Femtosecond fluorescence study of the reaction pathways and nature of the reactive S1 state of cis-stilbene

We report a femtosecond time-resolved fluorescence study of cis-stilbene, a prototypical molecule showing ultrafast olefinic photoisomerization and photocyclization. The time-resolved fluorescence signals were measured in a nonpolar solvent over a wide ultraviolet-visible region with excitation at 270 nm. The time-resolved fluorescence traces exhibit non-single exponential decays which are well fit with bi-exponential functions with time constants of τ(A) = 0.23 ps and τ(B) = 1.2 ps, and they are associated with the fluorescence emitted from different regions of the S(1) potential energy surface (PES) in the course of the structural change. Quantitative analysis revealed that the two fluorescent components exhibit similar intrinsic time-resolved spectra extending from 320 nm to 700 nm with the (fluorescence) oscillator strength of f(A) = 0.32 and f(B) = 0.21, respectively. It was concluded that the first component is assignable to the fluorescence from the untwisted S(1) PES region where the molecule reaches immediately after the initial elongation of the central C[double bond, length as m-dash]C bond, while the second component is the fluorescence from the substantially twisted region around a shallow S(1) potential minimum. The quantitative analysis of the femtosecond fluorescence data clearly showed that the whole isomerization process proceeds in the one-photon allowed S(1) state, thereby resolving a recent controversy in quantum chemical calculations about the reactive S(1) state. In addition, the evaluated oscillator strengths suggest that the population branching into the isomerization/cyclization pathways occurs in a very early stage when the S(1) molecule still retains a planar Ph-C[double bond, length as m-dash]C-Ph skeletal structure. On the basis of the results obtained, we discuss the dynamics and mechanism of the isomerization/cyclization reactions of cis-stilbene, as well as the electronic structure of the reaction precursor.     

Spatial-carrier phase-shifting digital holography utilizing spatial frequency analysis for the correction of the phase-shift error

We propose a single-shot digital holography in which the complex amplitude distribution is obtained by spatial-carrier phase-shifting (SCPS) interferometry and the correction of the inherent phase-shift error occurred in this interferometry. The 0th order diffraction wave and the conjugate image are removed by phase-shifting interferometry and Fourier transform technique, respectively. The inherent error is corrected in the spatial frequency domain. The proposed technique does not require an iteration process to remove the unwanted images and has an advantage in the field of view in comparison to a conventional SCPS technique.     

Experimental investigation of nanoparticle dispersion by beads milling with centrifugal bead separation

A new type of beads mill for dispersing nanoparticles into liquids has been developed. The bead mill utilizes centrifugation to separate beads from nanoparticle suspensions and allows for the use of small sized beads (i.e. 15-30 microm in diameter). The performance of the beads mill in dispersing a suspension of titanium dioxide nanoparticle with 15 nm primary particles was evaluated experimentally. Dynamic light scattering was used to measure titania particle size distributions over time during the milling process, and bead sizes in the 15-100 microm range were used. It was found that larger beads (50-100 microm) were not capable of fully dispersing nanoparticles, and particles reagglomerated after long milling times. Smaller beads (15-30 microm) were capable of dispersing nanoparticles, and a sharp peak around 15 nm in the titania size distribution was visible when smaller beads were used. Because nanoparticle collisions with smaller beads have lower impact energy, it was found by X-ray diffraction and transmission electron microscopy that changes in nanoparticle crystallinity and morphology are minimized when smaller beads are used. Furthermore, inductively-coupled plasma spectroscopy was used to determine the level of bead contamination in the nanoparticle suspension during milling, and it was found that smaller beads are less likely to fragment and contaminate nanoparticle suspensions. The new type of beads mill is capable of effectively dispersing nanoparticle suspensions and will be extremely useful in future nanoparticle research.     

Synthesis and properties of trefoil-shaped tris(hexadehydrotribenzo[12]annulene) and tris(tetradehydrotribenzo[12]annulene)

[reaction: see text] Trefoil-shaped tris(hexadehydrotribenzo[12]annulene) possessing a substructure of the ultimate two-dimensional C(sp)-C(sp(2)) network, graphyne, and the related tris(tetradehydrotribenzo[12]annulene) were synthesized, and their ground- and excited-state properties were investigated.     

HPLC profile of captopril disulfide that undergoes reversible cis-trans conversion among three isomers.

