Synthesis and Biological Properties of Enkephalin-like Peptides Containing Carboranylalanine in Place of Phenylalanine

The syntheses of [D -Ala², Car⁴, Leu⁵]-enkephalin, its amide, and of [D -Ala², Car⁴, Met⁵]-enkephalin amide are described in detail. The three compounds show pronounced morphine-like potencies in certain bio-assays, and were used to investigate the influence of electronic, steric and hydrophobic properties of the side-chains of amino acids no. 4 and 5 on opioid activity (see [13]).     

Synthesis and Biological Properties of Enkephalin-like Peptides Containing Adamantylalanine in Position 4 and 5

The syntheses of seven [D -ala-²]-enkephalin analogues, H-Tyr-ala-Gly-X-Y, with X-Y = Phe-Ada-OH, Phe-ada-OH, Phe-Ada-NH₂, Phe-ada-NH₂, Ada-Leu-OH, Ada-Leu-NH₂, and Ada-Ada-NH₂ are described. The compounds with Y = Ada (= L -Ada) or ada (= D -Ada) show pronounced morphine-like activities in certain bioassays, whereas those with X = Ada were most inactive. The analogues were used to explore the influence of steric, electronic, and hydrophobic properties of the side chains of X and Y on opioid activity (see [14]).     

Synthesis and Opiate Activity in vitro of Five New p-Nitrophenylalanine4-Enkephalin-like Peptides

Converging data obtained in biochemical and pharmacological bioassays for opiate activity are presented for five new enkephalin-like peptides. The main structural features of the analogues, the synthesis of which is described in detail, were the presence of D -alanine or D -serine in position 2, p-nitrophenylalanine in position 4 and of a free C-terminal carboxylic function. Confirming our previous observations [1], the substitution of phenylalanine by p-nitrophenylalanine enhanced the overall opiate activity but decreased the selectivity towards m?/δ-receptor sites. Tyrosyl-D -alanyl-glycyl-p-nitrophenylalanyl-adamantylalanine was particularly potent in all assays while tyrosyl-D -seryl-glycyl-p-nitrophenylalanyl-leucyl-threonine was very selective in the bioassays on isolated tissues and moderately selective in the binding assay. These results will have to be taken into account in future photoaffinity labelling and quantitative structure-activity relationships (QSAR) studies.     

新型偶氮苯金属配合物的合成与性能

合成了新型偶氮苯金属配合物。分别采用光谱分析、热分析及X射线衍射测试技术对产物进行了表征和测试。结果表明,连接偶氮苯和金属配合物之间碳链的长度对该化合物的相转变和荧光特性具有特殊的影响。该系列化合物在紫外光和热作用下具有99%以上的偶氮苯顺-反异构化反应效率;具有290和560 nm这2个波段的荧光发射光谱。由其中1个金属配合物分散在聚甲基丙烯酸甲酯网络而形成的介质可作为全息信息存储材料而实现全息图像的写入和读出。     

Synthesis,Characterization, Optical and Electrochemical Properties of Fulleropyrrolidines Containing Trifluoromethyl Group

Four novel [60]fullerene pyrrolidines containing trifluoromethyl (? CF₃) group have been synthesized via 1,3‐dipolar cycloaddition reaction, which have been characterized by UV‐Vis spectroscopy, fourier transform infrared spectroscopy, matrix‐assisted laser desorption ionization‐time of flight mass spectroscopy, and ¹H, ¹³C, ¹⁹F nuclear magnetic resonance spectrometer (¹H NMR, ¹³C NMR, ¹⁹F NMR). Their optical and electrochemical properties have been studied, and the results show that those fulleropyrrolidines containing ? CF₃ group have good fluorescence and electrochemical properties. Compared with C₆₀, they have negative shifts in varying degrees for half‐wave potentials, and may have potential applications for photovoltaic conversion materials since their lowest unoccupied molecular orbital (LUMO) levels are close to that of [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester.     

