Electronic and vibrational second-order nonlinear optical properties of protein secondary structural motifs

A perturbation theory approach was developed for predicting the vibrational and electronic second-order nonlinear optical (NLO) polarizabilities of materials and macromolecules comprised of many coupled chromophores, with an emphasis on common protein secondary structural motifs. The polarization-dependent NLO properties of electronic and vibrational transitions in assemblies of amide chromophores comprising the polypeptide backbones of proteins were found to be accurately recovered in quantum chemical calculations by treating the coupling between adjacent oscillators perturbatively. A novel diagrammatic approach was developed to provide an intuitive visual means of interpreting the results of the perturbation theory calculations. Using this approach, the chiral and achiral polarization-dependent electronic SHG, isotropic SFG, and vibrational SFG nonlinear optical activities of protein structures were predicted and interpreted within the context of simple orientational models.     

Random Copolymers of 1,5-Dioxepan-2-one

ABSTRACT

Copolymers of 1,5-dioxepan-2-one (DXO) and e-caprolactone (?-CL), δ-valerolactone (δ-VL) or L-lactide (LLA) have been synthesized and characterized. High molecular weight copolymers were obtained using stannous-2-ethyl hexanoate as catalyst in bulk. Reactivity ratios for the copolymerization of DXO and δ-VL were determined at 110°C as r_VL=0.5 and r_DXO=2.3. At high conversion, depolymerization of δ-VL occurred, resulting in lower molecular weight and variations in the copolymer composition.

Physical properties, such as crystallinity and melting temperature of the DXO-copolymers proved to be strongly dependent on the choice of comonomer and on the molar composition of the copolymers. DXO appears to be incorporated into the poly-?-caprolactone (PCL) crystals and to some extent into the poly-δ-valerolactone (PVL) crystals, resulting in a more gradual decrease in crystallinity with increasing amount of DXO.     

Negative ion electrospray mass spectrometry of nucleotides: ionization from water solution with SF6 discharge suppression

The total current and selected ion currents from the electrospray ionization (ES1) of 10^?5 M solutions of cocaine hydrochloride and deoxycytidine monophosphate (dCMP) monosodium salt in methanol and water solvents were compared in positive and negative ion modes, respectively, without and with SF₆, gas as a discharge suppressant. The ESI onset voltages (V_on), were the same for the positive and negative ion modes. The V_on, for methanol was much lower than that for water and in agreement with the equation of D. P. H. Smith, who attributes the difference to the higher surface tension of water. The onset of electric discharge (V_dis) without SF₆, occurred at lower capillary voltages for the negative relative to the positive ion mode for methanol; but V_dis is much higher than V_on for methanol, and discharges do not interfere with ESI operation. For water, V_on ≈ V_dis in the absence of SF₆, in the negative ion mode, and ESI operation is impossible without SF₆, discharge suppression. The discharge problem in the positive ion mode is less severe, but SF₆, is still very useful. A dynamic range of 10 ^?7–10^?5 M was obtained by selected ion monitoring of [dCMP - H]^? at 4.5 and 20 μL/min. flows. Subpicomole detection limits for the nucleotide salt were obtained under these conditions.     

Fusion around the barrier for 7Li+12C

Fusion cross-sections for the ⁷Li + ¹²C reaction have been measured at energies above the Coulomb barrier by the direct detection of evaporation residues. The heavy evaporation residues with energies below 3 MeV could not be separated out from the α-particles in the spectrum and hence their contribution was estimated using statistical model calculations. The present work indicates that suppression of fusion cross-sections due to the breakup of ⁷Li may not be significant for ⁷Li + ¹²C reaction at energies around the barrier.     

Secondary ion yields produced by keV atomic and polyatomic ion impacts on a self-assembled monolayer surface

A suite of keV polyatomic or 'cluster' projectiles was used to bombard unoxidized and oxidized self-assembled monolayer surfaces. Negative secondary ion yields, collected at the limit of single ion impacts, were measured and compared for both molecular and fragment ions. In contrast to targets that are orders of magnitude thicker than the penetration range of the primary ions, secondary ion yields from polyatomic projectile impacts on self-assembled monolayers show little to no enhancement when compared with monatomic projectiles at the same velocity. This unusual trend is most likely due to the structural arrangement and bonding characteristics of the monolayer molecules with the Au(111). Copyright 1999 John Wiley & Sons, Ltd.     

Photochemistry of the SO2, 2-pentene system at 3660 Å

The photolysis of SO₂ in the presence of cis- and trans-2-pentene has been investigated at 3660 Å and 22°C. Quantum yield measurements of the SO₂ photosensitized conversion of one isomer into the other are consistent with a mechanism in which the only participating excited electronic state of SO₂ is the SO₂(³B₁) state. Quantum yield measurements were made for a variation in P_SO2/P_isomer reactant ratios of 4.01–283 and 57.5–351 for the cis and trans isomers, respectively. The data are consistent with a mechanism in which a (SO₂-olefin)³ collision intermediate is the precursor to the photosensitized isomeric products. The intermediate undergoes unimolecular decay to yield the cis and trans isomers with probabilities of 0.26 ± 0.05 and 0.69 ± 0.04, respectively. Estimates of the quenching rate constants at 22°C for removal of SO₂(³B₁) molecules by cis- and trans-2-pentene are (0.633 ± 0.125) × 10¹¹ l./mole/sec and (1.00 ± 0.27) × 10¹¹ l./mole/sec, respectively. An experimentally determined photostationary composition, [trans-2-pentene]/[cis-2-pentene] = 2.3 ± 0.1 was in fair agreement with that of 1.7 ± 0.7 as predicted from kinetic data derived in this study.     

Computing singular solutions to nonlinear analytic systems

Summary A method to generate an accurate approximation to a singular solution of a system of complex analytic equations is presented. Since manyreal systems extend naturally tocomplex analytic systems, this porvides a method for generating approximations to singular solutions to real systems. Examples include systems of polynomials and systems made up of trigonometric, exponential, and polynomial terms. The theorem on which the method is based is proven using results from several complex variables. No special conditions on the derivatives of the system, such as restrictions on the rank of the Jacobian matrix at the solution, are required. The numerical method itself is developed from techniques of homotopy continuation and 1-dimensional quadrature. A specific implementation is given, and the results of numerical experiments in solving five test problems are presented.     

Regenerative cascade homotopies for solving polynomial systems

A key step in the numerical computation of the irreducible decomposition of a polynomial system is the computation of a witness superset of the solution set. In many problems involving a solution set of a polynomial system, the witness superset contains all the needed information. Sommese and Wampler gave the first numerical method to compute witness supersets, based on dimension-by-dimension slicing of the solution set by generic linear spaces, followed later by the cascade homotopy of Sommese and Verschelde. Recently, the authors of this article introduced a new method, regeneration, to compute solution sets of polynomial systems. Tests showed that combining regeneration with the dimension-by-dimension algorithm was significantly faster than naively combining it with the cascade homotopy. However, in this article, we combine an appropriate randomization of the polynomial system with the regeneration technique to construct a new cascade of homotopies for computing witness supersets. Computational tests give strong evidence that regenerative cascade is superior in practice to previous methods.