新型高分子材料——聚亚胺酮的合成与性能研究

通过傅-克酰基化反应合成了1,4-双-(4′-溴苯酰基)苯。以1,4-双-(4′-溴苯酰基)苯和芳香二胺为单体,通过钯催化的胺基化反应缩聚合成了新型高性能聚合物——聚亚胺酮(PIKs)。其结构由红外和核磁氢谱表征,表征结果与目标结构吻合良好。通过差示扫描量热仪(DSC)和热重分析(TG)等对PIKs的主要性能进行了测定,研究表明:该系聚合物有较高的玻璃化转变温度(Tg>230℃)、良好的热稳定性(高的热分解温度TD>500℃)及优秀的的溶解性能,其中PIK-3在室温下(20℃)可溶解在普通有机溶剂三氯甲烷(CHCl3)中。     

Evaluation of the PSMA-Binding Ligand 212Pb-NG001 in Multicellular Tumour Spheroid and Mouse Models of Prostate Cancer

Radioligand therapy targeting the prostate-specific membrane antigen (PSMA) is rapidly evolving as a promising treatment for metastatic castration-resistant prostate cancer. The PSMA-targeting ligand p-SCN-Bn-TCMC-PSMA (NG001) labelled with ²¹²Pb efficiently targets PSMA-positive cells in vitro and in vivo. The aim of this preclinical study was to evaluate the therapeutic potential of ²¹²Pb-NG001 in multicellular tumour spheroid and mouse models of prostate cancer. The cytotoxic effect of ²¹²Pb-NG001 was tested in human prostate C4-2 spheroids. Biodistribution at various time points and therapeutic effects of different activities of the radioligand were investigated in male athymic nude mice bearing C4-2 tumours, while long-term toxicity was studied in immunocompetent BALB/c mice. The radioligand induced a selective cytotoxic effect in spheroids at activity concentrations of 3–10 kBq/mL. In mice, the radioligand accumulated rapidly in tumours and was retained over 24 h, while it rapidly cleared from nontargeted tissues. Treatment with 0.25, 0.30 or 0.40 MBq of ²¹²Pb-NG001 significantly inhibited tumour growth and improved median survival with therapeutic indexes of 1.5, 2.3 and 2.7, respectively. In BALB/c mice, no signs of long-term radiation toxicity were observed at activities of 0.05 and 0.33 MBq. The obtained results warrant clinical studies to evaluate the biodistribution, therapeutic efficacy and toxicity of ²¹²Pb-NG001.     

Combinatorial Virtual Library Screening Study of Transforming Growth Factor-β2–Chondroitin Sulfate System

Transforming growth factor-beta (TGF-β), a member of the TGF-β cytokine superfamily, is known to bind to sulfated glycosaminoglycans (GAGs), but the nature of this interaction remains unclear. In a recent study, we found that preterm human milk TGF-β2 is sequestered by chondroitin sulfate (CS) in its proteoglycan form. To understand the molecular basis of the TGF-β2–CS interaction, we utilized the computational combinatorial virtual library screening (CVLS) approach in tandem with molecular dynamics (MD) simulations. All possible CS oligosaccharides were generated in a combinatorial manner to give 24 di- (CS02), 192 tetra- (CS04), and 1536 hexa- (CS06) saccharides. This library of 1752 CS oligosaccharides was first screened against TGF-β2 using the dual filter CVLS algorithm in which the GOLDScore and root-mean-square-difference (RMSD) between the best bound poses were used as surrogate markers for in silico affinity and in silico specificity. CVLS predicted that both the chain length and level of sulfation are critical for the high affinity and high specificity recognition of TGF-β2. Interestingly, CVLS led to identification of two distinct sites of GAG binding on TGF-β2. CVLS also deduced the preferred composition of the high specificity hexasaccharides, which were further assessed in all-atom explicit solvent MD simulations. The MD results confirmed that both sites of binding form stable GAG–protein complexes. More specifically, the highly selective CS chains were found to engage the TGF-β2 monomer with high affinity. Overall, this work present key principles of recognition with regard to the TGF-β2–CS system. In the process, it led to the generation of the in silico library of all possible CS oligosaccharides, which can be used for advanced studies on other protein–CS systems. Finally, the study led to the identification of unique CS sequences that are predicted to selectively recognize TGF-β2 and may out-compete common natural CS biopolymers.     

