Nuclear coupling and polarization in molecular transport junctions: beyond tunneling to function

Much current experimental research on transport in molecular junctions focuses on finite voltages, where substantial polarization-induced nonlinearities may result in technologically relevant device-type responses. Because molecules have strong polarization responses to changing charge state or external field, molecules isolated between electrodes can show strongly nonlinear current-voltage responses. For small applied voltages (up to approximately 0.3 volt), weak interaction between transporting electrons and molecular vibrations provides the basis for inelastic electron tunneling spectroscopy. At higher voltages and for certain time scale regimes, strong coupling effects occur, including Coulomb blockade, negative differential resistance, dynamical switching and switching noise, current hysteresis, heating, and chemical reactions. We discuss a general picture for such phenomena that arise from charging, strong correlation, and polarization (electronic and vibrational) effects in the molecule and at the interface.     

Thermoelectricity in molecular junctions

By trapping molecules between two gold electrodes with a temperature difference across them, the junction Seebeck coefficients of 1,4-benzenedithiol (BDT), 4,4'-dibenzenedithiol, and 4,4'-tribenzenedithiol in contact with gold were measured at room temperature to be +8.7 +/- 2.1 microvolts per kelvin (muV/K), +12.9 +/- 2.2 muV/K, and +14.2 +/- 3.2 muV/K, respectively (where the error is the full width half maximum of the statistical distributions). The positive sign unambiguously indicates p-type (hole) conduction in these heterojunctions, whereas the Au Fermi level position for Au-BDT-Au junctions was identified to be 1.2 eV above the highest occupied molecular orbital level of BDT. The ability to study thermoelectricity in molecular junctions provides the opportunity to address these fundamental unanswered questions about their electronic structure and to begin exploring molecular thermoelectric energy conversion.     

Selective disruption of gap junctional communication interferes with a patterning process in hydra

The cells that make up the body column of hydra are extensively joined by gap junctions, capable of mediating the rapid exchange of small hydrophilic molecules between the cytoplasms of neighboring cells. Both the rate of transfer of small molecules through the gap junctions and the rate of return of gap junction coupling after grafting experiments are sufficiently rapid to mediate events in the patterning of hydra tissue. Antibodies to the major rat liver gap junction protein (27,000 daltons) recognize a gap junction antigen in hydra and are effective in eliminating junctional communication between hydra cells. The antibodies perturb the head inhibition gradient in grafting operations, suggesting that cell-cell communication via gap junctions is important in this defined tissue patterning process.     

猪肠上皮紧密连接蛋白研究进展

紧密连接是肠上皮细胞间的主要连接方式,对维持猪肠道黏膜上皮机械屏障和通透性起着重要作用。紧密连接蛋白是构成肠道黏膜屏障、决定肠壁通透性的重要蛋白质分子,对紧密连接的组成和功能发挥有很大影响。其中,ZO-1(zonula occludens 1)、Occludin(OCLN)和Claudins(CLDN)是构成细胞间紧密连接的重要蛋白分子,在维持细胞极性和紧密连接屏障功能方面起着重要作用。文章综述了ZO-1、Occludin和Claudins等猪紧密连接蛋白的结构、生物学功能以及基因表达情况,并对近年来这些蛋白的研究进展进行归纳总结,为进一步研究猪紧密连接相关蛋白的功能,寻找腹泻和肠道炎症等疾病的治疗方案提供一定的理论基础。     

Surface functionalization of electrodes with molecular reagents

The use of molecular reagents to manipulate the properties of electrode surfaces has broad application in areas such as electrochemical synthesis, energy conversion and storage, displays, sensors, and new kinds of microelectronic devices. Surface modification of electrodes has contributed to a revival of interest in basic and applied research in electrochemistry and electrochemical devices. This article is focused on specific examples of systems modified electrodes where basic developments provide promising opportunities for applications stemming from the properties of molecules attached to an electrode surface.     

Composition and formation of intercellular junctions in epithelial cells

The polarized nature of epithelial cells is manifested by the nonrandom partitioning of organelles within the cells, the concentration of intercellular junctions at one pole, and the asymmetric distribution of proteins and lipids within the plasma membrane. These features allow epithelia to fulfill their specific tasks, such as targeted uptake and secretion of molecules and the segregation of different tissue compartments. The accessibility of Drosophila melanogaster and Caenorhabditis elegans to genetic and cell biological analyses, combined with the study of mammalian cells in culture, provides an ideal basis for understanding the mechanisms that control the establishment and maintenance of epithelial cell polarity and tissue integrity. Here, we focus on some of the best-studied junctions and membrane-associated protein complexes and their relation to cell polarity. Comparisons between fly, worm, and vertebrate epithelia reveal marked similarities with respect to the molecules used, and pronounced differences in the organization of the junctions themselves.     

