The Synthesis and Characterization of a Novel (E,E)-Dioxime and its Mono- and Heterotrinuclear Complexes Containing an 18-Membered Dioxadithiadiazamacrocycle

The novel (E,E)-dioxime, 5,6:17,18-dibenzo-11,12-(4-nitrobenzo)-2,3-bis(hydroxyimino)-7,16-dithia-10,13-dioxa-1,4-diazacyclooctadecane) (H2L), has been synthesized from reaction of (E,E)-dichloroglyoxime (1) with 2,3:14,15-dibenzo 8,9-(4-nitrobenzo)-4,13-dithia-7,10-dioxa-1,16-diazahegzadecane (2). The mononuclear Co(III) complex (4) of this dioxime was prepared by oxidation of the cobalt (II) complex. The -capped Co(III) complex (5) was synthesized by using a precursor Co(III) complex and boron trifluoride dietherate. The heterotrinuclear complexes (6) and (7) were prepared by reaction of (5) with NiCl2·6H2O and CdCl2·H2O, respectively. In addition, the homotrinuclear Cu(II) complex (8), has also been prepared by the reaction of this dioxime with CuCl2·H2O. The structures of the dioxime and its complexes were identified by using elemental analysis, 1H- and 13C-NMR, IR, and mass spectral data.

脱落酸对UV-C胁迫下小麦幼苗光合特性及抗氧化酶活性的影响

研究了UV-C辐射下短期和长期脱落酸(ABA)处理对小麦幼苗CO2同化作用、羧化效率、光合CO2响应以及抗氧化酶活性等的影响.结果表明,在无UV-C辐射情况下,短期和长期ABA处理能提高光合速率,比对照增加14·69%和20·46%,降低气孔导度,比对照降低14·74%和17·31%,但对胞间CO2浓度和羧化效率影响不大.当受到UV-C辐射时,光合速率、羧化效率、气孔导度和胞间CO2浓度逐渐降低.长期ABA处理变化最小,其次为ABA短期处理,对照降低最大.ABA处理能够提高小麦光合对CO2的响应,UV-C辐射抑制光合对CO2的响应.ABA处理能够提高小麦抗氧化酶(CAT、SOD、POD)活性而降低MDA含量.在UV-C辐射下,CAT活性先升高随后降低,在辐射处理1h时活性达最大值,ABA处理的SOD和POD活性先升高后降低,且ABA长期处理比短期处理增加明显,对照则逐渐降低.ABA处理可能通过提高小麦CO2同化作用和抗氧化酶活性增强对UV-C胁迫的抗性,且ABA长期处理比短期处理效果更明显.

外源一氧化氮对干旱胁迫下杨树光合作用的影响

NO是生物体中一种自由基分子,其NO对树木叶片光合作用的影响研究未见报道.本文研究了外源NO对杨树叶片水分状况、光合作用和抗氧化物酶活力的调节作用.不同浓度SNP处理对杨树叶片含水量具有显著影响,杨树叶片含水率随着SNP浓度的提高而增加.当SNP浓度增加到500μmol·L-1后各处理杨树叶片含水率变化趋于稳定.外源NO能提高水分胁迫下杨树叶片的光合、原初光能转化率Fv/Fm、Fm/Fo和Fv/Fo等的比值.其效果随水分胁迫时间的延长而降低.与此对应的是,短时间水分处理(1h)的杨树叶片SOD和POD抗氧化物酶的活性显著高于长时间(3h)水分胁迫处理.SNP能显著提高不同干旱时间处理组的POD活性,而对SOD活性影响不明显.同时,随SNP浓度的增加,POD和SOD活性呈现先升后降的趋势.因此,干旱胁迫可引起杨树叶片光合效率降低,出现氧化伤害症状,外源NO可诱导抗氧化物酶POD和SOD活性的升高,缓解原初光能转化率Fv/Fm、Fm/Fo和Fv/Fo等值的降低,从而延缓活性氧积累,减轻水分胁迫对杨树叶片光合作用的影响.

一氧化氮对杨树耐旱性的影响

探讨了外源NO对水分胁迫下杨树叶片质膜相对透性、叶片光合作用和氧化伤害保护酶的影响.结果表明,NO供体硝普钠(sodiumnitroprusside,SNP)能提高杨树叶片的含水率,在水分胁迫(PEG6000渗透液处理)下,能缓解叶片的水分丢失.NO对杨树叶片光合作用具有双重性,低浓度SNP(200、500μmol·L-1)能促进叶片的光合,高浓度SNP(1000、2000μmol·L-1)则明显抑制叶片的光合.较短时间水分处理胁迫(1h))的杨树叶片SOD和POD活性显著高于较长时间(3h)水分胁迫下叶片的酶活性.经SNP处理后,各处理组POD、SOD活性明显上升.同时,随SNP浓度的增加,POD和SOD活性表现出先上升后下降的趋势.外源NO可通过诱导POD和SOD活性的上升,延缓活性氧的积累,从而减轻水分胁迫对杨树的伤害,增强树木的耐旱能力.

