新型N-取代苯基-苯磺酰脲类化合物的合成

以4-氟苯磺酰氯或4-三氟甲基苯磺酰氯为原料,经氨化反应制得4-氟苯磺酰胺（2a）和4-三氟甲基苯磺酰胺（2n）;不同取代苯胺分别与三光气（BTC）反应制得一系列取代苯基异氰酸酯（4a~4m, 4t和4I）; 2分别与4经缩合反应合成了27个新型的N-取代苯基-4-氟（或三氟甲基）苯磺酰脲类化合物,其结构经1H NMR, IR和ESI-MS表征。     

多肽BRC4的固相法合成及其与RAD51（231-260）的相互作用

采用Fmoc固相合成策略,以Wang树脂为载体,Fmoc保护的氨基酸为原料,HOBT/HBTU/DIEA 为缩合剂,经RP-HPLC分离纯化合成了3条多肽(BRC4, BRC4-1和BRC4-2),纯度＞90%,其结构经MS（ESI）确证。采用圆二色光谱研究了BRC4, BRC4-1和BRC4-2与蛋白RAD51关键肽段RAD51（231-260）的相互作用。结果表明：3条多肽与RAD51(231-260)的相互作用强度为BRC4-1＞BRC4-2＞BRC4。     

杯芳烃钕/二正丁基镁/六甲基磷酰胺催化4-乙烯基吡啶的均聚及其与苯乙烯的共聚

聚4-乙烯基吡啶[P（4-VP）]是一种功能高分子,由于在吡啶环上有一个碱性的氮原子,它能进一步与酸反应生成各种盐,与卤代烃生成季铵盐以及与金属离子生成配合物,可用作高分子电解质,高分子试剂,高分子功能材料等,因此有不少文献对它的合成进行了报道,合成聚4-乙烯基吡啶及其与苯乙烯（St）的共聚物,除了用丁基锂作引发剂外,过渡金属的Ziegler-Natta催化剂,以及烷基铝和烷基锌等也常被用作催化剂,但用这些催化剂催化所得的聚4-乙烯基吡啶及其与苯乙烯的共聚物产率低,分子量小。     

BTC/DMF辅助的1-取代苯基-3,4-二取代吡唑类衍生物的合成

室温条件下,以各种取代苯肼和环状酮为起始原料,经脱水成腙和Vilsmeier试剂(BTC/DMF)环合两步反应合成了1-取代苯基-3,4---取代吡唑类衍生物(4a～4i),其结构经1H NMR,13C NMR,IR和MS表征,其中4b,4c,4e,4f和4h为新化合物.     

4-乙烯基吡啶-镍(钴)及丙烯酰胺-镍(钴)的制备、结构、聚合及聚合物的催化性能

制备了4-乙烯基吡啶-镍(钴)和丙烯酰胺-镍(钴)络合物并研究了它们的结构。在自由基引发剂的作用下,4-乙烯基吡啶-镍可进行溶液聚合,也可与苯乙烯共聚合,测定了单体的竞聚率。所得的聚(4-乙烯基吡啶-镍)及聚(4-乙烯基吡啶-钴)以NaBH_4还原后可作为一些有机化合物的加氢催化剂。由IR及XPS分析说明在丙烯酰胺-镍络合物中,与镍离子发生了络合作用的是羧基上的氧原子。     

Bio-based and Biodegradable Electrospun Fibers Composed of Poly(L-lactide) and Polyamide 4

Novel bio-based and biodegradable block copolymers were synthesized by "click" reaction between poly(L-lactide)(PLLA) and polyamide 4(PA4). Upon tuning the molar mass of PLLA block, the properties of copolymers and electrospun ultrafine fibers were investigated and compared with those of PLLA and PA4 blends. PLLA and PA4 were found incompatible and formed individual crystalline regions, along with reciprocal inhibition in crystallization. Electrospun fibers were highly hydrophobic, even if hydrophilic PA4 was the rich component. The crystallinity of either PLLA or PA4 decreased after electrospinning and PLLA-rich as-spun fibers were almost amorphous. Immersion tests proved that fibers of block copolymers were relatively homogeneous with micro-phase separation between PLLA and PA4. The fibrous structures of copolymers were different from those of the fibers electrospun from blends, for which sheath-core structure induced by macro-phase separation between homopolymers of PLLA and PA4 was confirmed by TEM, EDS, and XPS.     

