Molecular vibrations and force fields of alkyl sulfides: Part XV. C-S stretching vibrations of aliphatic alkyl sulfides

The C-S stretching vibrations of 28 aliphatic sulfides including one thiol are summarized, and all of the C-S stretching bands are classified into several groups. An extraordinarily low frequency associated with the ethyl group is discussed briefly.     

Carbon-13 NMR studies of the biologically active nor-diterpenoid dilactones from Podocarpus plants

Carbon-13 NMR signals of the biologically active norditerpenoid dilactones from Podocarpus plants were fully assigned by using selective ¹H decoupling, coupling constants (²J_CH), spin-lattice relaxation times (T₁) and correlation of the spectra of more than thirty dilactone congeners. The spectra of five nagilactones, B, C, D, E and F, which constitute representative members of three major structural types of the dilactones: (A) 8:14, 9:11-dienolide (α-pyrone) type, (B) 7α:8α-epoxy-9:11-enolide type, and (C) 7:8,9:11-dienolide type, were extensively analysed. Some characteristic steric interactions for the substituents on the ring system can be demonstrated from the spectral properties.     

Overtone intensities in resonance Raman scattering

A model calculation of resonance Raman scattering tensors has been carried out for a diatomic molecule with a harmonic potential for the ground state and a linear repulsive potential for the excited state. Expressions for scattering tensors have been obtained by using a series of recurrence formulas induced from the Green function of the nuclear hamiltonian of the repulsive potential of the excited state and nuclear wavefunctions for the harmonic potential. The relative scattering intensities of overtones depend on the gradient of the repulsive potential curve and are interpreted in terms of the overlap integrals between nuclear wavefunctions of upper and lower states.     

Raman probe using a single hollow waveguide

A simple Raman probe was realized using a single flexible hollow waveguide (HW). A HW coated with a silver film, which had reasonable transmission and little optical background noise, was used as a bidirectional transmission fiber for both the excitation and collection of Raman scattered light. The HW itself generated no Raman scattering or fluorescence noise during transmission. A complex filtering system at the end of the waveguide was thus unnecessary. In addition, the measured Raman spectra showed better signal-to-noise ratios than a conventional Raman fiber probe. The HW's suitability as a Raman fiber probe was also demonstrated.     

Carbonyl orientation determines regio- and enantioselectivity in 1,2-/1,4-reduction of an NAD model compound

An optically active, axially chiral NAD model compound(1) with a quinoline ring system was reduced by the chiral NADH model compound (4), affording a mixture of 1,2- and 1,4-dihydroquinolines. The carbonyl orientation governs the molecular arrangement in the transition state of the reaction and determines the regio- and enantioselectivity of the product.     

Development of a novel analytical method for determination of chondroitin sulfate using an in-capillary enzyme reaction

A novel analytical method for determination of total amount of chondroitin sulfate (CS) based on its conversion to desulfated chondro-disaccharide via an enzyme-catalyzed reaction, was developed. Using the in-capillary enzyme reaction, the method was also applied to the successful construction of an on-line analytical system. Within this system, electrophoretic migration was used to mix zones containing the enzyme mixture (chondroitinase ABC, chondro-4-sulfatase, chondro-6-sulfatase and 2-o-sulfatase) and the substrate (CS). The reaction was then allowed to proceed in the presence of a weak electric field and, finally, the product (desulfated chondro-disaccharide) of enzyme reaction migrated to the detector under the influence of an applied electric field. A polyvinyl alcohol-coated capillary was used to reduce protein adsorption. Desulfated chondro-disaccharide was successfully migrated toward the anode in 10 mM Tris-acetate buffer (pH 7.0) under reversed polarity and detected at 232 nm. The established method was validated and demonstrated to be applicable in the determination of total amount of CS in a commercial ophthalmic solution. No interference from the formulation excipients was observed. Good linearity was obtained, with correlation coefficients above 0.999. Recoveries and precisions ranged from 100.0 to 100.5%, and from 0.2 to 0.6% of the relative standard deviation, respectively. Good agreement was obtained between the established method and traditional photometric method based on carbazole reaction. In this study, application of the method to disaccharide compositional analysis was also performed.     

Vortex fluctuations in underdoped Bi(2)Sr(2)CaCu(2)O(8+delta) crystals

Vortex thermal fluctuations in heavily underdoped Bi(2)Sr(2)CaCu(2)O(8+delta) (T(c)=69.4 K) are studied using Josephson plasma resonance. From the zero-field data, we obtain the c-axis penetration depth lambda(L,c)(0)=230+/-10 micrometer and the anisotropy ratio gamma(T). The low plasma frequency allows us to study phase correlations over the whole vortex solid state and to extract a wandering length r(w) of vortex pancakes. The temperature dependence of r(w) as well as its increase with dc magnetic field is explained by the renormalization of the vortex line tension by the fluctuations, suggesting that this softening is responsible for the dissociation of the vortices at the first order transition.     

Dopant-pair structures segregated on a hydrogen-terminated Si(100) surface

Novel atomic structures on a H-terminated Si(100)-(2x1)-H surface were found using scanning tunneling microscopy (STM). The structures are distinguishable only from Si dimers in empty-state STM images. They were observed on arsenic- and phosphorus-doped substrates, but not on boron-doped substrates. Surface density of these structures was found to be proportional to the dopant density in the substrate. First-principles calculations clarify that they are consisting of dopant pairs that are segregated from the bulk material. Hydrogen atoms attached to the dopant pair are found to flip between two positions on the surface due to a quantum effect.