双核Pt(Ⅳ)配合物与Guanosine-5''''-Monophosphate和Glutathione反应的核磁共振光谱研究

合成了一个新型的双核Pt(Ⅳ)配合物{[cis-Pt(NH3)2Cl(OH)2]2(4,4'-methylenedianiline)}(NO3)2(化合物1)及相应的 15N标记化合物{[cis-Pt(15NH3)2Cl(OH)2]2(4,4'-methylenedianiline)}(NO3)2(化合物15N-1).利用1H NMR和ESMS进行了结构表征,化合物15N-1的2D[1H,15N]HSQC NMR发现,该化合物在水溶液中存在同分异构体.2D[1H,15N]HSQC NMR技术跟踪了化合物15N-1与Guanosine-5'-Monophosphate(5'-GMP)和Glutathione(GSH)的反应.结果显示,5'-GMP能在0.5 h内将化合物1还原,而GSH在6 h以后才能够部分的将化合物1还原.化合物1所表现出来的反应性能将有利于提高其治疗效果和降低毒副作用.     

两个具有相似（V10）阴离子骨架的化合物的合成和结构表征

本文描述了两个具有相似阴离子骨架的化合物,[Na2(H2O)10(NH4)4][V10O28](1)和[Na2(H2O)10(NH4)4][V9MoO28](2).化合物1的阴离子是一个常见的钒十骨架,而化合物2与化合物1是同晶异质体,化合物2的阴离子是混有一个钼原子的钒十骨架.X-射线晶体结构测定表明,这两个化合物均属于三斜晶系,P1空间群.晶胞参数分别为化合物1a=0.86024(4)nm,b=1.04561(5)nm,c=1.12828(4)nm,α=68.833(1)°,β=87.158(1)°,γ=67.065(1)°;化合物2a=0.86511(3)nm,b=1.04549(5)nm,c=1.12446(5)nm,α=69.071(1)°,β=87.145(1)°,γ=66.982(1)°.     

β-位取代卟啉镍衍生物的合成及其物性研究

合成了5,10,15,20-四(对癸烷氧苯基)-β-硝基卟啉镍(1)以及5,10,15,20-四(对癸烷氧苯基)-6'-硝基喹喔啉[2,3.b]卟啉镍(2),并通过核磁共振氢谱、红外光谱、质谱、元素分析等分析方法表征了它们的结构.由于β-位的取代,不但使化合物1和2的最大吸收较5,10,15,20-四(对癸烷氧苯基)卟啉镍(3)发生了红移,而且化合物1和2的第一氧化电位均大于化合物3.利用差示扫描量热法(DSC)研究了化合物1和2的液晶行为,结果表明:只有化合物1具有液晶性,其液晶行为表现为升温单变液晶,液晶相变温度始于77℃,相变区间为41℃.通过原子力显微镜(AFM)观察化合物1和2在硅基底上自组装薄膜的形貌,结果表明:化合物1的成膜性和有序性更好.利用密度泛函理论研究化合物1和2的优化几何构型与前线轨道分布,其结果与紫外可见光谱.DSC,AFM的结果一致.     

Rb2MGe3S8 (M=Zn,Cd): [MGe3S8]2–单元构型变换导致化合物从中心到非心的转变※

在本工作中, 利用高温固相法成功合成了两个碱金属硫属化合物Rb₂MGe₃S₈ [M=Zn (1), Cd (2)]. 化合物1, 2都为二维层状结构且均具备大的光学带隙, 化合物1和2的实验带隙分别为3.24和3.16 eV. 化合物1属于P-1中心对称群, 化合物2属于非心P2(1)2(1)2(1)空间群且具有一定的非线性光学(NLO)效应, 在粒径为50~75 μm时与KH₂PO₄ (KDP)相当(@1064 nm). 化合物2的激光损伤阈值为AgGaS₂的16.6倍. 化合物1, 2的分子式化学计量比相同但展示不同的对称性, 通过分析它们的晶体结构发现, 其基本构造单元[MGe₃S₈]^2–在两化合物中构型的不同导致化合物1、2对称性发生中心到非心的转变. 为了深入了解化合物2的NLO效应的起源, 基于密度泛函理论对其进行了电子能带结构和NLO极化率的理论计算.     

