Effect of halogen atom on electron spin polarization studied by CIDEP,using halogen substituted aromatic acyl compounds

The reaction and spin dynamics of the photocleavage reaction of 2-chloro-2′-acetylnaphthalene were studied by time-resolved FT-EPR and transient absorption (TA) spectroscopy. The photocleavage reaction from both singlet and triplet states was observed by TA and EPR experiments, although the radical cleavage reaction in the excited triplet state is energetically unfavourable. This feature has been explained by the ionic cleavage reaction due to the electro-negativity of the chlorine atoms. The time-resolved FT-EPR spectra were similar to those observed in the bromine substituted compound, 2-BAN, reported in a previous paper. The origin of the electron spin polarization was assigned to the radical triplet pair mechanism (RTPM) and free radical pair mechanism (F-pair RPM) from analysis of the time profiles of the spin polarization.     

x-RAY PHOTOELECTRON VALENCE BAND STUDIES ON FIREFLY D-(-)-LUCIFERIN

Abstract— The valence band spectrum of firefly D-(-)-luciferin (Ln) was measured for the first time by x-ray photoelectron spectroscopy (XPS). Since the conversion of Ln to decarboxydehydroluciferin (dcrL) by x-ray irradiation occurred even within ∼30 min, the effect of the irradiation on the valence band spectrum of Ln was investigated quantitatively. We found that the XPS valence band spectrum of Ln during irradiation for 3 h corresponds to the state density of Ln calculated by the LCAO-ASMO-SCF-CI method for π-electrons. Moreover, the weak coupling model for π-electron transfer between Ln and oxygen was proposed for the primary electronic process in Ln chemiluminescence, assuming that the calculated π-electron state densities of Ln in acidic and basic solutions reflect the characteristics of their XPS valence band spectra.     

ABSORPTION SPECTRA OF TCA-DENATURED RHODOPSIN AND OF A SCHIFF BASE COMPOUND OF RETINAL

Abstract— When TCA-denatured rhodopsin was frozen in liquid nitrogen, Λ_max was markedly shifted to longer wavelengths as the concentration of TCA increased. After TCA denaturation, species specific absorption disappeared and the absorption maxima of the squid pigments became identical with those of corresponding pigments of octopus.
In solutions at 5° the bathochromic shift of Λ_max of TCA denatured rhodopsin was observed at higher concentrations of TCA than in the frozen state. Λ_max of N-retinylidene-butylamine (NRB) was also displaced towards longer wavelengths with increasing concentrations of TCA. This bathochromic shift was enhanced by freezing. The mode of the bathochromic shift of Λ_max provoked by TCA was very similar both in the cases of denatured rhodopsin and of NRB. The absorption spectrum of NRB was identical in shape with that of TCA-denatured rhodopsin, as the half-band widths of both materials were about 5500 cm^-1 in the liquid state and 5000 cm^-1 in the frozen state. Λ_max of retinal and NRB were red shifted in polar and polarizable solvents.
It was concluded that the strong acidity and the relatively large polarizability of TCA are responsible for the bathochromic shift of Λ_max of the Schiff base in TCA-denatured rhodopsin.     

Cellulose/poly(acryloyl morpholine) composites: synthesis by solution coagulation/bulk polymerization and analysis of phase structure

Cellulose/poly(acryloyl morpholine) (CELL/PACMO) compo sites were synthesized by bulk polymerization in the gel state of cellulose impregnated with reactive ACMO monomer. The thermal transition behaviour and phase structure of the CELL/PACMO composites obtained in film form were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and solid-state 13C NMR spectroscopy. For compositions rich in PACMO (CELL 30 wt %), it was revealed by DSC and DMA that the synthesized samples gave a composition-dependent Tg value higher than that of PACMO homopolymer, and the magnitude of the lowering of their dynamic modulus E in the glass transition region became extremely small in comparison with the corresponding drop in E noted for plain PACMO samples. These observations were interpreted as being due to the development of an interpenetrating polymer network (IPN)-type organization, resulting from successful fixation of an original netw ork structure of cellulose gels into the polymerized bulks. From the measurements of proton spin-lattice relaxation times in the NMR study, the IPN-like composites were estimated to be substantially homogeneous on a scale of a few nanometers. 0969--0239 © 1998 Blackie Academic & Professional     

STUDY ON THE DUCTILE DEFORMATION DOMAIN OF THE SIMPLE SHEAR IN ROCKS——TAKING BRITTLE FAULTS OF THE COVERING STRATA IN THE SOUTHERN JIANGSU AREA AS AN EXAMPLE

A study on the ductile deformation domain of the brittle fault in the shallow level ofthe crust is a new probe field for the modern structural geology. Taking the southern Jiang-su Province area as an example the orientation measurement of quartz crystals, the com-positional texture observation of three pressure sensitive minerals and the rheological param-eter determination of dislocation densities, etc. have been demonstrated and analysed basedon typical samples in the present paper. In addition, their generation mechanisms arealso discussed from the cataclastic rheology, the dynamic differentiation and the simpleshearing, specially, from the Ode strength theory. Finally, a generative relationship betweenthe ductile deformation domain of the brittle fault system, in the regional layer--slip andthe formation of the stratabound ore deposit is shown as well.     

