鹅去氧胆酸分子印迹聚合物微球的制备及选择性分子识别

以鹅去氧胆酸(CDCA)为印迹分子, 甲基丙烯酸为功能单体, 丙烯酸乙二醇二甲基酯和三羟甲基丙烷三甲基丙烯酸酯为交联剂, 在氯仿中采用沉淀聚合法制得平均粒径为200~300 nm的分子印迹聚合物微球(MIPMS). 用红外光谱研究了印迹分子与功能单体之间的作用类型, 用透射电镜对聚合物的形貌进行了表征. 结果表明, 聚合物微球在合成过程中形成了两类结合位点, 该分子印迹聚合物对CDCA具有良好的特异吸附性能, 可用于胆汁酸的分离、纯化, 交联剂的种类可以影响分子印迹聚合物的形貌和吸附性能.     

乳液聚合法制备亚微米级分子印迹聚合物微球

以西咪替丁为印迹分子，2-丙烯酰胺-2-甲基丙磺酸(AMPS)为功能单体，三羟甲基丙烷三甲基丙烯酸甲酯(TRIM)为交联剂，采用乳液聚合法制备了亚微米级分子印迹聚合物微球．利用扫描电镜对此聚合物微球的形貌进行了观察，探讨了影响乳液稳定性、粒径大小与分布的主要因素，重点对聚合工艺和配方进行了优化，并将所得的聚合物用作吸附剂研究了其分子识别与选择性能．研究表明，乳液聚合法能够制得单分散性较好的、平均粒径在0．169μm～0．407μm的分子印迹聚合物微球，且该微球对其印迹分子呈现出较好的特异识别与选择性能，当以苯丙氨酸为竞争分子时，分离因子可达1．70．     

环丙沙星分子印迹聚合物的制备及其吸附特性的研究

以环丙沙星(CIP)为模板分子,α-甲基丙烯酸(MAA)为功能单体,三甲基丙烯酸三羟甲基丙烷酯(TRIM)为交联剂,进行热聚合.通过对于功能单体和交联剂的用量对分子印迹聚合物吸附性能的影响的研究,得到最佳的聚合配比为n(CIP):n(MMA):n(TRJM)=1:6:16,并以此配比制得了对环丙沙星具有特异选择性吸附的分子印迹聚合物.通过静态平衡结合法研究了模板聚合物的结合动力学以及该聚合物的结合能力和选择特性,通过Scatchard分析法研究了印迹聚合物对模板分子的结合特性.结果表明,该印迹聚合物具有良好的吸附能力和吸附选择性,静态吸附分配系数KD为41.64,分离因子α为1.62;该印迹聚合物中形成了2类不同的结合位点,经计算它们的离解常数分别为Kd1=5.249×10-5mol·L-1,Kd2=2.237×10-3mol·L-1.     

新型雌二醇分子印迹聚合物的合成与表征

以17β-雌二醇为模板分子,2-(甲基丙烯酰氧)乙基磷酸酯为功能单体,三羟甲基丙烷三甲基丙烯酸酯为交联剂,偶氮二异丁腈为引发剂,乙腈-甲苯(3+1)混合液为致孔剂,采用热聚合的方式合成雌二醇分子印迹聚合物。采用紫外光谱法、核磁共振和分子模板研究了分子印迹聚合物的结合机理和识别特性,该聚合物通过氢键作用形成1比2型配合物专一结合17β-雌二醇。红外光谱、电子扫描显微镜、材料孔隙度、热重分析和Scatchard曲线表明:分子印迹聚合物存在一定的孔隙结构,具有与模板分子相互作用的官能团和空间作用位点。     

种子溶胀悬浮聚合法制备分子印迹聚合物微球

 以酪氨酸为印迹分子 ,甲基丙烯酸为功能单体 ,三羟甲基丙烷三甲基丙烯酸酯 (TRIM )为交联剂 ,采用种子溶胀悬浮聚合法在水溶液中制备了一系列分子印迹聚合物微球 (MIPMs)。利用扫描电镜 (SEM)对此微球的粒径大小、粒径分布、表面孔与孔径分布等进行了分析研究 ,探讨了影响其形貌的主要因素 ,并将所得微球用作固定相研究了其分子选择吸附性能。研究表明 ,种子溶胀悬浮聚合法能够制得单分散性较好的、表面带有微孔的分子印迹聚合物微球 ,且该微球呈现出较好的特异吸附性能。     

基于金属卟啉的分子印迹聚合物的合成及其对三唑类杀菌剂识别性能研究

以三唑类杀菌剂氟环唑为印迹分子,5-(4-甲基丙烯酰氧苯基)-10,15,20-三苯基卟啉锌为功能单体,乙二醇二甲基丙烯酸酯为交联剂,合成了新型的基于金属卟啉的分子印迹聚合物.紫外-可见光谱研究表明印迹分子与功能单体在聚合前形成1∶1配合物.通过选择性吸附和固相萃取表征研究了该印迹聚合物对氟环唑及具有类似化学结构的三唑类杀菌剂的识别能力,并与非印迹聚合物进行了比较,结果表明印迹聚合物具有良好的特异性识别性能,同时,印迹聚合物的交联度及吸附溶剂的极性对印迹效果有着显著影响.     