基于2-(4-噻唑基)苯并咪唑配体和Cu~Ⅱ构筑的2个新的多酸基化合物

基于刚性配体2-(4-噻唑基)苯并咪唑和二价金属铜离子在水热条件下成功地合成了2个Keggin型多酸化合物[Cu~Ⅱ(L1)2(H_2O)]2[SiW_(12)O_(40)](1)和[(L_1)4(L_2)2(H_3PMo_(12)O_(40))_2]·5H_2O(2)(L1=2-(4-噻唑基)苯并咪唑,L_2=苯并咪唑).通过单晶X-射线、红外光谱和元素分析对化合物1和2进行了表征.在化合物1中,存在2个独立的结构单元:Keggin型多酸和蝴蝶状的络合物阳离子[Cu(L_1)_2(H_2O)]~(2+).化合物2为含有混合配体的超分子结构,由Keggin型多酸、4个游离的L_1和2个L_2配体组成.此外,研究了化合物1和2的电化学和光催化性能.     

溶剂对呋喃二羧酸与Mn(Ⅱ)自组装的结构调控

以呋喃二羧酸 (H2FDC) 与 Mn(II) 为研究对象,通过改变溶剂体系分别得到了化合物 Mn(FDC)(H2O)3 (1) 和化合物 [NH4]2?[Mn3(FDC)4]?2DMF?2H2O (2). 呋喃二羧酸与 Mn(II)在DMF与水的混合溶剂中形成了具有一维链状结构的化合物1,而在DMF溶剂中则形成了具有三维开放结构的化合物2,这反应了溶剂对产物结构具有重要的影响. 变温磁化率测试及量子蒙特卡洛方法拟合都表明化合物1和2 都表现为反铁磁性.     

柄型金属有机化合物(Ⅴ)——锗桥连茚基及取代茚基锆化合物的合成及催化烯烃聚合

锗桥连茚及取代茚配体相继与丁基锂及ZrCl4作用, 生成锗桥连茚基及取代茚基锆化合物Me2Ge(2-R1-4-R2-Ind)2ZrCl2[R1= R2= H(1); R1= Me, R2= H(2); R1= Me, R2= Ph(3)]. 化合物 1-3均为内消旋和外消旋异构体的混合物, 通过多次重结晶得到化合物1和2的纯外消旋异构体及化合物3的内消旋异构体. 由元素分析和 1H NMR 谱表征了化合物的分子结构. 研究了在甲基铝氧烷(MAO)的助催化下, 化合物1-3对乙烯和丙烯聚合的催化性能. 由锗桥连茚基化合物1-3得到的聚乙烯的分子量分布比一般茂金属催化剂略宽. 内消旋和外消旋异构体的混合物(3)由于两个催化活性中心不等同而使得到的聚乙烯的分子量分布相当宽. 外消旋异构体1和2催化丙烯聚合得到高等规聚丙烯.     

Malfilamentoside A的构型确定与新呋喃糖苷类化合物Malfilamentoside D（英文）

基于高效液相色谱-二级阵列检测器(HPLC-DAD)追踪方法,从高原土壤来源真菌Auxarthronum brinum SCSIO 40432发酵产物中分离获得8个化合物,包括malfilamentoside A (1)、新的芳香呋喃酮糖苷类化合物malfilamentoside D(2)及6个已知化合物(3～8).通过1D、2DNMR确定了化合物的平面结构,首次通过X射线单晶衍射确定了malfilamentoside A (1)的绝对构型,比较化合物1和2的电子圆二色谱(ECD)谱确定了malfilamentoside D (2)的立体构型.化合物1对黄嘌呤氧化酶有弱的抑制活性.     