含辣素衍生结构疏水缔合聚合物PAAH的合成、表征及溶液性质

以辣素功能结构单体N-（4-羟基-3-甲氧基-苄基）-丙烯酰胺（HMBA）为疏水单体,与丙烯酰胺（AM）和2-丙烯酰胺基-2-甲基丙磺酸钠（NaAMPS）通过自由基胶束共聚,制得三元疏水缔合聚合物P（AM-NaAMPS-HMBA）（简称PAAH）. 采用紫外-可见光谱、核磁共振氢谱、热重分析及扫描电子显微镜对共聚物的结构及形貌进行表征,利用原子力显微镜对聚合物水溶液的微观形貌进行观察,并对其溶解性、疏水缔合性、耐温性及抑菌性能进行了研究. 结果表明,所得共聚物中疏水单体含量与投料比基本一致;PAAH具有良好的速溶性,当聚合物浓度超过一定值后,溶液黏度急剧增加,且随着疏水单体含量增加,疏水缔合性能增强;原子力显微镜观察证实了聚合物水溶液中网络结构的存在. 与未改性的P（AM-NaAMPS）（简称PAA）共聚物相比,引入具有生物活性且带有刚性苯环结构的HMBA单体可使PAAH共聚物热稳定性增强,耐温性能提高,并赋予其优良的抑菌性能.     

含多甲氧基芳香基双查尔酮的合成、表征及光热性能

通过克莱森-施密特（Claisen-Schmidt）反应合成了一种新型双查尔酮衍生物1,4-二［3-（3,4,5-三甲氧基苯基）-2-丙烯酰基］苯（BTAB）。该化合物的结构通过核磁共振波谱仪（NMR）和质谱等技术手段得到确认。采用热综合分析方法测定了DSC／TG曲线,发现该化合物的熔点为230.6℃,热稳定性良好。测定了该化合物的紫外光谱和荧光光谱,λ_max／UV＝357.5 nm,λ_max／EM＝541 nm,表现出较大的紫外吸收波长和荧光发射波长。采用密度泛函理论方法计算获得了BTAB分子的最高占据轨道与最低空轨道能量和极化率,从前线分子轨道组成图发现存在分子内电荷转移现象。用单光束Z-扫描技术获得了BTAB的非线性光学特性,其三阶非线性吸收系数β＝3.15×10^－14m／W,五阶非线性吸收系数γ＝2.7×10^－28m³／W²,属于双光子吸收诱导激发态吸收。BTAB作为一种有用的非线性光学（NLO）候选材料具有潜在应用前景。     

Synthesis,Characterization and Electrochemical Properties of Stable Osmabenzenes Containing PPh3 Substituents

Progress in osmabenzene chemistry : The new stable osmabenzene phosphonium salts can be easily obtained from the reaction of [OsX₂(PPh₃)₃] with HC?CCH(OH)C?CH, which constitutes a valuable addition to previous metallabenzene synthetic methodologies (see scheme). The redox behavior of several osmabenzenes with different co‐ligands has been investigated.

     

新型侧基含磷共聚酯的合成、表征及性能

以精制对苯二甲酸（TPA）、乙二醇（EG）和含磷反应型阻燃剂9,10-二氢-9-氧杂-10-[2,3-二（2-羟基乙氧基）羰基丙基]-10-磷杂菲-10-氧化物为原料,利用熔融缩聚法合成了含磷量分别为0．35％、0．65％的阻燃聚酯。通过熔融纺丝法将聚酯制成纤维及织物,研究了纤维的染色性能,并通过极限氧指数法和垂直燃烧法研究了织物的阻燃性能。FT-IR和NMR研究结果表明：阻燃共聚酯含磷量为0．35％时,其氧指数（LOI）达31．5％,并无熔滴、烟雾产生,具有优异的阻燃性能和抗熔滴性能。DSC、TG和XPS的研究结果表明：侧基舍磷单元的引入降低了聚酯的Tg和Tm,较低的Tm将有利于材料加工性能的改善;阻燃聚酯侧基上的P-C、P-O键易断裂并挥发至气相中,从而降低了聚酯热稳定性,阻燃聚酯可能以气相阻燃机理为主发挥阻燃作用。此外,含磷共聚酯纤维具有较优异的染色性能。     

