一类新型杂环聚芳酰胺的合成与性能研究

采用二氮杂萘类双酚 4 (4 羟基苯基 ) 2 ,3 二氮杂萘 1 酮 (DHPZ)与对氯苯腈反应制得二腈化合物 ,进一步水解为二酸 .以此新型二酸与不同二胺聚合制得的聚芳酰胺均具有较高的耐热性能 ,其Tg 在 2 91～318℃ ,且易溶于极性非质子溶剂中 .聚合物的特性粘数为 1 17～ 1 5 0dL g(2 5℃ ,0 5 %inNMP) ,对所得聚酰胺进行性能研究 ,其拉伸强度为 71～ 86MPa ,断裂伸长率为 8%～ 13% ,拉伸模量为 0 86～ 1 0 2GPa ,电阻系数数量级为 10 1 4～ 10     

The first fluorescent diboronic acid sensor specific for hepatocellular carcinoma cells expressing sialyl Lewis X

Carbohydrate antigens with subterminal fucosylation have been implicated in the development and progression of several cancers, including hepatocellular carcinoma (HCC). Fluorescent sensors targeting fucosylated carbohydrate antigens could potentially be used for diagnostic and other applications. We have designed and synthesized a series of 26 diboronic acid compounds as potential fluorescent sensors for such carbohydrates. Among these compounds, 7q was able to fluorescently label cells expressing high levels of sLex (HEPG2) within a concentration range of 0.5 to 10 microM. This compound (7q) did not label cells expressing Lewis Y (HEP3B), nor cells without fucosylated antigens (COS7). This represents the first example of a fluorescent compound labeling cells based on cell surface carbohydrate structures.     

单体结构对聚酰胺类复合膜分离性能的影响

采用间苯二甲酰氯、均苯三甲酰氯、均苯四甲酰氯分别与间苯二胺、乙二胺、哌嗪在耐高温杂萘联苯聚醚砜酮(PPESK)超滤膜表面进行界面聚合,制备了7种具有不同功能层结构的新型超薄复合膜.采用红外、X射线衍射、原子力显微镜等测试手段对复合膜结构进行表征,测试了7种复合膜对0·2%的Na2SO4水溶液,0·2%NaCl水溶液的分离性能,分析了单体结构与复合膜分离性能的关系.     

一种杂环磺化聚芳醚腈酮质子交换膜材料的合成及表征

用含二氮杂萘酮结构类双酚DHPZ,3,3′-二磺酸钠基-4,4′-二氟二苯酮,2,6-二氯苯腈以及4,4′-二氟二苯酮,通过缩合共聚合反应合成了一系列不同磺化度、高分子量的磺化聚芳醚腈酮.聚合物特性粘数为0·58~2·0dL/g.用红外光谱(FT-IR),核磁共振谱(1H-NMR)表征了聚合物结构.用差示扫描量热仪(DSC)和热重分析仪(TGA)研究了聚合物的耐热性能,研究表明其玻璃化温度(Tg)可达352℃,5%热失重温度大于500℃.以N-甲基吡咯烷酮为溶剂,溶液浇铸法制备了聚合物膜,并测定了膜的溶胀率以及质子交换能力.结果表明,与Nafion膜相比,磺化聚芳醚腈酮膜在相同的质子交换能力条件下,溶胀率显著降低.     

Synthesis and Structure-Activity Relationships of Anticholinergics of Dibenzo[b,e] oxepin(thiepin) Hydroxycarboxylates

In order to investigate the relationships between the conformations of tricyclic hydroxycarboxylates and their anticholinergic activities, and to explore the effects of changing the linking groups between the two benzene rings in tricyclic compounds on anticholinergic activities and on the selectivity to the central nicotinic receptor, a series of new tricyclic anticholinergic compounds-dibenzo[b,e]oxepin (thiepin) hydroxycarboxylates (Fig. 1) were designed and synthesized.     

Stereochemistry of the Heterocyclic Alcohols Containing Piperidine Unit

The stereochemistry of the heterocyclic alcohols (R₁-OH~R₄-OH,see Fig.1) containing piperidine unit has been studied on the basis of the calculations of molecular mechanics and quantum chemistry. The calculations of alcohols (R₁-OH~R₄-OH) and their carboxylate derivatives were carried out, and the results of these calculations were listed in Tab.1 and Tab.2. It was showed that there existed the non-classical orbital super-conjugated interactions between the nitrogen atom and oxygen atom which caused the conformations to be more stable when the hydroxylic group lay at axial than at equatorial with respect to the piperidine ring in compounds (R₁-OH) and (R₃-OH). If the axial hydrogen atoms at C₂ and C₆ positions in the piperidine ring were substituted, or the molecular existed in the polar solutions, this non-classical orbital super-conjugated interactions would be much weak even diminished. In this case,the conformations were more stable when the hydroxylic group at equatorial than at axial in these compounds. These consistented with the experimental results.     

