一维Z形链状吡啶三唑-Zn(Ⅱ)化合物的合成、晶体结构及荧光性能

通过水热法成功合成了一例一维"Z"形链状结构的化合物[(4,3′-Hbpt)_2Zn(adp)]_n(1)(4,3′-Hbpt=3-(4-吡啶基)-5-(3-吡啶基)-1-H-1,2,4-三唑;adp=己二酸离子)),并通过X射线单晶衍射、元素分析、X射线粉末衍射和荧光光谱等方法对该化合物进行了结构表征和性质研究.X射线单晶衍射分析表明,化合物1属于单斜晶系,C2/c空间群,晶胞参数为a=1.938 8 nm,b=0.877 6 nm,c=1.844 1 nm,α=90°,β=109.1°,γ=90°,V=2.965 0 nm~3,D_c=1.470 g/cm~3,Z=4,F(000)=1 352,GOOF=0.957.在化合物1中,Zn~(2+)离子通过己二酸桥接形成一维"Z"形链状结构.此外,通过荧光光谱对化合物1的荧光性质进行了研究.     

丹参多酚酸盐改善扩张性心肌病心肌功能的作用机制

将代谢组学与分子生物学方法相结合,研究了丹参多酚酸盐治疗扩张性心肌病的作用机制.采用主成分分析(PCA)法,分析了健康组、模型组及丹参多酚酸盐给药组大鼠血清代谢轮廓,采用正交校正的偏最小二乘判别分析(OPLS-DA)法寻找潜在的生物标记物,共鉴定得到磷酯酰丝氨酸[16∶0/18∶1(9Z)]、溶血磷脂(16∶0)、溶血磷脂[20∶4(5Z,8Z,11Z,14Z)]、溶血磷脂[22∶6(4Z,7Z,10Z,13Z,16Z,19Z)]、胆固醇硫酸酯、胆汁酸、γ-亚麻酸、二十二碳五烯酸和9'-羧基-γ-生育酚9种潜在的生物标记物.其中,γ-亚麻酸、二十二碳五烯酸和9'-羧基-γ-生育酚的含量在模型组中下降,经丹参多酚酸盐治疗后含量上升.通过Western bloting法和酶联免疫吸附法证实丹参多酚酸盐通过影响体内与γ-亚麻酸和9'-羧基-γ-生育酚相关的超氧化物岐化酶(SOD)、丙二醛(MDA)及其下游Bcl-2和Bax蛋白分子表达量,从而减少氧化应激所致的心肌细胞凋亡数量,达到治疗阿霉素所致扩张型心肌病的目的.     

4-氧代-2-亚胺基噻唑烷-5-亚基乙酸乙酯类化合物的设计、合成及抗癌活性（英文）

以胺、异硫氰酸酯和炔酯为原料,通过三组分偶联环化制备了一系列4-氧代-2-亚胺基噻唑烷-5-亚基乙酸乙酯类化合物.采用噻唑蓝(MTT)法研究了目标化合物对人肝癌细胞Hep G2和人乳腺癌细胞MCF-7的体外抗癌活性,结果发现大多数化合物显示出明显的抗癌活性.与顺铂相比,(Z)-2-((Z)-2-((3,4-二氯苯基)亚氨基)-3-(3-(4-甲基哌嗪-1-基)丙基)-4-氧代噻唑烷-5-亚基)乙酸乙酯(4r)表现出最好的细胞毒性,对Hep G2和MCF-7的IC50值分别为0.88和0.80μmol/L,并且讨论了药物的初步构效关系.这些化合物对肿瘤细胞具有良好的生物活性,是一类有应用前景的化学治疗药物,值得进行后续研究.     

