A new analysis of molecular orbital wave functions based on resonance theory

A new method to evaluate the weights of resonance structures from molecular orbital wave function is proposed, which is based on the second quantization of singlet-coupling. The present method is useful to analyze molecules of which the electronic structures are well localizable. The evaluation is carried out through localization of molecular orbitals followed by algebraic calculation of density matrices. This method is applied to H(2)O, H(3)O(+), and BH(3). The calculated weights of covalent and ionic structures are in excellent agreement with those of the previous works and our chemical intuition.     

Comparison of Bartlett-type adjusted tests in the multiparameter case

Considering some Bartlett-type adjusted tests for a simple hypothesis about a multidimensional parameter, this paper clarifies similarities and dissimilarities with the one-parameter case developed in the 1990s, where a major emphasis is put on the issue posed by Rao and Mukerjee [C.R. Rao, R. Mukerjee, Comparison of Bartlett-type adjustments for the efficient score statistic, J. Statist. Plann. Inference 46 (1995) 137-146] on the power under a sequence of local alternatives. Not surprisingly, there is an infinite number of adjustments which extend Chandra-Mukerjee and Taniguchi approaches to the multiparameter case. Revisiting their ideas, this paper presents four specific cases (type K, K=0,1,2,3) and gives a sufficient condition under which our generalized adjustment for each case is uniquely determined, where type 0 is a counterpart of Chandra and Mukerjee’s original proposal for Rao’s test statistic, whereas the latter three types are introduced as double adjustments related to the Cordeiro and Ferrari approach. If the adjustment of type 1 is made instead of type K, K=0,2,3, it is shown that Chandra and Mukerjee’s approach is equivalent to Taniguchi’s approach in terms of the third-order local power. The same is partially true for type 0, depending on the model under consideration. However, the adjustments of type K, K=2,3, reveal, in general, the non-equivalence of these two approaches in terms of the third-order local power.     

Effect of high pressure treatment on sarcoplasmic reticulum

Abstract

This paper describes the changes in biochemical activities of sarcoplasmic reticulum(SR) and Ca²⁺ release from SR in the rabbit skeletal muscle subjected to a high pressure treatment(100∽300 MPa) to investigate the mechanism for pressure-induced meat tenderization and acceleration of meat conditioning. Pressure-dependent changes were observed in the both extra and basal ATPase activities of SR prepared from the muscles exposed to high pressure. Ca²⁺ uptaking ability of SR vesicles measured by fluorescent chelating reagent, indo-1, decreased with increasing pressure applied to the muscle. Ultrastructural studies revealed that Ca²⁺ which was mainly localized in the SR region of the untreated fiber bundles was translocated into myofibrils in the pressurized muscle. Obtained results in this report may be one of the causes for meat tenderization and acceleration of meat conditioning induced by high pressure treatment.     

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.     

A CO Adsorption Site Change Induced by Copper Substitution in a Ruthenium Catalyst for Enhanced CO Oxidation Activity

Ru is an important catalyst in many types of reactions. Specifically, Ru is well known as the best monometallic catalyst for oxidation of carbon monoxide (CO) and has been practically used in residential fuel cell systems. However, Ru is a minor metal, and the supply risk often causes violent fluctuations in the price of Ru. Performance‐improved and cost‐reduced solid‐solution alloy nanoparticles of the Cu‐Ru system for CO oxidation are now presented. Over the whole composition range, all of the Cu_xRu_1?x nanoparticles exhibit significantly enhanced CO oxidation activities, even at 70 at % of inexpensive Cu, compared to Ru nanoparticles. Only 5 at % replacement of Ru with Cu provided much better CO oxidation activity, and the maximum activity was achieved by 20 at % replacement of Ru by Cu. The origin of the high catalytic performance was found as CO site change by Cu substitution, which was investigated using in situ Fourier transform infrared spectra and theoretical calculations.     