以N为中心的阴离子离子液体的合成、表征及应用

首次通过不同阴离子的钾盐和不同的季铵化的咪唑,吡咯溴盐/氯盐进行离子交换,合成了一系列含氰基官能团的阴离子功能化离子液体。通过红外、核磁共振、质谱对离子液体的结构进行表征;通过TGA对离子液体的热稳定性进行测定,结果发现功能化离子液体具有良好的热稳定性,其分解温度在224-289℃范围内。将功能化离子液体[EMIm][N(CN)COC2H5]作为配体应用于无膦配体的Suzuki偶联反应,发现在反应中加入功能化离子液体[EMIm][N(CN)COC2H5]可以使反应收率提高10-20%。     

环腺苷二磷酸核糖类似物的合成、表征及性质

通过次黄嘌呤N1-位取代及分子内环合等反应, 合成了由带芳基支链的含氮链替代天然北区核糖结构的环腺苷二磷酸核糖(cADPR)类似物cIDPRN. 该化合物与Jurkat T淋巴细胞在37 ℃下孵育18 h后, 经毛细管电泳分析, 结果表明该化合物具有良好的稳定性. 荧光分光光度计测定, 结果表明, 在有钙离子和无钙离子环境下, 该化合物胞外给药后均能引起浓度依赖性的钙离子释放. 由以上结果确定该化合物为具有膜透性的促细胞内钙释放激动剂.     

Synthesis and Conformational Analysis of Pentapeptides Containing Enantiomerically Pure 2,2‐Disubstituted Glycines

The synthesis and conformational analysis of model pentapeptides with the sequence Z‐Leu‐Aib‐Xaa‐Gln‐Valol is described. These peptides contain two 2,2‐disubstituted glycines (α,α‐disubstituted α‐amino acids), i.e., Aib (aminoisobutyric acid), and a series of unsymmetrically substituted, enantiomerically pure amino acids Xaa. These disubstituted amino acids were incorporated into the model peptides via the ‘azirine/oxazolone method’. Conformational analysis was performed in solution by means of NMR techniques and, in the solid state, by X‐ray crystallography. Both methods show that the backbones of these model peptides adopt helical conformations, as expected for 2,2‐disubstitued glycine‐containing peptides.     

Synthesis,Characterization and Biological Investigations of Half-Sandwich Ruthenium(II) Complexes Containing Benzimidazole Moiety

Half-sandwich Ru(II) complexes belong to group of biologically active metallo-compounds with promising antimicrobial and anticancer activity. Herein, we report the synthesis and characterization of arene ruthenium complexes containing benzimidazole moiety, namely, [(η⁶-p-cymene)RuCl(bimCOO)] (1) and [(η⁶-p-cymene)RuCl₂(bim)] (2) (where bimCOO = benzimidazole-2-carboxylate and bim = 1-H-benzimidazole). The compounds were characterized by ¹H NMR, ¹³C NMR, IR, UV–vis and CV. Molecular structures of the complexes were determined by SC-XRD analysis, and the results indicated the presence of a pseudo-tetrahedral (piano stool) geometry. Interactions in the crystals of the Ru complexes using the Hirshfeld surface analysis were also examined. In addition, the biological studies of the complexes, such as antimicrobial assays (against planktonic and adherent microbes), cytotoxicity and lipophilicity, were performed. Antibacterial activity of the complexes was evaluated against S. aureus, E. coli, P. aeruginosa PAO1 and LES B58. Cytotoxic activity was tested against primary human fibroblasts and adenocarcinoma human alveolar basal epithelial cells. Obtained biological results show that the ruthenium compounds have bacteriostatic activity toward Pseudomonas aeruginosa PAO1 strain and are not toxic to normal cells. A molecular docking study was applied as a predictive source of information about the plausibility of examined structures binding with HSA as a transporting system.     

