Visualizing single-molecule diffusion in mesoporous materials

Periodic mesoporous materials formed through the cooperative self-assembly of surfactants and framework building blocks can assume a variety of structures, and their widely tuneable properties make them attractive hosts for numerous applications. Because the molecular movement in the pore system is the most important and defining characteristic of porous materials, it is of interest to learn about this behaviour as a function of local structure. Generally, individual fluorescent dye molecules can be used as molecular beacons with which to explore the structure of--and the dynamics within--these porous hosts, and single-molecule fluorescence techniques provide detailed insights into the dynamics of various processes, ranging from biology to heterogeneous catalysis. However, optical microscopy methods cannot directly image the mesoporous structure of the host system accommodating the diffusing molecules, whereas transmission electron microscopy provides detailed images of the porous structure, but no dynamic information. It has therefore not been possible to 'see' how molecules diffuse in a real nanoscale pore structure. Here we present a combination of electron microscopic mapping and optical single-molecule tracking experiments to reveal how a single luminescent dye molecule travels through linear or strongly curved sections of a mesoporous channel system. In our approach we directly correlate porous structures detected by transmission electron microscopy with the diffusion dynamics of single molecules detected by optical microscopy. This opens up new ways of understanding the interactions of host and guest.     

Kondo resonance in a single-molecule transistor

When an individual molecule, nanocrystal, nanotube or lithographically defined quantum dot is attached to metallic electrodes via tunnel barriers, electron transport is dominated by single-electron charging and energy-level quantization. As the coupling to the electrodes increases, higher-order tunnelling and correlated electron motion give rise to new phenomena, including the Kondo resonance. To date, all of the studies of Kondo phenomena in quantum dots have been performed on systems where precise control over the spin degrees of freedom is difficult. Molecules incorporating transition-metal atoms provide powerful new systems in this regard, because the spin and orbital degrees of freedom can be controlled through well-defined chemistry. Here we report the observation of the Kondo effect in single-molecule transistors, where an individual divanadium molecule serves as a spin impurity. We find that the Kondo resonance can be tuned reversibly using the gate voltage to alter the charge and spin state of the molecule. The resonance persists at temperatures up to 30 K and when the energy separation between the molecular state and the Fermi level of the metal exceeds 100 meV.     

Quantum phase transition in a single-molecule quantum dot

Quantum criticality is the intriguing possibility offered by the laws of quantum mechanics when the wave function of a many-particle physical system is forced to evolve continuously between two distinct, competing ground states. This phenomenon, often related to a zero-temperature magnetic phase transition, is believed to govern many of the fascinating properties of strongly correlated systems such as heavy-fermion compounds or high-temperature superconductors. In contrast to bulk materials with very complex electronic structures, artificial nanoscale devices could offer a new and simpler means of understanding quantum phase transitions. Here we demonstrate this possibility in a single-molecule quantum dot, where a gate voltage induces a crossing of two different types of electron spin state (singlet and triplet) at zero magnetic field. The quantum dot is operated in the Kondo regime, where the electron spin on the quantum dot is partially screened by metallic electrodes. This strong electronic coupling between the quantum dot and the metallic contacts provides the strong electron correlations necessary to observe quantum critical behaviour. The quantum magnetic phase transition between two different Kondo regimes is achieved by tuning gate voltages and is fundamentally different from previously observed Kondo transitions in semiconductor and nanotube quantum dots. Our work may offer new directions in terms of control and tunability for molecular spintronics.     

Probing cellular protein complexes using single-molecule pull-down

Proteins perform most cellular functions in macromolecular complexes. The same protein often participates in different complexes to exhibit diverse functionality. Current ensemble approaches of identifying cellular protein interactions cannot reveal physiological permutations of these interactions. Here we describe a single-molecule pull-down (SiMPull) assay that combines the principles of a conventional pull-down assay with single-molecule fluorescence microscopy and enables direct visualization of individual cellular protein complexes. SiMPull can reveal how many proteins and of which kinds are present in the in vivo complex, as we show using protein kinase A. We then demonstrate a wide applicability to various signalling proteins found in the cytosol, membrane and cellular organelles, and to endogenous protein complexes from animal tissue extracts. The pulled-down proteins are functional and are used, without further processing, for single-molecule biochemical studies. SiMPull should provide a rapid, sensitive and robust platform for analysing protein assemblies in biological pathways.     