Peculiarly shaped chromatograms of some compounds that consist of two reversible isomers have been reported. Those of a compound that consists of three reversible isomers are described here. Because disulfide of captopril has two cis-trans convertible bonds, it exists in three forms of cis-cis, cis-trans and trans-trans isomers. The disulfide has produced various HPLC-UV profiles under various conditions, such as three split peaks, three peaks with bridging plateaus and one broad peak. The effect of the column temperature and the eluent flow rate on the profile was investigated and explained by interconversion among three isomers. A profile analysis could provide some kinetic constants of this reaction.     

Plasma and heat flux characteristics of a supersonic ammonia or nitrogen/hydrogen-mixture direct-current plasma jet impinging on a flat plate

Spectroscopic and electrostatic probe measurements were made to examine plasma characteristics with or without a titanium plate under nitriding for a 10-kW-class direct-current arc plasma jet generator with a supersonic expansion nozzle in a low-pressure environment. Heat fluxes into the plate from the plasma were also evaluated with a Nickel slug and thermocouple arrangement. Ammonia and mixtures of nitrogen and hydrogen were used as a working gas. The NH/sub 3/ and N/sub 2/+3H/sub 2/ plasmas in the nozzle and in the downstream plume without a substrate plate were in thermodynamical nonequilibrium states. As a result, the H-atom electronic excitation temperature and the N/sub 2/ molecule-rotational excitation temperature intensively decreased downstream in the nozzle although the NH molecule-rotational excitation temperature did not show an axial decrease. Each temperature was kept in a small range in the plume without a substrate plate except for the NH rotational temperature for NH/sub 3/ working gas. On the other hand, as approaching the titanium plate, the thermodynamical nonequilibrium plasma came to be a temperature-equilibrium one because the plasma flow tended to stagnate in front of the plate. The electron temperature had a small radial variation near the plate. Both the electron number density and the heat flux decreased radially outward, and an increase in H/sub 2/ mole fraction raised them at a constant radial position. In cases with NH/sub 3/ and N/sub 2/+3H/sub 2/, a radical of NH with a radially wide distribution was considered to contribute to the better nitriding as a chemically active and non heating process.     

Structural Optimization of Interpenetrated Pillared‐Layer Coordination Polymers for Ethylene/Ethane Separation

With the goal of achieving effective ethylene/ethane separation, we evaluated the gas sorption properties of four pillared‐layer‐type porous coordination polymers with double interpenetration, [Zn₂(tp)₂(bpy)]_n ( 1 ), [Zn₂(fm)₂(bpe)]_n ( 2 ), [Zn₂(fm)₂(bpa)]_n ( 3 ), and [Zn₂(fm)₂(bpy)]_n ( 4 ) (tp=terephthalate, bpy=4,4′‐bipyridyl, fm=fumarate, bpe=1,2‐di(4‐pyridyl)ethylene and bpa=1,2‐di(4‐pyridyl)ethane). It was found that 4 , which contains the narrowest pores of all of these compounds, exhibited ethylene‐selective sorption profiles. The ethylene selectivity of 4 was estimated to be 4.6 at 298 K based on breakthrough experiments using ethylene/ethane gas mixtures. In addition, 4 exhibited a good regeneration ability compared with a conventional porous material.     

Hidden Isolated OH at the Charged Hydrophobic Interface Revealed by Two‐Dimensional Heterodyne‐Detected VSFG Spectroscopy

Water around hydrophobic groups mediates hydrophobic interactions that play key roles in many chemical and biological processes. Thus, the molecular‐level elucidation of the properties of water in the vicinity of hydrophobic groups is important. We report on the structure and dynamics of water at two oppositely charged hydrophobic ion/water interfaces, that is, the tetraphenylborate‐ion (TPB^?)/water and tetraphenylarsonium‐ion (TPA⁺)/water interfaces, which are clarified by two‐dimensional heterodyne‐detected vibrational sum‐frequency generation (2D HD‐VSFG) spectroscopy. The obtained 2D HD‐VSFG spectra of the anionic TPB^? interface reveal the existence of distinct π‐hydrogen bonded OH groups in addition to the usual hydrogen‐bonded OH groups, which are hidden in the steady‐state spectrum. In contrast, 2D HD‐VSFG spectra of the cationic TPA⁺ interface only show the presence of usual hydrogen‐bonded OH groups. The present study demonstrates that the sign of the interfacial charge governs the structure and dynamics of water molecules that face the hydrophobic region.