Detection of N-nitroso-bile acids at 285 nm in reverse-phase HPLC

In the present study, we developed a novel, simple, and specific detection method using an RP-HPLC at UV 285 nm for the separation and quantification of N-nitroso-bile acids. First, we found that N-nitroso-bile acids have a specific spectrophotometric absorbance at 285 nm. Using this 285 nm detection system, we could especially measure N-nitroso-bile acids, even in co-existence of non-N-nitroso-bile acids. Next, we observed the decomposition of N-nitroso-glychocholate under alkaline, acidic, and neutral conditions. N-nitroso-glychocholate rapidly decomposed under alkaline conditions (pH 9) (t(1/2) = 0.96 h), but remained fairly stable under acidic (pH 2) (t(1/2) = 12.8 h) and neutral (pH 7) (t(1/2) = 7.8 h) conditions. This study is the first report, which simply and specifically analyzes N-nitroso-bile acids using an RP-HPLC system.     

Syntheses, structures, and coordination chemistry of phosphole-containing hybrid calixphyrins: promising macrocyclic P,N2,X-mixed donor ligands for designing reactive transition-metal complexes

The syntheses, structures, and coordination chemistry of phosphole-containing hybrid calixphyrins (P,N2,X-hybrid calixphyrins) and the catalytic activities of their transition-metal complexes are reported. The 5,10-porphodimethene type 14pi-P,(NH)2,X- and 16pi-P,N2,X-hybrid calixphyrins (X = O, S, NH) are prepared via acid-promoted dehydrative condensation between a sigma4-phosphatripyrrane and the corresponding 2,5-bis[hydroxy(phenyl)methyl]heteroles followed by DDQ oxidation. Both spectroscopic and crystallographic data of the hybrid calixphyrins have revealed that the conformation and size of the macrocyclic platforms as well as the oxidation state of the -conjugated pyrrole-heterole-pyrrole (N-X-N) units vary considerably depending on the combination of heteroles. The sigma3-P,(NH)2,S- and sigma3-P,N2,S-hybrids react with Pd(OAc)2 and Pd(dba)2, respectively, to afford the same Pd(II)-P,N2,S-hybrid complex, in which the calixphyrin platform is regarded as a dianionic ligand. In the complexation with [RhCl(CO)2]2 in dichloromethane, the sigma3-P,N2,S-hybrid behaves as a neutral ligand to afford an ionic Rh(I)-P,N2,S-hybrid complex, whereas the sigma3-P,N2,NH-hybrid behaves as an anionic ligand to produce Rh(III)-P,N3-hybrid complexes. In the latter reaction, it is likely that a neutral Rh(I)-P,N3-hybrid complex, generated as a highly nucleophilic intermediate, undergoes C-Cl bond activation of the solvent. The complexation of AuCl(SMe2) with the sigma3-P,N2,X-hybrids (X = S, NH) leads to the formation of the corresponding Au(I)-monophosphine complexes. The spectral data and crystal structures of these metal complexes exhibit the hemilabile nature of the phosphole-containing hybrid calixphyrin platforms derived from the flexible phosphole unit and the redox active N-X-N units. The hybrid calixphyrin-palladium and -rhodium complexes catalyze the Heck reaction and hydrosilylations, respectively, implying that the metal center in the core is capable of activating the substrates under appropriate reaction conditions. The present results demonstrate the potential utility of the phosphole-containing hybrid calixphyrins as a new class of macrocyclic P,N2,X-mixed donor ligands for designing highly reactive transition-metal complexes.     

Theoretical study of pyrazolate-bridged dinuclear platinum(II) complexes: interesting potential energy curve of the lowest energy triplet excited state and phosphorescence spectra

