Single-molecule transistors: Electron transfer in the solid state

Single-molecule transistors (SMTs) incorporating individual small molecules are unique tools for examining the fundamental physics and chemistry of electronic transport in molecular systems at the single nanometer scale. We describe the fabrication and characterization of such devices, and the synthesis and surface attachment chemistry of novel transition metal complexes that have been incorporated into such SMTs. We present gate-modulated inelastic electron tunneling vibrational spectroscopy of single molecules, strong Kondo physics (T_K ∼ 75 K) as evidence of excellent molecule/electrode electronic coupling, and a demonstration that covalent attachment chemistry can produce SMTs that survive repeated thermal cycling to room temperature. We conclude with a look ahead at the prospects for these nanoscale systems.     

Canonical Proper-Time Formulation of Relativistic Particle Dynamics. II

Our purpose in this paper is to provide theframework for a generalization of classical mechanicsand electrodynamics, including Maxwell's theory, whichis simple, technically correct, and requires noadditional work for the quantum case. We first show thatthere are two other definitions of proper-time, eachhaving equal status with the Minkowski definition. Weuse the first definition, called the proper-velocity definition, to construct a transformationtheory which fixes the proper-time of a given physicalsystem for all observers. This leads to a new invariancegroup and a generalization of Maxwell's equations left covariant under the action of this group.The second definition, called the canonical variablesdefinition, has the unique property that it isindependent of the number of particles. This definition leads to a general theory of directlyinteracting relativistic particles. We obtain theLorentz force for one particle (using its proper-time),and the Lorentz force for the total system (using theglobal proper-time). Use of the global proper-time tocompute the force on one particle gives the Lorentzforce plus a dissipative term corresponding to thereaction of this particle back on the cause of itsacceleration (Newton's third law). The wave equation derivedfrom Maxwell's equations has an additional term, firstorder in the proper-time. This term arisesinstantaneously with acceleration. This shows explicitly that the longsought origin of radiationreaction is inertial resistance to changes in particlemotion. The field equations carry intrinsic informationabout the velocity and acceleration of the particles in the system. It follows that our theory isnot invariant under time reversal, so that the existenceof radiation introduces an arrow for the (proper-time ofthe) system.     

Freeze-out conditions in ultrarelativistic heavy-ion collisions

We present recent results on single particle transverse momentum distributions of pions, kaons and protons, measured in CERN Experiment NA44, of 200 AGeV/c S+S and 158 AGeV/c Pb+Pb central collisions. By comparing these data with thermal and transport models, freeze-out parameters like the temperatureT _fo and the chemical potentials (μ _q ,μ _s ) are extracted and discussed.     

Characterization of a new tailoring domain in polyketide biogenesis: the amine transferase domain of MycA in the mycosubtilin gene cluster

We report the expression and characterization of a truncated form of MycA from the Mycosubtilin gene cluster from Bacillus subtilis. The MycA fragment contains a new amino transferase (AMT) tailoring domain, allowing the first detailed study of a PLP-dependent enzyme operating in cis within the PKS and NRPS biosynthetic paradigm. As the AMT domain acts on covalently bound beta-ketothioesters, and is therefore a single-turnover system, electrospray ionization-Fourier transform mass spectrometry (ESI-FTMS) was used to observe the amine-transfer reaction both for amine donor substrate specificity and to regiospecifically determine enzyme-bound intermediates. We confirm the function of the AMT domain, dissect the mechanistic steps of amine transfer, identify the preferred amine source, and localize the beta-ketothioester substrate during amine transfer.     

Rearrangements and stereomutations of metallacycles derived from allenes and imidozirconium complexes

The mechanisms of the rearrangements and stereoinversion of azametallacyclobutenes generated via [2+2] cycloaddition of allenes and imidozirconium complexes have been studied. Metallacycles derived from allenes bearing beta-hydrogen atoms racemize at room temperature by reversible beta-hydride elimination, a process which is also responsible for their eventual conversion to monoazadiene complexes. Metallacycles derived from diarylallenes racemize by reversible thermal bond homolysis at 95 degrees C; racemization of these metallacycles is also catalyzed by mild oxidants.     

