介电泳技术制备具有分子荧光增强效应的电极间纳米间隙结构

将单个核壳结构纳米颗粒放置在金属纳米电极之间制备了纳米尺度间隙结构.利用介电泳技术,本文可控地将蛋白质层包裹的SiO₂@Au核壳结构纳米颗粒定位放置在被荧光分子覆盖的纳米电极之间,从而得到了夹在纳米颗粒和金属纳米电极之间的纳米间隙结构.初步的光致发光测量表明,制备的纳米间隙结构可以有效地增强间隙中分子的荧光信号.这一结果为后续实现基于纳米间隙电极的电致分子荧光奠定了基础.     

单分子尺度的光量子态调控与单分子电致发光研究

分子尺度上的光电相互作用研究可以为发展未来信息和能源技术提供科学基础.扫描隧道显微镜不仅可以用来观察和操纵纳米世界中的原子和分子,而且其高度局域化的隧穿电流还可以被用来激发隧道结中的分子,使之发光,以研究局域场下的分子光电特性.本文综述了中国科学技术大学单分子光电研究组近期在锌酞菁分子电致发光方面取得的科学进展,包括：1）利用有效的电子脱耦合与纳腔等离激元调控技术,实现了隧穿电子激发下的单个锌酞菁分子的电致荧光,并通过发展相关的光子发射统计测量方法,表征了单个分子在隧穿电子激发下的电致荧光具有单光子发射特性;2）发展了具有亚纳米空间分辨的荧光光谱成像技术,实现了对酞菁分子间相干偶极相互作用特征的实空间观察;3）对分子与纳腔等离激元之间的相干耦合作用进行了亚纳米精度的操控,在单分子水平上观察到了法诺共振和兰姆位移效应.这些研究结果不仅为研发基于有机分子的电泵纳米光源与单光子光源等分子光电器件提供了新的思路,而且为在单分子尺度上研究分子光电特性、分子间能量转移以及场与物质之间的相互作用规律等提供了新的表征方法.     

F?rster双分子猝灭作用对卟啉侧链聚合物荧光衰变的影响

通过采用时间分辨荧光光谱技术测量了一种卟啉侧链聚合物薄膜：卟啉丙烯酸酯—苯乙烯共聚物poly［porphyrin acrylate-styrene］ (P［(por)A-S］)在高激发密度下的瞬态荧光特性.实验发现,P［(por)A-S］样品的荧光衰减随聚合物分子浓度的增大而加快.利用Frster机制的双分子猝灭理论对其浓度猝灭的原因进行了分析,理论结果与实验结果符合较好.研究表明,在高激发密度的情况下,Frster机制的双分子作用是加快卟啉侧链聚合物初始荧光衰减和降低其发光效率的主要因素. 关键词： 双分子猝灭 Frster机制 瞬态荧光 卟啉侧链聚合物     

F(o)rster双分子猝灭作用对卟啉侧链聚合物荧光衰变的影响

通过采用时间分辨荧光光谱技术测量了一种卟啉侧链聚合物薄膜:卟啉丙烯酸酯-苯乙烯共聚物poly[porphyrin acrylate-styrene] (P[(por)A-S])在高激发密度下的瞬态荧光特性.实验发现,P[(por)A-S]样品的荧光衰减随聚合物分子浓度的增大而加快.利用Frster机制的双分子猝灭理论对其浓度猝灭的原因进行了分析,理论结果与实验结果符合较好.研究表明,在高激发密度的情况下,Frster机制的双分子作用是加快卟啉侧链聚合物初始荧光衰减和降低其发光效率的主要因素.     

