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.     

Trivial source modules in blocks with cyclic defect groups

We shall present a method to get trivial source modules easily just by looking at values of ordinary characters at non-identity p-elements in finite groups instead of doing huge calculation. The method is only for a case where defect groups are cyclic. Nevertheless, it works well at least when we want to prove Broué’s abelian defect group conjecture for blocks which have elementary abelian defect groups of order p ².     

EXAFS and XANES Studies on 3d Transition Metal Intercalation Compounds M x TiS2

Abstract

EXAFS and XANES spectra of Ti K-edge have been measured for 3d transition metal intercalation compounds M _x TiS₂ (M = Mn, Fe, Co and Ni; x ≤ 0.33). We have found that the interatomic distance between Ti and the first nearest neighbor S atoms, R(Ti-S), increases with the guest concentration x. The variation in XANES spectra with x reveals the reduction of the valence state of Ti atoms upon intercalation of M. From these results as well as the M K-edge EXAFS data studied previously, we have proposed a simple model on the local structure of M _x TiS₂ to reproduce the observed values of R(Ti-S) by averaging local shift of S atoms caused by intercalation.     

Chemical etching op fission tracks in ethylene-tetrafluoroethylene copolymer

The chemical etching of fission tracks in ethylene-tetrafluoro-ethylene copolymer was studied. Etched holes 3000–4000 Å in diameter was recognized by electron microscopy for a film bombarded by fission fragments in oxygen and etched in a 12N sodium hydroxide solution at 125°C. The radial etching rate at 125°C was 6–8 Å/hr, which is less than 17 Å/hr for polyvinylidene fluoride in the same sodium hydroxide concentration at 85°C. The smaller rate is a reflection of the larger chemical resistivity of ethylene-tetrafluoro-ethylene copolymer than polyvinylidene fluoride.     

The Projective Cover of the Trivial Module Over a Group Algebra of a Finite Group

We determine all finite groups G such that the Loewy length (socle length) of the projective cover P(k _G ) of the trivial kG-module k _G is four, where k is a field of characteristic p > 0 and kG is the group algebra of G over k, by using previous results and also the classification of finite simple groups. As a by-product we prove also that if p = 2 then all finite groups G such that the Loewy lengths of the principal block algebras of kG are four, are determined.     

Specific resistivity of dislocations and vacancies for super-pure aluminium at 4.2 K determined in-situ and post-recovery deformation and correlated to flow stress

ABSTRACT

The evolution of dislocations during shape-change of metal forms results from microstructural shear mechanism that is essential to enhance ductility. However, at room temperatures for face-centred cubic metals, this evolution results in the generation of vacancies that tend to form nano-voids, the growth of which leads to ductile failure. The correlated occurrence of dislocations and vacancies may be differentiated using the change of resistivity with plastic strain at 4.2?K, because resistivity is very sensitive to single vacancies compared to the formation of stacking faulted defects and dislocations. In order to assess the microstructure, the specific resistivity of these defect species was measured at 4.2?K, whereby thermal recovery processes are non-existent. The resistivity per dislocation line-length per volume was determined to be 1.87?×?10^?25?Ωm³ for super-pure aluminium. The change in resistivity directly correlated to the shear flow stress squared. Vacancy-like defects formed during plastic flow were correlated to the recoverable resistivity after 298?K anneal and the derived volume fraction (C_V) from mechanical data. The magnitude could be expressed as 12.9?×?10^?9?Ωm per C_V in % or as 1.21?×?10^?25?Ωm³ in terms of line-length of vacancies per volume. The choice of representation depends on the presumed vacancy distribution. However, the recoverable flow stress upon 298?K anneal only appear to be proportional to √ C_V at low strains; that is, at high strains the generated vacancies had transformed to defects that give rise to a small decrease in resistivity but a more notable increase in the flow stress. The possible mechanisms for this transformation are discussed.     

Calculations of electron inelastic mean free paths. XII. Data for 42 inorganic compounds over the 50 eV to 200 keV range with the full Penn algorithm

We have calculated inelastic mean free paths (IMFPs) for 42 inorganic compounds (AgBr, AgCl, AgI, Al₂O₃, AlAs, AlN, AlSb, cubic BN, hexagonal BN, CdS, CdSe, CdTe, GaAs, GaN, GaP, GaSb, GaSe, InAs, InP, InSb, KBr, KCl, MgF₂, MgO, NaCl, NbC_0.712, NbC_0.844, NbC_0.93, PbS, PbSe, PbTe, SiC, SiO₂, SnTe, TiC_0.7, TiC_0.95, VC_0.76, VC_0.86, Y₃Al₅O₁₂, ZnS, ZnSe, and ZnTe) for electron energies from 50 eV to 200 keV. These calculations were made with energy-loss functions (ELFs) obtained from measured optical constants for 15 compounds while calculated ELFs were utilized for the other 27 compounds. Checks based on ELF sum rules showed that the calculated ELFs were superior to the measured ELFs that we had used previously. Our calculated IMFPs could be fitted to a modified form of the relativistic Bethe equation for inelastic scattering of electrons in matter for energies from 50 eV to 200 keV. The average root-mean-square (RMS) deviation in these fits was 0.60%. The IMFPs were also compared with a relativistic version of our predictive Tanuma-Powell-Penn (TPP-2M) equation. The average RMS deviation in these comparisons was 10.7% for energies between 50 eV and 200 keV. This average RMS deviation is almost the same as that found in a similar comparison for a group of 41 elemental solids (11.9%) although relatively large deviations were found for cubic BN (65.6%) and hexagonal BN (34.3%). If these two compounds are excluded in the comparisons, the average RMS deviation becomes 8.7%. We found generally satisfactory agreement between our calculated IMFPs and values from other calculations and from experiments.     

Liquid-phase epitaxy of ZnSe from Zn-Ga solution

Undoped or Ga doped ZnSe single crystal layers with thicknesses between 3 and 13 μm were grown on ZnS_xSe_1?x (0 ? x ? 1) single crystal substrates by liquid phase epitaxy in a sealed tube system from a Zn or Zn-Ga alloy solution. Smooth and uniform epitaxial layers with high crystal perfection were obtained on the (111)- and (100)-oriented substrates. All the epitaxial layers were n-type and highly conductive (0.1 < ? < 10 Ω cm). A remarkable enhancement of the blue part of the photoluminescence spectra at room temperature was observed for the epitaxial layers grown from the Zn-Ga alloy solution.