Studies of synthetic polymers by nonradiative energy transfer

Nonradiative energy transfer between fluorescent labels attached to polymers has been used to characterize polymer miscibility, the interpenetration of chain molecules in solution, micelle formation in graft copolymers, the unfolding of collapsed chain molecules in polymer melts, and the transfer of energy absorbed by a large number of donor labels to a small number of acceptors by an "antenna effect." The change in the emission spectrum after ionomer solutions with different fluorescent counterions were mixed provided rate constants for counterion interchange. The fluorescence behavior of dispersions of donor-labeled polymers stabilized by a graft copolymer with acceptor fluorophores in the solution phase led to inferences about the morphology of the dispersed particles.     

Förster energy transfer in an optical microcavity

By studying the transfer of excitation energy between dye molecules confined within an optical microcavity, we demonstrate experimentally that F?rster energy transfer is influenced by the local photonic mode density. Locating donor and acceptor molecules at well-defined positions allows the transfer rate to be determined as a function of both mutual separation and cavity length. The results show that the F?rster transfer rate depends linearly on the donor emission rate and hence photonic mode density, providing the potential to control energy transfer by modification of the optical environment.     

Angular momentum conservation in dipolar energy transfer

Conservation of angular momentum is a familiar tenet in science but has seldom been invoked to understand (or predict) chemical processes. We have developed a general formalism based on Wigner's original ideas concerning angular momentum conservation to interpret the photo-induced reactivity of two molecular donor-acceptor assemblies with physical properties synthetically tailored to facilitate intramolecular energy transfer. Steady-state and time-resolved spectroscopic data establishing excited-state energy transfer from a rhenium(I)-based charge-transfer state to a chromium(III) acceptor can be fully accounted for by F?rster theory, whereas the corresponding cobalt(III) adduct does not undergo an analogous reaction despite having a larger cross-section for dipolar coupling. Because this pronounced difference in reactivity is easily explained within the context of the angular momentum conservation model, this relatively simple construct may provide a means for systematizing a broad range of chemical reactions.     

Neptune's partial rings: action of galatea on self-gravitating arc particles

Numerical simulations of Neptune's arcs show that self-gravity between macroscopic arc particles can prevent interparticle impacts and thereby stabilize their resonant confinement by Galatea, a satellite of Neptune. Stable subkilometer arc particles provide a source for replenishing the observed dust and explain the clumpy substructure seen in arcs. A few confining kilometer-sized particles between the major arc components can account for the observed arc widths spanning several resonance sites. The modeled distribution of dust is consistent with observations and helps to explain how embedded satellites may affect the structure and evolution of planetary ring systems.     

Supramolecular linear heterojunction composed of graphite-like semiconducting nanotubular segments

One-dimensionally connected organic nanostructures with dissimilar semiconducting properties are expected to provide a reliable platform in understanding the behaviors of photocarriers, which are important for the development of efficient photon-to-electrical energy conversion systems. Although bottom-up supramolecular approaches are considered promising for the realization of such nanoscale heterojunctions, the dynamic nature of molecular assembly is problematic. We report a semiconducting nanoscale organic heterojunction, demonstrated by stepwise nanotubular coassembly of two strategically designed molecular graphenes. The dissimilar nanotubular segments, thus connected noncovalently, were electronically communicable with one another over the heterojunction interface and displayed characteristic excitation energy transfer and charge transport properties not present in a mixture of the corresponding homotropically assembled nanotubes.     

Photon-mediated hybridization of frenkel excitons in organic semiconductor microcavities

Coherent excitations of intricate assemblies of molecules play an important role in natural photosynthesis. Microcavities are wavelength-dimension artificial structures in which excitations can be made to couple through their mutual interactions with confined photon modes. Results for microcavities containing two spatially separated cyanine dyes are presented here, where simultaneous strong coupling of the excitations of the individual dyes to a single cavity mode leads to new eigenmodes, described as admixtures of all three states. These "hybrid" exciton-photon structures are of potential interest as model systems in which to study energy capture, storage, and transfer among coherently coupled molecular excitations.     

Energy transfer across a metal film mediated by surface plasmon polaritons

Coupled surface plasmon polaritons (SPPs) are shown to provide effective transfer of excitation energy from donor molecules to acceptor molecules on opposite sides of metal films up to 120 nanometers thick. This variant of radiative transfer should allow directional control over the flow of excitation energy with the use of suitably designed metallic nanostructures, with SPPs mediating transfer over length scales of 10(-7) to 10(-4) meters. In the emerging field of nanophotonics, such a prospect could allow subwavelength-scale manipulation of light and provide an interface to the outside world.     