激子旋转弛豫对低掺杂卟啉侧链聚合物荧光衰变过程的影响

利用激子旋转扩散理论研究了一类低掺杂卟啉侧链聚合物中卟啉侧链基团的旋转对其发光动力学过程的影响.研究表明,卟啉侧链基团的旋转行为是导致激发态无辐射能量弛豫的重要途径.基团旋转越容易,能量弛豫速度越快,这可导致一个快速的荧光衰变动力学过程.在卟啉低掺杂浓度和聚合物分子链间距离较大的情况下,卟啉侧链基团的旋转成为影响荧光寿命和发光效率的主要因素.对实验测得的两种样品的荧光弛豫过程进行了拟合,理论结果与实验结果符合较好. 关键词： 激子旋转弛豫 瞬态荧光 卟啉侧链聚合物     

荧光法研究四(对甲氧基苯基)钴卟啉与牛血清白蛋白的相互作用

合成了四(对甲氧基苯基)钴卟啉,利用荧光光谱法研究了四(对甲氧基苯基)钴卟啉与牛血清白蛋白的相互作用,由实验数据计算求得该卟啉与牛血清白蛋白的双分子猝灭过程速率常数Kq=9.619×1012L·mol-1.s-1、结合常数KA=3.475×103L·mol-1、结合数n=0.6893,结果表明:四(对甲氧基苯基)钴卟啉与牛血清白蛋白之间发生了较强的静态荧光猝灭作用。     

尾式金属卟啉配合物的研究Ⅸ.苯丙氨酸基尾式卟啉及其锌配合物的合成和荧光性质

本文合成了L-苯丙氨酸基尾式卟啉及其锌配合物,研究了它们的荧光性质,观察到苯丙氨酸与卟啉环之间存在激发态分子内能量转移过程,讨论了影响卟啉特征荧光峰位置的配位化学因素.     

7 K下Ag(100)表面单个卟啉分子的位置依赖针尖增强拉曼光谱研究

本文在低温条件(∽7 K})下对吸附在Ag(100)表面上的单个空心卟啉分子进行了针尖增强拉曼光谱(TERS)研究. TERS光谱的位置依赖特性表明,单个分子内部不同化学组分的局域振动信息是可以区分的;而且进一步的TERS空间成像也表明不同的拉曼谱峰可以具有不同的空间分布特征,它们与相应的振动模式密切相关,甚至能够在亚纳米层次上识别与卟啉芯N-H键有关的振动模式. 这项研究将为深入理解单分子吸附构型的对称性以及单个分子内部的局域振动信息提供有效的手段.     

7K下Ag(100)表面单个卟啉分子的位置依赖针尖增强拉曼光谱研究（英文）

本文在低温条件(～7K)下对吸附在Ag(100)表面上的单个空心卟啉分子·进行了针尖增强拉曼光谱(TERS)研究.TERS光谱的位置依赖特性表明,单个分子内部不同化学组分的局域振动信息是可以区分的;而且进一步的TERS空间成像也表明不同的拉曼谱峰叫以具有不同的空间分布特征,它们与相应的振动模式密切相关,甚至能够在亚纳米层次上识别与卟啉芯N-H键有关的振动模式.这项研究将为深入理解单分子吸附构型的对称性以及单个分子内部的局域振动信息提供有效的手段.     

四磺酸基苯基卟啉荧光增强苯的高阶受激拉曼散射

报道了在液芯光纤内利用四磺酸基苯基卟啉荧光增强苯的高阶受激拉曼散射实验研究. 实验表明:利用荧光效应显著增强苯的高阶受激拉曼谱线的强度;高阶Stokes谱线的阈值明显降低;随着Stokes谱线阶数的增加,Stokes谱线宽度变窄. 用3.55 mJ小能量激光实现了液芯光纤内生物分子荧光增强受激拉曼散射. 此技术对实现宽带受激辐射、种子激光、生物大分子结构研究和生物分子的非生物利用等领域有广阔的应用前景. 关键词： 受激拉曼散射 荧光 液芯光纤     

