聚合物异核交叉弛豫及二维NOE谱

The heteronuclear cross-relaxation rates in polymers were determined by selective and conventional ~(13)C spin-lattice relaxation experiments, the proton-carbon distances were calculated by the theoretical formula, and two-dimensional NOE spectra of the polymers were also measured. The results showed that (1) the measured proton-carbon distances coincide with the distances from molecular models, (2) there is the observable dipolar cross-relaxation effect between the quaternary carbons and their neighboring protons, and (3) the optimum mixing times depend on the relaxation properties of the proton and carbon.     

N—乙基—N—苄基苯胺合成方法的改进

以苯胺和乙醇为原料，采用ＲａｎｅｙＮｉ为催化剂，合成了Ｎ－乙基苯胺，再在相转移催化剂作用下，经苄基化反应得到标题化合物，第一步合成方法的收率比通常方法的收率提高约３０％。     

致孔剂对HP（MA—VAc—MMA）载体孔结构的影响

以二乙烯苯和双丙烯酸多缩乙二醇酯为交联剂、聚醋酸乙烯酯（ＰＶＡｃ）或它与醋酸丁酯（ＢＡＣ）的混合物为致孔剂、ＢＰＯ为引发剂，用悬浮聚合随后水解的方法制得了部分水解聚（丙烯酸甲酯－醋酸乙烯酯－甲基丙烯酸甲酯）［ＨＰ（ＭＡ－ＶＡｃ－ＭＭＡ）］多孔载体，研究了ＰＶＡｃ及（ＰＶＡｃ＋ＢＡＣ）用量、分子量及混合比对ＨＰ（ＭＡ－ＶＡｃ－ＭＭＡ）孔结构的影响。结果表明，当ＰＶＡｃ的Ｍ＞２．５×１０５，ＰＶＡｃ／ＢＡＣ为２．３，用量为１０～２０％时，可制得孔隙率较高，孔径分布较窄，孔表面积较大的多孔载体。这种载体适用于微生物固定化。     

Immobilization of Polymer-Stabilized Noble Metal Colloids and Their Catalytic Properties for Hydrogenation of Olefins

Polymer-stabilized noble metal colloids were efficiently immobilized on silica by the addition of organic acids under mild conditions. The function of organic acids in the immobilization was studied by infrared spectroscopy. Transmission electron micrographs indicate that the immobilized colloids have a controlled particle size and size distribution. They serve as catalysts in the hydrogenation of cyclohexene and cyclopentadiene, the results of which show that this new type of immobilized colloid has high selectivity and good stability.     

N-[(2,2–propinyldiferrocenyl)methinyl]benzoyl hydrazone and its bivalent transition metal complexes

Transition Metal Chemistry -     

Immobilization of glucose oxidase with the blend of regenerated silk fibroin and poly(vinyl alcohol) and its application to a 1,1′- dimethylferrocene-mediating glucose sensor

The structure and properties of the blend of regenerated silk fibroin (RSF) and poly(vinyl alcohol) (PVA) were investigated. The two polymers in the blend are in the state of phase segregation. Infrared (IR) spectra indicate that the RSF in the blend maintains its intrinsic properties, thus, ethanol treatment can transfer silk I structure of RSF to silk II structure. The water absorption property and mechanical property of the blend are improved in comparison with those of RSF. The blend maintains the major merit of RSF, that is, it can immobilize glucose oxidase on the basis of the conformational transition from silk I structure to silk II structure. The properties of the immobilized enzyme are examined. Moreover, the second generation of glucose sensor based on the immobilized enzyme is fabricated and it has a variety of advantages including easy maintenance of enzyme, simplicity of construction, fast response time and high stability.     