Four kinds of 3,5-dialkylpyrazolate(R2pz)-bridged dinuclear platinum(II) complexes [Pt2(mu-R2pz)2(dfppy)2] (dfppy=2-(2,4-difluorophenyl)pyridine; R2pz=pyrazolate in 1, 3,5-dimethylpyrazolate in 2, 3-methyl-5- tert-butylpyrazolate in 3, and 3,5-bis(tert-butyl)pyrazolate in 4) were theoretically investigated by the DFT(B3PW91) method. The Stokes shift of their phosphorescence spectra was discussed on the basis of the potential energy curve (PEC) of the lowest energy triplet excited state (T1). This PEC significantly depends on the bulkiness of substituents on pz. In 1 and 2, bearing small substituents on pz, one local minimum is present in the T1 state besides a global minimum. The local minimum geometry is similar to the S0-equilibrium one. The T1 state at this local minimum is characterized as the pi-pi* excited state in dfppy, where the dpi orbital of Pt participates in this excited state through an antibonding interaction with the pi orbital of dfppy; in other words, this triplet excited state is assigned as the mixture of the ligand-centered pi-pi* excited and metal-to-ligand charge transfer excited state ((3)LC/MLCT). The geometry of the T1-global minimum is considerably different from the S0-equilibrium one. The T1 state at the global minimum is characterized as the triplet metal-metal-to-ligand charge transfer ((3)MMLCT) excited state, which is formed by the one-electron excitation from the dsigma-dsigma antibonding orbital to the pi* orbital of dfppy. Because of the presence of the local minimum, the geometry change in the T1 state is suppressed in polystyrene at room temperature (RT) and frozen 2-methyltetrahydrofuran (2-MeTHF) at 77 K. As a result, the energy of phosphorescence is almost the same in these solvents. In fluid 2-MeTHF at RT, on the other hand, the geometry of the T1 state easily reaches the T1-global minimum. Because the T1-global minimum geometry is considerably different from the S0-equilibrium one, the phosphorescence occurs at considerably low energy. These are the reasons why the Stokes shift is very large in fluid 2-MeTHF but small in polystyrene and frozen 2-MeTHF. In 3 and 4, bearing bulky tert-butyl substituents on pz, only the T1-global minimum is present but the local minimum is not. The electronic structure of this T1-global minimum is assigned as the (3)MMLCT excited state like 1 and 2. Though frozen 2-MeTHF suppresses the geometry change of 3 and 4 in the T1 state, their geometries moderately change in polystyrene because of the absence of the T1-local minimum. As a result, the energy of phosphorescence is moderately lower in polystyrene than in frozen 2-MeTHF. The T1-global minimum geometry is much different from the S0-equilibrium one in 3 but moderately different in 4, which is interpreted in terms of the symmetries of these complexes and the steric repulsion between the tert-butyl group on pz and dfppy. Thus, the energy of phosphorescence of 3 is much lower in fluid 2-MeTHF than in frozen 2-MeTHF like 1 and 2 but that of 4 is moderately lower; in other words, the Stokes shift in fluid 2-MeTHF is small only in 4.     

Heteropolynuclear complexes of 3,5-dimethylpyrazolate [Pt2M4(Me2pz)8] (M = Ag, Cu). Highly luminescent character of the triplet excited state based on mixed-metal cores

The platinum dimer and heteropolynuclear platinum complexes of 3,5-dimethylpyrazolate, [Pt2M4(mu-Me2pz)8] [M = H (1), Ag (2), Cu (3)], were synthesized and structurally characterized. They exhibit yellow, sky-blue, and orange luminescence, respectively, in the solid state. The absorption bands of 2 and 3 are mainly assigned to the combination of the metal-metal-to-ligand charge-transfer and [Pt2 --> Pt2M4] transitions by the time-dependent density functional theory (DFT) method. DFT calculations also indicate that the emissive states of 2 and 3 are 3[Pt2 --> Pt2Ag4] and 3[Cu(d) --> Pt2Cu4], respectively.     

Thallium selenate (Tl2SeO4) in a paraelastic phase by X‐ray powder diffraction

The structure of thallium selenate, Tl₂SeO₄, in a paraelastic phase (above 661 K) has been analysed by Rietveld analysis of the X‐ray powder diffraction pattern. Atomic parameters based on the isomorphic K₂SO₄ crystal in the paraelastic phase were used as the starting model. The structure was determined in the hexagonal space group P6₃/mmc, with a = 6.2916 (2) Å and c = 8.1964 (2) Å. From the Rietveld refinement it was found that two orientations are possible for the SeO₄ tetrahedra, in which one of their apices points randomly up and down with respect to [001]. One Tl atom lies at the origin with symmetry, the other Tl and one of the O atoms occupy sites with 3m symmetry, the Se atom is at a site with symmetry and the remaining O atom is at a site with m symmetry. Furthermore, it was also found that the Tl atoms display anomalously large positional disorder along [001] in the paraelastic phase.