Application of log D for the prediction of hydrophobicity in the advanced Marfey's method

In the advanced Marfey's method, the resolution between the diastereomers derivatized with 1-fluoro-2,4-dinitrophenyl-5-l-leucinamide (l-FDLA) and 1-fluoro-2,4-dinitrophenyl-5-d-leucinamide (d-FDLA) is reflected by the difference of hydrophobicity of the two functional groups at the asymmetric carbon. However, no effective method has been developed for the estimation of hydrophobicity so far. For this purpose, we introduced log D from the ACD Labs LogD and applied it to relatively simple primary amines, amino acids and secondary alcohols in the present study. It was found that the difference of the retention times (Δt_R) correlated with that of log D (Δlog D) for both diastereomers based on the obtained experimental results. Based on these results, the following procedure was proposed for the non-empirical determination of the absolute configuration of primary amines including amino acids and secondary alcohols: (1) estimate the hydrophobicity by the calculation of log D for the two substituent groups at the asymmetric carbon, (2) locate the trans-type arrangement of the two more hydrophobic substituents in the l-DLA derivative and judge the asymmetric carbon to be R or S in the trans-type that is eluted first, (3) derivatize the desired compound with l- or d-FDLA and analyze by LC/MS, and (4) compare the elution order with the prospective one and determine the absolute configuration at the asymmetric carbon. Furthermore, log D could also be used to predict the retention times of unavailable amino acids and small peptides, indicating that the combination of the advanced Marfey's method with log D would provide more reliable structural information on a mixture composed of amino acids and small peptides. The developed method is being applied to more complicated compounds.     

Synthesis and lithium ion insertion/extraction properties of hollandite-type MnO2 prepared by acid digestion of Mn2O3

Single-phase specimens of α-MnO₂ (hollandite-type) and β-MnO₂ (rutile-type) were synthesized by the acid digestion of Mn₂O₃ under reflux conditions. The type of polymorph of MnO₂ products was strongly dependent on the reaction temperature, type of acid used, and its concentration. The pH titration curve of α-MnO₂ displayed a monobasic acid behavior toward Li⁺, but β-MnO₂ showed a poor ion-exchange property. In contrast, both α-MnO₂ and β-MnO₂ acted as a rechargeable active material in a liquid organic electrolyte lithium cell. The initial discharge capacities of both electrodes exceeded 200 mAh/g (cut-off voltage: 2 V). After discharge–charge repetition, the α-MnO₂ structure was still retained without structure collapse, although the β-MnO₂ structure was destroyed. These findings show that Li⁺ ions can be inserted only into the hollandite-type tunnels in α-MnO₂ and cannot diffuse the rutile-type linkages in α-MnO₂ as well as those in β-MnO₂ without structure collapse.     

Donor–Acceptor Heterojunction Configurations Based on DNA–Multichromophore Arrays

Multichromophore arrays of bis(2‐thienyl)diketopyrrolopyrrole (DPP) and naphthalenediimide (NDI) with two Zn^II‐cyclens were constructed using thymidine DNA as a scaffold through the binding of the Zn^II‐cyclens with thymine bases. We demonstrate photocurrent generation in a donor–acceptor heterojunction configuration consisting of the DPP (donor) and NDI (acceptor) arrays co‐immobilized on an Au electrode. The co‐immobilized electrode exhibited good photocurrent responses because of the efficient charge separation between the DPP and NDI arrays. In contrast, an immobilized electrode consisting of randomly assembled DPP‐NDI arrays generated no photocurrent response because DPP formed ground‐state charge‐transfer complexes with NDI in the randomly assembled arrays. Therefore, our approach to generate donor–acceptor heterojunctions based on DNA–multichromophore arrays is a useful method to efficiently generate photocurrent.     

Well-defined fluorescent particles of ZnS:Cu. 1. Preparation and effects of annealing

As an application of the gel-sol procedure for the synthesis of monodispersed particles in large quantities, uniform particles of ZnS:Cu were prepared by different methods from concentrated Zn-chelate solutions of nitrilotriatic acid (NTA) with thioacetamide (TAA), in which the dopant copper ion was introduced as a coexisting mixed chelate with Zn-NTA (Method A), a Cu-NTA complex in a separate solution continuously added to a system of Zn-NTA and TAA (Method B), or a Cu(NO3)2 solution infiltrated into a dry powder of ZnS prepared by Method A (Method C). All powders thus prepared were annealed before the test of fluorescent properties. The main roles of annealing were to remove the grain boundaries of such particles as nonradiative recombination centers of excited electrons and holes and to achieve uniform distribution of dopants. However, the initial intraparticle distribution of the dopant, controlled by the different methods, decisively affected the fluorescent particles, even after the conversion of the polycrystalline particles to single-crystal particles by annealing.     

