β-环糊精星形聚合物负载苯丁酸氮芥性能

通过原子转移自由基聚合,以溴化改性β-环糊精为引发剂,合成了星形聚合物β-环糊精-聚甲基丙烯酸N,N-二甲氨基乙酯(β-CD-PDMAEMA).采用红外光谱和核磁共振氢谱确定了星形聚合物的结构.分别在乙醇和水介质中,以β-CD-PDMAEMA为载体负载抗癌药物苯丁酸氮芥(CLB).通过紫外吸收光谱分析比较了2种介质中β-CD-PDMAEMA对CLB的载药效率及在37℃、不同p H值下的体外释药性能,分析了释药机理.结果表明,与乙醇相比,以水为介质时CLB能更多地通过主客体作用进入星形聚合物内核β-CD的疏水空腔,从而有更高的载药率,药物突释期短、突释量少,具有持续、高效的释放性能. CLB的释放属于扩散控制机理,PDMAEMA臂的质子化程度影响释药速率和累积释药量,表现出明显的p H响应性,酸性环境更有利于CLB的释放.     

基于2-脲基-4[1氢]-嘧啶酮AADD四氢键体系的光谱行为研究

基于互补型四氢键体系缔合常数大、稳定性高的特点,本论文设计合成了一系列2-脲基-4[1氢]-嘧啶酮的衍生物分子,N-[(正丁基氨基)甲酰基]- 5-(9-蒽甲基)-6-甲基异胞嘧啶(An-MeUP)、N-[(正丁基氨基)甲酰基]-5-(β-萘甲基)-6-甲基异胞嘧啶(NaMeUP)、N-[(正丁基氨基)甲酰基]-6-(4-二甲氨基)苯基异胞嘧啶(DMAUP),发现这类分子在二氯甲烷或氯仿溶液中通过AADD四氢键作用形式存在.稳态和时间分辨技术揭示出2-脲基-4 [1氢]-嘧啶酮的衍生物分子具有丰富的光谱性质,能对光、质子、氟离子等外界的刺激产生高灵敏度的响应,为进一步开发其在超分子化学中的应用打下基础.     

血吸虫病化学治疗的研究 Ⅲ.双(对氨基苯氧基)硫间烷类化合物

对二(β-羟乙基)氨基苯酚与相应的α,ω-二氯代硫间烷缩合,形成1,5-双[对二(β-羟乙基)氦基苯氧基]-3-硫间戊烷(Ha)及1,8-双[对二(β-羟乙基)氨基苯氧基]-3,6-二硫间辛烷(IIIa)。对苯亚甲氦基苯酚同样缩合并再水解后变为1,5-双(对氨基苯氧基)-3-硫间戊烷(IIb)及1,8-双(对氨基苯氧基)-3,6-二硫间辛烷(IIIb)。3-对硝基苯氧基丙硫醇分别与二碘甲烷及溴化乙烯缩合,并将产物还原后形成1,9-双(对氨基苯氧基)-4,6-二硫间壬烷(III-d)及1,10-双(对氨基苯氧基)-4,7-二硫间癸烷(IIIe),后者并又制成其N-甲烷磺酸钠衍生物(IIIf)。     

3,4-二氫化雜二氮[1,3]萘-酮-[4]Ⅰ.3-(ω)-二烷氨基-烷基)-3,4-二氫化雜二氮[1,3]萘-酮-[4]的合成

隣氨基苯甲酸与N-(β-二乙氨基-乙基)-甲酰胺或N-(δ-二乙氨基-α-甲基-正丁基)甲酰胺缩合,分别形成3-(β-二乙氨基-乙基)3,4-二氢化杂二氮[1,3]萘-酮-[4]与3-(δ-二乙氨基-α-甲基-正丁基)3,4-二氢化杂二氮[1,3]萘-酮-[4]。 5-氯代-隣位氨基苯甲酸舆N-(β-二乙氨基-乙基)-甲酰胺或N-(δ-二乙氨基-α-甲基-正丁基)-甲酰胺缩合,分别形成6-氯代-3-β-二乙氨基-乙基-3,4-二氢化杂二氮[1,3]-萘酮-[4]及6-氯代-3-(δ-二乙氨基-α-甲基-正丁基)-3,4-二氢化杂二氮[1,3]萘酮-[4]。     

超分子体系中的分子识别研究37.几种磷酰基修饰β-环糊精对染料分子的识别

通过乙氧基-N,N-乙基磷酰氯与β-环糊精直接反应合成了单-[6-O-(二乙氨基-乙氧基)-磷酰基-β-环糊精(3)采用荧光光谱和紫外光谱滴定法测定了化合物(3)与结构相关的两种磷酰基修饰β-环糊精单-[6-O-(二苯氧基)-磷酰基]-β-环糊精(1),单-[6-O-(乙氧基羟基)-磷酰基]-β-环糊精(2),与一系列染料分子在磷酸缓冲溶液(pH7.20,0.1 mol·     