Immobilization of new Mn(salen) complex over MCM-41 and its activity in asymmetric epoxidation of styrene

New tetradentate chelates of bis-Schiff bases were synthesized and then these chiral salen ligands were immobilized over mesoporous MCM-41 by using the ion-exchange method. The efficiency of the chiral catalyst was examined in the asymmetric epoxidation of styrene. Chiral Mn(salen) complexes immobilized onto mesoporous MCM-41 were stable during the reaction without any leaching and exhibited relatively high enantioselectivity for epoxidation as compared with homogeneous complexes. This revised version was published online in August 2006 with corrections to the Cover Date.     

新穴类大环配体——双环-N,N′,N″-三-(1,4-苯基)-二-氨三乙酰胺和双环-N,N′,N″-三-(1,2-苯基)-二-氨三乙酰胺的合成与表征

首次用二步合成法合成了大环螯合剂ＬＨ６,合环反应不需要高稀释技术,用这种方法合成六酰胺螯合剂达到了预期的目标。此法也可以用来进行对称和不对称大环分子的合成。     

1:1型酸性络合染料的改性及其对羊毛的染色

以Palatine Fast系列染料为基础,通过在其染料分子中引入一种特殊的无色有机配位体得到一种改性酸性络合染料,分析其对羊毛的染色性能.采用一种带有羟基和羧基的二齿配位体与染料中的三价铬形成络合物,使染浴的pH值从2提高到羊毛的等电点附近.比较改性酸性络合染料和传统酸性络合染料染色工艺,结果表明,改性酸性络合染料对纤维的上染率和固色率都有提高,且羊毛损伤明显降低.     

PN(CH2)nP配体/Cr(III)/DMAO/AlEt3催化乙烯齐聚

合成并表征了N-(2-(二苯基膦酰)乙基)-N-甲基-1,1-二苯基膦胺(L1)、N-(2-(二苯基膦酰)乙基)-N-异丙基-1,1-二苯基膦胺(L2)和N-(3-(二苯基膦酰)丙基)-N-异丙基-1,1-二苯基膦胺(L3)3种新型PN(CH₂)_nP型配体。3种配体分别与CrCl₃(THF)₃、脱除挥发性组分的甲基铝氧烷(Dried methylaluminoxane,DMAO)和三乙基铝(Aluminumtriethyl,AlEt₃)组成催化体系,考察其催化乙烯齐聚的性能。结果表明：该类配体组成的催化体系,具有催化活性高和C₆～C₈线性α烯烃选择性高的特点;L2组成的催化体系,在4.0 MPa和100 ℃时,催化活性可达1.71×10.7 g/(mol Cr·h);在1.0 MPa和100 ℃时,1-己烯和1-辛烯总选择性达到93%。与配体L1相比,配体L2骨架N上的异丙基增加了催化剂空间体积,显著提高了催化活性及催化体系的热稳定性。     

水溶性配体三-(间磺酸钠基三苯基)膦的合成工艺研究

以硫酸为溶剂，新蒸三氧化硫为磺化剂，研究了三氧化硫浓度对由三苯基膦(TPP)合成三—(间磺酸钠基三苯基)膦(TPPTS)反应的影响；采用IR光谱技术确定磺化反应终点，利用质子保护原理改进了稀释方法，详细分析了后处理过程中TPPTS的损失。其最佳反应条件是：m(SO3)：m(TPP SO3 H2SO4)=1:2，n(SO3)：n(TPP)=12：1，m(H2SO4)：，m(TPP)=3：1，反应温度22℃，反应时间40h。按此工艺合成的TPPTS含两个结晶水，纯度高达95％，收率大于85％。     

乙烯四聚铬系催化剂配体双膦胺的研究进展

综述了乙烯四聚制1-辛烯催化体系中配体双膦胺(PNP)的研发现状,分析了PNP结构对铬系催化剂体系催化作用的影响。重点介绍了PNP由单核向双核、三核的开发进程,并讨论了其结构对催化剂稳定性、活性和选择性的影响。     

含有机硫配体的三元钨杂多化合物的制备及表征

研究了缺位取代的三元钨杂多化合物配位水被有机硫配体取代的杂多化合物的制备 .用二步合成法首次制备了 2种晶体 .[(C4H9) 4 N] 4H2 SiW11O39CuS(CH3) 2 和 [(C4H9) 4 N] 4H2 SiW11O39ZnS(CH3) 2 .通过电子光谱、拉曼和红外光谱、核磁共振谱、热分析等对其进行了表征 .