聚多巴胺修饰棉花固定金属离子用于磷酸化多肽的富集

本文通过多巴胺自聚合在天然的棉花纤维表面,构建了仿生聚多巴胺(PDA)膜层,然后利用儿茶酚羟基固定Ti~(4+),设计并合成了一种固定金属亲合色谱(Immobilized Metal Ion Affinity Chromatography,IMAC)材料Cotton@PDA-Ti~(4+),并将其用于磷酸化多肽的富集。该材料机械性能好,化学性能稳定和生物相容性好,且制备过程简单,通过简易的In-pipet-tip固相萃取(SPE)装置使整个富集操作过程简便快速。实验结果表明,Cotton@PDA-Ti~(4+)不仅可以从简单的蛋白酶解物(β-casein)中富集磷酸化多肽,并且在含有大量非磷酸化多肽的复杂体系样品中对磷酸化多肽也表现出良好的选择性。另外,利用Cotton@PDA-Ti~(4+)对磷酸化多肽进行富集也有较高的效率。我们将该材料应用于实际样品,如人体血清以及脱脂牛奶酶解物中磷酸化多肽的富集,均表现出了较好的选择性。说明该方法有可能用于磷酸化蛋白质组的全分析。     

磁共振血管成像在颈动脉狭窄检查中的对比研究

目的研究在颈动脉狭窄检查中采取磁共振血管成像的诊断价值。方法回顾性分析惠州市中心人民医院自2015年12月至2016年12月期间收治的39例颈动脉狭窄患者所有资料,将减影血管造影检查结果作为金标准实行磁共振血管成像检查,分析狭窄检测敏感性、准确性以及特异性。结果磁共振血管成像检查狭窄检测敏感性、准确性以及特异性发生率分别为97.43%、92.31%、94.87%。结论将磁共振血管成像应用在检查颈动脉狭窄中具有显著效果,可以提升准确符合率,值得广泛应用与研究。     

基于光谱分析的姜黄素碱性自氧化及其产物的抗氧化活性

在室温及弱碱性条件下进行姜黄素自氧化反应,应用柱色谱分离、紫外吸收光谱(UV)、红外光谱(IR)、核磁共振波谱(NMR)和质谱(MS)等分析技术,分离并鉴定了主要自氧化产物的化学结构.针对反应进程,采用高效液相色谱-二极管阵列检测器(HPLC-DAD)分析技术,从底物消除和产物生成2个方面进行了定性及定量研究.以抗坏血酸作阳性对照,采用1,1-二苯基-2-三硝基苯肼自由基(DPPH·)、羟自由基(·OH)和超氧阴离子自由基(O_2~(-·))体系,定量比较了产物和姜黄素的体外抗氧化活性.结果表明,姜黄素在室温及弱碱性条件下的降解消除以自氧化反应为主,姜黄素消除过程和自氧化产物生成过程均符合一级动力学特征.自氧化产物具有双环乙酰丙酮的骨架结构,并显示有DPPH·,·OH和O_2~(-·)等自由基清除活性,但作用强度均显著低于姜黄素,因此在姜黄素应用过程中应严格控制pH条件,避免发生自氧化反应.     

嘧啶衍生物与人血清白蛋白的相互作用

在模拟生理条件下,运用荧光光谱、激光闪光光解(LFP)和分子对接等技术研究了8种具有抗肿瘤活性的嘧啶衍生物(PDs,其中PDs A 5-FU为成药,PDs B-H为实验室自制)与人血清白蛋白(HSA)的相互作用.利用Stern-Volmer方程和激光闪光光解技术分析了PDs对HSA的荧光猝灭机制,PDs A和B为静态猝灭,PDs G和H为动态猝灭.用双倒数曲线法得出5种PDs与HSA的结合常数Ka和结合位点数n,在测定条件下5种PDs与载体结合位点数均为1,且均以弱结合力结合,通过热力学参数ΔH,ΔS和ΔG推测出PDs B,C和E与HSA之间的作用力为静电作用力和疏水作用力,PDs A和D与HSA之间的作用力是氢键和范德华力,分子对接结果与其一致.根据F9rster非辐射能量转移理论(FRET)分析了HSA和PDs之间的结合距离(r),其结果均小于4 nm,符合能量转移理论.进一步利用同步荧光、三维荧光和圆二色光谱考察了PDs与HSA结合过程中HSA空间构象的变化,结果显示,仅PDs A和C对HSA的芳香族氨基酸周围的疏水性略有增强作用.体外实验结果表明,HSA可以作为优良的载体来运输和储存PDs A~E,这为嘧啶衍生物的后续研究提供了可参考的实验数据.