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.     

Scale size of magnetic turbulence in tokamaks probed with 30-MeV electrons

Measurements of synchrotron radiation emitted by 30-MeV runaway electrons in the TEXTOR-94 tokamak show that the runaway population decays after switching on neutral beam injection (NBI). The decay starts only with a significant delay, which decreases with increasing NBI heating power. This delay provides direct evidence of the energy dependence of runaway confinement, which is expected if magnetic modes govern the loss of runaways. Application of the theory by Mynick and Strachan [Phys. Fluids 24, 695 (1981)] yields estimates for the "mode width" (delta) of magnetic perturbations: delta<0.5 cm in Ohmic discharges, increasing to delta = 4.4 cm for 0. 6 MW NBI.     

A Hilbert-Vlasov code for the study of high-frequency plasmabeatwave accelerator

High-frequency beatwave simulations relevant to the University of California at Los Angeles (UCLA) experiment with relativistic eulerian hybrid Vlasov code are presented. These Hilbert-Masov simulations revealed a rich variety of phenomena associated with the fast particle dynamics induced by beatwave experiment for a high ratio of driver frequency to plasma frequency ω_pump/ω_plasma ≈33. The present model allows us to extend detailed modeling to frequency ratios greater than the current practical maximum of 10 or so, for Vlasov or particle-in-cell (PIC) codes, by replacing the Maxwell equations by mode equations for the electromagnetic Vlasov code. Numerical results, including beat frequency chirping (i.e., pump frequency linearly decreasing with time), show that the amplitude limit due to relativistic detuning can be enhanced with accelerated particles up to the ultrarelativistic energies with a high-acceleration gradient of more than 25 GeV/m     

New theoretical and experimental infrared results on formaldehyde in solution

An extension of our combined procedure to determine a complete quartic force field and to resolve a vibrational problem thanks to a variational treatment is proposed for quantitative calculations of vibrational spectra in solution. Energies and gradients are obtained through a polarizable continuum model (PCM), the so-called self-consistent isodensity (SCI)-PCM. We present in this paper new experimental results dealing with formaldehyde in solution in cyclohexane, chloroform, THF, acetonitrile, DMSO and water; the obtained vibrational spectra are then compared with CCSD(T)/cc-pVQZ calculations. In addition, density functional theory (DFT) calculations have been carried out with the aim of both anticipating and positioning these approaches for larger sized molecules.     

Study of doxorubicin photodegradation in plasma, urine and cell culture medium by HPLC

An HPLC method was used to monitor the chemical stability of doxorubicin-HCl (DXR) to light in plasma, urine and cell culture medium at room temperature. The results indicated that DXR was very unstable in cell culture medium and urine when exposed to light. It was more stable in plasma under the same conditions. In all the cases, the decrease in the amount of DXR is greatly dependent on light intensity (no noticeable degradation was observed after 8 h in the dark). These observations may be important for the correct interpretation of the effects and the toxicity of doxorubicin on cells incubated in cell medium, and for determination of urinary or plasma pharmacokinetic parameters.     

DNA‐Based Polymers as Chiral Templates for Second‐Order Nonlinear Optical Materials

The unique symmetry properties of chiral systems allow the emergence of coherent second harmonic generation in polymeric materials lacking polar order. Deoxyribonucleic acid (DNA) treated with the surfactant cetyltrimethylammonium (CTMA) was drop‐cast to spontaneously form films that are active for coherent second harmonic generation (SHG). SHG images acquired as a function of incident and exigent polarization are in good agreement with theoretical predictions assuming nonpolar D_∞ symmetry for the double‐stranded DNA chains. Doping the DNA films with crystal violet substantially increases the efficiency of SHG, but does not significantly alter the polarization‐dependence, suggesting that the SHG generated upon doping arises from the same chiral‐specific origin, presumably templated by the DNA. These results raise the possibility of new design strategies for organic nonlinear optical materials based on soft chiral polymers that do not require polar order.     

New results on methylalkali systems: Accurate vibrational study of methylsodium

This paper presents results (structural parameters and anharmonic vibrational spectra) obtained for the methylsodium system at different levels of theory from DFT and post-HF [CCSD(T)] calculations. These theoretical results are faced with the existing experimental data. An interpretation of the experimental reference is proposed from our calculations about the monomer and the dimer compounds.