Asymmetric reduction of 7,8-difluoro-3-methyl-2H-1,4-benzoxazine. Synthesis of a key intermediate of (S)-(-)-ofloxacin (DR-3355)

An efficient, highly enantioselective synthesis of (S)-(-)-7,8-difluoro-2,3-dihydro-3-methyl-4H-1,4-benzoxazine, a key intermediate of (S)-(-)-ofloxacin, using various chiral sodium triacyloxyborohydrides as reducing agents is reported.     

Determination of cyanide using a microbial sensor

A microbial cyanide sensor was prepared, consisting of immobilizedSaccharomyces cerevisiae and an oxygen electrode. When the electrode was inserted into a solution containing glucose, the respiration activity of the microorganisms increased. The change in the respiration activity is monitored with the oxygen electrode. When cyanide is added to the sample solution, the electron transport chain reaction of the respiration system in the mitochondria is inhibited, resulting in a decrease in respiration. The inhibition is caused by cyanide binding with respiration enzymes such as the cytochrome oxidase complex in the mitochondrial inner membrane. Therefore, the cyanide concentration can be measured from the change in the respiration rate. When the sensor was applied to a batch system at pH 8.0 and 30°C, the cyanide calibration curve showed linearity in the concentration range between 0.3 μM and 150 μM CN-.     

Synthesis and properties of a novel fluorescent nucleobase, naphthopyridopyrimidine

A new base-discriminating fluorescent nucleoside, NPP, that can sharply distinguish between A and G bases opposite NPP is described. The hybridization of an ODN probe containing NPP with a target DNA facilitates the judgment of the type of purine base located at a specific site on the target DNA.     

Sensitive amplification immunoassay for human IgG and anti-human IgG by using an enzyme cascade system

A sensitive heterogeneous immunoassay for human IgG and anti-human IgG was developed using an enzyme cascade system in limulus amoebocyte as a signal amplification system. Lipopolysaccharide (LPS) was conjugated to human IgG and anti-human IgG was adsorbed on polystyrene beads. The LPS-labelled human IgG mixed with unlabelled human IgG was allowed to react in a competitive manner with the immobilized anti-IgG on the polystyrene bead surface. After B/F separation, the LPS activity in the supernatant (free) and LPS activity on the bead (bound) were measured by using the chromogenic limulus test. IgG could be measured in the range 10^?7-10^?11 g ml^?1. LPS-labelled anti-IgG and IgG absorbed on polystyrene beads were prepared, and LPS-labeled anti-IgG mixed with unlabelled anti-IgG was allowed to react again in a competitive manner with solid-phase IgG. The LPS activity specifically bound to the bead was then measured. Anti-IgG could be measured in the range 10^?7-10^?11 g ml^?1.     

Enhancing the information content of vibrational spectra through sample perturbation

Infrared and Raman band frequencies, intensities and line shapes are often sensitive to the local molecular environment determined by molecular conformation, surrounding matrix, temperature, pressure, etc. The variety of local environments experienced by a condensed-phase molecule can lead to vibrational spectra with broad bands containing many overlapped spectral features. The spectral resolution of these overlapped features can be enhanced by making perturbations to the sample environment. Examples of perturbations which can be applied to the sample to enhance the information content of infrared spectra are changes in temperature, concentration and mechanical strain. In each instance, the spectra obtained as a function of the perturbation can be cross-correlated to produce a two-dimensional correlation map defined by two independent wavenumber axes. in this representation, infrared bands which respond to the perturbation in a similar or different manner can be clearly identified. This information can be used to help resolve overlapped bands and make unambiguous band assignments.     

Phase diagram and phase structure of the sodium di-n-pentyl phosphate-water system.1H pulsed-gradient NMR self-diffusion,31P NMR and x-ray diffraction studies

Sodium di-n-pentylphos phate (DPP) has been synthesized, and the phase diagram of the DPP-water system consisting of five regions (I, II, III, IV, and V) has been determined. The phase structure has been investigated by¹H pulsed-gradient NMR self-diffusion,³¹P NMR and x-ray low angle diffraction methods. The results are summarized as follows. In region I, there exist two critical micelle concentrations (CMC), indicating that this region is in a monomer-micelle equilibrium and that variation in the aggregated state occurs at the second CMC. Region II is a two phase area in which regions I and IV coexist. In region III, hydrated crystals and an aqueous solution of DPP coexist. Region IV is a homogenous, transparent and fluid phase and the results of³¹P NMR spectra and x-ray diffraction patterns reveal the formation of a highly organized structure, similar to a lamellar-like structure. Region V is a homogenous, transparent and fluid phase and the self-diffusion coefficient value and³¹P NMR spectra show that its phase structure is very similar to that for the concentrated sample in region I.     

Liquid-crystalline phase development of a mesogen-jacketed polymer-application of two-dimensional infrared correlation analysis

Two-dimensional correlation spectroscopy has been applied to study PMPCS (poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene}), a representative example of mesogen-jacketed liquid crystalline polymers. With the precise analysis of a series of Fourier transform infrared (FTIR) spectra of PMPCS recorded at varied temperatures, a reasonable mechanism of the development of liquid crystalline (LC) phase is proposed. Before the phase transition, the conformational change of individual side chains occurs sooner than that of the backbone due to the larger motional freedom of the side chains. After the phase transition, however, the readjustment of still somewhat mobile backbone occurs before the ordered, rigid, and mutually interacting side chains. That is, phase transition leading to the LC phase formation brings in a new cooperative restriction of motions to the segments.     

Cadmium,copper and zinc concentrations in hair of inhabitants of a cadmium polluted area

To investigate the present situation of inhabitants living in the cadmium polluted area of Toyama Prefecture of Japan, 95 hair samples were analyzed by neutron activation method. The median and the geometric standard deviation were determined from a cumulative frequency distribution curve of the elemental concentrations for each of 3 groups: male, female without perm and female with perm which were divided furthermore by two age ranges: 20 age<50 and 50 age. These concentrations were compared with those in some organs and urine reported.     

Electrochemical generation of free nitric oxide from nitrite catalyzed by iron meso-tetrakis(4-N-methylpyridiniumyl)porphyrin

Electrochemical generation of free nitric oxide (NO) from nitrite (NO(2)(-)) catalyzed by iron meso-tetrakis(4-N-methylpyridiniumyl)porphyrin, [Fe(III)(TMPyP)](5+), has been developed in this study. To obtain free NO, a cathodic electrolysis and an anodic electrolysis were performed in two connected flow electrolytic cells in sequence. The flow electrolytic cell upstream was used for cathodic electrolysis, where the solution of [Fe(III)(TMPyP)](5+) and NO(2)(-) was reduced at -0.25 V (vs Ag/AgCl) into [Fe(II)(NO(2)(-))(2)(TMPyP)](2+) and [Fe(II)(NO)(TMPyP)](4+) in sequence. The flow electrolytic cell downstream was utilized for anodic electrolysis, where [Fe(II)(NO)(TMPyP)](4+) formed from the upstream cell was oxidized at +0.40 V (vs Ag/AgCl) into [Fe(III)(TMPyP)](5+) and free NO. Finally, NO was bubbled out from anodic electrolyte by argon gas. The mechanism and the optimum conditions for electrochemical generation of NO from NO(2)(-) catalyzed by [Fe(III)(TMPyP)](5+) were studied in detail by voltammetric and spectroelectrochemical methods.