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151.
152.
利用硼氢化钠还原法制备了金纳米粒子, 通过在其表面修饰链长不同的巯基羧酸, 得到了功能化纳米粒子. 利用荧光发射、紫外吸收和圆二色谱等手段研究了功能化金纳米粒子与蜂毒素分子之间的相互作用及其所诱导的蛋白质分子的构象变化. 研究结果表明, 功能化修饰的金纳米粒子可通过静电相互作用吸附蜂毒素(Melittin)并诱导其α-螺旋结构的形成, 且这种效应与巯基羧酸分子的链长直接相关. 相似文献
153.
α-SrMnO3电子结构的第一性原理研究 总被引:1,自引:0,他引:1
采用平面波赝势方法对钙钛矿型锰酸盐氧化合物α-SrMnO3的电子结构进行了第一性原理研究. 六方钙钛矿型结构α-SrMnO3化合物为磁性绝缘体, 磁基态对应于共面八面体及共顶点八面体间的磁性交换作用均为反铁磁性(AFM), 其禁带宽度为1.6 eV; 费米能级附近的Mn3d态与O2p态存在很强的杂化作用, 属于共价绝缘体, 这种强共价性使得Mn4+的自旋磁矩偏离理想值. 采用Noodleman的对称性破缺方法, 根据α-SrMnO3不同磁有序态的总能量拟合出α-SrMnO3中的自旋交换耦合常数. α-SrMnO3的局部微结构(Mn—O—Mn)决定了整个体系的特殊磁性交换作用. 共面及共顶点的八面体间均存在AFM交换作用, 并且共顶点八面体间的AFM作用比较强. 相似文献
154.
155.
合成了4种α-二亚胺镍催化剂Ar—NC(R1)C(R2)N—ArNiBr2[Ar=2,6-dimethylphenyl,R1=CnH2n+1,R2=CmH2m+1;其中Cat1:m=1,n=1;Cat2:m=2,n=1;Cat3:m=3,n=1;Cat4:m=2,n=2],考察了聚合温度、催化剂浓度和催化剂配体骨架碳原子上烷基取代基对乙烯聚合反应活性、聚合物链结构和结晶性能的影响.实验发现,当配体骨架上烷基取代基R1和R2不同时,催化剂具有较高的活性,且聚合物分子量也较高;其中,Cat2和Cat3在20℃,乙烯常压和5.8mmol/L催化剂用量下,乙烯聚合活性达1.86×103kgPE/(molNi.h)和1.92×103kgPE/(molNi.h),聚合物分子量(Mw)达6.82×105和1.019×105.聚乙烯链结构分析表明,甲基支链在聚乙烯支链中占主导地位,支化度主要受反应温度的影响;同时还发现,配体骨架碳原子上烷基取代基不同的二亚胺镍催化合成聚乙烯的长支链比例相对较高,特别是在较高反应温度40℃下,己基及以上长支链比例明显增加. 相似文献
156.
本文以聚(苯乙烯-异丙烯膦酸)-磷酸氢锆(ZPS-IPPA)为载体,对该载体进行氯甲基化、胺化修饰后与手性Salen Mn(Ⅲ)轴向配位,合成了一种新的固载型手性Salen Mn(Ⅲ)催化剂,采用FTIR,DR UV-Vis,XPS,SEM,TEM,TG等手段对催化剂进行表征.以次氯酸钠和间氯过氧苯甲酸为氧化剂,考察了固载催化剂对a-甲基苯乙烯不对称环氧化反应的催化性能,结果表明,固载型催化剂的催化活性比相应均相催化剂略低,但对映体选择性明显提高.在NaClO/PPNO氧化剂体系中0 ℃反应24h,a-甲基苯乙烯环氧化物的转化率达68%,e.e.值达99%.循环使用8次后催化效果无明显降低. 相似文献
157.
Starting from trifluoromethyl β-dicarbonyl compounds, a rare loss of CF3CO was observed in the amination reactions performed under heterogeneous conditions using NsONHCO2Et as the aminating agent and CaO or NaH as the base, while corresponding nonfluorinated β-dicarbonyl compounds under analogous conditions give non deacylated aminated compounds. This reaction can facilitate a direct synthesis of N-substituted α-amino esters or α-amino ketones. 相似文献
158.
Christina Matsingou 《Thermochimica Acta》2007,452(2):116-123
Differential scanning calorimetry (DSC) was used to study the effect of cholesterol on the perturbation of DPPC bilayers induced by eight bioactive structurally related labdanes isolated from the resin ‘ladano’ of Cistus creticus subsp. creticus (Cistaceae) or semisynthesized from the mother compounds. Labdanes themselves induced profound modifications in DPPC bilayer organization and thermotropic properties that were altered when cholesterol was incorporated in equimolar amounts to the labdanes. The present work shows that, up to 10 mol% of the equimolar mixture of cholesterol and the labdanes, the modifications evoked on DPPC bilayer organization are in accordance to these induced by the labdanes themselves. When the concentration exceeded 20 mol%, cholesterol influence dominated while the effect of the labdanes was suppressed and their interaction with the bilayer was probably prevented. The degree by which cholesterol modulated the labdane interaction with the bilayer depended on their structural characteristics that determine their localization in the bilayer interior. Polar groups that force the labdanes to localize themselves at the interfacial region broadened the concentration range by which labdanes interacted with the DPPC bilayer even in the presence of high concentration of cholesterol where cholesterol-rich domains are preferentially formed. On the other hand, labdanes possessing functional groups that promote their deeper penetration in the bilayer interior compete with cholesterol in a high extent for the same localization sites resulting in their possible elimination from the bilayer when the concentration of cholesterol present exceeds the 20 mol%. 相似文献
159.
Liping Li 《Journal of solid state chemistry》2007,180(10):2896-2904
Highly crystalline one-dimensional (1D) α-MnO2 nanostructures were synthesized by a hydrothermal method. All samples were characterized by X-ray diffraction, transmission electron microscope, thermogravimetric and differential scanning calorimeter, and infrared spectroscopy. During the formation reactions, the tunnel structure of 1D α-MnO2 was simultaneously modified by NH4+ species and water molecules. The amount of NH4+ species that were trapped in the tunnels is almost independent on the reaction temperature, while the total water content increased with the reaction temperature. The average diameter of α-MnO2 nanorods increased from 9.2 to 16.5 nm when the reaction temperature increased from 140 to 220 °C. 1D α-MnO2 was destabilized by a subsequent high-temperature treatment in air, which is accompanied by a structural transformation to 1D Mn2O3 of a cubic structure. At low temperatures, all 1D α-MnO2 nanorods showed two magnetic transitions that were characterized by a decreased Néel temperature with rod diameter reduction. According to the effective magnetic moments experimentally measured, Mn ions presented in the nanorods were determined to be in a mixed valency of high spin state Mn4+/Mn3+. 相似文献
160.
Michael D. Swift 《Tetrahedron letters》2007,48(22):3771-3773
A new approach for the stereoselective synthesis of (2R,3S)-2-amino-3,4-dihydroxybutyric acid, an α-amino acid from Lyophyllum ulmarium, has been accomplished using an ether directed aza-Claisen rearrangement. On investigation of optimal conditions for this key step it was shown for the first time that Au(I) can be used to catalyse this transformation. 相似文献