Trifluoroacetaldehyde: A useful industrial bulk material for the synthesis of trifluoromethylated amino compounds

The synthesis of various trifluoromethylated amino compounds was studied using trifluoroacetaldehyde, an industrial bulk material, as a starting compound. One general application of trifluoroacetaldehyde is the preparation of trifluoroethylamino derivatives via reductive amination reaction. This synthesis includes the formation of the corresponding N,O-acetal intermediates followed by their reduction using NaBH₄ or 2-picoline borane complex, affording the target trifluoroethylamino compounds in moderate to good yields (47-87%).Another general application of trifluoroacetaldehyde is the synthesis of chiral α-substituted trifluoroethylamino compounds. In this synthesis, trifluoroacetaldehyde was first converted into the chiral trifluoromethyl tert-butyl sulfinimine, which was subjected to 1,2-nucleophilic addition reactions across its CN double bond. The addition of phenyllithium afforded α-(phenyl)trifluoroethylamino derivative in 83% yield and with 96% de. Allylation and Reformatsky reactions produced the corresponding α-substituted trifluoroethylamino derivatives in 82 and 58% yields and with 90 and 91% de, respectively.     

Single-shot spectrometry for x-ray free-electron lasers

An experimental scheme to realize single-shot spectrometry for the diagnostics of x-ray free-electron lasers (XFELs) is presented. The combination of an ultraprecisely figured mirror and a perfect crystal form a simple, high-precision spectrometer that can cover an energy range from a few eV to a hundred eV with high resolution. The application of the spectrometer to determine XFEL pulse widths was investigated theoretically and experimentally. It has been shown that the present system can determine pulse widths from sub-fs to ps in a single shot even for spontaneous radiation. The system can be easily extended to even shorter pulses.     

Proper composition for superconductivity in Pb(Ba, Sr)2(Y, Ca)Cu3O7

Superconductivity and composition analysis of PbBaSr(Y, Ca)Cu₃O_y with fixed ratio of Sr/Ba = 1 were studied. Synthesis condition and superconductivity of Pb(Ba, Sr)₂(Y, Ca)Cu₃O_y with various ratio of Sr/Ba and Ca/Y were also studied. It was found that T_c increased with increasing Ca concentration, and that Sr-rich specimens allowed to contain more Ca. PbBa_0.8Sr_1.2Y_0.6Ca_0.4Cu₃O₇ showed superconductivity with zero-resistance temperature of 42 K, which was higher than PbBaSrY_0.7Ca_0.3Cu₃O₇ with maximum Ca content for Sr/Ba = 1. Decrease in averaged ionic radii of Ba and Sr in Sr-rich compositions would be favorable for the contraction of Cu-O bonds by hole-doping via Ca substitution for Y.     

Gauge-Higgs unification in the left–right model

We construct a supersymmetric left–right model in four dimension with gauge-Higgs unification starting from a SU(3)_c×SU(4)_w×U(1)_B−L gauge symmetry in five dimension. The model has several interesting features, such as, the CKM mixings in the quark sector are naturally small while for the neutrino sector it is not, light neutrino masses can be generated via the seesaw mechanism in the usual way, and the model has a U(1)_R symmetry which naturally forbid dimension five proton decay operators. We also discuss the grand unification of our model in SO(12) in five dimensions.     

Correction for Shift-variant Characteristics of Single Photon Emission Computed Tomography Acquisition System Using Sensitivity Functions

The single photon emission computed tomography (SPECT) imaging system has shift-variant characteristics due to non-uniform attenuation of gamma-ray, collimator design, scattered photons, etc. In order to provide quantitatively accurate SPECT images, these characteristics should be compensated in the reconstruction. This paper presents a new method to correct the shift-variant characteristics, which is based on a continuous-discrete mapping model and filtered backprojection (FBP) method, in which the projection data are assumed to be acquired by narrow ray sum beams in the FBP method and the assumed data set is expressed as a linear combination of the actual projection data. Narrow ray sum beams are approximated by a weighted sum of the original sensitivity functions. Thus, at the reconstruction the projection data are first modified using an approximation and the FBP method is then applied to the corrected projection data and a SPECT image is reconstructed. We further propose a technique that requires the inversion of smaller matrices than the conventional algebraic method; the amount of calculation and memory space become smaller and the stability of the calculation is greatly improved as well. The results of the numerical simulations are also demonstrated.     

Rosamine-based fluorescent chemosensor for selective detection of silver(I) in an aqueous solution

The synthesis and photophysical properties of a rosamine-based fluorescent chemosensor, RosAg, for detecting Ag ion in an aqueous solution are described. This fluorescent sensor has a negligible quantum yield (<0.005) in the absence of Ag(+), whereas a significant increase in fluorescence is observed upon complexation with Ag(+) under physiological conditions. The crystal structure of the silver complex with the chelator moiety of RosAg reveals a trigonal-planar coordination geometry in which three S atoms occupy the metal center. Although a strong coordinative interaction of Ag-N is not observed in the crystal structure, the (1)H NMR experiments suggest that aniline nitrogen is likely to be associated with the Ag(+) center in the solution state. This may inhibit the photoinduced electron transfer process and result in the enhancement of fluorescence.     

Fluorescent states of exciplex and charge-transfer complexes: experimental evidence for an identical fluorescent state

The exciplex (above ≈ 170°K) and the charge-transfer (CT) complex (below ≈ 130°K) fluorescences were observed in a nonpolar solution of 9,10-dicyanoanthracene and 2-methylnaphthalene. The fluorescence maxima, lifetimes and quantum yields of the exciplex and the CT complex show continuous changes from room temperature to 77°K suggesting an identical fluorescent state of the exciplex and CT complex.