Chemistry. Close encounters

No chemical reaction can take place without a collision between atoms or molecules. State-of-the-art experimental and theoretical techniques are providing ever more detailed insights into how such collisions proceed. In his Perspective, Crim highlights the report by Lorenz et al., who have succeeded in determining not only the amount but also the sense of rotation of NO molecules after collision with argon atoms. The results can only be explained when subtle quantum mechanical effects are considered.     

Toward the realization of a josephson computer

High-quality Josephson junctions, with both electrodes made from niobium and with an aluminum-oxide insulating barrier, were introduced in 1983. This niobium junction is very stable, reliable, controllable, and reproducible. Because of these excellent characteristics, these junctions can be applied to large-scale integrated (LSI) circuits, such as microprocessors having a few thousand gates and a few kilobits of memory. These circuits operate much faster and consume less power than any semiconductor circuit now available. Integrated Josephson circuits are now being tested in a closed-cycle refrigerator. The next step is to design a special-purpose, small-scale Josephson computer and to demonstrate its high performance.     

Restoration of LDL receptor activity in mutant cells by intercellular junctional communication

Exchange of small molecules between cells through intercellular junctions is a widespread phenomenon implicated in many physiological and developmental processes. This type of intercellular communication can restore the activity of low-density lipoprotein (LDL) receptors in mammalian cells that are deficient in the enzyme UDP-Gal/UDP-GalNAc 4-epimerase. Pure cultures of the 4-epimerase mutant are unable to synthesize normal carbohydrate chains on LDL receptors and many other glycoproteins and therefore do not express LDL receptor activity. When these cells are cocultivated with cells expressing normal 4-epimerase activity, the structure and function of LDL receptors are restored to normal by the transfer of this enzyme's products through intercellular junctions. The formation of functional junctions does not require normal glycosylation of membrane proteins. Because many convenient assays and selections for LDL receptor activity are available, this mutant can provide a powerful new tool for biochemical and genetic studies of intercellular junctional communication.     

Understanding reactivity at very low temperatures: the reactions of oxygen atoms with alkenes

A remarkable number of reactions between neutral free radicals and neutral molecules have been shown to remain rapid down to temperatures as low as 20 kelvin. The rate coefficients generally increase as the temperature is lowered. We examined the reasons for this temperature dependence through a combined experimental and theoretical study of the reactions of O(3P) atoms with a range of alkenes. The factors that control the rate coefficients were shown to be rather subtle, but excellent agreement was obtained between the experimental results and microcanonical transition state theory calculations based on ab initio representations of the potential energy surfaces describing the interaction between the reactants.     

利用瞬态荧光技术研究单重态激子裂变的电荷转移模型

有机材料中单重态激子的裂变过程,由于其在有机光伏器件中的潜在应用而成为一个科学研究的热点.传统的观点采用电荷转移模型来解释激子裂变过程,即认为2个参与裂变的分子之间通过两次的电荷转移来实现分子状态的改变.而在电荷转移的物理图像中,又包括双空穴转移方式和双电子转移方式两种可能性.为了检验电荷转移模型的合理性,将能够发生激子裂变过程的红荧烯分子分别混合于其他4种有机分子中,这4种有机分子被当作间隔分子,用来分离混合膜中掺杂的红荧烯分子.对红荧烯分子与间隔分子,二者间HOMO能级的能量差构成空穴转移的隧穿势垒,而二者间LUMO能级的能量差构成电子转移的隧穿势垒.对4个样品发光衰减曲线的测量与分析表明,激子裂变的速率与电子隧穿势垒的高度具有明显的关联,这从实验角度首次印证了双电子转移模型而否定了双空穴转移模型.     

Untangling desmosomal knots with electron tomography

Cell adhesion by adherens junctions and desmosomes relies on interactions between cadherin molecules. However, the molecular interfaces that define molecular specificity and that mediate adhesion remain controversial. We used electron tomography of plastic sections from neonatal mouse skin to visualize the organization of desmosomes in situ. The resulting three-dimensional maps reveal individual cadherin molecules forming discrete groups and interacting through their tips. Fitting of an x-ray crystal structure for C-cadherin to these maps is consistent with a flexible intermolecular interface mediated by an exchange of amino-terminal tryptophans. This flexibility suggests a novel mechanism for generating both cis and trans interactions and for propagating these adhesive interactions along the junction.     

