新型四苯基卟啉衍生物及其锌(Ⅱ)配合物的合成与性质研究

以四苯基卟啉(TPP)为原料,经过硝化、还原、酰胺化等反应合成了一种新型四苯基卟啉衍生物及其锌(Ⅱ)配合物,通过FAB-MS、IR、1 H-NMR和元素分析等方法鉴定了目标产物的结构,并对其发光性质进行了研究。结果表明,四苯基卟啉衍生物及其锌(Ⅱ)配合物的紫外-可见光谱和荧光光谱均发生了明显红移。     

四-(对酰氧基苯基)卟啉的合成及液晶性能研究

合成了4个系列的中位－四（对酰氧基苯基）卟啉化合物，通过元素分析，紫外－可见光谱，红外光声光谱和核磁共振氢谱等分析手段表征了4种卟啉自由碱化合物，并肜DSC和偏光显微镜研究这些化合物的液晶行为，探讨了碳链长度对卟啉自由碱液晶性能的影响。     

四苯基卟啉夹层石墨烯复合物的光电子特性研究

以四苯基卟啉和石墨烯为原料,用溶剂-非溶剂共沉淀法制备得到四苯基卟啉夹层石墨烯复合物,通过扫描电镜（SEM）、透射电镜（TEM）、荧光光谱和电化学循环伏安对所得复合物进行表征。分析结果表明,共沉淀过程使得四苯基卟啉成功包裹了石墨烯,它们之间存在电子转移,且四苯基卟啉在654nm和717nm处的荧光淬灭;四苯基卟啉-石墨烯复合物是一个很好的电子给体-受体体系,在新型显示器、光伏电池等方面有潜在的应用价值。     

meso-四(4-甲氧基苯基)卟啉在传感元件中的应用研究

将meso-四(4-甲氧基苯基)卟啉(TMP)作为传感材料,K⁺离子交换玻璃光波导(OWG)作为传感元件基底,通过氢氧化钠和盐酸调节卟啉溶液的pH值,将不同pH值的卟啉溶液通过旋转甩涂法固定于K⁺离子交换玻璃光波导表面制备出传感元件,并对其气敏性进行研究。实验结果表明,利用不同pH值的卟啉溶液制备的传感元件具有不同的气敏特性。其中,pH值为1.00的卟啉溶液制备的传感元件对乙二胺气体具有良好的选择性响应,用原溶液(pH=5.06)制备的传感元件对硫化物气体(H₂S,SO₂)表现出较高的灵敏度。     

meso-四-(4-甲氧基-3-磺酸苯基)卟啉在测定痕量金属的应用—锌的分光光度法测定

本文研究了在咪唑存在下 meso—四—(4—甲氧基—3—磺酸苯基)卟啉(TMPPS_4)与锌显色反应的最佳条件,建立了测定锌的新方法,灵敏度高,锌量在0—1.2μg/10mL 范围内遵守比耳定律,用于测定粮食中的锌时结果满意     

5-(4-L-苯丙氨酰基氨基苯基)-10,15,20-三苯基卟啉的合成与光学性质研究

以吡咯、苯甲醛、叔丁氧羰基(BOC)保护的氨基酸为原料,经5步反应合成了一种新型尾式氨基酸卟啉,用MS、1H-NMR及UV-Vis对产物进行了表征,并研究了其荧光光学性质.结果表明:新型尾式氨基酸卟啉只在652nm处有一强烈的发射峰,色纯度高,位于可见光的红光区,有望成为一种优良的红光材料.     

四(4-磺酸苯基)-卟啉在聚4-乙烯基吡啶接枝的乙烯-乙烯醇膜表面的吸附和自组装行为

四(4-磺酸苯基)-卟啉(TPPS)是一种水溶性卟啉,在一定条件下可以自组装形成超分子聚集体,将这种超分子聚集体与膜材料相结合,可以形成超分子负载膜。文中以乙烯-乙烯醇共聚物(EVAL)为膜材料,4-乙烯基吡啶(4VP)为单体,采用紫外辐照表面接枝法制备了表面带有P4VP接枝链的EVAL-P4VP接枝膜,利用非共价键作用将TPPS负载于EVAL原膜及EVAL-P4VP接枝膜上,研究了p H值、离子强度、接枝率等因素对TPPS吸附过程以及TPPS在膜表面存在形态和自组装行为的影响。结果表明,TPPS溶液中自身聚集及离子强度的增加对其在膜上的吸附产生不利影响;吸附过程可用Langmuir等温吸附模型进行描述;接枝率的增加、p H值的减小和吸附量的增加有利于TPPS在接枝膜表面形成J-聚集体。     

5-[对-(4-甲基亚苄基亚氨基)]-苯基-10,15,20-三苯基卟啉铜(Ⅱ)配合物的合成与性质

以吡咯、苯甲醛为原料,经过硝化、还原、缩合等一系列反应合成了5-[对-(4-甲基亚苄基亚氨基)]苯基-10,15,20-三苯基卟啉铜(Ⅱ)配合物,通过FT-IR、UV-vis、FAB-MS及1H NMR对产物进行了表征,并对化合物的发光性能和热稳定性进行了研究,实验结果显示其最大发光波长为650nm,位于可见光中的红光区;化合物在空气中初始分解温度为70℃.     

