Extreme fluorescence sensitivity of some aniline derivatives to aqueous and nonaqueous environments: mechanistic study and its implication as a fluorescent probe

Effects of solvent water on the photophysical properties of a series of meta- and para-substituted anilines have been investigated by means of time-resolved fluorescence, transient absorption, and photoacoustic measurements. Some aniline derivatives exhibit extremely short fluorescence lifetime (tau(f)) and small quantum yield (Phi(f)) in water (e.g., tau(f) = 45 ps and Phi(f) = 0.0019 for m-cyanoaniline (m-ANCN) in H(2)O), which is in marked contrast with their much larger values in nonaqueous solvents (tau(f) = 7.3 ns and Phi(f) = 0.14 for m-ANCN in acetonitrile). Photoacoustic and transient absorption measurements show that the remarkable fluorescence quenching of m-ANCN in water is attributed almost exclusively to fast internal conversion. The lifetime measurements of m-ANCN in H(2)O/acetonitrile binary solvent mixtures reveal that the quenching is related to variation of hydrogen-bonding interactions between the amino group and water molecules and the conformational change of the amino group upon electronic excitation. Similar fluorescence quenching due to solvent water is also found for N-alkylated m-ANCNs. The drastic differences in the fluorescence intensity and lifetime of m-ANCNs under hydrophobic and hydrophilic environments and also the large solvent polarity dependence of the fluorescence band position suggest the possibility that they can be utilized as fluorescent probes for investigating the microenvironment of biological systems. In suspensions of human serum albumin (HSA) in water, remarkable enhancement of the fluorescence intensity and lifetime is observed for m-ANCN and its N-alkylated derivatives, demonstrating that m-ANCNs can be a candidate for novel fluorescent probe with small molecular size.     

Some Inequalities Related to Transience and Recurrence of Markov Processes and Their Applications

For an irreducible symmetric Markov process on a (not necessarily compact) state space associated with a symmetric Dirichlet form, we give Poincaré-type inequalities. As an application of the inequalities, we consider a time-inhomogeneous diffusion process obtained by a time-dependent drift transformation from a diffusion process and give general conditions for the transience or recurrence of some sets. As a particular case, the diffusion process appearing in the theory of simulated annealing is considered.     

Rhodium-catalyzed allyl transfer from homoallyl alcohols to aldehydes via retro-allylation followed by isomerization into ketones

Retro-allylation of homoallyl alcohol by rhodium catalysis occurs to generate allylrhodium species. This allylrhodium reacts with aldehydes to give the corresponding secondary alcohols in situ. Isomerization of these alcohols proceeds in the same pots to furnish the corresponding saturated ketones in good yields. [reaction: see text]     

Cobalt-mediated cross-coupling reactions of primary and secondary alkyl halides with 1-(trimethylsilyl)ethenyl- and 2-trimethylsilylethynylmagnesium reagents

[reaction: see text] This paper describes cobalt-mediated cross-coupling reactions of alkyl halides with 1-(trimethylsilyl)ethenylmagnesium bromide and 2-(trimethylsilyl)ethynylmagnesium bromide, respectively. The cobalt system allows for employing secondary as well as primary alkyl halides as the substrates. The reactions offer facile formations of alkyl-alkenyl and alkyl-alkynyl bonds. The reaction mechanism would include single-electron transfer from a cobalt complex to alkyl halide to generate the corresponding alkyl radical. The cobalt system thus enables sequential radical cyclization/alkenylation and cyclization/alkynylation reactions of 6-halo-1-hexene derivatives.     