红树植物海杧果内生真菌Penicillium sp.中的抗菌活性成分

对红树植物海杧果内生真菌Penicillium sp.发酵液的乙酸乙酯提取物进行了柱层析分离, 得到3个化合物, 经MS, NMR, 1H-1H COSY, HMQC和HMBC等鉴定, 分别为4-(3-hydroxybutan-2-yl)-3,6-dimethylbenzene-1,2-diol(1), 4-(3-hydroxybutan-2-yl)-3-methyl-6-acetylbenzene-1,2-diol(2)和3,4,5-trimethyl-1,2-benzenediol(3). 其中化合物1和2为新化合物, 化合物3为新的天然产物. 抗菌活性测试结果表明, 化合物1和3均具有抗耐甲氧西林金黄色葡萄球菌的活性, 化合物2则未显示此活性.     

以芳香族多羧酸为配体的Ni(II)配位超分子的研制及光诱导下的表面电子行为

采用水热方法合成了2个Ni(II)配合物[Ni3(btc)2(H2O)14]·4H2O(1)和[Ni2(btec)(bipy)2(H2O)6]·2H2O(2), (H3btc=1,3,5-benzenetricarboxylic acid, H4btec=1,2,4,5-benzenetetracarboxylic acid, bipy=2,2'-bipyridyl). 通过X射线单晶衍射(XRD)、红外光谱(IR)、紫外-可见-近红外吸收光谱(UV-Vis-NIR)对化合物进行了表征. 结果表明, 化合物(1)是由2个均苯三甲酸根桥连的三核Ni(II)离子的化合物, 而化合物(2)是由1个均苯四甲酸根桥连的双核化合物, 分子中bipy分子作为端基配体. 分子中大量的水分子和羧酸根的存在使2个化合物分别被连成具有三维(3D)和二维(2D)结构的配位超分子化合物. 着重研究了化合物的表面光电压光谱(SPS), 并将其与UV-Vis-NIR吸收光谱进行了分析和对比, 发现SPS 中表面光伏响应带与UV-Vis-NIR 吸收光谱的吸收峰在数量和位置上都是一一对应的. 此外, 对比2个化合物的表面光电压光谱可以看出,配合物的结构及中心金属的配位微环境对其表面光伏响应带的强度、位置和形状均有一定影响.     

海洋来源真菌Penicillium pinophilum次级代谢产物中Azaphilones类化合物的分离及抗菌活性

采用硅胶、十八烷基硅烷键合硅胶填料(ODS)和Sephadex LH-20凝胶柱层析等手段从一株渤海来源真菌Penicillium pinophilum次级代谢产物中分离得到3个Azaphilones类化合物:Pinophilin G(1),Pinophilin B(2)和Sch 725680(3),其中,化合物1为新化合物.通过核磁共振波谱(1H NMR,13C NMR)、长程异核位移相关谱(HMBC)、NOSEY谱、异核位移相关谱(HSQC)和高分辨电喷雾质谱(HR-ESI-MS)确定了化合物1的平面结构和相对构型.通过比较实际电子圆二色谱(ECD)和量子化学计算方法计算的ECD光谱确定了化合物1的绝对构型.活性测试结果表明,化合物1和3均显示出不同程度的抗菌活性.     

Two pairs of phenolic enantiomers from the leaves of Eucommia ulmoides Oliver

Two pairs of new phenolic enantiomers, (+)-eucophenolic A (1a), (-)-eucophenolic B (1b), (-)-eucophenolic C (2a), (+)-eucophenolic D (2b) were isolated from the leaves of Eucommia ulmodies Oliver by chiral enantiomeric resolution. Their structures were elucidated based on extensive spectroscopic analysis. The absolute configurations of 1a/1b and 2a/2b were determined by empirical method and the calculated ECD and OR. All compounds were tested for Hep G2 tumour cell lines. However, no compounds showed potential cytotoxic activities against Hep G2 in vitro.     

