Vibrational energies for the X1A1, A1B1, and B1A1 states of SiH2/SiD2 and related transition probabilities based on global potential energy surfaces

Transition probabilities were evaluated for the X(1)A(1)-A(1)B(1) and A(1)B(1)-B(1)A(1) systems of SiH(2) and SiD(2) to analyze the X-->A-->B photoexcitation. The Franck-Condon factors (FCFs) and Einstein's B coefficients were computed by quantum vibrational calculations using the three-dimensional potential energy surfaces (PESs) of the SiH(2)(X(1)A(1),A(1)B(1),B(1)A(1)) electronic states and the electronic transition moments for the X-A, X-B, and A-B system. The global PESs were determined by the multireference configuration interaction calculations with the Davidson correction and the interpolant moving least-squares method combined with the Shepard interpolation. The obtained FCFs for the X-A and A-B systems exhibit that the bending mode is strongly enhanced in the excitation since the equilibrium bond angle greatly varies with the three states; the barrier to linearity is evaluated to be 21,900 cm(-1) for the X state, 6400 cm(-1) for the A state, and 230-240 cm(-1) for the B state. The theoretical lifetimes for the pure bending levels of the A and B states were calculated from the fluorescence decay rates for the A-X, B-A, and B-X emissions.     

Improvement of some pharmaceutical properties of nocloprost by β- and γ-Cyclodextrin Complexation

Inclusion complexation of nocloprost, a potent antiulcer prostaglandin derivative, with -, -, and -cyclodextrins (CyDs) in aqueous solutions has been studied by the solubility method and¹³C-NMR spectroscopy. The steric requirement of host-guest interaction was reflected in the magnitude of the stability constants and the thermodynamic parameters of the inclusion complexes. Solid complexes of nocloprost with - and -CyDs in a molar ratio of 1 : 2 were obtained on the basis of aBs-type phase solubility diagram. The X-ray diffraction data suggested that nocloprost is included in the cylindrical channel formed by coaxial alignment of -CyD molecules to give a channel type structure. Release and thermal behavior of the solid complexes was examined and compared with nocloprost itself. The results indicated that the -CyD complex may have great utility among the three CyDs, being a rapid dissolving form of nocloprost with improved thermal stability.     

Anticoagulant activity of immobilized thrombomodulin

Bovine lung thrombomodulin was partially purified, and immobilized on agarose gel (Sepharose 4B). Immobilized thrombomodulin inhibited the procoagulant activity of thrombin, and enhanced the thrombin-catalyzed protein C activation. The plasma recalcification time test showed that immobilized thrombomodulin prolonged plasma clotting time. It is suggested that the immobilization of thrombomodulin will provide an antithrombogenic biomaterial able to convert thrombin from a procoagulant to an anticoagulant enzyme.     

Symmetry or asymmetry in cheletropic additions forming cyclopropanes

Cheletropic additions forming cyclopropane rings were studied theoretically. Ten addition paths were traced by means of density-functional-theory calculations. Two 1,4-dienes, 1,4-pentadiene, and tricyclo[5.3.1.0^4,9]undeca-2,5-diene were adopted as substrates. CO, SO₂, C₂H₅PCl₂, CCl₂ and SiCl₂ were employed as cheletropic reagents (Xs). An orbital correlation diagram of the Woodward–Hoffmann (W–H) rule and frontier molecular orbital (FMO) interactions between them were investigated in detail. The FMO interactions, HOMO (1,4-diene)lumo (X) and homo (X)LUMO (diene), work reasonably for the progress of the reactions. Those cause the formation of two C–X bonds and a cyclopropane ring, and alternation of double bonds to single bonds. All the additions are concerted. The easiness of the ring formation depends upon the energy gap between HOMO and lumo and that between homo and LUMO, and the spatial directions of HOMO and LUMO extensions. Symmetry conservation of the W–H rule does not hold necessarily for those addition paths. The symmetry-breaking was discussed in terms of FMO interactions.Acknowledgement This work was supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Science and Culture, Japan and by Nishida Memorial Foundation for Fundamental Chemical Research.     

Synthesis,structure, and magnetic properties of dinuclear cobalt(II) complexes with a new phenol-based dinucleating ligand with four hydroxyethyl chelating arms

A new end-off type acyclic ligand with four hydroxyethyl arms, 2,6-bis[bis(2-hydroxyethyl)aminomethyl]-4-methylphenol [H(bhmp)], formed dinuclear cobalt(II) complexes [Co(2)(bhmp)(OAc)(2)]BPh(4) (1) and [Co(2)(bhmp)(OBz)(2)]BPh(4) (2). The complex 1.2.5CH(3)CN (C(50)H(62.5)BCo(2)N(4.5)O(9)) crystallizes in the monoclinic space group C2/c with dimensions a = 25.424(5) A, b = 13.376(2) A, c = 29.913(6) A, beta = 105.930(3) degrees, and V = 9781(3) A(3) and with Z = 8. X-ray diffraction analysis revealed a mu-phenoxo-bis(mu-acetato)dicobalt(II) core structure containing two octahedral cobalt(II) ions. Electronic spectra were investigated for 1 and 2 in the range 400-1800 nm, and the data were typical for the octahedral high-spin cobalt(II) complexes. Magnetic susceptibility was measured for 1 and 2 over the temperature range 4.5-300 K, and the data were analyzed well using our theoretical method. The best fitting parameters were kappa = 0.77, lambda = -116 cm(-1), Delta = 572 cm(-1), and J = -0.44 cm(-1) for complex 1 and kappa = 0.96, lambda = -93 cm(-1), Delta = 616 cm(-1), and J = -0.33 cm(-1) for complex 2.     

Theoretical prediction of optical absorption maxima for photosensory receptor mutants

We found a linear correlation between the theoretically predicted shifts and experimentally observed absorption spectra for various mutants of photoactive yellow protein, a photosensory receptor. Excitation energies of mutants were evaluated by the combination of the high level ab initio calculation for the chromophore inside and the low level ab initio calculation for the surrounding protein environment. Importantly, the electronic states of these two regions were treated both as variables and they are solved consistently to each other. The protein–chromophore interaction has been accurately reproduced by this method.     

Construction of a data base for cobalt-59 nuclear magnetic resonance spectrometry

The TOOL-IR. PDB and COOD systems are compared for the construction of data bases for ⁵⁹Co-n.m.r. bibliographic and spectral data. The spectral data used are the chemical shifts from several different standards, and the line widths and coupling constants (if present). The PDB system is effective for storage and retrieval of bibliographic data, but the COOD system is better for the retrieval of spectral data, and for combination of data files on literature and chemical shifts.     

Silylation of water glass. I. Solvent extraction and trimethylsilylation of silicic acid

Homogeneous trimethylsilylation of silicic acid in nonaqueous media was studied. The silylation process consisted of three steps: acidification of sodium silicate, solvent extraction. and trimethylation of silicic acid. Sodium silicate was first acidified with dilute sulfuric acid to form silicic acid: extraction followed with hydrophilic organic solvents. The Silicic acid obtained was finally allowed to react with trimethylchlorosilane to give trimethylsilylates with molecular weights of 1000–12,000. Optimum conditions for each step have been intensively sought to achieve trimethylsilylates in high yield. The trimethylsilylates exhibited excellent thermal stability and surface properties, such as water repellency and antifoaming properties, comparable to those of conventional polydimethylsiloxanes.