Covalently bridging gaps in single-walled carbon nanotubes with conducting molecules

Molecular electronics is often limited by the poorly defined nature of the contact between the molecules and the metal surface. We describe a method to wire molecules into gaps in single-walled carbon nanotubes (SWNTs). Precise oxidative cutting of a SWNT produces carboxylic acid-terminated electrodes separated by gaps of 相似文献   

Phase-coherent transport in graphene quantum billiards

As an emergent electronic material and model system for condensed-matter physics, graphene and its electrical transport properties have become a subject of intense focus. By performing low-temperature transport spectroscopy on single-layer and bilayer graphene, we observe ballistic propagation and quantum interference of multiply reflected waves of charges from normal electrodes and multiple Andreev reflections from superconducting electrodes, thereby realizing quantum billiards in which scattering only occurs at the boundaries. In contrast to the conductivity of conventional two-dimensional materials, graphene's conductivity at the Dirac point is geometry-dependent because of conduction via evanescent modes, approaching the theoretical value 4e(2)/pih (where e is the electron charge and h is Planck's constant) only for short and wide devices. These distinctive transport properties have important implications for understanding chaotic quantum systems and implementing nanoelectronic devices, such as ballistic transistors.     

Thermochemical Properties of Xenon Difluoride and Xenon Tetrafluoride from Mass Spectra

The standard heats of formation for gaseous xenon tetrafluoride and xenon difluoride and the average strength of the bonds in these molecules have been determined from appearance-potential data obtained with a mass spectrometer. The experimental values are compatible with theoretical estimates of these quantities.     

Chemistry. How to assemble a molecular junction

Junctions between metals and molecules play an important role in molecular electronics. Advances in this field are hampered by the lack of understanding of the electronic structure of organic-metal interfaces. In his Perspective, Kummel highlights the report by Nazin et al. (3), who have used scanning tunneling microscopy (STM) to assemble a metal-molecule-metal junction. Subsequently, they employed the STM tip to probe the atomic structure and local electronic properties of the metal-molecule interface in unprecedented detail. They find evidence for strong coupling between the molecular and metal states. Such coupling affects the conductivity of metal-molecule-metal junctions.     

Observation of all-metal aromatic molecules

Aromaticity is a concept invented to account for the unusual stability of an important class of organic molecules: the aromatic compounds. Here we report experimental and theoretical evidence of aromaticity in all-metal systems. A series of bimetallic clusters with chemical composition MAl4- (M = Li, Na, or Cu), was created and studied with photoelectron spectroscopy and ab initio calculations. All the MAl4- species possess a pyramidal structure containing an M+ cation interacting with a square Al4(2-) unit. Ab initio studies indicate that Al4(2-) exhibits characteristics of aromaticity with two delocalized pi electrons (thus following the 4n + 2 electron counting rule) and a square planar structure and maintains its structural and electronic features in all the MAl4- complexes. These findings expand the aromaticity concept into the arena of all-metal species.     

Polymer brushes

Polymers attached by one end to an interface at relatively high coverage stretch away from the interface to avoid overlapping, forming a polymer "brush." This simple picture may serve as the basis for models in diverse interfacial systems in polymer science, such as polymeric surfactants, stabilized suspensions of colloidal particles, and structures formed by block copolymers. The structure and dynamics of polymer brushes have been the subject of considerable theoretical and experimental activity in recent years. An account is given of recent advances in theoretical understanding of stretched polymers at interfaces, and the diverse experimental probes of systems modeled by brushes are briefly reviewed.     

Electrochemical reduction of horse heart ferricytochrome c at chemically derivatized electrodes

Platinum or gold electrodes derivatized with an N,N'-dialkyl-4,4'-bipyridinium reagent can be used to reduce horse heart ferricytochrome c, whereas reduction doses does not occur at the "naked" electrodes. From 3 to 17.7 millimoles per liter, the reduction of ferricytochrome c is mass transport-limited at electrode potentials more negative than about -0.6 volt against a saturated calomel reference electrode. Data for the photoreduction of ferricytochrome c at derivatized p-type silicon photocathodes show directly that the rate of reduction is mass transport-limited. Use of derivatized electrodes may allow convenient manipulation and analysis of biological molecules that do not ordinarily respond at conventional electrodes.