Preparation and characterization of dendrimer-templated Ag-Cu bimetallic nanoclusters

Ag-Cu bimetallic nanoclusters with different shapes were prepared by a co-complexation method in the presence of PAMAM dendrimers. Small and evenly sized spherical Ag-Cu bimetallic nanoparticles were obtained with N2H4.H2O as the reducing agent, and long rod-shaped bimetallic nanoclusters were prepared with NaBH4 as the reducing agent. The mechanisms of formation of Ag-Cu bimetallic nanolusters with different shapes were discussed. The different shapes of the cluster were likely caused by the differences in the reduction rate of metal ions with NaBH4 and N2H4.H2O. Structure characterization by TEM, UV-vis spectra, EDX, and TGA showed that, in the presence of PAMAM dendrimers, Ag-Cu alloy bimetallic nanorods were obtained with NaBH4 reduction, and Ag-Cu bimetallic nanoparticles were prepared with N2H4.H2O as the reducing agent.     

Design of Novel Binuclear Phthalocyanines formed by Dioxyphenyl Bridges: Synthesis and Investigation of Thermal and Antioxidant Properties

4, 4′‐(1, 4‐Phenylenebis(oxy)diphthalonitrile was synthesized by reaction of hydroquinone with 4‐nitrophthalonitrile. Binuclear metallophthalocyanines 2–4 were obtained by the reaction between 4, 4′‐(1, 4‐phenylenebis(oxy)diphthalonitrile and 4‐(benzo [d] 1 , 3 dioxol‐5‐ylmethoxy)phthalonitrile in the presence of metal salts. These new compounds were characterized by using elemental analysis, FTIR, ¹H‐NMR and UV/Vis spectroscopic data. Thermal properties of phthalocyanines 2‐4 were investigated by TG and DTA. In addition, antioxidant properties of compounds II , 3 and 4 were investigated. Their radical‐scavenging capacity and chelating effects was fully studied. The maximum 1, 1‐diphenyl‐2‐picrylhydrazyl radicals (DPPH) were obtained from compound 3 . Chelating effects on ferrous ions were 91.6 % at concentration of 100 mg L^–1 with compound II .     

新型“NH-叔丁亚砜-烯”配体的合成及其在转移氢化反应中的应用

邻叔丁基亚砜苄胺与2-乙烯基苯甲醛(或2-苯乙烯-苯甲醛)经缩合反应制得亚胺,再经硼氢化钠还原合成了两个新型的NH-叔丁亚砜-烯类三齿柔性配体(4a和4b),其结构经1H NMR,13C NMR和HR-MS表征。考察了4a或4b与Ir的络合物催化苯乙酮的转移氢化反应,转化率分别为94%和51%。     

9,10-二(4-烷氧基苯乙烯基)蒽衍生物的合成及其荧光性质

以蒽环为中心核,由中间体对烷氧基苯甲醛与9,10-二(亚甲基亚磷酸二甲酯)蒽通过Arbusov-Horner反应,合成了4个9,10-二(4-烷氧基苯乙烯基)蒽衍生物(4a～4d),其结构经1H NMR和FT-IR表征.对4的荧光性质进行了初步研究,结果表明:随着柔性链碳原子数目的增加,其荧光强度逐渐增强,4a～4d的最大荧光发射波长分别为525 nm,523 nm,517 nm和515 nm.     