(2-甲基丙烯酰胺)乙氧基-2-甲基丙烯酸乙二醇单酯基质分子印迹手性分离介质的合成与表征

通过甲基丙烯酰氯和二甘醇胺反应设计合成了一种交联剂(2-甲基丙烯酰胺)乙氧基-2-甲基丙烯酸乙二醇单酯,以自行合成的(2-甲基丙烯酰胺)乙氧基-2-甲基丙烯酸乙二醇单酯为交联剂,丙烯酰胺为功能单体,合成了一种用于手性分离的N-叔丁氧羰酰-L-色氨酸(N-Boc-L-Trp,N-[(tert-butoxy)carbonyl]-tryptophan)的分子印迹聚合物。评价了该分子印迹聚合物作为高效液相色谱柱填料对N-叔丁氧羰酰-色氨酸(N-Boc-Trp)的手性拆分能力。结果表明:当检测波长为280 nm,流动相为V(甲醇)∶V(水)=80∶20,流速0.8 mL/min时,该填料实现了对N-Boc-Trp外消旋混合物的手性拆分,显示出良好的选择识别性能。     

软骨藻酸分子印迹聚合物的制备及其固相萃取应用

以贝毒-软骨藻酸的结构类似物1,3,5-戊烷三羧酸为模板分子,4-乙烯基吡啶为功能单体,乙二醇二甲基双丙烯酸酯为交联剂,合成了对软骨藻酸具有较好选择性的分子印迹聚合物。经索氏提取去除模板分子后,在聚合物内部形成了与模板分子1,3,5-戊烷三羧酸以及结构类似物软骨藻酸尺寸、形状以及活性基团互补的结合位点。通过静态平衡结合实验研究了该聚合物的结合能力和选择性能,与化学组成相同的相应非印迹聚合物相比,1,3,5-戊烷三羧酸的分子印迹聚合物对软骨藻酸具有较高的吸附性能和选择性。用150mg印迹聚合物填充于1.0mL玻璃注射器制成的分子印迹固相萃取柱,采用离线模式,并结合高效液相色谱实现紫贻贝和海水中软骨藻酸的分离与检测。对于加标2mg/L的紫贻贝和海水样品,回收率分别达到(93.4±4.9)%和(89.7±3.2)%(n=3)。     

本体聚合法制备2-氯酚分子印迹聚合物及其性能评价

采用本体聚合法,以2-氯酚为模板分子,4-乙烯吡啶为功能单体,三羟甲基丙烷三甲基丙烯酸酯为交联剂合成了一系列分子印迹聚合物,并通过选择性实验和静态吸附实验对聚合物的选择性及吸附性能进行评价.结果显示:当以甲苯作为致孔剂,功能单体与模板分子的摩尔比为2:1时,聚合物对模板分子的印迹因子为1.71,亲和位点总数Bmax为0.1137 mmol/g,具有最优的选择性和吸附能力.     

基于离子液体辅助氯霉素分子印迹聚合物的制备及应用

以氯霉素(CAP)为模板,2-乙烯基吡啶(2-Vp)为功能单体,四氢呋喃和离子液体1-丁基-3-甲基咪唑四氟硼酸盐[BMIm]BF4的混合溶液为反应溶剂,乙二醇二甲基丙烯酸酯(EGDMA)为交联剂,偶氮二异丁腈(AIBN)为引发剂,合成了氯霉素的分子印迹及非印迹聚合物。优化功能单体、不同溶剂对印迹聚合物吸附性能的影响,结果表明,以2-乙烯基吡啶为功能单体,四氢呋喃和离子液体[BMIm]BF4(体积比1∶1)作为反应溶剂合成的分子印迹聚合物对氯霉素具有高的吸附容量,良好的特异性识别性能。氯霉素分子印迹聚合物的印迹因子为2.6,进行吸附-解吸附循环5次后,氯霉素印迹聚合物的性能稳定,可重复使用。将制备的氯霉素分子印迹聚合物作为富集材料,应用于鸡蛋样品中氯霉素的检测,回收率可达62.3%~81.1%,准确性好。     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.