单分子光学探针揭示易混聚合物受限纳米区域的动力学

常规的系综研究方法显示在动力学不对称的易混聚合物中存在着受限区域,但是不能给出受限区域的分布、尺度及受限区域内的动力学分布特征等.单分子光学探针被用来探测苯乙烯高聚物与苯乙烯寡聚物形成的易混聚合物薄膜中的受限纳米区域的动力学.实验发现易混聚合物中存在转动和固定不动的两种动力学形式的单分子,指示着单分子分别耦合到苯乙烯高聚物和苯乙烯寡聚物的聚合物链片段上.转动单分子的分布揭示了易混聚合物薄膜受限区域的分布特征.受限区域的尺度被估计为其可能接近于单分子探针的尺度(约2 nm).受限纳米区域中单分子的转动关联时间的分布揭示了受限纳米区域中聚合物动力学的分布特征.实验发现在含有更高浓度的苯乙烯高聚物的混聚物薄膜中具有更快的动力学行为,从而在单分子水平上揭示了易混聚合物中的受限纳米区域的动力学.     

甲基蓝-钛酸盐纳米聚合物薄膜的光谱和光学非线性研究

 为了满足光学非线性器件设备对工作材料的要求,探究具有高阶非线性效应的固态薄膜材料的制备方法,并对其光学特性进行表征,采用化学插入法,将甲基蓝染料分子插入到具有纳米量级的层状钛酸盐片间,制备了甲基蓝-钛酸盐纳米聚合物薄膜,通过吸收光谱和荧光光谱的测定,发现薄膜的吸收峰相对于染料溶液发生了明显的蓝移,表明染料分子在纳米片间是H-聚集排列。进一步应用单光束连续He-Ne激光Z-扫描技术研究了样品的非线性光学特性,结果显示：插入染料分子的钛酸盐纳米MB/HTO聚合物薄膜具有“负”的非线性折射率,在低功率连续激光作用下聚合物薄膜的非线性折射率系数n2的量级为10-10 m2/W。     

偶氮聚合物薄膜的吸收谱和二次谐波产生的温度特性

研究了一种偶氮聚合物薄膜的光谱和二阶非线性光学特性.研究结果表明,聚合体中的偶氮发色团以反式异构体形式存在.加热可使分子之间的相互作用减弱,聚集体的聚集程度降低;温度低于70℃时聚集体的结构不会发生变化,分子间相互作用的改变能够完全恢复;高于70℃降温后聚集体聚集程度的降低不能完全恢复.在一定温度下极化可使发色团偶极子定向有序排列,形成J-聚集体.偶氮聚合物薄膜的二阶非线性光学特性起源于偶极子模型,极化温度是影响极化膜二次谐波强度的重要因素之一,该偶氮聚合物薄膜的最佳极化温度约为90℃.     

纳米MEH-PPV阵列的光致发光

以多孔氧化铝为模板,将可溶性发光聚合物聚（2-甲氧基-5-（2’-乙基己氧基）-1,4-对苯乙炔）（MEH-PPV）镶嵌在纳米孔中,制备出高发光效率的纳米发光聚合物阵列,其光学特性与MEH-PPV薄膜显著不同。纳米孔内的MEH-PPV分子链形成链束,链束中的分子链数目依赖于制备纳米MEH-PPV阵列所用溶液的浓度。相对于稀溶液,在由浓溶液制备的纳米MEH-PPV阵列中,MEH—PPV链束的分子链数目较多,链间作用使MEH-PPV的能带展宽,能隙减小,因而浓溶液获得的纳米MEH—PPV阵列的光致发光峰红移。热处理纳米MEH-PPV阵列的PL谱表明,纳米孔内的聚合物分子链的弛豫运动受到限制。     

纳米二氧化钒薄膜的电学与光学相变特性

采用双离子束溅射氧化钒薄膜附加热处理的方式制备了纳米二氧化钒薄膜。在热驱动方式下,分别利用四探针测试技术和傅里叶变换红外光谱技术对纳米二氧化钒薄膜的电学与光学半导体-金属相变特性进行了测试与分析。实验结果表明,电学相变特性与光学相变特性之间存在明显的偏差,电学相变温度为63 ℃,高于光学相变温度,60 ℃;电学相变持续的温度宽度较光学相变持续温度宽度宽;在红外光波段,随着波长的增加,纳米二氧化钒薄膜的光学相变温度逐渐增大,由半导体相向金属相转变的初始温度逐渐升高,相变持续的温度宽度变窄。在红外光波段,纳米二氧化钒薄膜的光学相变特性可以通过光波波长进行调控,电学相变特性更适合表征纳米VO₂薄膜的半导体-金属相变特性。     

