Efficient asymmetric synthesis of α-amino acids through hydrogenation of α,β-dehydroamino acid residue in cyclic dipeptides

A series of cyclo (Δaminoacyl-L-Ala) ($\text{4}$) (Δ=α,β-dehydro) were prepared from cyclo(Gly-L-Ala) and corresponding aldehyde, and hydrogenated with Pd black in MeOH. Chiral inductions producing cyclo (L-aminoacyl-L-Ala) ($\text{5}$) from $\text{4}$ were 96–99% in the case of L-Aba (2-aminobutanoic acid), L-Val, L-Leu, and L-App (2-amino-5-phenylpentanoic acid) as an L-aminoacyl moiety in $\text{5}$. Pure L-Leu, L-Aba, and L-App were synthesized in preparative scale from corresponding $\text{4}$ through asymmetric hydrogenation and acid-hydrolysis.     

Improvements in Carrier-to-Noise-Ratio (CNR) of Lightwave Amplitude Modulated Vestigial-Sideband (AM-VSB) Transmission Systems by the Use of Optical Isolators

In lightwave community antena television (CATV) systems as well as other optical fiber communication networks, a transmitted optical signal is known to be degraded by an intensity noise produced within the fiber due to the interference between the signal and doubly reflected light. We report on the improvements to the signal degradation due to the double Rayleigh backscattering by inserting optical isolators in the trunk lines of the systems. A carrier-to-noise ratio (CNR) has been calculated as a function of the number and the insertion loss of the isolators. The calculated results indicate that there is an optimum number of isolators, and if the insertion loss is less than 0.3 dB, the CNR degradation can be restored by more than 60%. To test the calculated results, we conducted experiments for the specific case of employing one isolator, and obtained good agreements between the two.     

The absorption spectrum of localized electrons in crystalline 1,8-octanediol, γ-irradiated at 4.2 K

Crystalline 1.8-octanediol has been γ-irradiated and its optical absorption spectrum has been measured at 4.2 K. The spectrum consists of three partially resolved peaks with maxima at 740, 590, and 490 nm. The peaks cannot be separated by photobleaching or annealing. It is suggested that they arise from transitions inherent in each localized electron.     

Effects of localized triplet exciton on reactivity of photoinduced omega-bond dissociation in naphthyl phenyl ketones having pi,pi* lowest triplet (T1) states studied by laser flash photolysis

Photochemical properties of photoinduced omega-bond dissociation in naphthyl phenyl ketones having a phenylthiyl moiety as a leaving group, p-(alpha-naphthoyl)benzyl phenyl sulfide (NBPS) and 4-benzoyl-1-naphthylmethyl phenyl sulfide (BNMPS), in solution were investigated by laser flash photolysis techniques. Both ketones were shown to undergo photoinduced omega-bond cleavage of the C-S bond to release the phenyl thiyl radical (PTR) at room temperature. Irrespective of excitation wavelengths of NBPS, a quantum yield (Phi(rad)) of the PTR formation was obtained to be 0.1, whereas that for BNMPS was found to depend on the excitation wavelength, i.e., absorption bands from the ground state (S0) to the excited singlet states, S3, S2, and S1 of BNMPS; Phi(rad)(S3) = 0.77 and Phi(rad)(S2) = Phi(rad)(S1) = 1.0. By using triplet sensitization of p-phenylbenzophenone (PBP), efficiencies (alpha(rad)) of the radical formation in the lowest triplet state (T1(pi,pi*)) of NBPS and BNMPS were determined to be 0 and 1.0, respectively. The agreement between Phi(rad)(S1) and alpha(rad) values for BNMPS indicates that the C-S bond dissociation occurs in the T1 state via the S1 state via a fast intersystem crossing from the S1 to the T1 state. The wavelength dependence of the radical yields upon direct excitation of BNMPS was interpreted in terms of the C-S bond cleavage in the S3 state competing with internal conversion from the S3 to the S2 state. The smaller value of Phi(rad)(S3) than those of Phi(rad)(S1) and Phi(rad)(S2) was proposed to originate from the geminate recombination of singlet radical pairs produced by the bond dissociation via the S3 state. Photoinduced omega-cleavage of NBPS was concluded to take place only in the S1(n,pi*) state. Difference in reactivity of omega-cleavage between the triplet states of NBPS and BNMPS was interpreted in terms of localized triplet exciton in the naphthoyl moieties.     

Accurate distribution and its asymptotic expansion for the tetrachoric correlation coefficient

Accurate distributions of the estimator of the tetrachoric correlation coefficient and, more generally, functions of sample proportions for the 2 by 2 contingency table are derived. The results are obtained given the definitions of the estimators even when some marginal cell(s) are empty. Then, asymptotic expansions of the distributions of the parameter estimators standardized by the population asymptotic standard errors up to order O(1/n) and those of the studentized ones up to the order next beyond the conventional normal approximation are derived. The asymptotic results can be obtained in a much shorter computation time than the accurate ones. Numerical examples were used to illustrate advantages of the studentized estimator of Fisher’s z transformation of the tetrachoric correlation coefficient.     

Synthesis and properties of a new fluorescent bicyclic 4-N-carbamoyldeoxycytidine derivative

[reaction: see text] A bicyclic 4-N-carbamoyldeoxycytidine derivative (1, dC(hpp)) geometrically locked was synthesized as a new fluorescent nucleobase. The hybridization properties of oligodeoxynucleotides containing dC(hpp) were investigated by use of T(m) analysis. It was found that dC(hpp) forms stable base pairs not only with the complementary guanine base, but also with the adenine base. Interestingly, the fluorescence of dC(hpp) was suppressed only when a dC(hpp)-dG base pair was formed.     

Chemical Bonding in Polarised Push–Pull Ethylenes

1,1‐Diamino‐2,2‐bis(triflyl)ethylenes with both twisted and planar structures around the partial “C=C” bond were synthesised. Bonding properties in these compounds were analysed by an experimental approach using high‐resolution X‐ray diffraction data treated with X‐ray wavefunction refinement (XWR). In the twisted compound, a dominant contribution of the charge‐separated resonance structure was revealed. On the contrary, the nearly planar compound still showed π‐bonding character, however, with a considerable contribution of the charge‐separated resonance structure.     

Prospective trial of a navigator setting under left hepatic lobe on magnetic resonance cholangiopancreatography using a free-breathing prospective acquisition correction technique

PURPOSE: To prospectively compare the image acquisition time and image quality obtained by navigator setting under the left hepatic lobe vs. on the right diaphragm on magnetic resonance cholangiopancreatography (MRCP) using a free-breathing navigator-triggered prospective acquisition correction technique (PACE). MATERIALS AND METHODS: Fifty consecutive patients prospectively underwent three-dimensional T2-weighted turbo spin-echo MRCP using PACE with the navigator randomly set either under the left hepatic lobe or on top of the right diaphragm. Image acquisition time and subjective image quality were compared on a five-point scale using Student's t-test and Mann-Whitney's U test, respectively. RESULTS: There was no significant difference for mean acquisition time (6.1+/-1.6 vs. 6.3+/-1.2 min, P=.689) between the left hepatic lobe group and right diaphragm group. Mean subjective image quality was significantly worse in the left hepatic lobe group than in the right diaphragm group (4.1 vs. 4.7, P=.044). CONCLUSION: Setting the navigator under the left hepatic lobe for MRCP using PACE causes the data processing to be more difficult. As well, under current circumstances, it does not contribute to reducing acquisition time or improving the image quality.