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.     

外电场操控单分子的偶极取向极化特性研究

单分子偶极取向的有效操控对于提高单分子荧光收集效率及荧光共振能量转移等相关研究具有重要的意义.本文通过测量单分子荧光偏振特性的变化,研究了外部电场作用下极性单分子的偶极取向极化特性,实现了外电场对单分子偶极取向的有效操控.研究发现电场方向与单分子样品表面平行时,掺杂在聚甲基丙烯酸甲酯聚合物薄膜中的取向随机分布的极性单分子荧光偏振方向呈现出双峰统计分布规律,表明在溶剂挥发过程中外电场诱导极性单分子偶极取向进行了重新分布.     

室温单分子偶极取向与量子化再取向动力学实验研究

对室温下染料单分子进行了偶极取向和偶极再取向动力学的实验研究.利用共焦扫描显微镜光学系统与荧光偏振探测分析相结合的方法分别测量了聚合体薄膜中的单分子和无聚合体薄膜的单分子偶极方向变化特性,经采样统计测量镶嵌于聚合体薄膜中的单分子发生偶极再取向的概率约为5%—9%,无聚合体薄膜的单分子发生偶极再取向的概率约为26%.通过测量单分子荧光的偏振度轨迹曲线发现,偶极再取向存在着在多个偏振态之间的量子化跳跃行为. 关键词： 单分子 偶极取向 再取向 量子化跳跃     

利用单分子光学探针测量幂律分布的聚合物动力学

研究聚合物薄膜纳米尺度的动力学特性对于高性能材料的制备具有重要的意义.本文利用尼罗红单分子作为光学探针吸附在聚丙烯酸甲酯(PMA)聚合物链上,研究该聚合物薄膜的动力学特性.通过单分子散焦宽场荧光成像显微镜技术测量了单分子随PMA聚合物链转动弛豫的三维再取向特性,当环境温度高于PMA的玻璃点温度19 K时,发现处于PMA聚合物薄膜中的单分子光学探针的转动态和非转动态的持续时间概率密度服从指数截止的幂律分布.研究结果表明该温度下PMA聚合物薄膜的纳米环境动力学仍存在空间和时间异构性.     

基于跃迁偶极矩取向特征研究乙醚溶液中分子的各向异性度

利用偏振荧光光谱和偏振激发光谱研究了乙醚溶液中荧光分子跃迁偶极距的取向特征.实验结果表明,在垂直线偏振光照射下,乙醚溶液发射出峰值位于305 nm的荧光谱,对应的最佳激励光波长为256 nm.由偏振激发光谱分析得到荧光体的吸收跃迁偶极矩和发射跃迁偶极矩间夹角α的变化规律,揭示了荧光去偏振过程：在粘性溶液中的荧光分子具有一定的偶极取向,α随激发光波长发生变化,当激发波长接近最佳激发光波长时,吸收跃迁偶极矩和发射跃迁偶极矩间趋于平行,荧光的退偏效果较弱,偏振度最大.研究结果能为分子空间取向特征的理论研究提供参考.     

分子偶极聚合物驻极体的红外和可见光谱研究

本文利用红外和可见吸收光谱研究了具有二阶非线性光学活性的分子偶极聚合物驻极体材料中偶极子的取向稳定性与分子结构之间的关系，讨论了制备时所用的溶剂对材料微结构的影响。结果表明该材料在玻璃态温度下极化时，引起生色团分子偶极矩沿电场方向取抽，是建立在生色团分子共轭л体系被破坏的基础上，这是一种亚稳态。偶氮类分子的顺-反结构在光、热的作用下极易发生转变，是引起常温下生色团分子有序取向结构松驰的主要原因。制备时所用的溶剂将影响生色团分子在聚合物基底中的存在形式，进而影响分子偶极聚合物驻极体的稳定性。     

Teflon AF/非线性光学聚合物驻极体双层膜的极化稳定性

提出制备Teflon AF/非线性光学聚合物驻极体双层膜系统来提高主客体掺杂型非线性光学聚合物驻极体中偶极分子的有序取向稳定性的设想.样品用恒压电晕充电法极化,通过测量电光效应的等温衰减监测偶极子有序取向稳定性,用开路热刺激放电、等温表面电位衰减测量等手段分析了材料的电荷动态特性.结果表明双层膜系统中偶极分子有序取向稳定性明显优于单层非线性光学聚合物驻极体,其松弛规律可用KWW扩展指数函数来描述. 关键词：     

具有延长共轭的绿色发光蛋白生色团的反向溶剂化斯托克斯(Stokes)位移（英文）

受天然荧光蛋白启发的发色团结构在生物成像领域发挥着重要作用.本文通过计算的方法研究了一类新的绿色荧光蛋白发色团的光化学性质.首先,得到了这一类发色团在真空和溶液中热动力学稳定异构体;然后,计算了它的斯托克斯(Stokes)位移,并与实验数据进行对比.最后,观察到对于这类新的RFP生色团,它们吸收和发射波长发生了反向溶剂化偏移;通过分析,发现了导致反向溶剂化偏移的原因是在溶液中,电荷转移更加稳定,进而常见的旋转结构重组受到抑制.     