共轭聚合物单分子构象和能量转移特性研究

利用基于宽场显微光学系统的单分子散焦成像技术测量了不同构象poly[2,7-(9,9-dioctylfluorene)-alt-4,7-bis(thiophen-2-yl)benzo-2,1,3-thiadiazole](PFO-DBT)共轭聚合物单分子的光物理与动力学特性.通过分析共轭聚合物单分子的荧光轨迹和对应的发射偶极取向变化识别共轭聚合物单分子发光单元,发现延伸构象下的单分子呈现多发色团发光特性,而折叠构象下的单分子保持高效链间能量转移,呈现单个发色团发光特性.共轭聚合物单分子构象对能量转移效率的影响可用于研究基于共轭聚合物的光电器件和分子器件.     

偶氮苯侧链聚合物液晶薄膜的光致双折射和永久光学性存储研究

研究了一种含偶氮基侧链聚合物液晶薄膜,该液晶薄膜表现出显着的光致双折射(Δn～1.1×10^-2).当关闭写光作用后,光致双折射的大小没有任何衰减,表现出永久光存储特性.光致双折射的擦除可通过将样品加热到接近其清亮点温度,或用一束圆偏振光照射来实现.分析了偶氮侧链聚合物永久性光学存储的物理机制.     

半导体聚合物纳米荧光探针的制备及生物应用研究进展

半导体聚合物作为功能有机高分子材料被广泛应用于有机光电子器件领域的研究。近年来由半导体聚合物构成的荧光纳米粒子引起了广泛的研究兴趣。这类新型纳米探针具有光学吸收截面大、量子效率高、辐射跃迁速率快、光稳定性好等特性,在荧光成像和生物传感等领域获得了重要应用。本文简要概述了近年来半导体聚合物纳米粒子的研究进展,包括其光物理性质、表面功能化以及在细胞标记、体内成像、生物传感、单粒子示踪、药物输送和光动力学疗法等领域的应用。     

有机/无机薄膜凝胶动态过程的实时光学二次谐波产生研究

采用实时光学二次谐波产生(SHG)测量方法,以两亲性分子半花菁为掺杂探针分子,对溶胶-凝胶技术制备的玻璃薄膜的凝胶干燥的动态过程进行了研究.结合紫外—可见吸收光谱的测量,发现：因两亲性分子在膜中的自取向性可诱导出二阶光学非线性,溶胶-凝胶技术制备的有机/无机复合膜的凝胶干燥过程可通过薄膜SHG强度的变化半定量地反映.凝胶干燥收缩导致有序掺杂分子数减少,膜片的光学非线性减弱.该过程随薄膜处理温度的升高而急剧缩短;另外,有机分子在膜中的聚集程度随膜片处理温度的增加而很快减少. 关键词：     

高度取向的半导体聚合物薄膜的溶液浸涂法生长及其电荷传输特性研究

有效地控制有机半导体分子取向和堆积特性对实现高性能电子器件具有非常重要的意义,而发展简便高效的溶液相成膜技术是实现这一目的的重要途径.本文采用改进的溶液浸涂法,成功地成长出大面积宏观取向的半导体聚合物P(NDI2OD-T2)和PTHBDTP薄膜.偏光显微镜和极化的紫外-可见光吸收谱测量显示,薄膜中聚合物分子主链骨架沿成膜时液面下移方向择优取向.原子力显微镜观察到聚合物薄膜由纳米尺度的取向有序晶畴构成,畴的取向与分子链的取向一致.采用衬底-溶液界面处表面张力和溶剂蒸发诱导的分子自组织过程来解释浸涂法生长聚合物取向薄膜的微观机理.使用取向的P(NDI2OD-T2)薄膜制备场效应晶体管,显著地提高了电子迁移率(可达4倍),并实现高达19的迁移率各向异性度.这可归因于共轭的聚合物主链骨架择优取向引起电荷传导通路的变化.     

Three-dimensional single molecule rotational diffusion in glassy state polymer films

Measuring three-dimensional orientational motions of many individual molecules within glassy state poly(methyl methacrylate) has enabled nanoscopic probing of bulk-obscured polymer dynamics. Complementing bulk studies, the measured distributions of nanoscale barriers to rotational motion afforded by our single molecule orientational methods directly probe the spatial heterogeneity and nanoscopic alpha-relaxation dynamics deep within the glassy state.     