中位-四(羧基亚甲基)苯并卟啉锌的合成及其在染料敏化太阳能电池中的应用研究

利用热凝聚法合成四苯并卟啉锌的经典反应,加入过量的丁二酸钠代替原反应物乙酸钠,控制合成了中位-四(羧基亚甲基)苯并卟啉锌.由于羧基的引入,使卟啉分子能够锚定在二氧化钛表面.为转移卟啉激发态电子到二氧化钛的导带提供了通道,并改善了其在二氧化钛表面的分散性,从而使苯并卟啉锌敏化太阳能电池的效率明显提高.     

利用紫外光电子谱和第一性原理确定四苯基卟啉的结构与电子态

利用第一性原理确定了四苯基卟啉分子的结构模型,结果表明分子中的苯环与卟吩骨架的夹角为55°,且苯环的自由旋转导致卟吩骨架略微偏离平面形状。再利用紫外光电子谱（UPS）研究了四苯基卟啉在Ru（0001）面的沉积过程,饱和沉积后出现了分子的4个特征峰。对UPS的DV-Xα分析解释了上述光电子谱中四个特征峰的物理起源。     

Characterization and electrochemistry of interfacial self-assembled multi-manganese(III)-porphyrin arrays

Electrochemical behaviors and catalytic oxidation of nitrite have been investigated by using the indium tin oxide (ITO) electrodes modified by the Langmuir-Blodgett (LB) films of manganese porphyrin and its palladium-mediated multiporphyrin arrays. The multiporphyrin arrays were prepared at the air-water interface. Surface pressure-area isotherms indicated that monolayers of the porphyrin of MnTPyP (TPyP: tetrapyridylporphyrin) could be stabilized on the sodium tetraphenylboron and K₂PdCl₄ subphase surfaces, but not on the pure water surface. These monolayers were transferred onto quartz and ITO substrate surfaces with the use of vertical dipping method, and characterized by using transmission electron microscope, UV-vis absorption and X-ray photoelectron spectra. For the electrodes modified by the porphyrin LB films, reversible Mn^(II)TPyP ↔ Mn^(III)TPyP and Mn^(III)TPyP ↔ Mn^(IV)TPyP redox couples were recorded, and centered at about − 0.17 and 0.52 V vs. Ag/AgCl, respectively. A high-valent Mn^(V)TPyP intermediate was detected when the cyclic voltammograms were measured in an electrolyte solution containing sodium nitrite. These multiporphyrin arrays modified electrode showed very strong stability and reproductivity, resulting in potential applications in the development for the nitrite sensors and molecular catalysts of organic compounds.     

淀粉颗粒聚集态结构研究进展

详述了淀粉颗粒中直链淀粉和支链淀粉的分子结构和分布位置,结晶结构及聚集态结构,以及颗粒的晶体结构与形状之间的关系等最新研究成果,同时对淀粉颗粒聚集态结构的研究方向提出展望。认为直链淀粉是分散在支链淀粉分子中且更集中于颗粒表面;颗粒表面比颗粒内部的支链淀粉分子具有更多的短支链。A型多晶淀粉比B型多晶淀粉具有更为松散的内部结构,因而后者对酸和酶具有更强的抗性。     

Electron density distribution and bonding in ZnSe and PbSe using maximum entropy method (MEM)

The study of electronic structure of materials and bonding is an important part of material characterization. The maximum entropy method (MEM) is a powerful tool for deriving accurate electron density distribution in crystalline materials using experimental data. In this paper, the attention is focused on producing electron density distribution of ZnSe and PbSe using JCPDS X-ray powder diffraction data. The covalent/ ionic nature of the bonding and the interaction between the atoms are clearly revealed by the MEM maps. The mid bond electron densities between atoms in these systems are found to be 0.544 e/ų and 0–261 e/ų, respectively for ZnSe and PbSe. The bonding in these two systems has been studied using two-dimensional MEM electron density maps on the (100) and (110) planes, and the one-dimensional electron density profiles along [100], [110] and [111] directions. The thermal parameters of the individual atoms have also been reported in this work. The algorithm of the MEM procedure has been presented.     