Palladium assisted synthesis of 1-azaspirocycles

A facile, general route to 1-azaspirocycles utilizing a π-allyl palladium complex in the key cyclization step has been developed.     

A method for automatic identification of water and fat images from a symmetrically sampled dual-echo Dixon technique

Sampling water and fat signals symmetrically (i.e., at 0° and 180° relative phase angles) in a dual-echo Dixon technique offers high intrinsic tolerance to phase fluctuations in postprocessing and maximum signal-to-noise performance for the separated water and fat images. However, identification of which image is water and which image is fat after their separation is not possible based on the phase information alone. In this work, we proposed a semiempirical automatic image identification method that is based on the intrinsic asymmetry between the water and fat chemical shift spectra. Specifically, the approximately bimodal feature of the fat spectra and the observation that most in vivo tissues are either predominantly water or predominantly fat are used to construct a spectrum-based algorithm. Additional refinement is accomplished by considering the spatial distribution of the tissues that may have a coexistence of water and fat. The final improved algorithm was tested on a total of 131 three-dimensional patient datasets collected from different scanners and found to yield correct water and fat identification in all datasets.     

A sufficiency class for global (in time) solutions to the 3D Navier-Stokes equations

Let Ω be an open domain of class C² contained in R³, let L²(Ω)³ be the Hilbert space of square integrable functions on Ω and let H[Ω]?H be the completion of the set, , with respect to the inner product of L²(Ω)³. A well-known unsolved problem is that of the construction of a sufficient class of functions in H which will allow global, in time, strong solutions to the three-dimensional Navier-Stokes equations. These equations describe the time evolution of the fluid velocity and pressure of an incompressible viscous homogeneous Newtonian fluid in terms of a given initial velocity and given external body forces. In this paper, we use the analytic nature of the Stokes semigroup to construct an equivalent norm for H, which provides strong bounds on the nonlinear term. This allows us to prove that, under appropriate conditions, there exists a number u₊, depending only on the domain, the viscosity, the body forces and the eigenvalues of the Stokes operator, such that, for all functions in a dense set D contained in the closed ball B(Ω)?B of radius in H, the Navier-Stokes equations have unique, strong, solutions in C¹((0,∞),H).     

Land cover change using an energy transition paradigm in a statistical mechanics approach

This paper explores a statistical mechanics approach as a means to better understand specific land cover changes on a continental scale. Integrated assessment models are used to calculate the impact of anthropogenic emissions via the coupling of technoeconomic and earth/atmospheric system models and they have often overlooked or oversimplified the evolution of land cover change. Different time scales and the uncertainties inherent in long term projections of land cover make their coupling to integrated assessment models difficult. The mainstream approach to land cover modelling is rule-based methodology and this necessarily implies that decision mechanisms are often removed from the physical geospatial realities, therefore a number of questions remain: How much of the predictive power of land cover change can be linked to the physical situation as opposed to social and policy realities? Can land cover change be understood using a statistical approach that includes only economic drivers and the availability of resources? In this paper, we use an energy transition paradigm as a means to predict this change. A cost function is applied to developed land covers for urban and agricultural areas. The counting of area is addressed using specific examples of a Pólya process involving Maxwell–Boltzmann and Bose–Einstein statistics. We apply an iterative counting method and compare the simulated statistics with fractional land cover data with a multi-national database. An energy level paradigm is used as a basis in a flow model for land cover change. The model is compared with tabulated land cover change in Europe for the period 1990–2000. The model post-predicts changes for each nation. When strong extraneous factors are absent, the model shows promise in reproducing data and can provide a means to test hypothesis for the standard rules-based algorithms.