邻苯二甲酸二甲酯系材料中α-弛豫的降温介电谱测量与分析

对邻苯二甲酸二甲酯(dimethyl phthalate)、邻苯二甲酸二乙酯(diethyl phthalate)、邻苯二甲酸二丁酯(dibutyl phthalate)和邻苯二甲酸二异辛酯 (dioctyl phthalate)系列材料中, α-弛豫的降温介电谱进行了测量, 得出了相应材料α-弛豫的平均弛豫时间τ_α^a 随温度T的变化关系. 通过τ_α^a 的实验结果与经验的Vogel-Fulcher-Tammann)定律τ_α^a = τ_α⁰ exp (A/(T-T₀))的拟合, 获得了上述系列材料的τ_α⁰, A和T₀. 分析发现, 随邻苯二甲酸二甲酯系列分子侧链中碳原子数目n的变化, 材料的τ_α⁰, A, T₀ 和T_g 表现出一定的规律性, 具体为随n的增加, 即分子内部自由度的增多, A和T_g 都表现出近乎相同的先减后再增的趋势, 而1/τ_α⁰ 和T₀ 则表现出基本相同的先快速减小, 然后保持基本上不变的趋势. 关键词： 玻璃化转变 介电谱 α-弛豫')" href="#">α-弛豫 邻苯二甲酸二甲酯系列材料     

Dynamics of conformations,hydrogen bonds and translational diffusion of poly(methacrylic acid) in aqueous solution and the concentration transition in MD simulations

The dynamic behaviour of chain conformations, hydrogen bonds and translational diffusion of aqueous poly(methacrylic acid) (PMA) solution as a function of polymer volume fraction Φ_p across dilute to concentrated regimes inclusive of the pure polymer amorphous state was studied by molecular dynamics simulations. The behaviour of the relaxation time (τ) of the backbone dihedral angle auto-correlation function (ACF) reveals slower relaxation at higher level of polymer concentration and the existence of a concentration-driven relaxation transition for the aqueous polymer solution which occurs in the polymer volume fraction range, specifically 54% < Φ_p < 82% for this system. The relaxation constant τ for backbone dihedral angle exhibits a linear variation with Φ_p, indicating a first-order kinetic transition. The intermittent ACF for decay of the H-bond correlation shows that H-bonds among water molecules relax faster than those of the PMA–PMA and PMA–water type. The relaxation rate of PMA–water H-bonds shows a decrease up to Φ_p = 72% and becomes faster at Φ_p = 82% due to the confining influence of neighbouring PMA chains. PMA–water and water–water H-bond dynamics show transitions around Φ_p = 72% PMA. With increase in Φ_p PMA diffusion coefficient decreases exponentially and water diffusion coefficient decreases linearly, in agreement with experimental observations using fluorescence and nuclear magnetic resonance (NMR) spectroscopic studies.     

Structural evolution of low-pressure polymerised C60 with polymerisation conditions

We show in this paper that characteristic features in the Raman spectra, especially the frequency of the pentagonal pinch mode, can give information about the polymeric structure of pressure polymerised C₆₀. High-pressure treatment at 1 GPa below 510 K for 3 h results in the formation of a low fraction of dimers only, while treatment at the same pressure and time above 540 K affords a fully polymerised material. In the latter case, different relative fractions of dimers and polymer chains are obtained depending on whether the final reaction conditions were reached by isobaric or isothermal path. We suggest that this difference results from different reaction dynamics in the two cases. The polymerisation rate depends on T and p and on the rotational and orientational states of the molecules. At 1 GPa no polymerisation is observed in sc C₆₀, while in “hexagon” oriented sc C₆₀ at 1.7 GPa dimers are already formed 175 K below the fcc–sc transition and a fully polymerised material is obtained just below the transition to the fcc phase.     

Relation between rotational and translational dynamic heterogeneities in water

We use molecular dynamics simulations to probe the rotational dynamics of the extended simple point charge model of water for a range of temperatures down to 200 K, 6 K above the mode coupling temperature. We find that rotational dynamics is spatially heterogeneous; i.e., there are clusters of molecules that rotate significantly more than the average for a given time interval, and we study the size and the temporal behavior of these clusters. We find that the position of a rotational heterogeneity is strongly correlated with the position of a translational heterogeneity, and that the fraction of molecules belonging to both kinds of heterogeneities increases with decreasing temperature. We further find that although the two types of heterogeneities are not identical, they are related to the same physical picture.     

