Preparation of 1-hydroxyethyl-2-trideuteriomethyl-5-nitroimidazole

The title compound was prepared by two different procedures. The first route starts with acetonitrile-d₃ and goes through 2-trideuteriomethyl-5-nitroimidazole ( 6 ) (Scheme I). The second and more convenient process is direct labeling of metronidazole ( 1 ) with alkaline ethanol-d₁.     

Synthetic hologram made by variable magnification imaging system

For the purpose of improving the utilization efficiency of the gain bandwidth of active media and generating stable ultrashort light pulses, a passive-active mode locking technique has been applied to a cw Rhodamine 6G dye laser. A sufficient ability of this technique for the elimination of the multiple-pulse operation of the mode locking at a higher pumping level and a longer resonator length has been proved. Observed pulse-width by the SHG autocorrelation technique is 1.4 ps with assuming a sech² pulse profile.     

Facile synthesis of thiacalix[n]arenes (n=4, 6, and 8) consisting of p-tert-butylphenol and methylene/sulfide alternating linkage and metal-binding property of the n=4 homologue

2,14-Dithiacalix[4]arene 3₄ was conveniently prepared in 16% yield by acid-catalyzed cyclocondensation of 2,2^′-thiobis[4-tert-butylphenol] with formaldehyde. The present method also afforded the first isolation of the analogues with six and eight phenol units, 3₆ (10%) and 3₈ (5%), respectively. Solvent extraction showed that 3₄ had high selectivity toward Cu²⁺ ion at pH 5.5 by coordination of the bridging sulfur with cooperative donation of the adjacent phenolate oxygens.     

Photoviscoelastic analysis of thermal stress in a quenched epoxy beam

This paper reports on a procedure for photoviscoelastic analysis where the axes of principal stress, principal strain and polarization of light coincide in the presence of a large temperature change. More specially, the transient-thermal stress and strain due to stress in an epoxy beam subjected to quenching from both the upper and lower surfaces, are determined using the time-temperature-equivalent law for stress, strain and birefringence. The transient-thermal stress and strain in the beam were determined experimentally using hereditary integrations from the measurement of the transient temperature and birefringence due to the quenching of the beam. The transient thermal stress and strain were also calculated theoretically using the linear-viscoelastic theory. The experimentally determined thermal stress agrees closely with the theoretical results. The experimentally determined strain agrees qualitatively with the theoretical values. Thus, it is concluded that the photoviscoelastic technique is useful in analyzing the proposed problem.Paper was presented at 1982 SESA/JSME Spring Meeting held in Maui and Oahu, HI on May 23–28, 1982.     

Smell and Stress Response in the Brain: Review of the Connection between Chemistry and Neuropharmacology

The stress response in the brain is not fully understood, although stress is one of the risk factors for developing mental disorders. On the other hand, the stimulation of the olfactory system can influence stress levels, and a certain smell has been empirically known to have a stress-suppressing effect, indeed. In this review, we first outline what stress is and previous studies on stress-responsive biomarkers (stress markers) in the brain. Subsequently, we confirm the olfactory system and review previous studies on the relationship between smell and stress response by species, such as humans, rats, and mice. Numerous studies demonstrated the stress-suppressing effects of aroma. There are also investigations showing the effects of odor that induce stress in experimental animals. In addition, we introduce recent studies on the effects of aroma of coffee beans and essential oils, such as lavender, cypress, α-pinene, and thyme linalool on the behavior and the expression of stress marker candidates in the brain. The transfer of volatile components into the brain is also discussed while using the results of thyme linalool as an example. These studies may provide a good opportunity to connect chemical research at the molecular level with neuropharmacological approaches in the future.     

A new approach for quantitative analysis of l-phenylalanine using a novel semi-sandwich immunometric assay

Here, we describe a novel method for l-phenylalanine analysis using a sandwich-type immunometric assay approach for use as a new method for amino acid analysis. To overcome difficulties of the preparation of high-affinity and selectivity monoclonal antibodies against l-phenylalanine and the inability to use sandwich-type immunometric assays due to their small molecular weight, three procedures were examined. First, amino groups of l-phenylalanine were modified by “N-Fmoc-l-cysteine” (FC) residues and the derivative (FC-Phe) was used as a hapten. Immunization of mice with bovine serum albumin/FC-Phe conjugate successfully yielded specific monoclonal anti-FC-Phe antibodies. Second, a new derivatization reagent, “biotin linker conjugate of FC-Phe N-succinimidyl ester” (FC(Biotin)-NHS), was synthesized to convert l-phenylalanine to FC-(Biotin)-Phe as a hapten structure. The biotin moiety linked to the thiol group of cysteine formed a second binding site for streptavidin/horseradish peroxidase (HRP) conjugates for optical detection. Third, a new semi-sandwich-type immunometric assay was established using pre-derivatized l-phenylalanine, the monoclonal anti-FC-Phe antibody, and streptavidin/HRP conjugate (without second antibody). Using the new “semi-sandwich” immunometric assay system, a detection limit of 35 nM (60 amol per analysis) and a detection range of 0.1–20 μM were attained using a standard l-phenylalanine solution. Rat plasma samples were analyzed to test reliability. Intra-day assay precision was within 6 % of the coefficient of variation; inter-day variation was 0.1 %. The recovery rates were from 92.4 to 123.7 %. This is the first report of the quantitative determination of l-phenylalanine using a reliable semi-sandwich immunometric assay approach and will be applicable to the quantitative determination of other amino acids.     

Symmetry switching of the fluorescent excited state in alpha,omega-diphenylpolyynes

By using MO calculations based on DFT, absorption, and fluorescence spectroscopy, we have comprehensively studied the low-lying excited singlet states of alpha,omega-diphenylpolyynes (DPY) having 1-6 triple bonds. The a(g) vibrational modes of the C(triple bond)C stretching and of the phenyl ring motion were observed in the fluorescence spectra of diphenylacetylene and 1,4-diphenylbutadiyne. On the other hand, in the fluorescence spectra of the long DPY with the triple-bond number (N) more than two, the phenyl ring motion with a(g) symmetry disappeared and the b(1g) modes of the phenyl ring twisting (approximately 400 cm(-1)) and of the C-H bending (approximately 900 cm(-1)) were detected. The observed fluorescent states of DPY with N < or = 2 and N > or = 3 are assigned to the 1(1)B(1u) (pi(x)pi(x*)) and 1(1)A(u) (pi(x)pi(y*) and/or pi(y)pi(x*)) states, respectively, based on the vibronic structures, the relatively short lifetimes, and the solvatochromic shifts of the fluorescence spectra. Not only the allowed transition of 1(1)B(1u) <-- S(0) but also the forbidden transition of 1(1)A(u) <-- S(0) was detected in the fluorescence excitation spectra of the long DPY with N > or = 3. The low-lying excited state with A(u) symmetry is characteristic in polyyne, which does not exist in polyene. The oscillator strength (f) of the first absorption band in DPY decreases with an increase in N, which is the opposite behavior of the all-trans-alpha,omega-diphenylpolyenes. The N-dependence of the f value is understood by the configuration interaction between the 1(1)B(1u) and 2(1)B(1u) (pi(y)pi(y*)) states, which is consistent with the reduction of the nonlinear optical response of polyyne.