Synthesis, single crystal X-ray analysis, and TEM for a single-sized Au11 cluster stabilized by SR ligands: The interface between molecules and particles

An SR-modified Au cluster with a sub-nanometer size, Au₁₁(S-4-NC₅H₄)₃(PPh₃)₇ (1), has been synthesized by NaBH₄ reduction of Au(S-py)(PPh₃) or by reacting [Au₉(PPh₃)₈](NO₃)₃ with HS-4-py in good yield. Its molecular structure has been elucidated by single crystal X-ray diffraction, and TEM observation has been achieved for the first time for this size of SR-modified Au clusters. The core structure is best described in terms of an incomplete icosahedron. CV measurements in CH₂Cl₂ have suggested that the cluster does not coagulate in solution with significant concentration.     

Influence of Gravitational Settling on Turbulent Droplet Clustering and Radar Reflectivity Factor

This study investigates the influence of gravitational settling of droplets on turbulent clustering and the radar reflectivity factor. A three-dimensional direct numerical simulation (DNS) of particle-laden isotropic turbulence is performed to obtain turbulent droplet clustering data. The turbulent clustering data are then used to calculate the power spectrum of droplet number density fluctuations. The results show that the gravitational settling modulates the power spectrum more significantly as the settling becomes larger. The gravitational settling weakens the intensity of clustering at large wavenumbers for St≤1, whereas it significantly enlarges the intensity for St>1. The dependence on the Taylor-microscale-based Reynolds number is also investigated to discuss the contribution of large-scale eddies to the settling influence. The results show that large-scale eddies modulate the small scale clustering structure of large St droplets. The increment of radar reflectivity factor due to turbulent clustering is estimated from the power spectrum for the case of St=1.0. The result shows that the influence of gravitational settling on the radar reflectivity factor can be significant for the case of large settling velocity droplets.     

Detailed Cloud Microphysics Simulation for Investigation into the Impact of Sea Spray on Air-Sea Heat Flux

This paper reports on the development of a numerical weather simulation model combined with a detailed spectral-bin cloud microphysics model that can explicitly consider the droplet motion and droplet-atmosphere interactions of sea spray. Sea spray is composed of liquid droplets ejected from the sea surface into the evaporation layer, where it enhances heat as well as momentum exchanges between the atmosphere and the sea. In our study, we analyzed the results of idealized 3D simulations to investigate the impact of sea spray on latent heat exchanges and their consequent impact on boundary layer cloud development. The results show that sea spray enhances the latent heat flux by up to 62 % for the surveyed 10m-height velocities, which ranged from 12 to 42 m/s. They also show that sea spray moistening significantly enhances boundary layer cloud development.     

Direct Detection of Al–O–Al Structure in Aluminosilicate Specimens: A Use of Homo-Nuclear DQMAS NMR

A general strategy of Al–O–Al structure in various aluminosilicate was evaluated by combining triple-quantum magic angle spinning (3QMAS) and double-quantum homo-nuclear correlation under magic angle spinning (DQMAS) solid-state nuclear magnetic resonance (NMR) measurements with the aid of high magnetic field NMR (800 MHz for ¹H Larmor frequency). The results show that in many cases the direct detection of Al–O–Al sites in aluminosilicate crystals and glasses is possible; hence the extent of aluminum avoidance can be directly elucidated. Specifically, experimental evidence of Al–O–Al linkages in several aluminosilicate materials with Si/Al >1 was straightforwardly confirmed; and the existence of Al–O–Al is considered to have little correlation with the Si/Al ratio, but it may be strongly related to the cation and local structural arrangement. In addition, the presence of tri-clusters of (Si, Al)O₄-tetrahedra in aluminosilicate framework was proposed, which was thought to act as nuclei for formation and incorporation of cations to achieve charge neutrality.     

Stereocontrolled synthesis of an indole moiety of sespendole and stereochemical assignment of the side chain

Two possible diastereomers of the indole moiety of sespendole were synthesized from 3-hydroxy-4-nitrobenzaldehyde in a highly stereoselective manner. Comparison of (1)H and (13)C NMR spectra of the two synthetic materials with those sespendole leads us to propose that the relative stereochemistry of the epoxyalcohol is syn.     

Simultaneous enantiomeric determination of MDMA and its phase I and phase II metabolites in urine by liquid chromatography–tandem mass spectrometry with chiral derivatization

A liquid chromatography–electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) procedure was developed for the simultaneous determination of enantiomers of the prevalent designer drug 3,4-methylenedioxymethamphetamine (MDMA) and its phase I and phase II metabolites in urine with chiral derivatization. The analytes in urine were directly derivatized with chiral Marfey’s reagent, N ^α- (5-fluoro-2,4-dinitrophenyl)-d-leucinamide, without extraction. The diastereomers of the N ^α-(2,4-dinitrophenyl)-d-leucinamide derivatives generated were determined by LC-MS/MS. Satisfactory chromatographic separation was achieved for the enantiomers of MDMA and its metabolites 3,4-methylenedioxyamphetamine, 4-hydroxy-3-methoxymethamphetamine (HMMA), HMMA glucuronide, and HMMA sulfate on a semimicro octadecylsilane column using linear gradient elution. With use of multiple reaction monitoring mode, the limits of detection of these analytes ranged from 0.01 to 0.03?μg/mL. Linear calibration curves were obtained for all enantiomers from 0.1 to 20?μg/mL in urine. The method showed sufficient reproducibility and quantitative ability. This is the first report of a simple LC-MS/MS-based analytical procedure with direct chiral derivatization in aqueous media that allows simultaneous enantiomeric determination of drugs and their metabolites, including glucuronide and sulfate derivatives.     