国际比对钢中碳硫含量的测定

参加由北京中实国金实验室能力验证研究有限公司组织实施的NIL PT–0501–1钢中碳硫含量的测定(国际比对)能力验证。采用GB/T 20123–2006《钢中总碳硫含量的测定高频感应炉燃烧后红外线吸收法》测定碳硫含量。在试验过程中,通过减少试样质量,控制称样温度,用有证参考物质绘制工作曲线,由测得的峰值计算碳硫含量。将所得结果采用稳健统计技术处理中的Z比分数进行了评定,碳含量Z比分评定结果为Z=1.0,硫含量Z比分评定结果为Z=0.7,均小于2.0,结果满意。实验室碳硫分析数据能够得到国际国内同行的互认。     

一种新的分子内O→Sn络合物(Z)-1-[2-(三苯基锡基)乙烯基]-环辛醇的合成与鉴定

对分子内络合物(Z)-1-[2-(三苯基锡基)乙烯基]-环辛醇及其碘代螯合物进行了合成和鉴定,并通过X-射线四圆衍射对(Z)-1-[2-(三苯基锡基)乙烯基]-环辛醇的结构进行了表征.     

6-N-烷基-6-氮杂-2-氧代-3-氧杂-4-甲氧基-双环[3.1.0]己烷的合成、立体化学及抗癌活性研究

以3-溴-5-甲氧基-2(5H)-呋喃酮和伯胺为原料,在均相中用三乙胺作碱性催化剂,可以得到一对非对映异构体(1Z,4E,5Z)-6-N-烷基-6-氮杂-2-氧代-3-氧杂-4-甲氧基-双环[3.1.0]己烷(4)和(1Z,4Z,5Z)-6-N-烷基-6-氮杂-2-氧代-3-氧杂-4-甲氧基-双环[3.1.0]己烷(5).目标分子4和5经IR,1HNMR,13CNMR,EIMS进行了表征,并做了结肠癌细胞(HCT-8)、肝癌细胞(BEL-7402)、人胃癌细胞(BGC-823)、肺腺癌细胞(A549)和人卵巢癌细胞(A2780)的抗癌活性实验,其中5c和5d对HCT-8,BGC-823,A549和A2780等癌细胞有一定的抑制作用.此研究结果不仅丰富了该领域研究的理论基础,而且对某些新型药物的研制具有一定的指导意义.     

磺酰脒基桥连的锌卟啉-富勒烯化合物构型对光诱导电子转移机理的影响

通过"一锅法"多组分偶联反应合成了一种新型磺酰脒基桥连的卟啉-富勒烯化合物ZnP-H-C₆₀. 该化合物具有Z式和E式2种异构体, 其中Z式异构体中含有分子内氢键. 光物理研究结果表明, 2种异构体中的卟啉与富勒烯之间都可以发生光诱导电子转移, 但其相应的电子转移机理却完全不同. 在Z式异构体中, 卟啉或富勒烯被激发后直接发生电荷分离而形成电荷分离态, 其电荷分离机理是通过氢键进行电子传递; 在E式异构体中, 由于卟啉和富勒烯之间存在空间电子相互作用, 被激发后先形成卟啉-富勒烯激基复合物, 再进一步发生电荷分离形成电荷分离态, 电荷分离通过空间电子转移实现.     

纺织品中4-氨基偶氮苯的测定能力验证分析

“P00012-2011-T07纺织品中禁用偶氮染料的测定(测试项目:4-氨基偶氮苯)”能力验证严格按照能力验证计划运作要求实施,并采用稳健统计法对测试结果进行统计,测试样品指定值为54.8 mg/kg,标准化四分位距(NIQR)为6.8941 mg/kg.共有12个省市、自治区的61家实验室参加本次能力验证,采用Z比分数对各实验室结果进行评价,结果满意率为86.9％.     