Soft magnetization of a semi-hard/soft magnetic bilayer produced by oblique-incidence evaporation

The possibility of achieving soft magnetization in semi-hard magnetic films such as Fe, Fe_93.5Si_6.5, Fe₅₀Co₅₀ and Fe₇₀Co₃₀ is investigated by depositing films on an Fe₂₀Ni₈₀ underlayer by oblique-incidence evaporation. The magnetic anisotropy of the underlayer is strengthened to a depth of several lattice parameters by vapor deposition of the film at an oblique angle to the substrate surface. This method also allows magnetic anisotropy to be induced in strongly isotropic semi-hard magnetic overlayers to a thickness of a few thousands Angstroms. The coercive force of bilayer films measured along the hard-axis is reduced remarkably by this process, and the strength of the anisotropy field is demonstrated to be readily controllable. When magnetic anisotropy exists in both magnetic layers, a significant change is observed in the magnetization processes of the semi-hard magnetic layer and the coercive forces in the hard magnetization direction is dramatically reduced. Soft magnetization of the semi-hard magnetic layer cannot be achieved when magnetic anisotropy exists in only one of the magnetic layers.     

Observing the Stimulated Raman Gain Spectra of Solutions Using an Infrared Pump Pulse with Narrow Linewidth and a Low-Noise CW Probe Laser

Stimulated Raman gain (SRG) spectroscopy using infrared pump pulses with narrow linewidth and a low-noise cw probe infrared laser was proposed. High-resolution Raman spectra of solutions were obtained. The SRG spectra of crystal GaP, benzene, and toluene were measured to confirm the spectral resolution and sensitivity over the terahertz (THz) region. We discuss the polarization dependence of the spectral measurement of carbon tetrachloride. Our system can detect organic molecules in aqueous solutions.     

A numerical study on the formation of diffusion flame islands in a turbulent hydrogen jet lifted flame

This paper presents a numerical study on the formation of diffusion flame islands in a hydrogen jet lifted flame. A real size hydrogen jet lifted flame is numerically simulated by the DNS approach over a period of about 0.5 ms. The diameter of hydrogen injector is 2 mm, and the injection velocity is 680 m/s. The lifted flame is composed of a stable leading edge flame, a vigorously turbulent inner rich premixed flame, and a number of outer diffusion flame islands. The relatively long-term observation makes it possible to understand in detail the time-dependent flame behavior in rather large time scales, which are as large as the time scale of the leading edge flame unsteadiness. From the observation, the following three findings are obtained concerning the formation of diffusion flame islands. (1) A thin oxygen diffusion layer is developed along the outer boundary of the lifted flame, where the diffusion flame islands burn in a rather flat shape. (2) When a diffusion flame island comes into contact with the fluctuating inner rich premixed flame, combustion is intensified due to an increase in the hydrogen supply by molecular diffusion. This process also works for the production of the diffusion flame islands in the oxygen diffusion layer. (3) When a large unburned gas volume penetrates into the leading edge flame, the structure of the leading edge flame changes. In this transformation process, a diffusion flame island comes near the leading edge flame. The local deficiency of oxygen plays an important role in this production process.     

Determination of indium by graphite furnace atomic absorption spectrometry after coprecipitation with chitosan.

A sensitive and simple method for the determination of trace amounts of indium in water samples by graphite furnace atomic absorption spectrometry (GFAAS) after coprecipitation with chitosan was investigated. Indium was quantitatively preconcentrated from water samples by coprecipitation with chitosan at pH 7.0-9.0. The coprecipitant was easily dissolved with acetic acid, and indium in the resulting solution was determined by GFAAS. The addition of lanthanum as a chemical modifier was more effective for the atomic absorbance of indium. The detection limit (S/N > or = 3) for indium was 0.04 microg dm(-3), and the relative standard deviations (n = 5) were 3.5-4.5% at 1.0 microg/100 cm3. The results obtained in this study indicate that the proposed method can be successfully applied to the determination of trace indium in water samples.     

Dynamics of Photoelectrons and Structural Changes of Tungsten Trioxide Observed by Femtosecond Transient XAFS

The dynamics of the local electronic and geometric structures of WO₃ following photoexcitation were studied by femtosecond time‐resolved X‐ray absorption fine structure (XAFS) spectroscopy using an X‐ray free electron laser (XFEL). We found that the electronic state was the first to change followed by the local structure, which was affected within 200 ps of photoexcitation.