用淋洗法修复张士灌区CdPb污染沉积物的研究

采用淋洗法,以组成为0.5m ol·L-1C aC l2和0.1m ol·L-1H C l的复合药剂作为淋洗剂处理沈阳张士灌区C d、Pb污染沉积物(C d39m g·kg-1,Pb1250m g·kg-1),在pH=1.0、反应时间30m in、淋洗剂液固比3∶1、搅拌速度500r·m in-1、温度25℃的条件下,复合淋洗剂对C d和Pb的去除率分别达到70.8%和29.3%。粒级分析表明,沉积物中C d和Pb主要存在于细粒部分,因此,分级处理能够减少处理量,降低成本。一定酸度下C l-的络合作用可能是复合淋洗剂的主要强化淋洗机制。

由一株真菌产生的抑制血管细胞粘附分子-1基因表达的活性物质的研究

以血管细胞粘附分子-1（VCAM－1）基因为靶位点，使用含有荧光素酶报告基因的转染细胞株筛选模型M-4细胞从微生物的代谢产物中高通量筛选能够抑制VCAM－1基因表达的生物活性物质，以期找到能够治疗诸如类风湿性关节炎等免疫性疾病的新型药物。在筛选过程中使用有机溶媒萃取、ODS反相柱层析、HPLC制备等方法，从真菌FO－5897的发酵液中分离到了一个对测活用细胞株的荧光素酶报告基因的表达有中等强度抑制作用的化合物，其IC50为13．8μmol／L，经各种理化性质及1H－NMR分析确定该化合物与文献报道的具有降血脂和抗癌作用的化合物Ascofuranone的结构相同。

Efficient and divergent synthesis of cyclophosphamide analogues from 2-arylamino-3-acetyl-5, 6-dihydro-4H-pyrans

A facile and efficient one-pot synthesis of substituted cyclophosphamidic chlorides and their analogues has been developed from readily available enaminones, 2-arylamino-3-acetyl-5,6-dihydro4H-pyrans.

含3-氨基(N-氨基酞酰亚胺)的新型聚酰亚胺合成与表征

合成了一种不对称含肼二胺单体3-氨基(N-氨基酞酰亚胺),通过1H NMR、IR确认了其结构,并用15NNMR证实了该化合物两种氨基活性存在差异。采用传统的一步法用对氯苯酚做溶剂,用该二胺单体与二酐4,4’-BP-DA,4,4’-ODPA 4,4’-BTDA,4,4’-HQDPA和BPADA聚合得到一系列新型聚合物,并进行了表征。其中由4,4’-HQDPA和BPADA聚合得到的聚酰亚胺薄膜,有较好的机械性能。

手性指数的研究及其应用

该工作对手性化合物的构效关系进行了研究,其内容包括:(1)对二维拓扑指数A_(mi)进行了扩展,即在指数的衍生中加入手性碳原子的因素,使之成功地应用于14个手性化合物活性的预测;(2)描述了构象独立的手性指数(CICC法)和构象依赖的手性指数(CDCC法),采用CDCC和CICC预测了80个二级醇的~1H NMR化学位移差的符号,并由此可以确定该类化合物的绝对构型;(3)描述了原子构象依赖的手性指数(aCDCC),并将这种方法用于手性仲醇的α-碳原子的~(13)C NMR在不同手性溶剂中的化学位移差的预测,获得了满意的结果.

淀粉-丙烯酰氧乙基三甲基氯化铵接枝共聚物的制备与表征

采用过硫酸铵(APS)为引发剂,将玉米淀粉与丙烯酰氧乙基三甲基氯化铵(DAC)接枝聚合,制备了一系列分子中含有阳离子季铵基团的淀粉——DAC接枝共聚物。研究了单体用量、引发剂用量、反应温度和反应时间对接枝体系阳离子度的影响,探讨了过硫酸铵引发淀粉接枝DAC共聚反应的基本规律。并用FTIR、X-ray和1H-NMR等表征手段对接枝共聚物进行了结构分析。

Enhanced amplified spontaneous emission by assistant Forster energy transfer in DCJTB-C545T-Alq(3) coguest-host system

Amplified spontaneous emission (ASE) characteristics of a red fluorescent dye 4-(dicyanomethylene)-2-t-butyl-6(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) were significantly improved by assistant Forster energy transfer. The coguest-host system was composed of an electron transport organic molecule tris(8-hydroxyquinoline) aluminum (Alq(3)) as host and a green fluorescent dye (10-(2-benzothiazolyl)-1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizin-11-one) (C545T) as assistant dopant codoped with the guest red dye DCJTB as emitter in a matrix of polystyrene (PS).

