Orientation of Cs 6p 2P3/2 atomic photofragments in a magnetic field: interference in the photodissociation of diatomic molecules

In a magnetic field, Cs₂ molecules were excited from the ground X¹Σ⁺_g(v_X=0,J_X=55) level to the D ¹Σ⁺_u(v=46,J=54) level by dissociation laser light linearly polarized parallel to the field, for which the magnetic sublevels were degenerated and thus all the transitions between them were simultaneously stimulated. Probe laser light excited the dissociated Cs 6p²P_3/2 atomic fragments to 6p²D_3/2 level and the resultant 6p²P_1/2 - 6d²D_3/2 emission was detected as the function of the wavelength of the probe light. The populations of the 6p²P_3/2,mj magnetic sublevels were determined from the relative strengths of the 6p²P_3/2,mj - 6d²D_3/2,m'j transitions induced by the probe light. Non-zero orientation O₀ was found in the ensemble of dissociated Cs 6p²P_3/2 atomic fragments. The orientation O₀ increased as the magnetic field strength increased. It was demonstrated both experimentally and theoretically that the orientation O₀ was induced through the interference in the excitation and dissociation paths in the presence of an external magnetic field, even when all degenerated transitions between the magnetic sublevels of the molecules are simultaneously excited by the light linearly polarized parallel to the field.     

Photocontrollable cation extraction with crowned oligo(spirobenzopyran)s.

The photoinduced changes of metal-ion extractability of crown ether derivatives bearing three or four spirobenzopyran moieties and their analogues were studied using 1,2-dichloroethane as the organic solvent. Under dark conditions, these compounds extracted Cu2+, Ag+, and Pb2+ with their counteranions from the aqueous phase to the organic phase. The extraction equilibrium constants of the photochromic crown ether derivatives for Cu2+ and Ag+ were determined successfully. Under UV-light irradiation conditions, the extraction of Cu2+ by crowned tris(spirobenzopyran) was enhanced, while that of Ag+ was suppressed. During the competitive metal-ion extraction of crowned oligo(spirobenzopyran)s between Cu2+ and Ag+, the metal-ion selectivity was reversed explicitly by photoirradiation.     

A non‐linear k–ε model with realizability for prediction of flows around bluff bodies

The incompressible flow around bluff bodies (a square cylinder and a cube) is investigated numerically using turbulence models. A non‐linear k–ε model, which can take into account the anisotropy of turbulence with less CPU time and computer memory then RSM or LES, is adopted as a turbulence model. In tuning of the model coefficients of the non‐linear terms are adjusted through the examination of previous experimental studies in simple shear flows. For the tuning of the coefficient in the eddy viscosity (=C_μ), the realizability constraints are derived in three types of basic 2D flow patterns, namely, a simple shear flow, flow around a saddle and a focal point. C_μ is then determined as a function of the strain and rotation parameters to satisfy the realizability. The turbulence model is first applied to a 2D flow around a square cylinder and the model performance for unsteady flows is examined focussing on the period and the amplitude of the flow oscillation induced by Karman vortex shedding. The applicability of the model to 3D flows is examined through the computation of the flow around a surface‐mounted cubic obstacle. The numerical results show that the present model performs satisfactorily to reproduce complex turbulent flows around bluff bodies. Copyright © 2003 John Wiley & Sons, Ltd.     

Baseline noise and measurement uncertainty in liquid chromatography.

The stochastic properties of baseline noise in HPLC systems with a UV photo-diode array, photo-multiplier and gamma-ray detector were examined by dividing the noise into auto-correlated random process (Markov process) and an independent process (white noise). The present work focused on the effect of the stochastic noise properties on a theoretical estimation of the standard deviation (SD) of area measurements in instrumental analyses. An estimation theory, called FUMI theory (Function of Mutual Information), was taken as an example. A computer simulation of noise was also used. It was shown that the reliability (confidence intervals) of theoretical SD estimates mainly depends on the following factors: the ratio of the white noise and Markov process occurring in the baselines; the number of data points used for the estimation; the width of a target peak for which the SD is estimated.     

Influence of blood proteins on biomedical analysis. XII. Effects of glycation on gliclazide (oral hypoglycemic drug)-binding with serum albumin in diabetics.

The sera of diabetic patients showed an inverse correlation (r = -0.67, n = 57) between free gliclazide (oral hypoglycemic drug) level and the fructosamine value. The binding capacity of the primary binding site for gliclazide in the albumin molecule was increased from 4.5 x 10(-4) to 8.0 x 10(-4) M-1 by glycation of albumin, but not that of the secondary binding site (1.2 x 10(-4) M-1). This suggests that the glycation of albumin increases its total binding capacity for gliclazide, resulting in a low free gliclazide level. Therefore, a low hypoglycemic activity of the drug is observed when it is administered to diabetic patients with hyperglycemia.     

Optical resolution of racemic amino acid derivatives with molecularly imprinted membranes bearing oligopeptide tweezers

Molecularly imprinted polymeric membranes were prepared from various oligopeptide tweezers by the adoption of N‐α‐tert‐butoxycarbonyl‐D ‐tryptophan (Boc‐D ‐Trp) or N‐α‐tert‐butoxycarbonyl‐L ‐tryptophan (Boc‐L ‐Trp) as a print molecule. The chiral recognition ability of the formed molecular recognition sites was dependent on the absolute configuration of the print molecule adopted in the membrane preparation (molecular imprinting) process, whereas the candidate oligopeptide tweezers consisted of the L ‐amino acid residues. In other words, the membranes imprinted by the D ‐isomer recognized the D ‐isomer in preference to the corresponding L ‐isomer, and vice versa. The affinity constant between the target molecule and the chiral recognition site from the oligopeptide tweezers was higher than that from a single‐strand oligopeptide derivative. Those membranes selectively transported the enantiomer, which was preferentially incorporated into the membrane by dialysis. The permselectivities for these membranes exceeded their adsorption selectivities. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 385–396, 2005     

Isolation and characterization of isolectins from Erythrina variegata seeds.

Three isolectins were isolated from seeds of Erythrina variegata (Linn.) var. Orientalis by ion-exchange chromatography, followed by affinity chromatography on lactose-Sepharose 4B and acid-treated Sepharose 4B columns. The purified isolectins (EVLI, EVLII and EVLIII) are all specific for galactopyranosides and N-acetylgalactosamine, and their affinities for simple sugars are EVLIII greater than EVLII greater than EVLI. EVLI and EVLIII are homodimers made up of an A-subunit of molecular mass 36,000 and a B-subunit of molecular mass 33,000, whereas EVLII is a heterodimer composed of the A- and B-subunits. Upon treatment with trifluoromethansulphonic acid, the molecular masses of both subunits decreased to 31,000. Rechromatography of EVLII on the acid-treated Sepharose 4B column again produced the homodimeric lectins (EVLI and EVLIII). It is suggested that the constituent subunits of Erythrina variegata isolectins are eschangeable with each other in vitro.     

Demonstration of laser-frequency upshift by electron-density modulations in a plasma wakefield

In a plasma wake wave generated by a high power laser, modulations of the electron density take the shape of paraboloidal dense shells, moving almost at the speed of light. A counterpropagating laser pulse is partially reflected from the shells, acting as relativistic flying mirrors, producing a time-compressed frequency-multiplied pulse due to the double Doppler effect. The counterpropagating laser pulse reflection from the plasma wake wave accompanied by its frequency multiplication (with a factor from 50 to 114) was detected in our experiment.