Long wavelength InAs self-assembled quantum dots embedded in GaNAs strain-compensating layers

We investigated the effect of GaNAs strain-compensating layers (SCLs) on the properties of InAs self-assembled quantum dots (QDs) grown on GaAs (0 0 1) substrates. The GaNAs material can be used as SCL thereby minimizing the net strain, and thus is advantageous for multi-stacking of InAs QDs structures and achieving long wavelength emission. The emission wavelength of InAs QDs can be tuned by changing the nitrogen (N) composition in GaNAs SCLs due to both effects of strain compensation and lowering of potential barrier height. A photoluminescence emission at 77 K was clearly observed for sample with GaN_0.024As_0.976 SCL. Further, we observed an improvement of optical properties of InAs QDs by replacing the more popular GaAs embedding layers with GaNAs SCLs, which is a result of decreasing non-radiative defects owing to minimizing the total net strain.     

Angle-resolved photoemission spectroscopy of perovskite-type transition-metal oxides and their analyses using tight-binding band structure

Nowadays it has become feasible to perform angle-resolved photoemission spectroscopy (ARPES) measurements of transition-metal oxides with three-dimensional perovskite structures owing to the availability of high-quality single crystals of bulk and epitaxial thin films. In this article, we review recent experimental results and interpretation of ARPES data using empirical tight-binding band-structure calculations. Results are presented for SrVO₃ (SVO) bulk single crystals and La_{1? x} Sr _x FeO₃ (LSFO) and La_{1? x} Sr _x MnO₃ (LSMO) thin films. In the case of SVO, from comparison of the experimental results with calculated surface electronic structure, we concluded that the obtained band dispersions reflect the bulk electronic structure. The experimental band structures of LSFO and LSMO were analyzed assuming the G-type antiferromagnetic state and the ferromagnetic state, respectively. We also demonstrated that the intrinsic uncertainty of the electron momentum perpendicular to the crystal surface is important for the interpretation of the APRES results of three-dimensional materials.     

Atomistic study of GaSe/Ge(111) interface formed through van der Waals epitaxy

Layered materials can be grown on various substrates through van der Waals epitaxy (vdWE) regardless of lattice mismatch. The atomistic study of the film-substrate interface in vdWE is becoming increasingly important due to their expected applications as two-dimensional (2D) materials. In this contribution, we have grown GaSe thin films on Ge(111) substrates by molecular beam epitaxy and studied the GaSe/Ge(111) interface using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). Cross-sectional HAADF-STEM observations revealed that the grown layers adopt predominantly the expected wurtzite-like structure and stacking, but layers with zinc-blende-like structure, similar to Ga₂Se₃ but apparently different, and other layer stacking sequences, exist locally near the film-substrate interface. These results demonstrate that even in vdWE, structural changes can occur in the grown layers adjacent to the substrate, highlighting the importance of such interface for synthesizing and applying ultimately thin 2D materials.     

Nature of magnetic coupling between Mn ions in As-grown Ga1-xMnxAs studied by X-ray magnetic circular dichroism

The magnetic properties of as-grown Ga1-xMnxAs have been investigated by the systematic measurements of temperature and magnetic field dependent soft x-ray magnetic circular dichroism (XMCD). The intrinsic XMCD intensity at high temperatures obeys the Curie-Weiss law, but a residual spin magnetic moment appears already around 100 K, significantly above the Curie temperature (T_{C}), suggesting that short-range ferromagnetic correlations are developed above T_{C}. The present results also suggest that the antiferromagnetic interaction between the substitutional and interstitial Mn (Mn_{int}) ions exists and that the amount of the Mn_{int} affects T_{C}.     

Origin of metallic states at the heterointerface between the band insulators LaAlO3 and SrTiO3

We have studied the electronic structure at the heterointerface between the band insulators LaAlO3 and SrTiO3 using in situ photoemission spectroscopy. Our experimental results clearly reveal the formation of a notched structure on the SrTiO3 side due to band bending at the metallic LaAlO3/TiO2-SrTiO3 interface. The structure, however, is absent at the insulating LaAlO3/SrO-SrTiO3 interface. The present results indicate that the metallic states originate not from the charge transfer through the interface on a short-range scale but from the accumulation of carriers on a long-range scale.