Neuronal mechanism of epileptogenesis in EL mouse

The convulsions of the EL mouse (EL) were described by Imaizumi et al. in 1954 and were established as epilepsy by Suzuki in 1976. The EL mouse has been kept as an inbred strain and is considered one of the best animal models originated in Japan. The mode of inheritance is autosomal dominant, and environmental risk factors for seizure occurrence are hypothesised to contribute to the polygenic background. Paroxysmal activities in the EL brain arise from the parietal cortex (PCX) and are augmented in the hippocampus, demonstrated by electrophysiology and autoradiography using 2-deoxy glucose when clinical symptoms of seizures appeared. The neurons in the EL PCX, where GABA activity is lower than that of DDY PCX demonstrate increased excitability to proprioceptive sensory input. After repetitive seizure-provoking stimuli, seizures are more easily induced, eventually occurring spontaneously. This phenomenon of “abnormal plasticity” is also observed in the EEG, decreasing GABA activity, expression of the immediately early gene, and various biochemical and molecular processes. This phenomenon is similar to the learning or progressive process of certain neurological diseases.     

Photocleavage reaction of bromine substituted aromatic acyl compounds studied by CIDEP and transient absorption spectroscopy

The photocleavage of the CBr bond in bromoacetylnaphthalene is investigated by transient absorption and time resolved EPR spectroscopy. In the transient absorption of 2-bromo-2′-acetylnaphthalene, the absorption band observed at λ_max ~440 nm is assigned to the triplet state of the parent molecule. After decay of the triplet absorption, a long lived absorption band is observed at λ_max ~380 nm, which is assigned to naphthoylmethyl radical. The yield of this radical is not dependent on the concentration of oxygen even though the absorption band of the triplet state was quenched by addition of oxygen. Thus we conclude that the spin multiplicity of the precursor molecule is singlet. The CW time resolved EPR spectrum shows a typical E?/A CIDEP pattern of three hyperfine lines of the naphthoylmethyl radical. This result suggests some contribution from triplet precursor molecules. However, a careful analysis of the time profile of the CIDEP intensity observed by FT-EPR revealed that the polarization is generated from the radical pair mechanism (RPM) from the encountered pair of two free naphthoylmethyl radicals and the radical-triplet pair mechanism. RPM polarization by the geminate radical pair, formed by the Br atom and the naphthoylmethyl radical, is not observed. This fact indicates that large spin-orbit coupling (Δg and/or fast spin relaxation by g anisotropy) spoils the RPM polarization. The finding is in contrast to the recent observation of RPM polarization in the Cl cleavage reaction of 1-(chloromethyl)naphthalene.     

JF1/B6F1 Ngly1−/− mouse as an isogenic animal model of NGLY1 deficiency

N-Glycanase 1 (NGLY1) deficiency is a congenital disorder caused by mutations in the NGLY1 gene. Because systemic Ngly1^−/− mice with a C57BL/6 (B6) background are embryonically lethal, studies on the mechanism of NGLY1 deficiency using mice have been problematic. In this study, B6-Ngly1^−/+ mice were crossed with Japanese wild mice-originated Japanese fancy mouse 1 (JF1) mice to produce viable F₂ Ngly1^−/− mice from (JF1×B6)F₁ Ngly1^−/+ mice. Systemic Ngly1^−/− mice with a JF1 mouse background were also embryonically lethal. Hybrid F1 Ngly1^−/− (JF1/B6F1) mice, however, showed developmental delay and motor dysfunction, similar to that in human patients. JF1/B6F1 Ngly1^−/− mice showed increased levels of plasma and urinary aspartylglycosamine, a potential biomarker for NGLY1 deficiency. JF1/B6F1 Ngly1^−/− mice are a useful isogenic animal model for the preclinical testing of therapeutic options and understanding the precise pathogenic mechanisms responsible for NGLY1 deficiency.     

Water vapour density measurement in halogen lamps using near-infrared semiconductor laser spectrometry II Actual lamp bulb measurement

Non-destructive, quantitative measurement for the amount of water vapour included in halogen lamp bulbs has been carried out. Residual water vapour density in lamp bulbs was confirmed as several hundreds of ppm by using a working curve obtained by InGaAsP/InP semiconductor laser spectrometry in the 1.36m spectral region.     

SLEEP TIME MONITORING BY ACCELEROMETER IN TWO SUBJECTS FOR 1 YEAR

The authors conducted sleep time monitoring using an activity-detecting device on a married couple. The subjects were a 39-year-old man and a 36-year-old woman. They were continuously monitored for 1 year or a half-year from 1998 to 1999. Their daily activities were not limited. The male works in an office 5 days a week and stays at home on weekends. The female is a farmer and works in the field when the weather is clear. They usually went to bed at 10-11 p.m. and got up around 6 a.m. the next morning on weekdays. The activity-monitoring device, Actiwatch^®, was installed on the wrists of their non-dominant arms. The number of body movements was calculated by the summation of the active electricity number. There was no significant monthly difference in the mean nightly total sleep time (TST) by analysis of variance in either the husband or the wife. When nocturnal and diurnal sleep were combined for the analysis, the mean value in April or May, 1999, was significantly larger than the values in July, August, December or October, although only in the husband. The sleep time for Saturday or Sunday was significantly extended as compared to that of a weekday. Power spectrum analysis showed the TST cycle to predominate on all 7 days in the week in both subjects.