A fully automated amino acid analyzer using NBD-F as a fluorescent derivatization reagent

A fully automated amino acid analyzer using NBD-F (4- fluoro-7-nitro-2,1,3-benzoxadiazole) as a fluorescent derivatization reagent was developed. The whole analytical process was fully automated from derivatization, injection to HPLC separation and quantitation. The derivatization reaction conditions were re-evaluated and optimized. Amino acids were derivatized by NBD-F for 40 min at room temperature in the borate buffer (pH 9.5). The derivatives were separated within 100 min and fluorometrically detected at 540 nm with excitation at 470 nm. The detection limits for amino acids were in the range of 2.8-20 fmol. The calibration curves were linear over the range of 20 fmol to 20 pmol on column with the correlation coefficients of 0.999. The coefficients of variation were less than 5% at 3 pmol injection for all amino acids. Amino acids in rat plasma were determined by the proposed HPLC method.     

Acid-base characterization of molecular weight fractionated humic acid

Acid-base properties of molecular weight fractionated humic acids (HAs) were investigated by the acid-base potentiometric titration. The acidic group contents (C(A(t))) and the average values of apparent pK (pK(app)) were evaluated by applying a modified Henderson-Hasselbalch equation to the experimental titration curves. The average values of pK(app) of the fractionated and unfractionated HAs were about 4.1-4.4, and the distribution of pK(app) values could be represented by the relationships between alpha and pK(app) plots in the range 2-8. The C(A(t)) values increased with a decrease in molecular size, as did the aromaticity. This suggests that the acidic group contents are related to the aromaticity of the HA.     

Carrier transport and its effect on the turn-on delay time in strained GalnAsP/InP multiple quantum well lasers

The effects of carrier transport on turn-on delay time in multiple quantum well lasers were investigated both theoretically and experimentally. By using rate equation analysis with two components of the carrier density inside and outside of the quantum wells, we found that carrier transport caused two important effects: one is the stationary effect of a significant reduction in carrier density in quantum wells; the other is an increase in differential carrier lifetime.As an experimental investigation, compressively strained 1.3 m GalnAsP/InP multiple quantum well (MQW) lasers were fabricated and their turn-on delay times were measured and investigated. The short-cavity buried-heterostructure lasers showed low-threshold current (2 to 3 mA) and small turn-on delay time (<200 ps) at biasless 30 mA pulse current. Although these performances are suitable for high-speed digital transmission, it was found that the carrier lifetimes derived from the turn-on delay measurement were larger for strained quantum well lasers than for conventional quantum well lasers and double heterostructure lasers. These phenomena are explained using the carrier transport model and are discussed. The solutions for further reduction in carrier lifetime and turn-on delay are discussed.     

The mechanism and rate of dtμ formation in solid hydrogen

The partial spectral distribution function for muonic molecule formation turns out to play an important role in understanding the effect of interactions with surrounding spectator molecules. We formulate and numerically calculate it for a solid hydrogen. First of all, in addition to a conventional Lorentzian peak centered at a resonance energy , there appears another very broad peak in the spectral distribution, which extends from the resonance energy to energies higher by the Debye energy _D of the solid. It is shown that the latter corresponds to the spectral distribution of phonon excitations caused by a sudden dt formation. Secondly, a strong intensity borrowing from the Lorentzian peak to the broad one occurs. Thanks to this fact, a large formation rate is yielded for subthreshold transitions. The comparison with Vesman's spectral distribution function, namely, of a dt formation for an isolated D₂, is made.     

Ruthenium-catalyzed hydration of 1-alkynes to give aldehydes: insight into anti-Markovnikov regiochemistry.

The mechanism of the selective conversion of 1-alkynes to aldehydes by hydration was investigated by isolating organic and organometallic byproducts, deuterium-labeling experiments, and DFT calculations. The D-labeled acetylenic hydrogen of 1-alkyne was found exclusively in the formyl group of the resulting aldehydes. After the reaction, the presence of metal-coordinated CO was confirmed. All of the experimental results strongly suggest the involvement of a metal-acyl intermediate with the original acetylenic hydrogen also bound to the metal center as a hydride, with the next step being release of aldehyde by reductive elimination. Theoretical analyses suggest that the first step of the catalytic cycle is not oxidative addition of acetylene C [bond] H or tautomerization of eta(2)-alkyne to a vinylidene complex, but rather protonation of the coordinated 1-alkyne at the substituted carbon to form a metal-vinyl intermediate. This cationic intermediate then isomerizes to Ru(IV)-hydride-vinylidene via alpha-hydride migration of the vinyl group to the metal center, followed by attack of the vinylidene alpha-carbon by OH(-) to give the metal-hydride-acyl intermediate.     

Hard X-ray generation using femtosecond irradiation of PbO glass

We have generated hard X-rays by front- and back-side femtosecond laser irradiation of PbO-rich glass. The actual Pb content of glasses was corroborated by Pb M-line emission intensities with an uncertainty of less than 20%. The elements K and As at concentrations of a few mol% were detected. X-ray generation by back-side irradiation helped to avoid an air breakdown; however, self-focusing and filamentation limited the achievable light intensity and effectiveness of X-ray generation. Characteristics and mechanisms of X-ray generation from the front- and back-side of glasses are discussed.     

Fragment distribution of thermal decomposition for lignin monomer by QMD calculations using the excited and charged model molecules

Simulations with a quantum molecular dynamics (QMD) method (MD with MO) were demonstrated on the thermal decomposition of lignin monomer at the ground state including excited and positive charged states. Geometry and energy optimized results of the lignin monomer at the singlet and triplet states in single excitation, and at (+2) positive charged state by semi-empirical AM1 MO calculations were used as the initial MD step of QMD calculations. In the QMD calculations, we controlled the total energy of the system using Nóse-Hoover thermostats in the total energy range of 0.69-0.95 eV, and the sampling position data with a time step of 0.5 fs were carried out up to 5000 steps at 50 different initial conditions. The calculated neutral, positive and negative charged fragment distributions of the monomer model with 0.82 eV energy control were obtained as 90.6, 3.5, and 5.9% to the total fragments, respectively. The ratios seem to correspond well with to the values observed experimentally in SIMS.