生物活性复合材料在生物矿化过程中的微观形貌与离子浓度变化

采用3-羟基丁酸酯-3-羟基戊酸酯的共聚物(PHBV)与磷酸三钙(TCP)、羟基磷灰石(HA)、生物活性玻璃(BG)等进行复合,获得了性能优良的生物活性骨组织工程支架材料和骨修复材料.研究和比较了3种复合材料在体外模拟生理环境中发生的生物矿化反应,对比了反应前后因矿化物的形成导致的表面微观形貌的变化,通过检测反应液离子浓度的变化对不同材料的矿化过程和生物活性进行了定量表征.研究结果表明,3种复合材料在模拟生理溶液中发生生物矿化的过程和程度不同,其中PHBV/BG的生物活性反应最为明显.     

丙烯酸在牙釉质表面的紫外光共辐射接枝

龋坏的过程是牙釉质脱矿和再矿化长期交替进行的过程,当脱矿大于再矿化时,就导致了釉质脱矿从而引起龋病的发生[1]。本文设想在牙釉质表面接枝一些羧基活性官能团,为进一步在牙釉质表面引入牙釉蛋白分子提供活性基团和接位空穴,并为深入探讨牙釉蛋白诱导牙釉质的再矿化提供基础     

原位聚合法制备纳米二氧化硅/聚氨酯复合树脂

采用高压剪切分散（HPSH）的方法先将纳米SiO2分散在合成聚氨酯原料中,再应用原位聚合的方法制备了纳米SiO2/聚氨酯复合树脂。 用热重分析、动态机械热分析（DMTA）和扫描电子显微镜等测试技术研究了纳米SiO2的用量及其分散方法对聚氨酯树脂的热稳定和力学性能的影响。 结果表明,二苯甲基二异氰酸酯（MDI）中的-NCO和纳米SiO2表面的-OH发生了化学反应,SiO2表面的包覆率约为7%;通过高压剪切分散的方法能够使纳米SiO2在聚氨酯基体中均匀的分散开来,粒径为30~40 nm,而超声处理的纳米SiO2会聚集约为200 nm聚集体。 当SiO2的添加质量分数为3%时复合树脂（HPSH处理SiO2）的拉伸强度和断裂伸长率均达到最大值,分别为84.3 MPa和438.7%。 此外,与纯树脂相比,复合树脂(4%纳米SiO2)的Tg、Td和T-50%分别增加了17.2、9和21 ℃。     

衰减全反射-红外成像研究聚乳酸/生物活性玻璃复合材料的体外矿化过程

采用衰减全反射-红外成像技术(ATR-FTIR mapping)对多孔聚乳酸/生物活性玻璃(PLLA/BG)复合材料在PBS缓冲液中的矿化过程进行了研究。光谱分辨率为8 cm!1,累加扫描8次,基于A1044/A1755的吸光度比值生成红外图像。成像结果表明,随着矿化进行,材料表面产生的羟基磷灰石(HA)也逐渐增多,当矿化进行到84 d后,材料表面大部分已被HA覆盖。但随着矿化时间的继续延长,矿化不均匀性也逐渐加剧。矿化曲线显示矿化过程存在4个阶段:矿化初期(前21 d),产生的HA很少;矿化增长期(21~70 d),BG逐渐转变为HA;快速增长期(70~91 d),矿化加速,并在91 d时达到最大;矿化后期(91 d后),曲线先显示平稳然后又从105 d起出现下降。研究表明,红外成像技术有望成为骨组织工程支架材料的重要研究工具。     

表面官能团作用下的牙釉质原位再矿化研究

采用酸蚀后的牙釉质作为早期龋缺损模型,在缺损牙釉质表面修饰-SO3-功能基团,分别在人工唾液和含氟人工唾液中进行原位再矿化的研究。利用X-射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、能谱仪(EDS)、选区电子衍射(SAED)研究原位再矿化晶体的组成和结构。结果表明,在人工唾液和含氟人工唾液中,表面修饰的官能团均可有效促进牙釉质再矿化。在含氟人工唾液中生成了沿c轴取向生长的具有较大长径比的棒状氟羟基磷灰石(FHA),这种FHA晶体具有类牙釉质的成分和结构,对修复早期龋有重要的意义。     