两种含有十二元环的层状稀土硫酸盐的合成、结构表征及性质研究

通过溶剂热合成技术,我们得到了两种新的二维层状稀土硫酸盐:[Tb₂(SO₄)₅][(CH₃)₂NH₂]₄(1)和[Y₂(SO₄)₅][(CH₃)₂NH₂]₄(2),并通过X-射线衍射、元素分析及红外、热重对化合物进行了表征。两种化合物都属于三斜晶系,P1空间群。其中化合物1:a=0.9887(3)nm,b=1.1061(3)nm,c=1.5354(4)nm,α=70.45(0)°,β=75.12(0)°,γ=67.11(0)°,Z=2;化合物2:a=0.9816(5)nm,b=1.1001(5)nm,c=1.5286(8)nm,α=70.44(1)°,β=75.45(1)°,γ=67.48(1)°,Z=2。通过对晶体结构进行表征我们发现两种化合物都含有二维层状无机骨架结构,该层由2种不同类型的双链和十二元环构成。我们还对化合物1的荧光性质进行了研究,其在369nm的激发波长下表现出了Tb³⁺ 的特征发射。     

含氰基基团的以C为中心的不对称阴离子离子液体的合成、表征及应用

首次通过不对称阴离子的钠盐/钾盐和不同的季胺化的咪唑,吡咯溴盐/氯盐进行离子交换,合成了一系列含氰基官能团的不对称阴离子功能化离子液体。通过红外、核磁共振、质谱和元素分析对离子液体的结构进行表征;通过TGA对离子液体的热稳定性进行测定,结果发现不对称功能化离子液体具有良好的热稳定性,其分解温度在219-319℃范围内。将功能化离子液体[Bmim][C(CN)2COCH3]作为弱配体应用于模型的Suzuki偶联反应,发现在反应中加入功能化离子液体[Bmim][C(CN)2COCH3]可以使反应收率提高10-15%。     

一种含二茂铁基的多枝状分子的合成、表征及其性质研究

采用新的方法合成了一种二茂铁衍生物——均三（二茂铁乙烯基）苯，通过元素分析、红外光谱、核磁共振氢谱、质谱、紫外可见光谱等对其进行了表征。用循环伏安法对其电化学性质进行了初步研究，用Z-扫描技术测试了它的非线性光学性能。结果表明，该化合物具有良好的电化学及非线性光学性质。     

过氧铌杂多配合物位置异构体的合成、表征及催化性能

合成了6种钨硅杂多配合物异构体α、β_i-M₃H₂[SiW₁₁(NbO₂)O₃₉]·H₂O(M=Me₄N⁺(TMA),Bu₄N⁺(TBA),Et₄N⁺(TEA);β_i=β₁,β₂,β₃)。IR光谱、UV光谱、极谱、I^--S₂O₃^2-滴定证明合成的杂多配合物中有NbO₂基存在, ¹⁸³W NMR光谱证明其阴离子具有Keggin结构,催化实验结果表明,合成的化合物对烯烃环氧化反应具有催化活性,且过氧杂多配合物的催化活性高于非过氧杂多配合物,β异构体的催化活性高于α。     

哌啶并噻吩并嘧啶酮衍生物的合成、表征及生物活性

应用中间体碳二亚胺分别与伯胺、仲胺及醇在醇钠催化条件下合成9个未见报道的新型哌啶并噻吩并嘧啶酮衍生物.产物的结构经元素分析、1H NMR、MS及单晶X衍射检测得以确认.探讨了所有化合物的杀菌活性,结果表明部分化合物表现出较好的抑菌活性,其中化合物7b对黄瓜灰霉、水稻纹枯、小麦赤霉的抑制率分别为76.19%,68.83%和56.52%.     

Insights on the Synthesis of N-Heterocycles Containing Macrocycles and Their Complexion and Biological Properties

Macrocyclic chemistry has been extensively developed over the past several decades. In fact, the architecture of new macrocyclic models has undergone exponential growth to offer molecules with specific properties. In this context, an attempt is made in this study to provide an overview of some synthetic methods allowing the elaboration of N-heterocycles containing macrocycles (imidazole, triazole, tetrazole, and pyrazole), as well as their applications in the complexation of metal cations or as pharmacological agents.