A pair of epimeric cassane-type diterpenoids and a new labdane-type derivative from Caesalpinia decapetala

Caesaldecins A and B (1a/1b), a pair of epimeric cassane-type diterpenoids containing an ether linkage between C-6 and C-20 and an α,β-butenolide ring in the northern hemisphere, were isolated from the leaves of the medicinal plant Caesalpinia decapetala (Roth) Alston, along with a new labdane-type diterpenoid, termed as 8(17),11(Z),13(E)-trien-15,18-dioic acid (2). Structures of 1 and 2 were established by extensive spectroscopic analyses, including HRESIMS, 1D and 2D NMR, and electronic circular dichroism (ECD) calculations. The in vitro antibacterial and inhibitory activities against a panel of bacteria and cancer cell lines were evaluated, respectively. Compound 2 displayed moderate antibacterial activity against the methicillin-resistant Staphylococcus aureus subsp. aureus (MRSA) with an MIC₅₀ value of 5.99?μg?mL^?1.     

Two Antimicrobial Heterodimeric Tetrahydroxanthones with a 7,7′-Linkage from Mangrove Endophytic Fungus Aspergillus flavus QQYZ

Mangrove endophytic fungi represent significant and sustainable sources of novel metabolites with unique structures and excellent biological activities, attracting extensive chemical investigations. In this research, two novel heterodimeric tetrahydroxanthones, aflaxanthones A (1) and B (2), dimerized via an unprecedented 7,7′-linkage, a sp³-sp³ dimeric manner, were isolated from the mangrove endophytic fungus Aspergillus flavus QQYZ. Their structures were elucidated through high resolution electrospray ionization mass spectroscopy (HRESIMS) and nuclear magnetic resonance (NMR) spectroscopy, the absolute configurations of them were determined by a single-crystal X-ray diffraction combined with calculated electronic circular dichroism (ECD) spectra and a 1D potential energy scan. These compounds were evaluated for antifungal activities in vitro and exhibited broad-spectrum and potential antifungal activities against several pathogenic fungi with minimum inhibitory concentration (MIC) values in the range of 3.13–50 μM. They also performed moderate antibacterial activities against several bacteria with MIC values in the range of 12.5–25 μM. This research enriched the resources of lead compounds and templates for marine-derived antimicrobial drugs.     

Induced secondary metabolites from the endophytic fungus Aspergillus versicolor through bacterial co-culture and OSMAC approaches

Two new cryptic 3,4-dihydronaphthalen-(2H)-1-one (1-tetralone) derivatives, aspvanicin A (1) and its epimer aspvanicin B (2), as well as several known cryptic metabolites (3–8), were obtained from the ethyl acetate extract of the co-culture of the endophytic fungus Aspergillus versicolor KU258497 with the bacterium Bacillus subtilis 168 trpC2 on solid rice medium. When A. versicolor was cultured axenically in liquid Wickerham medium supplemented with 3.5% DMSO, an additional three known secondary metabolites (9–11) were isolated that were lacking when the fungus was fermented on rice medium. The structures of the new compounds were elucidated using one- and two-dimensional NMR spectroscopy as well as HRESIMS. The relative and absolute configurations of 1 and 2 were determined by the combination of NMR and electronic circular dichroism (ECD) analysis aided by DFT conformational analysis and TDDFT-ECD calculations. The ECD calculations revealed that although the sign of the blue-shifted overlapping n-π¹ ECD transition follows the helicity rule of cyclic aryl ketones, the calculation of low-energy conformers and ECD spectra was necessary to determine the stereochemistry. All metabolites were assessed for their antibacterial and cytotoxic activities; one of the new diastereomers, compound 2, showed moderate cytotoxic activity against the mouse lymphoma cell line L5178Y.     

Hyperisampsins N and O,two new benzoylated phloroglucinol derivatives from Hypericum sampsonii

Twenty-one benzoylated phloroglucinol derivatives bearing homoadamantyl frameworks were isolated from the aerial parts of Hypericum sampsonii, including two new ones named hyperisampsins N and O (1 and 2). The structures of 1 and 2 were elucidated by extensive NMR and mass spectrometric analyses. Their absolute configurations were further determined by using TDDFT ECD calculations. Compounds 2, 7, and 8 were evaluated for their cytotoxic activities against five human cancer cell lines, of which, 2 and 8 exhibited significant cytotoxic activities toward HL-60 cell and moderate activities against others cell lines.     