新型-meso-四(4-十四氨基甲酰苯基)卟啉及其-金属（Co）配合物的合成与液晶性能

对羧基苯甲醛和吡咯经缩合反应制得meso-四(4-羧基苯基)卟啉(1); 1与氯化亚砜反应得meso-四(4-氯甲酰基苯基)卟啉(2); 2与n-十四胺反应制得meso-四(4-十四氨基甲酰苯基)卟啉(3); 3与CoC_l2经配位反应合成了meso-四(4-十四氨基甲酰苯基)卟啉钴(4)。 3和4为新化合物,其结构经U-Vis, ¹H NMR和IR表征。偏光显微镜和DSC检测结果表明： 3和4具有液晶性能。     

Generation of acyloxyketenes from unstable mesoionic 1,3-dioxolium-4-olates and their reaction with ketenophiles to give [2 + 2] cycloadducts

Fast ring opening of mesoionic 1,3-dioxolium-4-olates, generated by Rh(2)(OAc)(4)-catalyzed decomposition of phenyldiazoacetic anhydride derivatives, to acyloxyphenylketenes was demonstrated by trapping the ketenes with several ketenophiles. Reactions of phenyldiazoacetic anhydride derivatives with several ketenophiles such as dihydrofuran, carbodiimides, and imines were carried out. No 1,3-dipolar cycloadducts of the latter with 1,3-dioxolium-4-olates were observed. Instead, only their [2 + 2]-cycloadducts with the acyloxyketenes generated by ring-opening of the initially formed 1,3-dioxolium-4-olates were isolated. In the reaction with cyclopentadiene, 1,3-dipolar cycloadducts with 1,3-dioxolium-4-olates were formed as main products along with the [2 + 2]-ketene adduct. PM3 calculation of heats of formation of 2,5-diphenyl-1,3-dioxolium-4-olate and the corresponding benzoyloxyphenylketene indicates that the ring-opened acyloxyketenes are ca. 9 kcal/mol more stable than the corresponding 1,3-dioxolium-4-olates.     

Synthesis of new bis-1,2,4-triazole derivatives

A series of new 1,2/1,3-bis[o-(N-methylidenamino-3-aryl-5-phenyl-4H-1,2,4-triazole-4-yl)phenoxy]ethane/propane derivatives 4 were prepared in good yields by treatment of 4-amino-3-aryl-5-phenyl-4H-1,2,4-triazoles 2 with certain bis-aldehydes 1.Compounds 4 were reduced with NaBH(4) to afford the corresponding 1,2/1,3-bis[o-(N-methylamino-3-aryl-5-phenyl-4H-1,2,4-triazole-4-yl)phenoxy]ethane/propane derivatives 5. All new compounds were characterized by IR, (1)H-NMR, (13)C-NMR and mass spectral data.     

新型5-取代吲哚-3-甲酰胺化合物的合成

以5-取代吲哚为原料,经维尔斯迈尔-哈克反应制得5-取代吲哚-3-甲醛(2a~2e); 2a~2e在DMF催化下,与盐酸羟胺反应制得5-取代吲哚-3-甲腈（3a~3e）; 3a~3e在H₂O₂和NaOH溶液中水解合成了5-取代吲哚-3-甲酰胺（4a~4e, 4b~4e为新化合物）,产率62.0%~75.0%,其结构经¹H NMR, ¹³C NMR和ESI-MS表征。     

Tri- and pentacalix[4]pyrroles: synthesis, characterization and their use in the extraction of halide salts

Calixpyrrole-based oligomeric compounds were synthesized by "click chemistry" from the corresponding alkyne- and azide-functionalized calix[4]pyrroles. Calix[4]pyrrole 3, possessing an alkyne functional group, was prepared through a mixed condensation of pyrrole with acetone and but-3-ynyl 4-oxopentanoate. Another alkyne-group-containing calix[4]pyrrole 5 was obtained by treatment of 4'-hydroxyphenyl-functionalized calixpyrrole 4 with propargyl bromide. Tetrakis(azidopentyl)-functionalized calix[4]pyrrole 7 was synthesized by reacting NaN(3) with tetrabromopentyltetraethylcalix[4]pyrrole 6, which was prepared through a condensation reaction of pyrrole and 7-bromohept-2-one. Oligomeric calixpyrrole compounds were found to be capable of extracting tetrabutylammonium chloride and fluoride salts from aqueous media. Extraction abilities of the oligomeric compounds were monitored by NMR and UV/Vis spectroscopy and thermogravimetric analysis.     

