合物

以廉价低毒的Cp*Co(Ⅲ)I2(CO)作为催化剂,N嘧啶基-6-甲酸甲酯基吲哚、苯乙炔作为原料,通过钴催化C-H键烯基化反应在室温条件下,以91%的收率制备了一例吲哚骨架的小分子荧光化合物.对其性质进行了初步探究.发现该化合物具有良好的发光性能,并拥有大Stokes位移.该化合物通过C—H键官能化反应制备,简化了反应路线,提高了反应的原子经济性以及步骤经济性,具有作为荧光染料的应用前景.     

2,2''''—二苯基—[2,3''''—联—1H—吲哚]—3(2H)—酮的过氧酸氧化反应

2，2’—二苯基—[2，3’—联—1H—蚓跺]—3（2H）—酮（1）的过氧苯甲酸氧化反应主成2—苯基—3H—吲哚—3—酮（3）和（或）2—苯基—4H—3，1—苯并嗪—4—酮（6），对反应机理进行了探讨．     

铜催化N-芳基丙烯酰胺与丙酮成环合成吲哚酮

发展了一种高效、简单的铜催化活泼烯烃羰基化成环合成吲哚酮的方法.以氯化亚铜为催化剂,二叔丁基过氧化物（DTBP）为氧化剂,丙酮为溶剂兼反应物,在100 ℃条件下与N-芳基丙烯酰胺类化合物发生自由基串联环化反应,高效地合成了一系列吲哚酮衍生物.探索不同温度、催化剂、溶剂等因素对反应的影响,并推导此环化反应的机理过程.     

[3+3]环化反应合成1-芳基-4-芳甲酰基吡啶衍生物

选择性修饰吡啶骨架.以3-芳甲酰亚甲基-2-氧化吲哚和烯胺酮为原料,在乙醇钠作催化剂,乙醇作溶剂,100℃条件下反应.通过[3+3]环化反应,合成了四环稠合的吡啶衍生物.条件温和、产率高、原料廉价,体现了原子经济性和成键有效性.实现了吡啶骨架1位的芳基化,4位的芳甲酰基化.     

Geomorphology visualization modeling and tidal current virtual reality for coastal ocean

The new technology of geomorphology visualization modeling and virtual reality for tidal current numerical simulation are the important methods utilized in coastal ocean research. In the project of studying the evolutionary trend of radial sand ridges in South Yellow Sea of China, this method becomes the key to reveal the correlation between the seabed topography and the hydrodynamic factor—— tidal current. It is proved that using the geomorphology visualization and tidal virtual reality techniques, oceanog-raphers might be able to intuitively discover the interaction pattern of sand ridges and tidal current, predicting the development of sand ridge stability in the future. Furthermore, a prolotypic software system——VROcean was designed and implemented to examine the performance of the new visualization technology on the contrast to traditional methods.     

RP-HPLC同时测定冷水花属3种植物中2种黄酮苷的含量

 建立反相高效液相色谱法同时测定冷水花属湿生冷水花、冷水花、粗齿冷水花植物中木犀草苷和大波斯菊苷2种黄酮类化合物含量的方法.采用Agilent ZORBAX SB-C₁₈(250mm×4.6mm,5μm)色谱柱,以乙腈-0.2%乙酸水溶液为流动相进行洗脱,检测波长350nm,流速0.mL·min^-1,柱温25℃.结果木犀草苷和大波斯菊苷分别在2.48~79.36μg·mL^-1、1.68~53.76μg·mL^-1范围内线性关系良好,木犀草苷平均回收率为98.06 %,RSD为1.11%;大波斯菊苷平均回收率为99.18%,RSD为0.98 %.所建立的冷水花HPLC含量测定方法结果准确可靠,可用于不同品种冷水花植物中木犀草苷和大波斯菊苷的含量测定.     

松花江吉林市段江水与沉积物中多环芳烃的分布、 来源和生态风险

在丰水期、 枯水期和平水期分别采集松花江吉林市段的江水和沉积物样品, 先用气相色谱 质谱联用仪(GC MS)测定其中16种多环芳烃（PAHs）的含量, 再通过比值法对各水期江水和沉积物中的PAHs进行来源识别, 并分别利用商值法和风险效应值法评价江水和沉积物的生态风险. 结果表明: 松花江吉林市段丰水期、 枯水期和平水期江水中PAHs的质量浓度分别为0.917~3.974 μg/L,0.980~3.293 μg/L和0.771~4.127 μg/L; 丰水期和平水期沉积物中PAHs的质量比分别为1 035.5~1 732.0 ng/g和1 188.5~1 632.0 ng/g; 不同水期江水中的PAHs质量浓度变化较大, 沉积物中的PAHs质量比变化较小; PAHs为石油源和燃烧源混合输入所致; 江水中PAHs的生态风险较小, 表层沉积物中的PAHs具有一定的生态风险.     

超声波一直接沉淀法制备CuS纳米溶胶

将超声波应用于以氯化铜(CuCl2·2H2O)和硫化钠(Na2S·9H2O)为原料的直接沉淀法制备CuS纳米溶胶,对产物进行透射电子显微镜(TEM)检测及X射线衍射仪(XRD)分析,结果显示,纳米溶胶中CuS平均粒径20～40 nm,并呈规则的纳米球形,粒度分布均匀,分散性好.     