新型手性基团修饰的金属卟啉的合成及性质研究

合成了一种手性基团修饰的金属卟啉化合物[5-对(L-亮氨酰氧乙氧基)苯基-10, 15, 20-三苯基卟啉锌]. 通过元素分析、紫外可见光谱、红外光谱、圆二色光谱及核磁共振波谱对该化合物进行了较详细的表征. 同时, 采用分子力学方法搜索了主体的最低能量构象, 从理论上进一步解释实验结果. 利用Z扫描技术测定了该化合物的三阶非线性光学性质.     

5-苯基-1H-3吡唑酰腙化合物的合成及其结构表征

采用"一锅法"合成了5-苯基-1H-3-吡唑甲酸乙酯,进而合成了9种5-苯基-1H-3-吡唑酰腙化合物,通过元素分析、红外光谱、核磁共振氢谱等测试技术对这9个化合物的结构进行了表征. 将5-苯基-1H-3-吡唑甲酸乙酯水解得到5-苯基-1H-3-吡唑甲酸,此化合物与Cu(AcO)2配位,得到一个铜的三核配合物晶体,该晶体属单斜晶系,空间群为C2/c,晶胞参数为a=2.576 7(3) nm,b=1.1 94 4(1) nm,c=1.412 7(2) nm,β=98.993(2)°,V=4.294 1(9) nm 3,Z=4,Dc=1.629 g/cm 3,R1=0.035 5,结果更进一步确定了吡唑环的结构.     

Analysis of the Impedance Frequency Spectrum of a Passive Iron Electrode by Combined Impedance and Photoadmittance Measurements

The frequency spectra of electrochemical impedance Z, photocurrent i, and photopotential E are obtained for a passive Fe electrode in 0.2 M KOH in a frequency range 1.3 to 8300 Hz. The validity of relationship E/i = –Z is proved experimentally. The oxide film impedance Z _F is calculated from the frequency spectrum of E with expression Z _F = –E/g. The generation current g is found from the photocurrent frequency spectrum. The frequency impedance spectrum Z _F/S of the oxide/solution interface is determined with equation Z _F/S = Z – Z _F – R _el, where R _el is the solution resistance.     

Systematic trends in the line strengths of E1 transitions in the carbon isoelectronic sequence

Line strengthsS for the dipole allowed transitions within then=2 complex of the carbon isoelectronic sequence have been fitted in the formZ ² S=A+B/(Z–C), whereZ is the nuclear charge of a particular ion. The constantsA,B andC are determined by using a non-linear least square method. The data forS is taken from the configuration interaction calculations which included internal, semi-internal and all external type correlations for ions in the rangeZ=8–26. It is shown that the values ofA obtained from the fit for all the transitions are in excellent accord with the ab-initio values obtained in the hydrogenic limitZ provided near degeneracy effects are included.     

Identification and Synthesis of New γ-Lactones from Tuberose Absolute (Polianthes tuberosa)

Six unsaturated γ-lactones, (Z)-5-octen-4-olide ( 1 ), (Z)-5-decen-4-olide ( 2 ).(Z)-6-nonen-4-olide ( 3 ), (Z)-6-dodecen-4-olide ( 4 ), (Z, Z)-6,9-dodecadien-4-olide ( 5 ), and tuberolide ( 6 ) have been identified for the first time in tuberose absolute (from Polianthes tuberosa L.). All structures were corroborated by synthesis and all, except 3 and 4 , are new.

1 The name ‘tuberolactone’ has been suggested for (Z, Z)-2,7-decadien-5-olide [1]. We propose the name ‘tuberolide’ for the bicyclic lactone 6 . (IUPAC name (1R*,5S*,Z)-6-(2′-pentenyl)-2-oxabicyclo[3.3.0]octan-3-one).

An improved method for the stereoselective synthesis of (±)-cis-bicyclo [4.3.0]-non-3-en-7-one ( 23 ) by an AlCl₃-catalyzed Diels-Alder reaction is reported.     