Optical microscopy using a single-molecule light source

Rapid progress in science on nanoscopic scales has promoted increasing interest in techniques of ultrahigh-resolution optical microscopy. The diffraction limit can be surpassed by illuminating an object in the near field through a sub-wavelength aperture at the end of a sharp metallic probe. Proposed modifications of this technique involve replacing the physical aperture by a nanoscopic active light source. Advances in the spatial and spectral detection of individual fluorescent molecules, using near-field and far-field methods, suggest the possibility of using a single molecule as the illumination source. Here we present optical images taken with a single molecule as a point-like source of illumination, by combining fluorescence excitation spectroscopy with shear-force microscopy. Our single-molecule probe has potential for achieving molecular resolution in optical microscopy; it should also facilitate controlled studies of nanometre-scale phenomena (such as resonant energy transfer) with improved lateral and axial spatial resolution.     

空间连接的选择性估计

空间连接是空间数据库中非常重要和耗时的操作，而空间连接的选择性估计对于查询优化器能否选择一个较好的执行计划至关重要。本文介绍了3种空间连接的选择性估计方法，并对其进行了比较分析。     

Exchange-biased quantum tunnelling in a supramolecular dimer of single-molecule magnets

Various present and future specialized applications of magnets require monodisperse, small magnetic particles, and the discovery of molecules that can function as nanoscale magnets was an important development in this regard. These molecules act as single-domain magnetic particles that, below their blocking temperature, exhibit magnetization hysteresis, a classical property of macroscopic magnets. Such 'single-molecule magnets' (SMMs) straddle the interface between classical and quantum mechanical behaviour because they also display quantum tunnelling of magnetization and quantum phase interference. Quantum tunnelling of magnetization can be advantageous for some potential applications of SMMs, for example, in providing the quantum superposition of states required for quantum computing. However, it is a disadvantage in other applications, such as information storage, where it would lead to information loss. Thus it is important to both understand and control the quantum properties of SMMs. Here we report a supramolecular SMM dimer in which antiferromagnetic coupling between the two components results in quantum behaviour different from that of the individual SMMs. Our experimental observations and theoretical analysis suggest a means of tuning the quantum tunnelling of magnetization in SMMs. This system may also prove useful for studying quantum tunnelling of relevance to mesoscopic antiferromagnets.     

绿色化学与化学教育

介绍了绿色化学的产生、发展、目标和研究内容 论述了进行绿色化学教育的重要性和必要性     

美国汉学研究的选择性

"汉学"起源于欧洲,旨在对中国文化进行研究。二战以后,"汉学"研究重心逐渐转移到美国,且汉学研究的兴趣也逐渐偏离早期汉学家的初衷。"汉学"被"中国学"取代,政治、经济、军事等研究成为主流。     

高职化学教学中的绿色化学教育

绿色化学是近年来化学科学领域提出的新概念,旨在设计和研究没有或有尽可能小的环境负作用,并且在技术上和经济上可行的化学品和化学过程,从而在源头上预防化学污染．高职化学教学中渗透绿色化学教育贲无旁贷,具体做法是：培养绿色化学意识;设计和进行绿色化学实验等．     

Progress of AFM single-cell and single-molecule morphology imaging

Atomic force microscopy (AFM) can probe single living cells and single native membrane proteins in natural fluid environments with label-free high spatial resolution. It has thus become an important tool for cellular and molecular biology that significantly complements traditional biochemical and biophysical techniques such as optical and electron microscopy and X-ray crystallog-raphy. Imaging surface topography is the primary application of AFM in the life sciences. Since the early 1990s, researchers have used AFM to investigate morphological features of living cells and native membrane proteins with impressive results. Steady improvements in AFM techniques for imaging soft biological samples have greatly expanded its applications. Based on the authors’ own research in AFM imaging of living cell morphologies, a review of sample preparation procedures for single-cell and single-molecule imaging experiments is presented, along with a summary of recent progress in AFM imaging of living cells and native membrane proteins. Finally, the challenges of AFM high-resolution imaging at the single-cell and single-molecule levels are discussed.     