Intramolecular long-distance electron transfer in organic molecules

Intramolecular long-distance electron transfer (EI) has been actively studied in recent years in order to test existing theories in a quantitative way and to provide the necessary constants for predicting ET rates from simple structural parameters. Theoretical predictions of an "inverted region," where increasing the driving force of the reaction will decrease its rate, have begun to be experimentally confirmed. A predicted nonlinear dependence of ET rates on the polarity of the solvent has also been confirmed. This work has implications for the design of efficient photochemical charge-separation devices. Other studies have been directed toward determining the distance dependence of ET reactions. Model studies on different series of compounds give similar distance dependences. When different stereochemical structures are compared, it becomes apparent that geometrical factors must be taken into account. Finally, the mechanism of coupling between donor and acceptor in weakly interacting systems has become of major importance. The theoretical and experimental evidence favors a model in which coupling is provided by the interaction with the orbitals of the intervening molecular fragments, although more experimental evidence is needed.     

Dark structures in molecular radiationless transitions determined by ultrafast diffraction

The intermediate structures formed through radiationless transitions are termed "dark" because their existence is inferred indirectly from radiative transitions. We used ultrafast electron diffraction to directly determine these transient structures on both ground-state and excited-state potential energy surfaces of several aromatic molecules. The resolution in space and time (0.01 angstrom and 1 picosecond) enables differentiation between competing nonradiative pathways of bond breaking, vibronic coupling, and spin transition. For the systems reported here, the results reveal unexpected dynamical behavior. The observed ring opening of the structure depends on molecular substituents. This, together with the parallel bifurcation into physical and chemical channels, redefines structural dynamics of the energy landscape in radiationless processes.     

耦合Brusselator振子的动力学行为研究

初步研究了由2个完全相同的 Brusselator 振子经过耦合组成的系统的动力学特征。研究结果表明,在较弱的耦合强度下,系统的动力学性质发生了根本性的变化,由混沌状态转变为周期性运动。不同于其他无延时耦合的系统,随着耦合强度的增强,系统又从周期运动转变为混沌运动。     

耦合Brusselator振子的动力学行为研究

初步研究了由2个完全相同的Brusselator振子经过耦合组成的系统的动力学特征。研究结果表明,在较弱的耦合强度下,系统的动力学性质发生了根本性的变化,由混沌状态转变为周期性运动。不同于其他无延时耦合的系统,随着耦合强度的增强,系统又从周期运动转变为混沌运动。     

Imaging protein kinase Calpha activation in cells

Spatially resolved fluorescence resonance energy transfer (FRET) measured by fluorescence lifetime imaging microscopy (FLIM), provides a method for tracing the catalytic activity of fluorescently tagged proteins inside live cell cultures and enables determination of the functional state of proteins in fixed cells and tissues. Here, a dynamic marker of protein kinase Calpha (PKCalpha) activation is identified and exploited. Activation of PKCalpha is detected through the binding of fluorescently tagged phosphorylation site-specific antibodies; the consequent FRET is measured through the donor fluorophore on PKCalpha by FLIM. This approach enabled the imaging of PKCalpha activation in live and fixed cultured cells and was also applied to pathological samples.     

Accelerated electron transfer between metal complexes mediated by DNA

DNA-mediated long-range electron transfer from photoexcited 1,10-phenanthroline complexes of ruthenium, Ru(phen)2(3)+, to isostructural complexes of cobalt(III), rhodium(III), and chromium(III) bound along the helical strand. The efficiency of transfer depended upon binding mode and driving force. For a given donor-acceptor pair, surface-bound complexes showed greater rate enhancements than those that were intercalatively bound. Even in rigid glycerol at 253 K, the rates for donor-acceptor pairs bound to DNA remained enhanced. For the series of acceptors, the greatest enhancement in electron-transfer rate was found with chromium, the acceptor of intermediate driving force. The DNA polymer appears to provide an efficient intervening medium to couple donor and acceptor metal complexes for electron transfer.     

量子点中双极化子和磁双极化子的研究进展

综述了近年来对抛物线性限制势量子点中强耦合双极化子和磁双极化子的部分研究工作.从抛物量子点中2个电子-声子体系的哈密顿量出发,采用Lee-Low-Pines-Huybrechts变分方法,研究了量子点中强耦合双极化子的振动频率、诱生势和有效势随电子-声子耦合强度、两电子相对距离和量子点半径的变化规律;采用Tokuda改进的线性组合算符法研究了温度和LO声子效应对强耦合双极化子的有效质量和平均声子数的影响.基于Lee-Low-Pines幺正变换,采用Pekar类型变分法研究了抛物量子点中强耦合磁双极化子的内部激发态性质,当考虑自旋和外磁场影响时,研究了二维量子点中强耦合磁双极化子基态的能量、声子平均数以及第一激发态的能量、声子平均数随量子点受限强度、介电常数比、电子-声子耦合强度和磁场的回旋共振频率的变化规律.     