热塑性结晶型全芳族聚酯酰亚胺的制备与聚集态结构

以对-亚苯基-双苯偏三酸酯二酐(BTAH)与4,4'-二胺基二苯醚(ODA)为单体采用两步法合成了一种全芳族热塑性结晶型聚酯酰亚胺.盖示扫描量热(DSC)结果显示其玻璃化转变温度为192℃,且聚合物在熔融过程中表现出熔融双峰.X射线衍射(WAXD)结果显示聚合物在室温以及在410℃和420℃处理后均在2θ为18°,23...     

多元氨基酸共聚物的合成及性能表征

以本体聚合方法合成了可生物降解的多元氨基酸共聚物,并采用差示扫描量热分析(DSC)、热重(TGA)和X射线衍射(XRD)等手段对所合成的共聚物进行了表征.结果表明,所合成的多元氨基酸共聚物在常温下可微溶于某些非质子有机溶剂及质子强酸,提高温度可明显提高其溶解性;所合成共聚物为一种半结晶性聚合物,其结晶部分主要为6-氨基...     

Structural and electronic properties of C and BN nanotubes based on periodic fullerenes: A density functional theory study

The structural and electronic properties of C and BN nanotubes based on periodic fullerenes were studied using density functional theory. It was shown that these tubular structures are stable. The electronic band structures and density of states indicated that the C nanotubes based on periodic fullerenes are metals. The energy band gap was appeared by substitution of C atoms with B and N atoms. The BN nanotubes based on periodic fullerenes show semiconducting properties. Our results suggest that the nanotubes based on periodic fullerenes can be used to design of nanoelectronic devices.     

Comparative study of adsorption properties of Turkish fly ashes. I. The case of nickel(II), copper(II) and zinc(II)

The objective of this study was to compare two different Turkish fly ashes (Afsin-Elbistan and Seyitomer) for their ability to remove nickel [Ni(II)], copper [Cu(II)] and zinc [Zn(II)] from an aqueous solution. The effect of contact time, pH, initial metal concentration and fly ash origin on the adsorption process at 20+/-2 degrees C were studied. Batch kinetic studies showed that an equilibrium time of 2h was required for the adsorption of Ni(II), Cu(II) and Zn(II) on both the fly ashes. The maximum metal removal was found to be dependent on solution pH (7.0-8.0 for Ni(II), 5.0-6.0 for Cu(II) and 6.0-7.0 for Zn(II)) for each type of fly ash. With an increase in the concentrations of these metals, the adsorption of Ni(II) and Zn(II) increased while the Cu(II) adsorption decreased on both the fly ashes. Adsorption densities for the metal ions were Zn(II)>Cu(II)>Ni(II) for both the fly ashes. The effectiveness of fly ash as an adsorbent improved with increasing calcium (CaO) content. Adsorption data in the range of pH values (3.0-8.0) using Ni(II) and Cu(II) concentrations of 25+/-2mg/l and Zn(II) concentration of 30+/-2mg/l in solution were correlated using the linear forms of the Langmuir and Freundlich equations. The adsorption data were better fitted to the Langmuir isotherm since the correlation coefficients for the Langmuir isotherm were higher than that for the Freundlich isotherm. The fly ash with high calcium content (Afsin-Elbistan) was found to be a metal adsorbent as effective as activated carbon and, therefore, there are good prospects for the adsorptions of these metals on fly ash with high calcium content in practical applications in Turkey.     

PbSe(001)表面特性的第一性原理研究

用第一性原理的密度泛函理论计算了PbSe（001）表面的几何结构和电子特性。计算结果表明：PbSe（001）表面几层原子出现明显的振荡弛豫现象,但没发生重构,第一、二原子间距减小,第二、三层原子间距增大,同时也发现表面层原子出现褶皱。该表面的直接带隙出现在X点,在导带底和价带顶附近出现4个表面共振态,另外两个表面态分别出现在-4．0eV附近和-11．5eV附近。     

共晶Ni_(53)Si_(47)合金的液-固态结构相关性

利用高温液态X射线衍射仪研究了共晶Ni53Si47合金的液态结构。在衍射强度曲线的小角部分发现预峰,且预峰的强度随温度的降低而增强;研究表明,熔体中原子团簇结构稳定,有序度随温度降低而提高;通过纳米晶粒模型进一步研究了该合金的液-固态结构相关性,指出熔体衍射强度曲线上的预峰是化合物NiSi液态结构的一种体现,该合金液态结构与固态结构具有一定的相关性。