Length dependence of rectification in organic co-oligomer spin rectifiers

The rectification ratio of organic magnetic co-oligomer diodes is investigated theoretically by changing the molecular length. The results reveal two distinct length dependences of the rectification ratio: for a short molecular diode, the chargecurrent rectification changes little with the increase of molecular length, while the spin-current rectification is weakened sharply by the length; for a long molecular diode, both the charge-current and spin-current rectification ratios increase quickly with the length. The two kinds of dependence switch at a specific length accompanied with an inversion of the rectifying direction. The molecular ortibals and spin-resolved transmission analysis indicate that the dominant mechanism of rectification suffers a change at this specific length, that is, from asymmetric shift of molecular eigenlevels to asymmetric spatial localization of wave functions upon the reversal of bias. This work demonstrates a feasible way to control the rectification in organic co-oligomer spin diodes by adjusting the molecular length.     

EELS characterization of radiolytic products in frozen samples

Electron energy loss spectroscopy (EELS) was used to obtain information about the radiation chemistry of frozen aqueous specimens in the electron microscope by observing the hydrogen and oxygen K-edges. Measurements on frozen solutions of 30% hydrogen peroxide revealed the presence of molecular oxygen identified by a distinct 531-eV peak at the O K-edge even for electron doses below 100 e/nm2. The molecular oxygen content of irradiated H?O? solution was determined by least squares fitting of O K-edge reference spectra from water and gas-phase oxygen. It was found that the fraction of molecular oxygen to water oxygen was in the range 0.03-0.05. EELS from pure frozen water showed no features attributable to molecular oxygen or molecular hydrogen (K edge at ~13 eV) even at high electron doses above 10? e/nm2. Spectra from frozen sucrose and protein solutions and their mixtures, however, did show evolution of a molecular hydrogen peak at ~13 eV for doses above 10? e/nm2, consistent with previous measurements and indicative of hydrogen bubble formation. Molecular oxygen was not observed in any of the frozen solutions of organic compounds indicating that oxygen is not a major product of free radical decay, in contrast to molecular hydrogen formation.     

基于三磷酸腺苷调节的分子马达单向能量跃迁模型

分子马达的梯跳运动和在过阻尼溶液中动力学原理尚未揭示清楚, 从分子马达输运特点和实验现象出发, 构建满足朗之万方程的单向能量跃迁模型, 并通过Monte Carlo方法分析了分子马达的随机动力学行为. 结果表明, 在合适的跃迁能量作用下, 分子马达可以利用噪声进行稳定的梯跳运动和有效的输运, 但负载力会减弱分子马达系统的输运能力; 轨道周期势虽影响分子马达速度的大小但不会改变其运动方向, 分子马达运动方向由跃迁能量决定; 另外, 虽然在不同的噪声强度时平均速度不为零, 但是分子马达系统的高效输运对噪声有一定选择性. 关键词： 分子马达 能量跃迁 朗之万方程 噪声强度     

Manipulation of the Kondo effect via two-dimensional molecular assembly

We report the manipulation of a Kondo resonance originating from the spin-electron interactions between a two-dimensional molecular assembly of TBrPP-Co molecules and a Cu(111) surface at 4.6 K. By manipulating nearest-neighbor molecules with a scanning tunneling microscope tip we are able to tune the spin-electron coupling of the center molecule inside a hexagonal molecular assembly in a controlled step-by-step manner. The Kondo temperature increases from 105 to 170 K with decreasing the number of nearest neighbor molecules from six to zero. The scattering of surface electrons by the molecules located at edges of the molecular layer reduces the spin-electron coupling strength for the molecules inside the layer. Investigations of different molecular arrangements indicate that the observed Kondo resonance is independent on the molecular lattice.     

Conductivity of carbon-based molecular junctions from ab-initio methods

Carbon nanomaterials (CNMs) are prompting candidates for next generational electronics. In this review we provide a mini overview of recent results on the conductivity of carbon-based molecular junctions obtained from ab-initio methods. CNMs used as nanoelectrodes and molecular materials in molecular junctions are discussed. The functionalities that include the nanomechanically controlled molecular conductance switches, negative differential resistance devices, and electronic rectifiers realized by using CNMs have been demonstrated.     