新型可溶性聚芳酰胺及其共聚物的合成与性能研究

采用新型二胺 1,2 二氢 2 (4 氨基苯基 ) 4 [4 (4 氨基苯氧基 ) 苯基 ] 二氮杂萘 1 酮与对苯二甲酸、间苯二甲酸、萘二酸进行均聚或共聚 ,所得聚芳酰胺的Tg 均高于 30 0℃ ,且易溶于非质子极性溶剂中 ,聚合物的特性粘数为 1 2 6～ 1 5 1dL g(2 5℃ ,NMP) ,拉伸强度为 6 2～ 89MPa ,断裂伸长率为 5 %～ 9% ,拉伸模量为 2 2～ 2 9GPa ,电阻系数为 10 1 4 ～ 10 1 6     

聚酰胺表面结构及其对复合膜分离性能的影响

以杂萘联苯聚芳醚超滤膜为支撑层,通过间苯二胺(MPD)、哌嗪(PIP)与均苯三甲酰氯(TMC)的界面聚合制备复合膜.用红外光谱和X射线衍射分别分析了超薄功能层的化学结构与聚集态,用原子力显微镜观察了膜表面形貌,并用统计学方法计算了膜表面的平均粗糙度等特性参数,研究了MPD/PIP比例对膜表层化学结构、形貌和分离性能的影响.结果表明,随着二胺单体MPD/PIP比例从0/100提高到100/0,功能层聚酰胺的聚集态具有从无定形向部分结晶转变的趋势,复合膜表面平均粗糙度由17.8nm提高到71.9nm,膜对NaCl的截留率由26%提高到99%,而通量则由130L.m-2.h-1降低到12L.m-2.h-1.复合膜具有良好的稳定性,温度由25℃提高到80℃,通量提高了2倍左右,而对NaCl的截留率基本不变.     

Effects of sulfone/ketone in poly(phthalazinone ether sulfone ketone) on the gas permeation of their derived carbon membranes

A series of copolymer, poly(phthalazinone ether sulfone ketone)s (PPESKs) with the sulfone over ketone unit (S/K) ratio varying from 20/80, 50/50 to 80/20, were used as precursors to prepare carbon membranes. The effects of chemical structure as S/K ratio of PPESKs on the microstructure and gas separation performance of their derived carbon membranes were mainly investigated. The properties of PPESKs were detected in terms of density, fractional free volume, char yield, interlayer distance and glass transition temperature. During the formation process of carbon membranes (i.e., stabilization and pyrolysis), the changes in functional groups, microstructural parameters and gas permeation were monitored by FTIR, X-ray diffraction, TEM and single gas permeation techniques. The results have shown that the microstructure and gas permeation of obtained carbon membranes are significantly affected by the S/K ratio in precursor PPESKs. Carbon membranes exhibit higher selectivity and lower permeability when prepared at low pyrolytic temperature (i.e., 650 °C and 800 °C) and from PPESKs with S/K ratio equaling 50/50, followed with 20/80 and 80/20. As for carbon membranes prepared at high pyrolytic temperature (i.e., 950 °C), the selectivity order of them is well in accordance with S/K mole ratio in precursor PPESKs: 20/80 > 50/50 > 80/20, and vice versa for permeability.     

Enhanced properties of phthalonitrile resins under lower curing temperature via complex curing agent

High curing temperature has been restricting the application and development of phthalonitrile resin. A complex curing agent containing melamine (ME) and ZnCl₂ was developed to promote the curing reaction of resorcinol‐based phthalonitrile resin (DPPH). The thermal stability of ME can be significantly enhanced via adding ZnCl₂, which was due to the interaction between ZnCl₂ and amino group in ME. Moreover, the activities of pristine ZnCl₂ and ME were improved via mixing, especially, the curing temperature for DPPH can be effectively reduced. Even at a curing temperature of 300°C, the 5% weight loss temperature of the resulting resin cured with complex curing agent still exceeded 500°C, which was much higher than those with pristine curing agents. In addition, the good long‐term oxidation stability and relatively low water absorption can also be obtained in the resins cured with novel curing agent. This work affords a facile route for designing high‐performance curing agent to improve the curing process of phthalonitrile resin.