基于共轭聚合物的纳米粒子用于肿瘤的近红外二区荧光成像及光热治疗

为提高生物组织荧光成像质量以及对肿瘤的高效光热治疗,设计合成了一种新型的窄带隙共轭聚合物(BDT-TTQ),并通过纳米沉积的方式将聚合物制备成水溶性纳米粒子(BDT-TTQ NPs).该共轭聚合物纳米粒子在1000~1200 nm近红外二区范围具有较好的吸收,在1064 nm的激发光下能实现1200~1400 nm的近红外二区荧光成像. BDT-TTQ NPs纳米粒子粒径分布较窄,形貌呈规则的球形且分散均匀,具有好的生物相容性.该纳米粒子既可以在体外实现较高的近红外二区荧光成像穿透深度,又可以实现对小鼠活体血管的高清晰度的近红外二区荧光成像.此外,BDT-TTQ NPs纳米粒子在1064 nm激光下展现出优异的光热转换效率,具有较高的光毒性,对体外的肿瘤细胞以及小鼠的异质瘤具有高的光热杀伤能力.     

环糊精包结络合作用诱导的水溶性聚芴纳米粒子的制备

首先合成了单取代的β环糊精ATRP引发剂(β-CD-Br),利用核磁、质谱等对其进行了表征,并通过ATRP聚合制备了端基为β-环糊精的水溶性聚合物聚甲基丙烯酸N,N-二甲基氨基乙酯(β-CD-PDMAEMA).聚合物β-CD-PDMAEMA可以通过环糊精与金刚烷之间的主客体包结络合作用与端基为金刚烷的聚芴(PFADA)形成水溶性的聚芴纳米粒子.重点探讨了β-CD-PDMAEMA与PF-ADA的质量比和不同的组装方法对纳米粒子尺寸及分布的影响,研究表明质量比为4∶1时通过向2种聚合物的THF混合溶液中缓慢加水的方法可得到流体力学半径(R_h)为80 nm、PDI为0.11的纳米粒子.最后利用透射电子显微镜和原子力显微镜对纳米粒子的形貌进行了表征,进一步依照纳米粒子的R_h随温度升高的实验可以证实纳米粒子具有明显的核壳结构,其中刚性的聚芴为核半径约为50 nm,水溶性的PDMAEMA聚合物为壳.     

The enhancement of 21.2%-power conversion efficiency in polymer photovoltaic cells by using mixed Au nanoparticles with a wide absorption spectrum of 400 nm–1000 nm

Au nanoparticles(NPs) mixed with a majority of bone-like, rod, and cube shapes and a minority of irregular spheres, which can generate a wide absorption spectrum of 400 nm–1000 nm and three localized surface plasmon resonance peaks, respectively, at 525, 575, and 775 nm, are introduced into the hole extraction layer poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate)(PEDOT:PSS) to improve optical-to-electrical conversion performances in polymer photovoltaic cells. With the doping concentration of Au NPs optimized, the cell performance is significantly improved: the short-circuit current density and power conversion efficiency of the poly(3-hexylthiophene): [6,6]-phenylC60-butyric acid methyl ester cell are increased by 20.54% and 21.2%, reaching 11.15 m A·cm-2and 4.23%. The variations of optical, electrical, and morphology with the incorporation of Au NPs in the cells are analyzed in detail, and our results demonstrate that the cell performance improvement can be attributed to a synergistic reaction, including: 1) both the localized surface plasmon resonance- and scattering-induced absorption enhancement of the active layer, 2) Au doping-induced hole transport/extraction ability enhancement, and 3) large interface roughness-induced efficient exciton dissociation and hole collection.     

A Lanthanide-transition Metal Coordination Polymer：{[CuEu（Hbidc）_2（H_2O）_4]·H_2O}_n（H_3bidc=1H-benzimidazole-5,6-dicarboxylic Acid）

The title complex 1,{[CuEu(Hbidc)2(H2O)4]·H2O}n(H3bidc = 1H-benzimidazole-5,6-dicarboxylic acid),has been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P1,with a = 7.791(2),b = 12.058(3),c = 12.109(3),α = 82.189(5),β = 72.407(5),γ = 89.184(4)°,V = 1073.7(5)3,C18H18CuEuN4O13,Mr = 713.86,Dc = 2.208 g/cm3,μ(MoKα) = 3.967 mm-1,F(000) = 700,GOOF = 0.950,Z = 2,the final R = 0.0531 and wR = 0.1068 for I > 2σ(I).Complex 1 possess a tape-like chain structure consisting of Eu2C8O4 and Cu2Eu2C18N4O4 metallic rings alternatively arranged and is the first 3d-4f heterometallic complex based on the 1H-ben-zimidazole-5,6-dicarboxylato ligand(Hbidc).Plenty of hydrogen-bonding and π...π stacking interactions connect the 1D chains to construct a 3D supramolecular architecture.     

