Solvent effect of fluorescence on/off switching of diarylethene linked to excited-state intramolecular proton transfer fluorophore

Efficient fluorescence on/off switching of a dyad consisting of a photochromic diarylethene and a fluorescence dye based on excited state intramolecular proton transfer (ESIPT) was designed and demonstrated. Diarylethenes linked to (2-(2-methoxy-5-methylphenyl)benzothiazol-6-yl)- and (2-(2-hydroxy-5-methylphenyl)benzothiazol-6-yl)-9,9-dioctylfluorene moieties (1a and 2a, respectively) exhibited fluorescence on/off switching upon alternating irradiation with ultraviolet and visible light in various solvents. The fluorescence on/off contrast of 2a was found to be higher than that of 1a in n-hexane because the overlap integral between the absorption spectrum of the diarylethene closed-ring form and the fluorescence spectrum of 2a is larger than that of 1a. Diarylethene 2a exhibited green fluorescence with large Stokes shift in n-hexane, which is ascribed to the ESIPT process from the enol form to the keto form. In contrast, the fluorescence of 2a in N,N-dimethylsulfoxide (DMSO) was mainly observed as blue fluorescence from enol form, while diarylethene 1a exhibited blue fluorescence in n-hexane and DMSO. The fluorescence on/off contrast of 2a in n-hexane was higher than that in DMSO because of the difference in the spectral overlaps in n-hexane and DMSO.     

On the electrical discharge in d.c. and high frequency fields simultaneously

Summary When a d.c. and a h.f. field are perpendicularly superposed in a electrical discharge (p 10–10^–4 mm Hg), three types of discharge can exist, classified from the standpoint of d.c. conduction: (1) d.c. glow type, d.c.-dominant discharge with additional ionization by h.f. field; (2) space chargelimited type, the same as the conduction in the floating double probe in a plasma produced by h.f. field; (3) an intermediate stage between the first and second types, herein referred to as transition type. According to our analysis of the transition type at low pressure, the value of in high electric fields can be deduced from the measurement.     

Photoinduced nitric oxide release from a nitrobenzene derivative in mitochondria

We report a novel NO donor (RpNO), containing a 2,6-dimethylnitrobenzene moiety for photocontrollable NO release and a rhodamine moiety for targeting to mitochondria. Photorelease of NO from RpNO in aqueous solution was confirmed by means of ESR analysis. Cellular release of NO from RpNO was confirmed with the aid of DAF-FM DA, an NO-specific fluorescence probe. RpNO was colocalized with MitoTracker Green FM, a mitochondrial stain, in HCT116 colon cancer cells and exhibited photodependent cytotoxicity. Our results indicate that RpNO is an effective NO donor for time-controlled, mitochondria-specific NO treatment.     

Selective photocatalytic oxidation of alcohols to aldehydes in water by TiO2 partially coated with WO3

Semiconductor TiO₂ particles loaded with WO₃ (WO₃/TiO₂), synthesized by impregnation of tungstic acid followed by calcination, were used for photocatalytic oxidation of alcohols in water with molecular oxygen under irradiation at λ>350 nm. The WO₃/TiO₂ catalysts promote selective oxidation of alcohols to aldehydes and show higher catalytic activity than pure TiO₂. In particular, a catalyst loading 7.6 wt % WO₃ led to higher aldehyde selectivity than previously reported photocatalytic systems. The high aldehyde selectivity arises because subsequent photocatalytic decomposition of the formed aldehyde is suppressed on the catalyst. The TiO₂ surface of the catalyst, which is active for oxidation, is partially coated by the WO₃ layer, which leads to a decrease in the amount of formed aldehyde adsorbed on the TiO₂ surface. This suppresses subsequent decomposition of the aldehyde on the TiO₂ surface and results in high aldehyde selectivity. The WO₃/TiO₂ catalyst can selectively oxidize various aromatic alcohols and is reusable without loss of catalytic activity or selectivity.     

