Synthesis of spiro-cyclopropane derivatives containing multiple chiral centers

Tandem asymmetric double Michael addition/internal nucleophilic substitution of the novel chiral source, 5-(l-menthyloxy)-3-bromo-2(5H)-furanone with nucleophilic alcohol compounds has been investigated. The tandem asymmetric reaction can afford four new stereogenic centers with one reaction and give optically pure spiro-cyclopropane derivatives 5a--5d which are difficult to obtain by routine methods. The synthetic method for 5a--5d was studied in detail and the new compounds were identified on the basis of their analytical data and spectroscopic data, such as [α]~(20),IR,~1H NMR,~(13)C NMR, MS and elementary analysis. The absolute configuration of the sprio [5-l-menthyloxy-3-bromo butyrolactocyclopropane-3″, 3′(4′-methyloxy-5′-menthyloxybutyrolactone)] (5a) was established by X-ray crystallography. The work can provide important synthetic strategy in synthesis of some new optically active spiro-cyclopropane analogues and some biologically active molecules with complex structure.     

多孔双相磷酸钙骨组织工程生物支架的制备及性能研究

以碳酸钙(CaCO3)和磷酸(H3PO4)为原料,用湿法合成了双相磷酸钙陶瓷粉体,再采用激光成型技术处理聚氨酯泡沫载体,通过有机泡沫浸渍法合成多孔双相磷酸钙生物支架.采用X射线衍射仪(XRD),红外光谱分析(FT-IR)和扫描电镜(SEM)对样品的组成和形貌进行了表征.结果表明:制得的粉体为双相磷酸钙粉体,包含β-TCP和HAP两相,其中β-TCP为主相,其质量比占86.7;;制得的多孔支架为双相磷酸钙生物支架,孔隙率为90;以上,抗压强度为0.12 MPa,多孔支架具有规则直通孔与不规则三维通孔相结合的孔洞结构,直通孔孔径范围为1.0～1.3 mm,三维通孔孔径范围为200 ～ 700 μm,满足骨组织工程支架对多孔材料的孔径要求;双相磷酸钙粉体和双相磷酸钙生物支架均表现为无细胞毒性.     

手性二环[3.3.0]辛-3-烯类化合物的合成

研究了5-(1-孟氧基)-3-溴-2(5H)-呋喃酮新手性源(1)与某些碳亲核试剂发生的串联不对称Michael加成/分子内亲核取代反应,反应中生成2个新的手性中心得到一般方法难以合成的光学纳二环[3.3.0]辛-3-烯类化合物.通过[α]、IR、UV、¹HNMR、¹³CNMR、MS、元素分析以及X射线四圆衍射等方法确定了手性二环[3.3.0]辛-3-稀类化合物化学结构和绝对构型.     

氧化石墨烯/羟基磷灰石复合材料对酸蚀牛牙釉质体外再矿化的影响

考察不含氧化石墨烯(GO)的羟基磷灰石(HAP)和含GO质量分数为0.1;的氧化石墨烯/羟基磷灰石复合材料(GO/HAP)对酸蚀牛牙釉质体外再矿化的影响.通过场发射扫描电镜、EDX能谱、X射线衍射仪和维氏显微硬度测试仪,对再矿化前/后牛牙釉质表面和剖面形貌、表面元素、晶体结构和力学性能进行表征.结果 表明:GO/HAP复合材料在酸蚀牙釉质表面生成了结合力较弱的花状晶体,将这些晶体超声剥离后发现脱矿釉质表面和釉柱间隙均得到良好的修复.剖面形貌分析显示,GO/HAP复合材料使釉质深层脱矿得到良好修复,促进了牙釉质棱晶间大量微小晶粒的生成,以及脱矿釉柱间隙中有序排列晶体的生成.同时,经GO/HAP处理后,酸蚀牙釉质表面的Ca/P摩尔比和晶体成分均得到良好的恢复.     

聚乙二醇/氮化硼复合材料相变导热性能及其结晶行为

本文采用熔融共混浇筑的方法制备了聚乙二醇/氮化硼(PEG/BN)相变复合材料,并研究了不同尺度片状BN对相变复合材料导热性能和结晶行为的影响。 通过扫描电子显微镜(SEM)、热常数分析仪、红外热成像分析仪和差示扫描量热仪(DSC)研究了相变复合材料的微观形貌、导热系数和相变过程,并利用莫志深法对DSC结果进行了非等温结晶动力学分析。 结果表明,较大片状直径(50 μm)的BN可以更有效地提高聚乙二醇的导热系数,当BN填料质量分数为40%时,相变复合材料的导热系数可达到5.04 W/(m·K)。 在快速降温条件下,片径为50 μm的BN填料可以缩短PEG的半结晶时间,提高结晶速率,使相变复合材料具有较大的相变焓。     

α,β-不饱和内酯的光化学反应研究进展

α,β-不饱和内酯的光化学反应可广泛应用于核苷、稠环生物碱、萜类、甾类等多种光学活性物质与天然产物的合成中.根据不同的反应类型,综述了2(5H)-呋喃酮等α,β-不饱和内酯的光化学1,4-加成反应、1,4-加成-并环反应、[2+2]环加成反应和复杂环加成反应的新进展.     

基于云推理模型的武器装备研制风险评估研究

武器装备研制过程充满了不确定性和风险,因此对武器装备研制风险进行研究对于实现武器装备研制目标具有重要的意义.界定了武器装备研制风险相关概念,介绍了云推理理论,构建了武器装备研制风险的云推理评估模型,实现了定性变量与定量变量相互映射,最后,通过实例对模型进行了验证.     

Synthesis and Crystal Structure of Spiro[1-bromo-4- methoxy-5-oxa-6-oxo-bicyclo[3.1.0]hexane-2,2''-(3''- cyclohexanoxy-4''-methoxybutyrolactone]

The crystal of the title compound 6 has been prepared and determined by X-ray diffraction analysis. It belongs to the orthorhombic system, space group P212121 with a = 10.195(2), b = 11.955(2), c = 14.335(3)(A), C16H21BrO7, Mr = 405.24, V = 1747.0(6) (A)3, Z = 4, Dc = 1.541 g/cm3, μ = 2.387 mm-1, F(000) = 832, R = 0.0266 and wR = 0.0348 for 2110 observed reflections with I > 2σ(I). The crystal exhibits a characteristic spiral structure consisting of one cyclopropane and two butyrolactones with envelope configuration. The intermolecular hydrogen bond between C(16)- H(16)…O(1) and C(3)-H(3)…O(2) has been observed in the crystal lattice.     

A highly enantioselective synthesis of 5- (ι-menthyloxy) -4-substituted-3-chloro-2(5H) -furanones

In this paper, stereocontrolled tandem Michael addition-elimination reaction of the novel chiral source, S-(ι-menthyloxy)-3,4-dichloro-2(5H)-furanone, with various thiols and amines has been investigated. A series of new enantiomerically pure compounds, 5-(ι-menthyloxy)-4-substituted-3-cnloro-2(5H)-furanones, were obtained in good yields with d. e.(?)98% under mild conditions.     

超支化聚酰胺-酯单体的常温快速合成

以取代马来酸酐和二乙醇胺为原料,在常温下快速(2 h)合成了一系列的超支化聚酰胺-酯AB:单体,其结构经FT-IR表征.用中和滴定法跟踪测定反应体系的酸值,根据酸值与反应进度的关系,讨论了快速合成的意义.提出了可能的反应机理.