Binding/antibinding analyses for diatomic interactions. The effect of nuclear charge on one-electron chemical bonding

For a one-electron homonuclear diatomic system with arbitrary nuclear charge Z, the change in the nature of diatomic interaction and its density origin are quantitatively examined as a function of Z by the method of binding/antibinding analyses based on the Hellmann-Feynman theorem. In the Is_g ground state, two energy extrema, potential barrier at a large internuclear distance and potential minimum at a smaller distance, appear for 1<Z<1.44. The binding part of the partitioned Hellmann-Feynman forces suffers little effect of Z, and these two extrema are attributed respectively to the increase in the nuclear repulsion and to the decrease in the antibinding part of the partitioned forces. In the antibonding 2p_u state, a stable molecule is formed for Z<1. This appearance of the bonding nature is shown to have its origin in the binding part which is almost unchanged by the decrease of Z.     

Zur Chemie der Pyrrolpigmente, 54. Mitt.: Phytochrommodellstudien: Ein 2,3-Dihydrobilatrien-abc-3-Cholesterylderivat

The diastereomeric 2,3-Dihydrobilatrienes-abc derivatives (4Z, 9Z, 15Z)-7 and (4Z, 9Z, 15E)-7 bearing a cholesterylacetate moiety in position 3 of the chromophore are prepared. The reaction sequence contains an isomerisation step providing quantitative enantioselective formation of the chiral center in position 3. Configurations and conformations of the diastereomers are elucidated using¹H- and¹³C-NMR spectra, NOE-difference spectra, 2D-NMR experiments (NOESY) and arguments from UV-VIS and CD data. It is concluded that the hydrophobic interactions between chromophore and cholesteryl-fragment yield a compact conformation where the two substructures are in close contact with each other. On the other hand these interactions seem to be too weak to induce significant changes in the chemistry, absorption spectra and conformational characterics of the bile pigment chromophore. Therefore hydrophobic interactions between chromophor and apolar amino acid residues of the protein in phytochrome should be of minor relevance for determining spectroscopic shifts.

     

Zur Totalsynthese von Human-Sekretin

Summary The synthesis of the heptacosapeptide amide with the primary structure of Human-secretin is described. For this purpose 7 fragments were designed, i.e. H-Gly-Leu-Val-NH₂ 25–27b,Z-Arg(Z ₂)-Leu-Leu-Gln-OH 21–24,Z-Arg(Z ₂)-Leu-Gln-OH 18–20,Z-Arg(Z ₂)-Glu(OtBu)-Gly-Ala-OH 14–17,Z-Arg(Z ₂)-Leu-OH 12–13,Z-Thr(tBu)-Ser(tBu)-Glu(OtBu)-Leu-Ser(tBu)-OH 7–11,Adoc-His(Adoc)-Ser(tBu)-Asp(OtBu)-Gly-Thr(tBu)-Phe-OH 1–6 these fragments were consequently assembled to the overall protected total sequence using the Wünsch/Weygand-method with dicyclohexylcarbodiimide. After deprotection by exposure to trifluoroacetic acid in presence of 1,2-ethanedithiol and water as scavenger, the isolated crude product was purified by column chromatography on CM-Sepharose, fast flow. This synthetized Human-secretin showed the full biological activity in comparison to Porcine-secretin.

Herrn Prof. Dr. E. Bayer zum 65. Geburtstag gewidmet.     

Synthesis of 7E,9Z-dodecadienyl acetate,the sex pheromone ofLobesia botrana Shiff

Two syntheses of 7E,9Z-dodecadienyl acetate from 1,3-butadiyne were carried out using either 2E,4Z-heptadienyl acetate or 1-bromo-3E,5Z-octadiene as the key intermediates. The latter underwent organocopper cross-coupling with the respective complementary Grignard reagents (prepared from the corresponding 1-tert-butoxy--chlorohydrins) as alkylating agents.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 766–768, April, 1993.     