N-取代苯基-卤代邻羟基苄胺的合成、表征及抑菌活性

通过卤代水杨醛与取代芳胺缩合、NaBH4还原, 合成了15种N-取代苯基-卤代邻羟基苄胺化合物, 其中14种未见报道. 化合物的结构经IR, 1H NMR, MS与元素分析表征确证. 抑菌测试表明, 在质量浓度为0.05%时, 化合物对白色念珠菌的抑菌率高达100%, 具有强抑菌活性, 对金黄色葡萄球菌、大肠杆菌有一定的抑菌活性. 该类化合物对不同菌株的抑菌活性具有明显的选择性和特异性, 是一类极具潜力的抗真菌化合物. 构效分析表明, 胺基苯环上取代基的类型对化合物抑菌活性有重要影响, 引入F, Cl等卤原子, 能显著增强化合物的抑菌活性, 而引入NO2, OCH3等强吸、供电基团, 能显著降低其抑菌活性; 邻羟基苯环上引入卤原子的类型和数量对化合物抑菌活性有一定影响, 5-溴代化合物比5-氯代化合物、3,5-二溴代化合物对大肠杆菌的抑菌活性更高.     

Eremophilane sesquiterpenes from the endophytic fungus Xylaria sp. GDG-102

A new eremophilane sesquiterpene, xylareremophil (1), together with five known eremophilanes, 1α,10α-epoxy-3α-hydroxyeremophil-7(11)-en-12,8β-olide (2), 1,10α,13-trihydroxyeremophil-7(11)-en-12,8-olide (3), 1α,10α-epoxy-13-hydroxyeremophil-7(11)-en-12,8β-olide (4), mairetolides B (5) and G (6) were isolated from the endophytic fungus Xylaria sp. GDG-102 cultured from Sophora tonkinensis. Their structures were elucidated on the basis of spectroscopic data analysis. The absolute configurations of 1 was determined by comparing computed electronic circular dichroism (ECD) and optical rotation (OR) with experimental results. Compounds 1, 5 and 6 showed antibacterial activities against Proteus vulgaris, Micrococcus luteus, Micrococcus lysodeikticus and Bacillus subtilis with MIC values of 25–100 μg/mL.     

Synthesis and Antibacterial Activities of 1,4-Disubstituted Phenyl-5-(halo-2-hydroxyphenyl)imino-1,2,3-triazole

According to the superposition principle of reinforcement of biological activities, 24 novel 1,4- disubstituted phenyl-5-(halo-2-hydroxyphenyl)imino-1,2,3-triazoles was synthesized and characterized by 1H NMR, ¹³C NMR, elemental analysis and IR. All the target compounds were screened for their antibacterial potential in vitro against Monilia albican, Escherichia coli and Staphylococcus aureus. It was shown that all the compounds possessed efficient antibacterial activities at a concentration of 0.1 mg/mL, even at a concentration of 0.01 mg/mL, some of the compounds still exhibited antibacterial activities against Escherichia coli and Monilia albican. At last, the structure- activity relationship was discussed based on the antibacterial results.     

Synthesis of methacrylate monomers with antibacterial effects against S. mutans

A series of polymerizable quaternary ammonium compounds were synthesized with the aim of using them as immobilized antibacterial agents in methacrylate dental composites, and their structures were characterized by FT-IR, (1)H-NMR, and (13)C-NMR analysis. Their antibacterial activities against the oral bacterium Streptococcus mutans were evaluated in vitro by a Minimum Inhibitory Concentration test, and the results showed that 2-dimethyl-2-hexadecyl-1-methacryloxyethyl ammonium iodide (C16) had the highest antibacterial activity against S. mutans, and 2-dimethyl-2-pentyl-1-methacryloxyethyl ammonium iodide (C5) and 2-dimethyl-2-octyl-1-methacryloxyethyl ammonium iodide (C8) did not show any inhibition.