First-principles study of the switching mechanism of [2]catenane molecular electronic devices

We present a first-principles study of the coherent charge transport properties of bistable [2]catenane molecular monolayers sandwiched between Au(111) electrodes. We find that conduction channels around the Fermi level are dominated by the two highest occupied molecular orbital levels from tetrathiafulvalene (TTF) and dioxynaphthalene (DNP) and the two lowest unoccupied molecular orbital levels from tetracationic cyclophane (CBPQT4+), and the OFF to ON switching results from the energetic shifts of these orbitals as CBPQT4+ moves from TTF to DNP. We show that the superposition principle can be adopted for predicting the function of the composite device.     

Modeling hydrogen exchange of proteins by a multiscale method

We proposed a practical way for mapping the results of coarse-grained molecular simulations to the observables in hydrogen change experiments. By combining an atomic-interaction based coarse-grained model with an all-atom structure reconstruction algorithm, we reproduced the experimental hydrogen exchange data with reasonable accuracy using molecular dynamics simulations. We also showed that the coarse-grained model can be further improved by imposing experimental restraints from hydrogen exchange data via an iterative optimization strategy. These results suggest that it is feasible to develop an integrative molecular simulation scheme by incorporating the hydrogen exchange data into the coarse-grained molecular dynamics simulations and therefore help to overcome the accuracy bottleneck of coarse-grained models.     

Angle-resolved photoemission of chain-like molecules: the electronic band structure of sexithiophene and sexiphenyl

Here we report the electronic π-band structure of sexithiophene obtained from 6T(010) oriented films. The angle-resolved valence band photoemission results taken parallel and perpendicular to the molecular axis are compared to those of sexiphenyl and interpreted in terms of intra- and inter-molecular band dispersion. We show that the strong photoemission intensity variations with emission angle parallel to the molecular axis are well reproduced by the Fourier transforms of the molecular orbitals of the isolated molecules. These results imply that ARUPS can yield quite detailed information about molecular geometry, both in terms of molecular orientation and internal structure.     

一种实现冷分子囚禁的可控制静电双阱方案

提出了采用双环形载荷导线和两透明电极系统实现冷分子静电囚禁的可控制静电双阱的新方案,计算了带电圆导线和带电板所产生的静电场分布,从几个方面分析了这个囚禁方案的优点. 提出了一种有效的冷分子装载方法,并研究了双阱到单阱的演化过程. 研究表明,该可控制静电双阱方案不仅方便装载与操控弱场搜寻态的极性冷分子,而且在分子物质波的干涉、纠缠、冷碰撞,甚至进行双阱分子BEC研究等分子光学领域中有着广阔的应用前景. 关键词： 极性冷分子 静电囚禁 可控制静电双阱 分子光学     

Tunneling Dynamics Between Atomic and Molecular Bose-Einstein Condensates

Tunneling dynamics of multi-atomic molecules between atomic and multi-atomic molecular Bose-Einstein condensates with Feshbach resonance is investigated.It is indicated that the tunneling in the two Bose-Einstein condensates depends on not only the inter-atomic-molecular nonlinear interactions and the initial number of atoms in these condensates,but also the tunneling coupling between the atomic condensate and the multi-atomic molecular condensate.It is discovered that besides oscillating tunneling current between the atomic condensate and the multi-atomic molecular condensate,the nonlinear multi-atomic molecular tunneling dynamics sustains a self-locked population imbalance:a macroscopic quantum self-trapping effect.The influence of de-coherence caused by non-condensate atoms on the tunneling dynamics is studied.It is shown that de-coherence suppresses the multi-atomic molecular tunneling.Moreover,the conception of the molecular Bose-Einstein condensate,which is different from the conventional single-atomic Bose-Einstein condensate,is specially emphasized in this paper.