Noninnocence in Metal Complexes: A Dithiolene Dawn

Noninnocence in inorganic chemistry traces its roots back half a century to work that was done on metal complexes containing unsaturated dithiolate ligands. In a flurry of activity in the early 1960s by three different research groups, homoleptic bis and tris complexes of these ligands, which came to be known as dithiolenes, were synthesized, and their structural, electrochemical, spectroscopic, and magnetic properties were investigated. The complexes were notable for facile one-electron transfers and intense colors in solution, and conventional oxidation-state descriptions could not account for their electronic structures. The bis complexes were, in general, found to be square-planar, including the first examples of this geometry for paramagnetic complexes and different formal dn configurations. Several of the neutral and monoanionic tris complexes were found to have trigonal-prismatic coordination, the first time that this geometry had been observed in molecular metal complexes. Electronic structural calculations employing extended Hückel and other semiempirical computational methods revealed extensive ligand–metal mixing in the frontier orbitals of these systems, including the observation of structures in which filled metal-based orbitals were more stable than ligand-based orbitals of the same type, suggesting that the one-electron changes upon oxidation or reduction were occurring on the ligand rather than on the metal center. A summary of this early work is followed with a brief section on the current interpretations of these systems based on more advanced spectroscopic and computational methods. The take home message is that the early work did indeed provide a solid foundation for what was to follow in investigations of metal complexes containing redox-active ligands

Ions in Fluctuating Channels: Transistors Alive

Ion channels are proteins with a hole down the middle embedded in cell membranes. Membranes form insulating structures and the channels through them allow and control the movement of charged particles, spherical ions, mostly Na+, K+, Ca++, and Cl-. Membranes contain hundreds or thousands of types of channels, fluctuating between open conducting, and closed insulating states. Channels control an enormous range of biological function by opening and closing in response to specific stimuli using mechanisms that are not yet understood in physical language. Open channels conduct current of charged particles following laws of Brownian movement of charged spheres rather like the laws of electrodiffusion of quasi-particles in semiconductors. Open channels select between similar ions using a combination of electrostatic and 'crowded charge' (Lennard-Jones) forces. The specific location of atoms and the exact atomic structure of the channel protein seems much less important than certain properties of the structure, namely the volume accessible to ions and the effective density of fixed and polarization charge. There is no sign of other chemical effects like delocalization of electron orbitals between ions and the channel protein. Channels play a role in biology as important as transistors in computers, and they use rather similar physics to perform part of that role. Understanding their fluctuations awaits physical insight into the source of the variance and mathematical analysis of the coupling of the fluctuations to the other components and forces of the system.Comment: Revised version of earlier submission, as invited, refereed, and published by journa

Pair production in a strong electric field: an initial value problem in quantum field theory

We review recent achievements in the solution of the initial-value problem for quantum back-reaction in scalar and spinor QED. The problem is formulated and solved in the semiclassical mean-field approximation for a homogeneous, time-dependent electric field. Our primary motivation in examining back-reaction has to do with applications to theoretical models of production of the quark-gluon plasma, though we here address practicable solutions for back-reaction in general. We review the application of the method of adiabatic regularization to the Klein-Gordon and Dirac fields in order to renormalize the expectation value of the current and derive a finite coupled set of ordinary differential equations for the time evolution of the system. Three time scales are involved in the problem and therefore caution is needed to achieve numerical stability for this system. Several physical features, like plasma oscillations and plateaus in the current, appear in the solution. From the plateau of the electric current one can estimate the number of pairs before the onset of plasma oscillations, while the plasma oscillations themselves yield the number of particles from the plasma frequency. We compare the field-theory solution to a simple model based on a relativistic Boltzmann-Vlasov equation, with a particle production source term inferred from the Schwinger particle creation rate and a Pauli-blocking (or Bose-enhancement) factor. This model reproduces very well the time behavior of the electric field and the creation rate of charged pairs of the semiclassical calculation. It therefore provides a simple intuitive understanding of the nature of the solution since nearly all the physical features can be expressed in terms of the classical distribution function.Comment: Old paper, already published, but in an obscure journa

Energetics of ion competition in the DEKA selectivity filter of neuronal sodium channels

The energetics of ionic selectivity in the neuronal sodium channels is studied. A simple model constructed for the selectivity filter of the channel is used. The selectivity filter of this channel type contains aspartate (D), glutamate (E), lysine (K), and alanine (A) residues (the DEKA locus). We use Grand Canonical Monte Carlo simulations to compute equilibrium binding selectivity in the selectivity filter and to obtain various terms of the excess chemical potential from a particle insertion procedure based on Widom's method. We show that K$^{+}$ ions in competition with Na$^{+}$ are efficiently excluded from the selectivity filter due to entropic hard sphere exclusion. The dielectric constant of protein has no effect on this selectivity. Ca$^{2+}$ ions, on the other hand, are excluded from the filter due to a free energetic penalty which is enhanced by the low dielectric constant of protein.Comment: 14 pages, 7 figure

Hardware simulation of Ku-band spacecraft receiver and bit synchronizer, volume 1

A hardware simulation which emulates an automatically acquiring transmit receive spread spectrum communication and tracking system and developed for use in future NASA programs involving digital communications is considered. The system architecture and tradeoff analysis that led to the selection of the system to be simulated is presented

A finite-temperature liquid-quasicrystal transition in a lattice model

We consider a tiling model of the two-dimensional square-lattice, where each site is tiled with one of the sixteen Wang tiles. The ground states of this model are all quasi-periodic. The systems undergoes a disorder to quasi-periodicity phase transition at finite temperature. Introducing a proper order-parameter, we study the system at criticality, and extract the critical exponents characterizing the transition. The exponents obtained are consistent with hyper-scaling

Hardware simulation of KU-band spacecraft receiver and bit synchronizer, phase 2, volume 1

The acquisition behavior of the PN subsystem of an automatically acquiring spacecraft receiver was studied. A symbol synchronizer subsystem was constructed and integrated into the composite simulation of the receiver. The overall performance of the receiver when subjected to anomalies such as signal fades was evaluated. Potential problems associated with PN/carrier sweep interactions were investigated

Ground State Spin Structure of Strongly Interacting Disordered 1D Hubbard Model

We study the influence of on-site disorder on the magnetic properties of the ground state of the infinite U 1D Hubbard model. We find that the ground state is not ferromagnetic. This is analyzed in terms of the algebraic structure of the spin dependence of the Hamiltonian. A simple explanation is derived for the 1/N periodicity in the persistent current for this model.Comment: 3 pages, no figure

Androgen Receptor and Vasopressin Receptor (AVPR1a) Genetic Polymorphisms are not associated with Marital Status or Fertility among Ariaal Men of Northern Kenya

A growing body of scholarship implicates testosterone and vasopressin in male reproductive behavior, including in humans. Since hormones exert their effects through their respective receptors, an open question has been whether genetic polymorphisms in the androgen receptor and vasopressin 1a receptor (AVPR1a) impact human male social behavior. Here, we sought to test for associations between polymorphisms in the coding region of the androgen receptor and promoter region of AVPR1a in relation to marital status and fertility among pastoralist Ariaal men of northern Kenya. None of the three polymorphisms were related to marital status (single, monogamously married, polygynously married) or fertility (number of current living children). We discuss these null findings in light of existing data