对羟基苯甲醛磷酸酯席夫碱衍生物的合成及其抗抑郁活性

以对羟基苯甲醛为起始原料,经醚化和酯化反应制得中间体4-（2-羟乙氧基）苯甲醛磷酸二甲酯（2）; 2分别与伯胺经缩合反应合成了4个对羟基苯甲醛磷酸酯席夫碱衍生物（4a~4d）,其结构经¹H NMR, ¹³C NMR, IR和ESI-MS确证。采用应急模型对4a~4d进行抗抑郁活性研究。初步结果表明： 2和4-（2-羟乙氧基）苯甲醛磷酸二甲酯甲氧基胺席夫碱（4d）表现出较好的抗抑郁活性,2的活性优于丙咪嗪,4d的活性与丙咪嗪接近。     

Synthesis and Fungicidal Activities of 4H-Imidazolin-4-ones Containing Sulfur Substituent

4H-Imidazolin-4-ones 3 and 4 were synthesized respectively by base catalytic reactions of 4-methylthiophenol or phenthiol with carbodiimides 2 , which were obtained via aza-Wittig reaction of iminophosphorane 1 with aromatic isocyanates. 3 and 4 exhibited good fungicidal activity against Pellicularia sasakii.     

脂蛋白脂酶激活剂艾溴利平类似物的合成

合成了两个新型的艾溴利平类似物——N-2 -硝基-4-氯苯基-4-[(膦酸二乙酯基)甲基]苯甲酰肼(5,总收率28.1％)和N-2-四氮唑基-4-氯苯基-4-[(膦酸二乙酯基)甲基]苯甲酰胺(7,总收率30.5％).以对氯甲基苯甲酸为原料,经酯化、水解和酰氯反应制得中间体4-[(膦酸二乙酯基)甲基]苯甲酰氯(4);4与2-硝基-4-氯苯肼盐酸盐反应合成了5.4先与2-氨基-5-氯苯腈反应制得N-2-氰基-4-氯苯基-4-[(膦酸二乙酯基)甲基]苯甲酰胺(6);6再与叠氮化钠反应合成了7.其结构经1 H NMR和IR表征.     

新型1-(4-取代苯基)-3-[4-(4-氧香豆素基)苯基]硫脲衍生物的合成及其抑菌活性

以4-羟基香豆素为原料,经氯化、醚化和异硫氰酸化3步反应制得中间体——4-(4-异硫氰酸酯苯氧基)香豆素(3);3与取代芳香胺经加成反应合成了9个新型的1-(4-取代苯基)-3-[4-(4-氧香豆素基)苯基]硫脲衍生物(4a~4i),其结构经1H NMR,13C NMR,IR和MS(ESI)表征。采用浑浊度法测试了4的抑菌活性。结果表明:4a、4b、4e和4f抑制烟草青枯菌活性EC50值分别为112.02、121.39、88.72和86.90μg·mL~(-1),优于噻菌铜(130.25μg·mL~(-1));4a、4b、4e和4f抑制番茄青枯菌活性EC50值分别为107.89、110.69、82.43和82.48μg·mL~(-1),优于噻菌铜(123.94μg·mL~(-1))。     

Synthesis and Antimicrobial Activity of 4‐(10H‐Phenothiazin‐2‐yl)‐pyrimidin‐2(1H)‐one/thione Derivatives

A series of chalcones 3a , 3b , 3c , 3d containing phenothiazine nucleus were prepared by Claisen–Schmidt condensation. The chalcones on treatment with urea, thiourea, phenyl urea, and phenyl thiourea in alcoholic KOH yielded compounds 4a , 4b , 4c , 4d , 4e , 4f , 4g , 4h , 4i , 4j , 4k , 4l , 4m , 4n , 4o , 4p , and the structures of these compounds were confirmed by spectral and elemental analyses. The newly synthesized compounds were evaluated for antimicrobial activity.