Japanese version of voice handicap index for subjective evaluation of voice disorder

Recently, the Voice Handicap Index (VHI), developed in the United States, has been highlighted as a means to assess a patient's perceptions of the severity of his or her voice disorder. The VHI is based on a self-administered questionnaire that quantifies the degree of a patient's disability related to his/her voice disorder. The questionnaire was translated into Japanese and applied to Japanese patients with various kinds of disordered voice or dysphonia. The results were analyzed and the usefulness discussed. In this study, 546 patients (281 males and 265 females) were included. Mean VHI scores were 36.2/120 in males and 44.1/120 in females. In the male patients, VHI scores were the highest among teens. However, VHI scores did not vary with age in the female patients. Patients with vocal fold paralysis, functional dysphonia, psychological dysphonia, and spasmodic dysphonia showed relatively high VHI scores, whereas those with laryngeal granuloma and laryngopharyngeal reflux disease showed low scores. In most diseases, functional and physiological scores were higher than emotional scores. In any treated patients, those with vocal nodule, vocal polyp, polypoid vocal fold, and recurrent laryngeal nerve paralysis, VHI scores decreased after therapeutic intervention. These findings suggest that the Japanese VHI is a useful tool for monitoring a patient's psychological status, choosing appropriate treatment, and assessing the therapeutic outcome.     

Spontaneous emission control of CdSe/ZnS nanoparticle monolayer in polymer nanosheet waveguide assembled on a one-dimensional silver grating surface

We present spontaneous emission control of a core-shell CdSe/ZnS nanoparticle array assembled with polymer ultrathin films consisting of polymer nanosheets on a silver grating substrate, which served as a unique and simple photonic cavity. The grating-coupled waveguide modes enabled 10(3) order luminescence enhancement and one-fourth spectral narrowing. The light emission from a CdSe/ZnS nanoparticle array can be controlled by tuning the film thickness of hybrid polymer nanoassemblies, which provides multiple emission performance with good tuning ability from red to green at low-power continuous wave laser excitation (～μW).     

Rapid transformation from spherical nanoparticles, nanorods, cubes, or bipyramids to triangular prisms of silver with PVP, citrate, and H2O2

Rapid sphere-to-prism (STP) transformation of silver was studied in aqueous AgNO(3)/NaBH(4)/polyvinylpyrrolidone (PVP)/trisodium citrate (Na(3)CA)/H(2)O(2) solutions by monitoring time-dependent surface plasmon resonance (SPR) bands in the UV-vis region, by examining transmission electron microscopic (TEM) images, and by analyzing emitted gases during fast reaction. Roles of PVP, Na(3)CA, and H(2)O(2) were studied without addition of a reagent, with different timing of each reagent's addition, and with addition of H(2)O(2) to mixtures of spheres and prisms. Results show that prisms can be prepared without addition of PVP, although it is useful to synthesize smaller monodispersed prisms. A new important role of citrate found in this study, besides a known role as a protecting agent of {111} facets of plates, is an assistive agent for shape-selective oxidative etching of Ag nanoparticles by H(2)O(2). The covering of Ag nanoparticles with carboxylate groups is necessary to initiate rapid STP transformation by premixing citrate before H(2)O(2) addition. Based on our data, rapid prism formation starts from the consumption of spherical Ag particles because of shape-selective oxidative etching by H(2)O(2). Oxidative etching of spherical particles by H(2)O(2) is faster than that of prisms. Therefore, spherical particles are selectively etched and dissolved, leaving only seeds of prisms to grow into triangular prisms. When pentagonal Ag nanorods and a mixture of cubes and bipyramids were used as sources of prisms, rod-to-prism (RTP), cube-to-prism (CTP), and bipyramid-to-prism (BTP) transformations were observed in Ag nanocrystals/NaBH(4)/PVP/Na(3)CA/H(2)O(2) solutions. Shape-selective oxidative etching of rods was confirmed using flag-type Ag nanostructures consisting of a triangular plate and a side rod. These data provide useful information for the size-controlled synthesis of triangular Ag prisms, from various Ag nanostructures and using a chemical reduction method, having surface plasmon resonance (SPR) bands at a desired wavelength.     

Optical path-length matrix method for estimating skin spectrum

In this article, we propose a new method??the optical path-length matrix method (OPLM)??as a faster alternative to the Monte Carlo for multi-layered media (MCML), which is often used to simulate the skin spectrum. Theoretically, peripheral oxygen saturation can be estimated by iterating MCML, but it is not a realistic strategy because it requires huge computation time. The optical path-length matrix is obtained as the probabilistic density histograms of the optical path length in skin using MCML, and once the matrix is obtained, skin spectral reflectance can be calculated by accumulating all combinations of elements in the matrix and by setting an absorption coefficient based on the Beer-Lambert law. The computational time of OPLM was approximately 26,000 times faster than that of MCML.