螺芴氧杂蒽LB膜的制备及光谱特性研究

为了研究聚芴材料DSFX-SFX分子在气液两相表面的行为,分子处于溶液、LB膜及粉末状态的光学特性,以及分子有序排列对其发光特性的影响,制备了聚芴材料DSFX-SFX的X型LB膜,研究了π-A等温曲线,测量了其紫外-可见吸收谱和稳态荧光光谱。结果表明,分子以face-on形式平躺在亚相表面,单分子面积为4.78 nm2。在氯仿溶液中吸收峰位在354 nm,归属于分子中三聚氧杂蒽部分与芴环间π-π*电子跃迁;荧光发射峰位在396,419,445 nm(肩峰),归属于发色团三聚氧杂蒽,是芴环与氧杂蒽环之间的电荷转移。在LB膜中,吸收谱和荧光光谱与其溶液光谱相比,整体红移6 nm。结果表明:在LB膜中,两个分子形成激基缔合物,与单分子状态相比,激基缔合物的HOMO升高而LUMO降低。与粉末状态相比,该材料在LB膜中有很强的荧光发射,表明该材料形成有序排列超薄膜有利于荧光发射。     

3发色团激发态分子内质子转移机理的研究

采用密度泛函(DFT)和含时密度泛函理论(TDDFT)方法对一种新合成的发色团(3)在非质子性溶剂DMSO中的激发态分子内质子转移机制进行了理论研究.基于3发色团的基态和激发态优化结构,计算得到了该发色团中与氢键相关的键长和键角的大小,以及与氢键相连接的O-H键红外振动光谱,发现分子内氢键在激发态下有增强的趋势.理论计算得到的吸收谱和荧光谱的峰值与实验测得的结果吻合得很好,证明了所采用的理论方法的正确性与合理性.最终,通过对该发色团的分子内电荷转移与电荷分布的分析,证实了激发态分子内质子转移发生的可能性,并说明了其转移过程的发生机制.     

Imaging single quantum dots in three-dimensional photonic crystals

Performing fluorescence wide-field microscopy we have imaged single semiconductor quantum dots deep inside a 3-dimensional photonic crystal prepared from colloidal polymer beads. Exploring the emission diffraction patterns in defocused images of quantum dots we demonstrate that the direction-dependent photonic stop band imprints an anisotropy to the angular emission of a single quantum dot. Hence a single, quasi-point-like emitter is manipulated to radiate its photons only to certain well-defined directions by means of the anisotropic light propagation in photonic crystals. The experiments thus provide new routes to evaluate local, frequency selective optical properties in 3-dimensional photonic crystals employing single emitters.     

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.     

离焦系统下的单分子三维取向研究

提出了一种新思路来确定单分子的三维取向,在全内反射荧光显微成像的基础上,在显微镜的油镜上加一个水层,水和油的折射率不同造成光程差,产生离焦,利用全内反射产生隐失波激发了单分子的纵向分量,并在探测器前增加了一个分光镜,把光路分成偏振方向相互垂直的两束光,使得探测器上的光场分布包含单分子三维取向的信息。推导了隐失场激发的偶极矩光场在探测器上的光强分布表达式,通过分析偏振方向相互垂直的两束光在探测器上的不同的强度分布,来判断单分子偶极矩的三维取向。     

Study of optical properties of electrospun light-emitting polymer fibers

We realize light-emitting polymer fibers based on both optically inert polymers doped by molecules exhibiting optical gain and optically active conjugated polymers. Waveguiding properties of the produced polymer structures are demonstrated, with a loss coefficient of around 10³ cm⁻¹. We also find that single polymer fibers doped with gain molecules form Fabry–Pérot cavities, showing photoluminescence spectra with modes equally spaced by 1.7 nm. Coherent emission is demonstrated from fibers made upon increasing the excitation fluence above threshold values of the order of a few tens of μJ/cm².     

Single-layered photovoltaics based on cyano-substituted pyrazoloquinoline chromophores

The efficiency of a single-layered photovoltaic (PV) cell was increased by up to 44% by using cyano-substituted pyrazoloquinoline chromophores. The role of the incorporated chromophore in changing the effective exciton radius formed by Coulombic chromophore–polymer interactions was analyzed using density functional theory (DFT) quantum chemical simulations. Both the ground-state dipole moments of chromophore, as well as their electrostatic interactions with the conjugated conducting polymer chains, are shown to play an important role. In particular, incorporation of the highly polarised cyano group leads to enhancement of the ground-state dipole moments and enables an open-circuit voltage up to 1.107 V, an enhancement of at least 40% compared to pyrazoloquinoline without cyano groups. At the same time, the exciton length determined by chromophore–matrix interactions and polaronic effects demonstrate a stronger correlation with the observed PV efficiencies.     

Fourier-domain methodology for depth-selective photothermoacoustic imaging of tissue chromophores

Development of a novel photothermoacoustic (PTA) imaging technique utilizing a frequency-modulated (chirped) optical excitation and Fourier-domain methodology for depth-selective imaging of tissue chromophores is presented. Use of frequency-domain signal detection rather than short-pulse time-resolved measurements of pressure transients give an advantage of higher SNR typical to coherent detection techniques. Additionally, we introduce chirped optical excitation to generate linear frequency modulated PTA response which enables unambiguous and precise depth measurements of tissue chromophores. In order to obtain depth profilometric information from the frequency-domain PTA (FD-PTA) measurements, we describe implementation of two signal processing algorithms: matched filter compression and heterodyne mixing with coherent detection. We show that direct relationship between chromophore depth and spectrum of photothermo acoustic signals can be established to enable depth-selective tissue imaging. Application of amplitude and phase FD-PTA imaging is demonstrated in experiments with light-scattering phantoms and chicken breast tissues containing subsurface inclusions. The potential of the FD-PTA method for noninvasive tissue tomography and molecular imaging is discussed.