The E.S.R. spectrum of the tropolonyl radical

The many-body diagrammatic Rayleigh-Schrödinger perturbation theory (RSPT) is used for the calculation of ionization potentials of open-shell systems with one unpaired electron. This theoretical approach is tested on the simple examples of NO₂ and NF₂ molecules described by the INDO semi-empirical hamiltonian. The first- and second-order results are presented.     

Method of phase extraction between coupled atom interferometers using ellipse-specific fitting

We present a method of analysis involving ellipse-specific fitting of sinusoidally coupled data from two gravimeters in a gradiometer configuration. This method permits rapid extraction of induced gradient phase shifts in the presence of common-mode vibrational phase noise. Gravity gradients can be accurately measured in the presence of large vibrational accelerations.     

Effect of pigment packaging on diffuse reflectance spectroscopy of samples containing red blood cells

We present the results of diffuse reflectance measurements made on the surface of a tissue-simulating phantom containing intact human erythrocytes. These measurements indicate that the absorption spectrum of hemoglobin in its natural environment is significantly different from that measured in homogeneous fluid solution, especially in the spectral regions of highest absorption. We show that this difference can be explained by the pigment packaging theory developed by Duysens [Biochim. Biophys. Acta 19, 1 (1956)] and that the adoption of basis spectra that take this effect into account improves the accuracy of fitting diffuse reflectance spectra.     

Irradiation-induced magnetism in graphite: a density functional study

Recent experiments indicate that proton irradiation triggers ferromagnetism in originally nonmagnetic graphite samples while He ion bombardment has a much smaller effect. To understand the origin of irradiation-induced magnetism, we have performed spin-polarized density functional theory calculations of the magnetic properties of the defects which are most likely to appear under irradiation vacancies and vacancy-hydrogen complexes. Both defects are magnetic, but as for the latter we find that H adsorption on one of the vacancy dangling bonds gives rise to a magnetic moment double that of the naked vacancy. We show that for small irradiation doses vacancy-hydrogen complexes result in a macroscopic magnetic signal which agrees well with the experimental values.     

Ozonolysis of tetramethylethylene: characterization of cyclic and open-chain oligoperoxidic products

The ozonolysis of tetramethylethylene (TME) in solution to high conversion in nonparticipating solvents at -60 degrees C yields predominantly oligoperoxides. For the first time, these products have been characterized using electrospray ionization mass spectrometry (ESI-MS) under soft ionization conditions. The predominant structure formed in reactions carried out in pentane (up to 2.0 M TME) is shown to be the cyclic hexamer of acetone carbonyl oxide (oligocarbonyl oxide with degree of polymerization, n = 6), but cyclic structures with n up to 19 are observed. A small proportion of the oligoperoxides formed are open-chain compounds with end groups that suggest that chain termination of oligocarbonyl oxides can occur through reaction with either water or hydrogen peroxide. Ozonolysis in dried butyl acetate similarly produces mainly cyclic oligoperoxides. However, ozonolyses carried out in undried butyl acetate yield mainly open-chain oligoperoxides, confirming that propagating carbonyl oxide chains are readily terminated by water. Relative amounts of the open-chain oligomers so-formed suggest that undried butyl acetate contains ca. 0.1% w/w water. The ozonolysis of TME in the participating solvent, methanol, at -60 degrees C yields 2-methoxyprop-2-yl hydroperoxide via reaction of acetone carbonyl oxide with methanol; no oligoperoxidic products are formed in this case.     

REVERSIBLE BLEACHING OF Chlamydomonas reinhardtii RHODOPSIN in vivo

Abstract— The effect of hydroxylamine on the phototactic activity of Chlamydomonas reinhardtii was investigated. The following results were obtained: (1) wild type cells, irradiated for 10 min with green light immediately after addition of 1 mM hydroxylamine, showed a 20 min transient loss of phototactic activity, (2) irradiation of cells, preincubated in the dark with 4 mM. hydroxylamine for 30 min, diminished the phototactic sensitivity permanently by more than 100-fold without loss of cell motility. (3) The phototactic sensitivity completely recovered within 3(1 min of the removal of hydroxylamin from carotenoid-containing cells or from carotenoid-negative cells upon addition of 11- cis or all- trans retinal. Our explanation is bleaching of rhodopsin by more than 99% and reconstitution by de novo synthesized or by added retinal.     

Probing organic layers on the TiO2(110) surface

In this work, we use first principles simulations to provide features of the dynamic scanning force microscopy imaging of adsorbed organic layers on insulating surfaces. We consider monolayers of formic (HCOOH) and acetic (CH(3)COOH) acid and a mixed layer of acetic and trifluoroacetic acids (CF(3)COOH) on the TiO(2)(110) surface and study their interaction with a silicon dangling bond tip. The results demonstrate that the silicon tip interacts more strongly with the substrate and the COO(-) group than the adsorbed acid headgroups, and, therefore, molecules would appear dark in images. The pattern of contrast and apparent height of molecules is determined by the repulsion between the tip and the molecular headgroups and by significant deformation of the monolayer and individual molecules. The height of the molecule on the surface and the size of the headgroup play a large role in determining access of the tip to the substrate and, hence, the contrast in images. Direct imaging of the molecules themselves could be obtained by providing a functionalized tip with attraction to the molecular headgroups, for example, a positive potential tip.