A molecular orbital study of trans-polyenes to 18 double bonds

Calculations involving molecular orbitals have appeared in the chemical literature over the past few years, but all have used smalltrans-polyenes. We now report extended Huckel molecular orbital calculations ontrans-polyenes of up to 18 double bonds (36 carbons and 38 hydrogen atoms). Information obtained from these calculations include total energies, bond gaps, and net charges on each atom. Also found is that the band gap approaches 1.41 eV as the number of double bonds approaches infinity. This value is quite close to reported experimental values. Data are also presented for polyenes assuming equal C-C bond lengths.     

Electrochemical behavior of silver thin films interfaced with yttria-stabilized zirconia

Thin silver films (100–800 nm) were deposited by physical vapor deposition (PVD) on yttria-stabilized zirconia solid electrolyte. The electric percolation as a function of the film thickness was studied during deposition and annealing using a two-electrode in-situ resistance measurement technique. Electrical percolation was achieved in as-deposited films greater than 5.4?±?0.4 nm; however, thermal treatment (550 °C in air) resulted in film dewetting for Ag films as thick as 500 nm and formation of electronically isolated Ag nanoparticles, as was confirmed by SEM and XPS. In thermally treated samples, stable electronic conductivity associated with a continuous percolated network was only observed in samples greater than 600 nm in thickness. The effect of polarization on the electrochemical reactions at the three-phase (electrode-gas-electrolyte) and two-phase (electrode-electrolyte) boundaries of the electrode was investigated by solid electrolyte cyclic voltammetry (SECV) at 350 °C and P _O2?=?6 kPa. With the application of positive potential, silver oxide (Ag₂O) was found to form along the three-phase boundary and then extends within the bulk of the electrode with increasing anodic potentials. By changing the hold time at positive potential, passivating oxide layers are formed which results in a shift in favor of the oxygen evolution reaction at the working electrode. This oxide forms according to a logarithmic rate expression with thick oxides being associated with decrease in current efficiency for subsequent oxide formation.     

Racemic and Quasi‐Racemic X‐ray Structures of Cyclic Disulfide‐Rich Peptide Drug Scaffolds

Cyclic disulfide‐rich peptides have exceptional stability and are promising frameworks for drug design. We were interested in obtaining X‐ray structures of these peptides to assist in drug design applications, but disulfide‐rich peptides can be notoriously difficult to crystallize. To overcome this limitation, we chemically synthesized the L ‐ and D ‐forms of three prototypic cyclic disulfide‐rich peptides: SFTI‐1 (14‐mer with one disulfide bond), cVc1.1 (22‐mer with two disulfide bonds), and kB1 (29‐mer with three disulfide bonds) for racemic crystallization studies. Facile crystal formation occurred from a racemic mixture of each peptide, giving structures solved at resolutions from 1.25 Å to 1.9 Å. Additionally, we obtained the quasi‐racemic structures of two mutants of kB1, [G6A]kB1, and [V25A]kB1, which were solved at a resolution of 1.25 Å and 2.3 Å, respectively. The racemic crystallography approach appears to have broad utility in the structural biology of cyclic peptides.     

The enumerative geometry of surfaces and modular forms

Let be a surface, and let be a holomorphic curve in representing a primitive homology class. We count the number of curves of geometric genus with nodes passing through generic points in in the linear system for any and satisfying .

When , this coincides with the enumerative problem studied by Yau and Zaslow who obtained a conjectural generating function for the numbers. Recently, Göttsche has generalized their conjecture to arbitrary in terms of quasi-modular forms. We prove these formulas using Gromov-Witten invariants for families, a degeneration argument, and an obstruction bundle computation. Our methods also apply to blown up at 9 points where we show that the ordinary Gromov-Witten invariants of genus constrained to points are also given in terms of quasi-modular forms.     

Self-induced "electroclick" immobilization of a copper complex onto self-assembled monolayers on a gold electrode

We report the self-induced "electroclick" immobilization of the [Cu(II)(6-ethynyl-TMPA)(H(2)O)](2+) complex, by its simple electro-reduction, onto a mixed azidoundodecane-/decane-thiol modified gold electrode. The redox response of the grafted [Cu(II/I)(TMPA)] at the modified electrode is fully reversible indicating no Cu coordination change and a fast electron transfer.     

Electronic properties and band structure of IrSe2

Transport coefficient measurements (DC conductivity and thermoelectric power) were performed on compacted bars of polycrystalline IrSe₂ in the 100–570 K temperature range. The experimental results are interpeted on the basis of an n-type compensated semiconductor model. At low temperatures, a narrow band which originates from non-stoichiometry mainly participates in the conduction by thermally activated hopping of small polarons. The charge balance adopted by anionic groups is discussed. The schematic band model which is retained takes into account all the transport properties and the ion charge balance Ir³⁺Se^2-(Se₂)^2-_{1/ 2}. Moreover, IrSe₂ has recently been shown to function as a cathode material in lithium batteries.     

Comparison of algorithms for the symbolic computation of the NP spin coefficients and curvature components

Algorithms for the symbolic computation of the NP spin coefficients and curvature components for a given null coframe based on the structural equations of Cartan and the complex vectorial formalism of Debever are described. The efficiency of the algorithms is compared theoretically and also empirically in a number of test cases using implementations in the computer algebra system Maple. The test results confirm the theoretical superiority of the algorithm based on Debever's formalism over the one based directly on Cartan's first structural equations for the computation of the spin coefficients both with respect to execution time and storage requirements. The algorithm for the computation of the curvature components based on Debever's formalism is generally superior to the one based on Cartan's second structural equations but the advantage is not as marked as for the spin coefficients.     

Simultaneous anion and cation exchange chromatography of whey proteins using a customizable mixed matrix membrane

Membrane chromatography can overcome some of the limitations of packed bed column chromatography but preparation of adsorptive membranes usually involves complex and harsh chemical modifications. Mixed matrix membranes (MMMs) require only the physical incorporation of an ion exchange resin into the membrane polymer solution prior to membrane casting. An advantage of MMMs not previously exploited is that resins with differing adsorptive functionalities can be conveniently embedded within a single membrane at any desired ratio. This presents the opportunity to customize an adsorptive membrane to suit the expected protein profile of a raw feed stream e.g. bovine whey or serum. In this work, a novel mixed mode interaction MMM customized to extract all major proteins from bovine whey was synthesized in a single membrane by incorporating 42.5 wt% Lewatit MP500 anionic resin and 7.5 wt% SP Sepharose cationic resin into an ethylene vinyl alcohol base polymer casting solution. The mixed mode MMM developed was able to bind both basic and acidic proteins simultaneously from whey, with binding capacities of 7.16±2.24 mg α-lactalbumin g(-1) membrane, 11.40±0.73 mg lactoferrin (LF)g(-1) membrane, 59.21±9.90 mg β-lactoglobulin g(-1) membrane and 6.79±1.11 mg immunoglobulin Gg(-1) membrane (85 mg total protein g(-1) membrane) during batch fractionation of LF-spiked whey. A 1000 m(2) spiral-wound membrane module (200 L membrane volume, 1m(3) module volume) is predicted to be able to produce approximately 25 kg total whey protein per h.