Synthesis and characterisation of novel imidazolium-based ionic liquid crystals with a p-nitroazobenzene moiety

A novel series of compounds with different counter anions, i.e. 1-{[4-(4-nitrophenylazo)phenyloxy]}alkyl-3-methyl-1H-imidazol-3-ium bromide salts (C-n , n=3, 6, 10) and tetrafluoroborate salts (D-n , n=3, 6, 10), were synthesised by the incorporation of an imidazolium group into paraffin side chain-terminated 4-nitroazobenzene derivatives. Their chemical structures were determined by H-1 NMR, C-13 NMR, UV spectroscopy and elemental analysis.

温度敏感性PNIPAM-b-PZLL-b-mPEG三嵌段共聚物的合成与自组装研究

通过大分子引发剂引发ε-苄氧羰基-L-赖氨酸-N-羧酸酐(Lys-NCA)开环聚合和大分子缩合的方法合成了聚(N-异丙基丙烯酰胺)-b-聚(ε-苄氧羰基-L-赖氨酸)-b-聚乙二醇单甲醚三嵌段共聚物(PNIPAM-b-PZLL-b-mPEG).用GPC和1H-NMR对其结构进行了表征.用芘荧光探针法证明了该三嵌段聚合物形成胶束的性质并测定了临界胶束浓度(CMC).动态光散射(DLS)研究表明,在固定PNIPAM-b-PZLL链段长度的情况下,mPEG分子量为2000时,胶束在温度高于临界溶解温度(LCST)时发生聚集,mPEG分子量为5000时,胶束在LCST以上没有发生聚集.

Novel Re(I) dendrimers: synthesis, characterization and theoretical studies

Four novel diimine rhenium(I) carbonyl complexes with the formula [Re(CO)(3)(L) Br], where L = 2-(4-(9H-carbazol-9-yl) phenyl)-1H-imidazo[4,5-f][1,10] phenanthroline (P1), 2-(4-(3,6-di-tert-butyl-9H-carbazol-9-yl) phenyl)-1H-imidazo-[4,5-f][1,10] phenanthroline (P2), 2-(4-(6-(9H-carbazol-9-yl)-9H-3,9'-bicarbazol-9-yl) phenyl)-1H-imidazo[4,5-f][1,10] phenanthroline (D1), and 2-(4-(3', 6'-di-tert-butyl-6-(3,6-di-tert-butyl-9H-carbazol-9-yl)-9H-3,9'-bicarbazol-9-yl) phenyl)-1H-imidazo[4,5-f][1,10] phenanthroline (D2), have been successfully synthesized and fully characterized by (HNMR)-H-1, IR, and UV-Vis, etc. The luminescence quantum yields (LQYs) of the parent Re(I) complexes P1 and P2 are 0.13 and 0.16, respectively, which are much higher than the previously reported Re(I) dendrimers. The HOMOs and the LUMOs of P1 and P2 are calculated to be mainly composed of [d(Re) + pi(CO + Br)] and pi*(L) orbital, respectively.

Synthesis, photophysical properties, and theoretical studies on pyrrole-containing bromo Re(I) complex

Two bromo rhenium(I) carbonyl complexes with the formula of [Re(CO)(3)(L)Br], where L = 1,10-phenanthroline (Phen-Re) and 5-(1H-pyrrol-1-yl)-1,10-phenanthroline (Pyph-Re), were successfully synthesized with the aim to analyze the effect of the pyrrole (Py) moiety on the photophysical properties of Pyph-Re. It was found that the triplet metal-to-ligand charge-transfer d pi (Re) --> pi*(N-N) emission of Phen-Re and Pyph-Re centered at ca. 527 nm with the luminescence quantum yield (LQY) of 0.015 and ca. 578 nm with the LQY of 0.011, respectively. At the same time, the geometrical structures of the ground state and the absorption spectral properties of Phen-Re and Pyph-Re were also calculated with the 6-31G* basis set employed on C, H, N, O, and Br atoms, and LANL2DZ adopted on Re atom.