Structural study of a series of layered rare-earth hydroxide sulfates

We report structure analysis of a new family of rare-earth hydroxides Ln(2)(OH)(4)SO(4)·2H(2)O (Ln = Pr, Nd, Sm, Eu, Gd, Tb) from synchrotron X-ray and electron diffraction data. Rietveld profile analysis revealed that all members were isostructural and crystallized in a face-centered monoclinic system A2/m (No. 12), in which the monoclinic angles were approximately equal to the right angle, varying from 90.387(1)° for Pr sample to 90.0718(3)° for Tb sample. The structure consisted of LnO(9) polyhedra connected by μ(3)-hydroxyl groups and μ(2)-water molecules, forming a corrugated two-dimensional layer, which was pillared by bidentated sulfate ions. This series of compounds had a supercell a' = 2a, b' = 2b because of the local orientation ordering of SO(4)(2-). Structural features along the series, such as unit-cell parameters and average Ln-O distances, represented a progressive contraction associated with the shrinking radius of the lanthanide cations from Pr to Tb.     

Easy access to fully functionalized chiral tetrahydro-β-carboline alkaloids

A four-step synthetic route to fully substituted chiral tetrahydro-β-carbolines (THBCs) is described. Starting from the (R,S,S)-Friedel-Crafts/Henry adduct obtained from three-component coupling of an indole, nitroalkene, and aldehyde catalyzed by imidazoline-aminophenol-CuOTf, the (1S,3S,4R)-THBCs were readily synthesized in a three-step operation including reduction of the nitro-functionality and Pictet-Spengler cyclization.     

Environment-dependent ultrafast photoisomerization dynamics in azo dye

Azoaromatic dyes have been extensively investigated over the past decade due to their potential use in a variety of optical devices that exploit their ultrafast photoisomerization processes. Among the azoaromatic dyes, Disperse Red 19 is a commercially available azobenzene nonlinear optical chromophore with a relatively high ground-state dipole moment. In the present study, we used ultrafast time-resolved spectroscopy to clarify the dynamics of a push-pull substituted azobenzene dye. Solution and film samples exhibited different ultrafast dynamics, indicating that the molecular environment affects the photoisomerization dynamics of the dye.     

Mixing parameters for geometry optimization using the Hamiltonian algorithm

We study the mixing parameters for the search of an optimal geometry using the Hamiltonian algorithm (HA) combined with ab initio molecular orbital calculations. We choose the C?CC?CC?CC dihedral angle of the butane molecule as an example. HF/3-21G level calculations are employed as the molecular orbital calculations. The distributions of the eigenvalues of mixing coefficients are fitted with the linear, quadratic, and quartic functions. Analyses of HA calculations both up to 2,000 and 60,000 iterative calculations show a possibility that the mixing process reduces the number of iterations. The low energy HF/3-21G, B3LYP/6-31G**, and PCM B3LYP/aug-cc-pVDZ optimized structures of the N-acetyl l-histidine N??-methyl amide and four water molecule supermolecule were also determined using the HA optimization method and compared to the recently determined thought to be global minimum energy structure.     

Exploring the thermochromism of sulfite-embedded polyoxometalate capsules

The Dawson-type polyanion [α-Mo(18)O(54)(SO(3))(2)](4-), with two SO(3)(2-) templates embedded inside a polyoxomolybdate(vi) cage, exhibits thermochromism over an exceptionally wide temperature range (～500 K). The temperature dependence of the cluster structure, established from X-ray crystallography, IR and Raman spectroscopy and DFT calculations, is related to a decreasing HOMO-LUMO gap in the near UV with increasing temperature. We postulate this is due to geometrical changes that affect both the occupied and unoccupied frontier molecular orbitals of this cluster anion.     

Real-time spectroscopy of Frenkel exciton system

We performed selective excitations of the first- and second-excited Frenkel exciton states (Q- and B-excitons) with use of sub-40-fs and sub-5-fs visible laser pulses. The transient absorption signals exhibit oscillatory features associated with molecular vibrations. From an analysis of the spectral profiles of the phase and amplitude of the oscillation, the experimental result is well explained by the modulated transition dipole moment, which is caused by the dynamic intensity borrowing from the intense B-transition to the weak Q-transition.