碳化法国梧桐絮制备碳微米管及作为超级电容器电极的研究

利用法国梧桐絮(花粉)的管状结构,通过简单的碳化处理制备了碳微米管。并用扫描电子显微镜、X-射线衍射光谱仪、拉曼光谱仪和X射线光电子能谱仪对碳微米管进行了详细分析。碳微米管的外径为20~30μm,壁厚约为1μm。其内外壁存在着许多微孔和介孔,BET比表面积为265 m2.g-1。碳微米管具有典型的电化学双电层电容性能,表现出优异的稳定性,展示了在超级电容器方面的应用潜力。     

平滑转换向量误差修正模型的非线性协整SupLM检验

本文考虑平滑转换向量误差修正模型的非线性协整检验问题,相对于传统的两步检验法,给出已知协整向量下的直接检验非线性协整的SupLM检验方法,通过定义平滑转换协整模型,给出SupLM检验统计量,在原假设下得到检验统计量的渐近分布和相关的bootstrap算法,模拟结果和实例计算表明了该方法的有效性。     

Electrochemical,thermal,and photophysical properties of novel two-photon absorption chromophores

Electrochemical, thermal, and photophysical properties of novel two- （BPODPA）, four- （BBPOPA）, and six-branch （TBPOA） triphenylamine chromophores are studied. The decomposition temperature of chro- mophores reaches 373 - 412 ℃. The electrochemical properties is explored by cyclic voltammetry. The ionization potential of chromophores is in the range of 5.14 - 5.18 eV. Excitation at 400 nm reveals emission peaks at 483 - 487 nm and the fluorescence quantum yields are 0.73 - 0.75 in CH2Cl2. Two-photon absorption （TPA） properties of chromophores are measured by nonlinear transmission method. The maximum TPA cross-section values are measured at 758 nm to be 20369 GM （1 GM=10^-50 cm^4 -s/photon） for TBPOA, 7024 GM for BBPOPA, and 1227 GM for BPODPA, respectively. When pumped with 800-nm laser irradiation, chromophores show strong two-photon excited blue-green fluorescence at 502 - 518 nm. These results provide a basis for understanding the electronic and optical properties of the conjugated multi-branch chromoohore in terms of the underlying molecular and electronic structures.     

有机/聚合物π半导体的四元设计原理

从物质结构的角度来看,有机/聚合物半导体是以组合π-轨道为主要电荷载流子输运通道的分子凝聚态固体.其化学本质是π系统,可以通过π-轨道的分子工程技术来巧妙地合成.本文以自己课题组的工作为主线,从物理有机化学的角度,阐述了有机/聚合物半导体设计的基本四要素,即电子结构、空间位阻、构象与拓扑以及超分子弱作用.同时,总结了四个单元要素在有机/聚合物半导体设计方面的研究进展,并展望了四元设计正成为科学家的一种重要思维模式.     

组合材料方法研究膜厚对Ni/SiC电极接触性质的影响

采用组合材料方法研究了金属Ni膜厚对Ni/SiC接触性质的影响.16个膜厚均为18 nm的Ni/SiC电极具有较为一致的肖特基接触性质;膜厚从10 nm增加到160 nm,肖特基接触的电流-电压（I-V）曲线随膜厚发生显著变化.分析表明这种变化源于膜厚对理想因子n和有效势垒高度Ф_B的影响.1000℃快速退火后,这些肖特基接触都转变为欧姆接触,Ni₂Si是主要的生成物.I-V曲线测 关键词： 碳化硅 肖特基接触 欧姆接触 组合材料方法     

磁固相萃取-高效液相色谱联用测定尿样中的1-羟基芘

采用磁固相萃取-高效液相色谱-荧光检测方法(MSPE-HPLC-FD)分析了尿样中芘代谢物1-羟基芘(1-Hydroxyperene 1-OHP).2mL尿样以0.1 mol/L醋酸钠溶液(pH 4.5)稀释至4 mL,酶水解后,再以0.1 mol/L醋酸钠溶液(pH 5.0)稀释至10mL,采用十八烷基膦酸改性的磁性介孔纳米粒子(50 mg)为萃取介质,对其进行MSPE富集,涡旋萃取1 min,甲醇解吸3min.解吸液经氮气吹干重新定容后,进行液相色谱分析.本方法在0.01～ 1.00 μg/L范围内线性良好(R2=0.9996);检出限为0.001μg/L日内相对标准偏差小于9.7％(n=5),日间相对标准偏差小于12.9％.将本方法应用于多个人体尿液样品中1-OHP含量的检测,结果满意.为确保结果的科学性和可靠性,测定结果用尿肌酐含量进行了归一化.