Recombinant soluble TRAIL induces apoptosis of cancer cells

TRAIL is a tumor necrosis factor family member that selectively induces apoptosis of cancer cells but not of normal cells. To develop TRAIL into a potential cancer drug, three different sizes of soluble TRAIL fragments, including sTRAIL(74—281), sTRAIL(95—281) and sTRAIL(101—281), were expressed in E. coli and purified to homogeneity. Apoptosis assays indicated that sTRAIL(95—281) and sTRAIL(101—281), but not sTRAIL(74—281), can potently induce apoptosis of various cancer cell lines in 6 h, suggesting that the N-terminal fragment of aa101 has inhibitory effect on TRAIL-induced apoptosis. Moreover, we found that some cancer cells were resistant to TRAIL and the resistant cells could be converted into sensitive cells by treatment with the protein synthesis inhibitor cycloheximide, suggesting that one or more short-lived proteins are responsible for cells’ resistance to TRAIL.     

人力资源管理--薪酬设计薪酬模式薪酬激励

阐述了薪酬设计应遵循团队原则和隐性报酬原则的必然性，给出的薪酬目标设计的双赢模式则是企业与员工共同参与薪酬制度的制定，分析了基于职位、技能和缋效的薪酬定位的利井，提出了实施薪酬激励的原则。     

Approach to synthesis of novel chiral 3-chloro-2(5H)-furanone and its application in asymmetric reactions

The synthetic method of the novel chiral synthon, 5-l-menthyloxy-3-chloro-2-(5H)-furanone 5a and its application in asymmetric reactions were investigated. 5a is easily obtained in highly optical purity, and acts as a stable acceptor of Michael addition with oxygen nucleophiles in tandem double Michael addition / internal nucleophilic substitution to offer the spiro-cyclopropane derivative containing four stereogenic centers 8, which it is difficult to obtain by routine methods. The synthetic methods for 5a and 8 are reported in detail and the new compounds are identified on the basis of their analytical data and spectroscopic data, such as UV, IR,¹H NMR,¹³C NMR, MS and elementary analysis. The absolute configuration of the interesting spiro-cyclopropanes, spiro [1-chloro-4-(l-menthyloxy)-5-oxo-6-oxa-biscyclo[3.1.0]hexane-2,3′-(4′-/-menthyloxy-5′-l-menthyloxybutyrolactone)] 8 was established by X-ray crystallography. This result can provide important synthetic strategy in synthesis of some complex molecules containing spiro-cyclopropane skeleton with multiple chiral centers.     

Alteration of the specificity ofPst I restriction endonuclease

The influence of factors on the substrate-specificity ofPst I restriction endonuclease has been studied with the method of electrophoresis. The results show that, the specificity ofPst I almost can not be influenced by the single alteration of the concentration of Tris·HCl, Mg²⁺ or Na⁺ in the reaction system, but it can be altered by the reduction of any two of them. The specificity can not be altered by the single alteration of pH or the replacement of Mg²⁺ with Mn²⁺. The addition of glycerol or dimethylsulphoxide (DM-SO) to the reaction system results in the relaxation of the substrate-specificity ofPst I, but dimethyl-methylformide, glycol and ethyl alcohol can not bring about the alteration ofPst I specificity. Through the method of cloning and sequencing, the nucleotides of No. 1 and 6 in the recognition sequence ofPst I have changed (1C→A or 6G→T). Used with the enzyme analysis of an artificially synthetic DNA segment containing a special sequence, the nucleotides of No. 1 and 6 have both changed (1C→A and 6G→T). The recognition sequence ofPst I is speculated to be changed from CTGCA→G to TGCA→. Foundation item: Supported by the Research Fund for the Doctoral Program of Higher Education. Biography: Zou Guo-lin (1947-), male, professor. research direction, biochemistry.     

Sequence analysis of peptides with biological activities using electrospray-Fourier trans form ion cyclotron resonance mass spectrometry

The mass spectra of five peptides with biological activities are reported. All mass spectra were recorded using a 4.7-T Fourier transform ion cyclotron resonance mass spectrometer equipped with an external electrospray source. The accurate molecular weights for the five peptides prepared by solid phase synthesis were measured as 1765.9013, 1063.5420, 1092.5254, 820.3804 and 1078.5193, respectively. All the data were obtained with the external calibration. Differences between observed and theoretical monoisotopic molecular weights were in the (0.2—1.0)×10^-6 range. The complete primary sequence for the five polypeptides were determined using the method of in-source electrospray ionization/collision induced dissociation (ESI/CID). All the intact y series ions and b series ions were obtained from various peptides respectively, thus determining the sequences of the five polypeptides. We found that the measured accurate molecular mass of sample 4 was not in agreement with that expected from the planned synthetic peptide. The sequences of sample 4 were determined through analysis. The corresponding accurate masses of b series ions and y series ions were gained, which proved that it was correct to re-determine the sequences.