肿瘤的化学治疗Ⅱ. 与普鲁卡因,辛可卡因等局部麻醉剂有关的氮芥类化合物的合成

1.本文报告对-双-(2-氯乙基)-氨基苯甲酸(β-二乙氨基)-乙酯(Ⅳ,普鲁卡因氮芥),对-双-(2-氯乙基)苯甲酸(β-二甲氨基)-乙酯(Ⅴ),对-双-(2-氯乙基)-氨基苯硫羟甲酸(β-二乙氨基)-乙酯盐酸盐(Ⅶ,硫卡因氮芥),N-(β-二乙氨基)-乙基-对-双-(2-氯乙基)-氨基苯甲酰胺(Ⅷ)及一些有关化合物的合成。2.自2-氯-6-硝基-辛可宁酰氯(X)或辛可卡因(ⅫⅠ)开始分别经五步或四步反应合成 N-(β-乙氨基)-乙基-2-丁氧基-6-双-(2-氯乙基)-氨基-辛可宁酰胺(ⅩⅥ,辛可卡因氮芥)。3.化合物Ⅳ,ⅩⅥ和 N-(β-二乙氨基)-乙基-2-丁氧基-6-硝基-辛可宁酰胺(Ⅻ)均具局部麻醉作用,其中以Ⅻ为最强,但其相应的双-羟乙基化合物Ⅲ和ⅩⅤ都无麻醉作用。化合物Ⅳ,Ⅴ,Ⅶ,Ⅷ和ⅩⅥ在体外对肉瘤180和艾氏腹水瘤细胞均有抑制作用。     

肿瘤的化学治疗 Ⅵ.几种[双-(β-氯乙基)-氨基]-吲??-2-羧酸的合成

1.本文叙述了从2,4-二硝基苯甲醛开始经过七步反应合成6-[双-(β-氯乙基)-氨基]-吲哚-2-羧酸(Ⅵb). 2.从相应的硝基吲哚-2-羧酸(Ⅶa和Ⅶb)经还原,羟乙基化,氯化,水解制成5-[双-(β-氯乙基)-氨基]-吲哚-2-羧酸(Ⅵa)和7-[双-(β-氯乙基)-氨基]-吲哚-2-羧酸(Ⅵc). 3.制备了双-(β-氯乙基)-吲哚-2-甲酰胺(ⅩⅥ),吲哚-2-甲酰-乙烯亚胺(ⅩⅦ)和3-碘代吲哚-2-羧酸(ⅩⅧ)业已制备.     

肿瘤的化学治疗 Ⅴ.几种隣位取代-对-[双-(2-氯乙基)氨基]苯丙氨酸的合成

1.本文叙述自邻位取代-对硝基甲苯(Ⅴ)开始经过六步反应合成了邻位取代-对-[双-(2-氯乙基)-氨基]苯丙氨酸(Ⅳ);取代基是:甲氧基,氟,氯,溴和碘. 2.合成了二肽衍生物:α-甲酰氨基-β-{邻甲氧基-对-[双-(2-氯乙基)-氨基]-苯}丙酰-苯丙氨酸乙酯(Ⅻ)和α-甲酰氨基-β-{邻甲氧基-对-[双-(2-氯乙基)氨基]苯}丙酰-缬氨酸乙酸(Ⅷ). 3.邻甲氧基-对-[双-(2-氯乙基)-氨基]苯丙氨酸(Ⅳa)对肉瘤180、梭形细胞肉瘤、艾氏腹水瘤、Yoshida腹水瘤、Guerin癌和Walker瘤都有显著的抑制作用.     

盐酸克伦特罗与鲱鱼精DNA相互作用的研究北大核心CSCD

建立了紫外吸收光谱研究盐酸克伦特罗(CLB)与鲱鱼精DNA(hsDNA)相互作用的分析方法,初步探讨CLB与hsDNA相互作用的机理。在pH=7.00的磷酸盐缓冲溶液(PBS)中CLB与hsDNA存在相互作用。在温度为20℃时,CLB与hsDNA的结合常数K为1.23×104 L/mol,CLB与hsDNA相互作用的焓变△H=-13.67kJ/mol;熵变△S=31.67J/(mol·K),自由能△G=-22.99kJ/mol,确定了CLB与DNA的结合焓驱动占主导地位,结合方式可能为静电沟槽式结合。     

基于酶-抗体共固定二氧化锆纳米信号探针的瘦肉精安培免疫传感器研究

制备了基于酶-抗体共固定二氧化锆(ZrO2)纳米探针进行信号放大的盐酸特伦克罗瘦肉精(CLB)检测安培免疫传感器。首先,利用ZrO2纳米粒子负载葡萄糖氧化酶(Glucose oxidase,GOD)和CLB抗体(Clen-buterol antibody,anti-CLB),制得纳米探针(ZNPs/GOD-anti-CLB signal probe,简称ZNPG)。同时将聚二烯丙基二甲基氯化铵[Poly(diallyldimethylammonium chloride),PDDA]、氯化血红素(Hemin)和纳米金(AuNPs)层层组装到多壁碳纳米管(MWCNTs)修饰的丝网印刷电极(SPCE)表面,制得SPCE│MWCNTs/(PDDA/Hemin/AuNPs)n电流型传感器,可对H2O2产生还原催化电流。检测CLB时,将样品和ZNPG一起加入预先包埋好CLB的96孔板底部。样品CLB与板底CLB共同竞争结合孔溶液中的纳米探针ZNPG。反应结束后加入葡萄糖,板底ZNPG-CLB免疫复合物上的GOD催化葡萄糖氧化产生H2O2,可通过传感器检测。电流下降值(ΔI)与样品CLB成反比,可用于CLB的定量分析。由于ZNPG上具有高的GOD酶标记密度,故可以显著放大检测信号,提高检测灵敏度。在最佳条件下(pH 7.0,温育时间30 min,温育温度37℃),此传感器对CLB的检测范围为0.003～100μg/L,检测下限为1 ng/L,比酶联免疫分析法(ELISA)法灵敏度提高2个数量级,在猪饲料样品中进行加标回收实验,平均回收率达93.6%,相对标准偏差(RSD)小于2.5%,精密度好。同时该传感器具有可重复使用、灵敏快速,适合于食物样品中痕量CLB现场检测。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.