Surface Corrugation in Rotational and Diffractive Scattering of O2 from LiF (001)

A quantum dynamic calculation on a five-dimensional O₂/LiF (001) model system is performed using the multi-configuration time-dependent Hartree method. The obtained results show that the mechanism of rotational and diffractive excitation in details: Comparison with the rotational excited state, the initially non-rotational state is seen to favor the inelastic scattering in the rotational excitation process. The surface corrugation can damp the quantum interferences and produce a greater amount of rotational inelastic scattering at the expense of the elastic process in the rotational excitation process. The diffraction process and the average energy transferred into the rotational and diffractive mode are also discussed.     

Dynamics of chain molecules in disordered materials

The dynamic behavior of hard chains in disordered materials composed of fixed hard spheres is studied using discontinuous molecular dynamics simulations. The matrix induces entanglements in the chain fluid, i.e., for high matrix densities the diffusion coefficient D scales with the chain length N as D is approximately N(-2). At high matrix densities the rotational relaxation time becomes very large but the translational diffusion is not affected significantly; i.e., the chains display a dynamic heterogeneity reminiscent of probe diffusion in supercooled liquids and glasses. We show that this is because some chains are trapped, and move via a hopping mechanism. There are no signatures of this dynamic heterogeneity in the matrix static structure, however, which is identical to that of a hard-sphere liquid.     

二十面体团簇的遗传:一个与快凝Cu56Zr44合金玻璃形成能力有关的动力学参数

采用分子动力学方法模拟研究了液态Cu₅₆Zr₄₄合金在不同冷速γ与压力P下的快速凝固过程, 并通过基于Honeycutt-Andersen键型指数的扩展团簇类型指数法对其微结构演变特性进行了分析. 结果表明: 快凝玻璃合金的局域原子组态主要是(12 12/1551)规则二十面体、以及 (12 8/1551 2/1541 2/1431)与(12 2/1441 8/1551 2/1661) 缺陷二十面体. 通过原子轨迹的逆向跟踪分析发现: 从过冷液体中遗传下来的二十面体对快凝合金的玻璃形成能力(GFA)具有重要影响, 不仅其可遗传分数F_i =N_{300 K←Tg}ⁱ/N_Tg 与GFA密切相关, 而且其遗传起始温度(T_onset)与合金约化玻璃转变温度T_rg = T_g/T_m也存在很好的对应关系.     

基于准弹性中子散射谱分析水化硅酸钙(C-S-H)中受限水的动态

研究水化硅酸钙(C-S-H)中受限水动态的一种重要手段是准弹性中子散射(quasi-elastic neutron scattering, QENS)实验. C-S-H样品的QENS谱数据可通过跳跃扩散和转动扩散模型进行分析拟合, 进而导出C-S-H样品微纳孔中水动态的相关物理参数: 不动水指数C、转动扩散系数D_r、均方位移< u² >、自扩散系数D_t及平均停留时间τ₀. 本文对水与水泥质量比为30%的C-S-H样品, 测量温度为230-280 K的QENS谱进行了分析, 得到的拟合参数可定量描述C-S-H样品内不同尺度的微纳孔中受限水随温度变化的动态过程. 转动扩散系数D_r随散射矢量Q的变化可知, Q值较大时, 水分子的转动对QENS谱影响较大. 均方位移 < u² > 随Q值的不同而变化, 其拟合值可区分C-S-H样品中的不动水、强受限水和受限水. 在Q较小时, D_t 和τ₀ 的拟合值随温度而变化, 并分别在230和240 K突然增大, 由此揭示温度为230-240 K 时, C-S-H 样品中受限水分子的动态特性发生了转变.     

Origins of nonexponential decay in single molecule measurements of rotational dynamics

Recent reports have demonstrated that the correlation function of the fluorescence dichroism signal, measured as a probe of single molecule rotational dynamics, should not manifest a single exponential decay even for isotropic diffusion. This has called into question the attribution of observed nonexponential behavior in supercooled fluids and polymer systems to dynamical heterogeneity. We show here that, for the case of a high numerical aperture objective, the dichroism decay becomes indistinguishable from a single exponential. As a consequence, observed nonexponential decays can be associated with complex rotational dynamics. These effects are illustrated via simulated rotational trajectories for isotropic diffusion of a dipole.