CaO-P2O5-SiO2系统溶胶-凝胶生物活性多孔材料在SBF中的性能研究

利用溶胶-凝胶生物活性材料粉末二次烧结工艺,制备了CaO-P2O5-SiO2系统溶胶-凝胶生物活性多孔材料,并利用体外实验（in vitro）方法和XRD,SEM及FTIR技术研究了此烧结材料的显微形貌、晶相、生物活性和可降解性能.结果表明,经800℃烧结5 min后,有少量硅磷酸钙[Ca5（PO4）2SiO4,5CPS]析出,在模拟体液（SBF）中浸泡,随着时间的增长,材料表面最初形成的无定形钙磷化合物矿化成碳酸羟基磷灰石（HCA）纳米团簇,并逐渐相互融合形成HCA覆盖层;HCA只在烧结体的玻璃相（SG相）表面生成,在5CPS微晶相表面未发现HCA,该材料在37℃恒温的SBF溶液中具有较高的生物活性和可降解性能.     

CaO-P2O5-SiO2系统溶胶-凝胶生物活性多孔材料在SBF中的性能研究

利用溶胶-凝胶生物活性材料粉末二次烧结工艺,制备了CaO-P2O5-SiO2系统溶胶-凝胶生物活性多孔材料,并利用体外实验(in vitro)方法和XRD,SEM及FTIR技术研究了此烧结材料的显微形貌、晶相、生物活性和可降解性能.结果表明,经800℃烧结5 min后,有少量硅磷酸钙[Ca5(PO4)2SiO4,5CPS]析出,在模拟体液(SBF)中浸泡,随着时间的增长,材料表面最初形成的无定形钙磷化合物矿化成碳酸羟基磷灰石(HCA)纳米团簇,并逐渐相互融合形成HCA覆盖层;HCA只在烧结体的玻璃相(SG相)表面生成,在5CPS微晶相表面未发现HCA,该材料在37℃恒温的SBF溶液中具有较高的生物活性和可降解性能.     

新型内表面反相限进填料的制备与评价

通过在硅烷化硅胶内表面和外表面分别键合己胺和聚乙烯醇,制备了能够在线直接进样分析生物样品的新型内表面反相限进填料。采用元素分析、电镜观察对该限进填料的结构进行了表征。以普萘洛尔、阿替洛尔、苯巴比妥、卡马西平作溶质探针,并以Merck公司生产的限进填料柱作参比,对合成的限进填料的色谱性能进行了研究。研究结果表明,所制备的限进填料有较好的蛋白质排阻能力、富集能力和反相色谱性能,能同时实现排阻生物大分子杂质和富集小分子被分析物的功能,可作为在线、快速直接进样检测分析生物样品的预处理柱,适用于普萘洛尔血浆的直接进样分析。     

医用CVIC/C复合材料表面仿生沉积生物活性钙磷涂层

为了在医用化学气相渗透工艺(CVI)C/C复合材料表面制备生物活性钙磷涂层,用阴极声电化学工艺处理CVIC/C复合材料,再将试样浸泡于过饱和钙磷溶液中,使其诱导钙磷晶体生长.XPS研究表明,经声电工艺处理后,CVIC/C复合材料表面发生了改性;SEM,XRD和FTIR研究表明,在过饱和钙磷溶液中,未经声电化学处理的CVIC/C复合材料不具有诱导钙磷晶体生长的功能,而改性的CVIC/C表面能够诱导钙磷晶体生长,形成片状五水磷酸八钙(OCP)涂层.同时讨论了OCP沉积的形成机理.     

新型混合固定相的制备与性能评价

通过共聚交联方法将长链碳烯-苯乙烯包覆到锆胶表面上, 得到聚合物包覆固定相, 再对该填料进行磺化引入离子官能团到聚合物表面, 得到混合型固定相. 用扫描电镜和红外光谱对这些填料进行了表征, 考察了混合型固定相的毛细管电色谱性能, 并用该填料分离了苯甲酸和苯胺等化合物.     

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%.     

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.     

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.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

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.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

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.