Synthesis of (7Z,9Z)-dodecadienyi acetate,a component of sex pheromones of the leafrollersEpinotia andEucosma,using conjugated diynols

Two analogous routes to the title pheromones were elaborated based on organocuprate cross-coupling ofZ,Z-dienic electrophiles, (2Z,4Z)-1-acetoxy-2,4-heptadiene (6) and (3Z,5Z)-1-bromoctadiene (8), with -tert-butoxy-1-chloropentane and -butane, respectively. Optimal conditions for the reduction of 2,4-heptadiyn-1-ol and 3,5-octadiyn-1-ol to the respectiveZ,Z-alkadienols as precursors for the electrophiles were found. Treatment of diynols with activated zinc in aqueous alcohol provided high geometrical purity of the product (94 %). In both cases, copper-catalyzed cross-coupling afforded 1-tert-butoxy-7,9-dodecadiene (four stereoisomers), acetolysis of which gave the target pheromone contaminated by stereoisomers. In the case of allylic electrophile6, the reaction occurred with the loss of the initial configurational purity, whereas the use of homoallylic bromide8 ensured almost complete retention of the configuration of the double bonds and obtaining the target pheromone of 87 % configurational purity.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1656–1660, September, 1993.     

Z/E‐Isomerism of 3‐[4‐(dimethylamino)phenyl]‐2‐(2,4,6‐tribromophenyl)acrylonitrile: crystal structures and secondary intermolecular interactions

The Z and E isomers of 3‐[4‐(dimethylamino)phenyl]‐2‐(2,4,6‐tribromophenyl)acrylonitrile, C₁₇H₁₃Br₃N₂, ( 1 ), were obtained simultaneously by a Knoevenagel condensation between 4‐(dimethylamino)benzaldehyde and 2‐(2,4,6‐tribromophenyl)acetonitrile, and were investigated by X‐ray diffraction and density functional theory (DFT) quantum‐chemical calculations. The (Z)‐( 1 ) isomer is monoclinic (space group P2₁/n, Z′ = 1), whereas the (E)‐( 1 ) isomer is triclinic (space group P, Z′ = 2). The two crystallographically‐independent molecules of (E)‐( 1 ) adopt similar geometries. The corresponding bond lengths and angles in the two isomers of ( 1 ) are very similar. The difference in the calculated total energies of isolated molecules of (Z)‐( 1 ) and (E)‐( 1 ) with DFT‐optimized geometries is ∼4.47 kJ mol⁻¹, with the minimum value corresponding to the Z isomer. The crystal structure of (Z)‐( 1 ) reveals strong intermolecular nonvalent Br…N [3.100 (2) and 3.216 (3) Å] interactions which link the molecules into layers parallel to (10). In contrast, molecules of (E)‐( 1 ) in the crystal are bound to each other by strong nonvalent Br…Br [3.5556 (10) Å] and weak Br…N [3.433 (4) Å] interactions, forming chains propagating along [110]. The crystal packing of (Z)‐( 1 ) is denser than that of (E)‐( 1 ), implying that the crystal structure realized for (Z)‐( 1 ) is more stable than that for (E)‐( 1 ).     

Beiträge zur Chemie der Pyrrolpigmente, 75. Mitt. Phytochrom-Modell-Studien: Stereochemische Untersuchungen an einem zwischen den pyrrolischen Ringen A und C peptidartig überbrückten 2,3-Dihydrobilatrien-abc

The sterochemistry of a 2,3-dihydrobilatriene-abc bridged between the pyrrolic rings A and C by means of a (S)-lysine fragment was investigated in two solvent systems using 2D-¹H-NMR and absorption spectroscopic techniques. The molecule adopts a circular helical geometry designated as (3S,4Z,9Z,15Z,5sp,10sp,14sp) in chloroform solutions. ForHMPT solutions however, an extended geometry characterized by (3S,4E,9E,15Z,5sp,10ap,14sp) was observed. The chiroptical properties of these two systems which are stabilized by the bridging moiety are discussed.