Two-dimensional x-ray waveguides and point sources

We show that resonant coupling of synchrotron beams into suitable nanostructures can be used for the generation of coherent x-ray point sources. A two-dimensionally confining x-ray waveguide structure has been fabricated by e-beam lithography. By shining a parallel undulator beam onto the structure, a discrete set of resonant modes can be excited in the dielectric cavity, depending on the two orthogonal coupling angles between the beam and the waveguide interfaces. The resonant excitation of the modes is evidenced from the characteristic set of coupling angles as well as the observed far-field pattern. The x-ray nanostructure may be used as coherent x-ray point sources with a beam cross section in the nanometer range.     

Electron tunneling through organic molecules in frozen glasses

Reaction rates extracted from measurements of donor luminescence quenching by randomly dispersed electron acceptors reveal an exponential decay constant of 1.23 per angstrom for electron tunneling through a frozen toluene glass (with a barrier to tunneling of 1.4 electron volts). The decay constant is 1.62 per angstrom (the barrier, 2.6 electron volts) in a frozen 2-methyl-tetrahydrofuran glass. Comparison to decay constants for tunneling across covalently linked xylyl (0.76 per angstrom) and alkyl (1.0 per angstrom) bridges leads to the conclusion that tunneling between solvent molecules separated by approximately 2 angstroms (van der Waals contact) is 20 to 50 times slower than tunneling through a comparable length of a covalently bonded bridge. Our results provide experimental confirmation that covalently bonded pathways can facilitate electron flow through folded polypeptide structures.     

Electron transfer: classical approaches and new frontiers

Electron transfer, under conditions of weak interaction and a medium acting as a passive thermal bath, is very well understood. When electron transfer is accompanied by transient chemical bonding, such as in interfacial coordination electrochemical mechanisms, strong interaction and molecular selectivity are involved. These mechanisms, which take advantage of "passive self-organization," cannot yet be properly described theoretically, but they show substantial experimental promise for energy conversion and catalysis. The biggest challenge for the future, however, may be dynamic, self-organized electron transfer. As with other energy fluxes, a suitable positive feedback mechanism, through an active molecular environment, can lead to a (transient) decrease of entropy equivalent to an increase of molecular electronic order for the activated complex. A resulting substantial increase in the rate of electron transfer and the possibility of cooperative transfer of several electrons (without intermediates) can be deduced from phenomenological theory. The need to extend our present knowledge may be derived from the observation that chemical syntheses and fuel utilization in industry typically require high temperatures (where catalysis is less relevant), whereas corresponding processes in biological systems are catalyzed at environmental conditions. This article therefore focuses on interfacial or membrane-bound electron transfer and investigates an aspect that nature has developed to a high degree of perfection: self-organization.     

低维周期量子点中极化子压缩效应

研究了低维周期对称量子点中极化子的压缩效应。通过引入单模压缩态,改进了Lee-Low-Pines和Huybrechts(LLP-H)方法,并计算了压缩态下极化子的能量。该计算方法不仅适用于所有的耦合常数范围,而且还可以考虑LLP-H方法中忽略了的哈密顿量中声子算符的线形项以及双线形项。将该计算方法所得到的低维周期对称量子点中极化子基态下极化子结合能和势能与LLP-H方法的计算结果相比较,计算结果更加精确。     

关于多场耦合问题的几个概念探讨

从湍流脉动的高阶关联项以及湍流的雷诺方程出发，指出了动量场、能量场、质量场等相互耦合现象可以湍流脉动关联项和时均项中同时存在，并提高了脉动合和时间均耦合的概念，指出了在引入湍流模型即对雷诺时均方程使用湍流统计矩方程进行了封闭后，动量，能量及质量之间的耦合现象可由时均耦合来描述。介绍了多相耦合的概念及求解耦合问题的基本思路和方法。     

耕地格局时空动态变化过程和差异分析——以浙江安吉为例

【目的】耕地是“人类-环境”关系的纽带和桥梁,也是农业土地系统最为重要的组成部分,掌握耕地格局时空动态变化过程和差异,有利于促进耕地合理利用的调整优化,实现耕地资源的可持续性和集约化利用。【方法】基于遥感和地理信息技术,综合采用土地利用动态度模型、土地利用扩展程度综合指数、土地利用转移矩阵等地理计量模型,研究分析1998-2009年浙江安吉耕地格局动态变化的过程与差异。【结果】该区域耕地动态变化过程复杂,水田与旱地是该区域发生转出的主要地类,从转移类型来看,多转移为林地、城镇用地与园地;从转移过程来看,2003-2009年较1998-2003年更加缓和平稳,基本没有发生较为剧烈的变动;2003-2009年,转入为耕地的地类极为单一,转移面积有限,各地类在数量和空间分布上较1998-2003年期间都趋于更加稳定;2003-2009年的耕地变化活跃度要低于1998-2003年,表明2003年以后区域耕地在利用程度与广度方面更加缓和平稳。【结论】区域产业结构和用地政策调整直接影响着耕地格局动态变化的过程和特点,本研究提出的分析方法能快速、客观反映区域耕地的动态变化过程和差异特征,为耕地时空演变研究提供了一种新思路。