Ten years of tension: single-molecule DNA mechanics

The basic features of DNA were elucidated during the half-century following the discovery of the double helix. But it is only during the past decade that researchers have been able to manipulate single molecules of DNA to make direct measurements of its mechanical properties. These studies have illuminated the nature of interactions between DNA and proteins, the constraints within which the cellular machinery operates, and the forces created by DNA-dependent motors.     

乙酰乙酸酯类化合物肟化顺反异构选择性

对乙酰乙酸甲酯(MAA)、乙酰乙酸乙酯(EAA)、乙酰乙酸叔丁酯(TBAA)进行肟化,研究肟化剂、溶剂效应及温度对产物顺反异构的影响。采用硫酸和亚硝酸钠为肟化剂,乙酸乙酯和水为溶剂,MAA、EAA在(15~20)℃反应最佳;采用甲基异丁基酮和水为溶剂,TBAA在(20~25)℃反应最佳。经高效液相色谱检测,MAA、EAA、TBAA的最佳顺反异构(ZE型)转化率分别为94.5%3.9%;95.1%3.4%;92.1%5.6%。     

Dependence of single-molecule junction conductance on molecular conformation

Since it was first suggested that a single molecule might function as an active electronic component, a number of techniques have been developed to measure the charge transport properties of single molecules. Although scanning tunnelling microscopy observations under high vacuum conditions can allow stable measurements of electron transport, most measurements of a single molecule bonded in a metal-molecule-metal junction exhibit relatively large variations in conductance. As a result, even simple predictions about how molecules behave in such junctions have still not been rigorously tested. For instance, it is well known that the tunnelling current passing through a molecule depends on its conformation; but although some experiments have verified this effect, a comprehensive mapping of how junction conductance changes with molecular conformation is not yet available. In the simple case of a biphenyl--a molecule with two phenyl rings linked by a single C-C bond--conductance is expected to change with the relative twist angle between the two rings, with the planar conformation having the highest conductance. Here we use amine link groups to form single-molecule junctions with more reproducible current-voltage characteristics. This allows us to extract average conductance values from thousands of individual measurements on a series of seven biphenyl molecules with different ring substitutions that alter the twist angle of the molecules. We find that the conductance for the series decreases with increasing twist angle, consistent with a cosine-squared relation predicted for transport through pi-conjugated biphenyl systems.     

Discovery of single-molecule electret properties in the endohedral fullerene Gd@C82

The recent history of nanocarbon materials has been dominated by the spectacular rise of graphene and its myriad applications [1].in this phase of rapid develop...     

Modulating the magnetic relaxation of lanthanide-based single-molecule magnets

In the area of molecular magnetism,single molecule magnets (SMMs) containing lanthanide elements are of immense scientific and technological interest because of their large energy barriers and high measured hysteresis temperature.Although there has been significant progress in the synthesis and characterization of lanthanide-based SMMs,there are still challenges,for instance,how single-ion anisotropy of lanthanide elements can be exploited,and how zero-field tunneling of magnetization can be suppressed.This article is devoted to the progress in various methodologies for modulating magnetic relaxation,especially in terms of crystal field and magnetic interactions.The crystal field plays a dominant role in creating single-molecule magnets with largely anisotropic f-elements,while the strong coupling between magnetic centers is able to suppress quantum tunneling of magnetization efficiently.     

The v-v energy transfer of highly vibrationally excited states (II)

The vibrational energy transfer from highly vibrationally excited CO to H₂O molecules is studied by time-resolved Fourier transform infrared emission spectroscopy (TR FTIR). Following the 193 nm laser photolysis of CHBr₃ and O₂ the secondary reactions generate CO(v). The infrared emission of CO(v → v−1) is detected by TR FTIR. The excitation of H₂O molecules is not observed. By the method of the spectral simulation and the differential technique, 8 rate constants for CO(v)/H₂O system are obtained: (1.7 ±0.1), (3.4 ±0.2), (6.2 ±0.4), (8.0 ±1.0), (9.0 ±2.0), (12 ±3), (16 ±4) and (18 ±7) (10¹³cm³ · molecule^-1· s^-1). At least two reasons lead to the efficient energy transfer. One is the contributions of the rotational energy to the vibational energy defect and the other is the result of the complex collision. With the SSH andab initio calculations, the quenching mechanism of CO(v) by H₂O is suggested.