Strong instability of solitary waves for nonlinear Klein–Gordon equations and generalized Boussinesq equations

We study here instability problems of standing waves for the nonlinear Klein–Gordon equations and solitary waves for the generalized Boussinesq equations. It is shown that those special wave solutions may be strongly unstable by blowup in finite time, depending on the range of the wave's frequency or the wave's speed of propagation and on the nonlinearity.     

Radiation sterilization of enzyme hybrids with biodegradable polymers

Ionizing radiations, which have already been utilized for the sterilization of medical supplies as well as gas fumigation, should be the final candidate to decontaminate “hybrid” biomaterials containing bio-active materials including enzymes because irradiation induces neither heat nor substances affecting the quality of the materials and our health. In order to check the feasibility of ⁶⁰Co-gamma rays on these materials, we selected commercial proteases including papain and bromelain hybridized with commercial activated chitosan beads and demonstrated that these enzyme-hybrids suspended in water showed the significant radiation durability of more than twice as much as free enzyme solution at 25-kGy irradiation. Enhanced thermal and storage stability of the enzyme hybrids were not affected by the same dose level of irradiation, either, indicating that commercial irradiation sterilization method is applicable to enzyme hybrids without modification.     

Secondary hypervalent I(III)...O interactions: synthesis and structure of hypervalent complexes of diphenyl-lambda3-iodanes with 18-crown-6

Reported here for the first time are the synthesis and characterization of supramolecular complexes between diaryl-lambda(3)-iodanes and 18-crown-6 (18C6). Slow evaporation of solvents afforded 1:1 and 2:1 complexes between Ph(2)IBF(4) and 18C6 as stable crystals, depending on the conditions. X-ray crystal structures of these complexes indicated that each iodine atom contacts with the three adjacent oxygen atoms of 18C6 through two hypervalent secondary bonding and a weak interaction. (1)H NMR analyses and CSI-MS spectra showed that, in dichloromethane solution, Ph(2)IBF(4) exclusively forms the 1:1 complex with 18C6 (binding constant K(a), 1.02 x 10(3) M(-)(1)). The binding constants decrease with the increased solvent donor ability (Gutmann's DN). Changing the heteroatom ligand from BF(4) to the less nucleophilic PF(6) and AsF(6) increased the binding constant by about six times. Substitution of an electron-withdrawing group onto the para position of Ph(2)IBF(4) tends to increase in the complex stability. A linear Hammett relationship (rho = 0.59) between log K(a) and sigma(p)(+) values of substituents indicates that the diaryl-lambda(3)-iodanes with electropositive iodine(III) interact more efficiently with 18C6. Decreased binding magnitude was measured with 15C5, dibenzo-18C6, dibenzo-21C7, and dibenzo-30C10.     

A new stereoselective synthesis of 2-subsdtituted 1,3-bis(trimethylsilyl)propene derivatives and their conversion to cyclopentane and cyclohexane derivatives

Ester $\text{2}$ on treatment with sodium salt of sulfone or sulfoxide afforded 2-substituted 1,3-bis(trimethylsily)propene $\text{3}$ in good yield, from which cyclopentane and cyclohexane derivatives bearing a trimethylsilyl group in the molecules were synthesized.     

Stereoselective acid-catalyzed homoallylic rearrangement of cyclopropylsilylmethanols: an efficient route to Z-homoallyl derivatives

Treatment of cyclopropylsilylmethanols derived from cyclopropyl silyl ketones with acid catalyst gives the corresponding silyl-substituted homoallyl derivatives in high yields with good stereoselectivity, independent of the substituents on the cyclopropyl ring. Cyclopropylsilylmethanols having a n-, s-butyl or phenyl group on the carbinyl carbon react to afford the E-homoallyl derivatives selectively. On the other hand, the reaction of cyclopropylsilylmethanols having a tert-butyl group gives Z-isomers exclusively. The following protiodesilylation of the resulting homoallyl derivatives proceeds with retention of configuration.     

A new synthesis of 1,3-dienes from allyl sulfides and allyl sulfones using tri-n-butylstannylmethyl iodide

Allyl 2-pyridyl sulfide $\text{6}$ or allyl phenyl sulfone $\text{7}$ on treatment with n-butyllithium in tetrahyrofuran followed by tri-n-butylstannylmethyl iodide ($\text{4}$) afforded directly the 1,3-diene $\text{8}$ in good yield.     

Noncatalytic kinetic study on site-selective H/D exchange reaction of phenol in sub- and supercritical water

The site-selective H/D exchange reaction of phenol in sub- and supercritical water is studied without added catalysts. In subcritical water in equilibrium with steam at 210-240 degrees C, the H/D exchange proceeds both at the ortho and para sites in the phenyl ring, with no exchange observed at the meta site. The pseudo-first-order rate constants are of the order of 10(-4) s(-1); 50% larger for the ortho than for the para site. In supercritical water, the exchange is observed also at the meta site with the rate constant in the range of 10(-6)-10(-4) s(-1). As the bulk density decreases, the exchange slows down and the site selectivity toward the ortho is enhanced. The enhancement is due to the phenol-water interaction preference at the atomic resolution. The site selectivity toward the ortho is further enhanced when the reaction is carried out in benzene/water solution. Using such selectivity control and the reversible nature of the hydrothermal deuteration/protonation process, it is feasible to synthesize phenyl compounds that are deuterated at any topological combination of ortho, meta, and para sites.     

Structural modulation of Cu(I) and Cu(II) complexes of sterically hindered tripyridine ligands by the bridgehead alkyl groups

Structures of Cu(I) and Cu(II) complexes of sterically hindered tripyridine ligands RL = tris(6-methyl-2-pyridyl)methane (HL), 1,1,1-tris(6-methyl-2-pyridyl)ethane (MeL), and 1,1,1-tris(6-methyl-2-pyridyl)propane (EtL), [Cu(RL)(MeCN)]PF(6) (1-3), [Cu(RL)(SO(4))] (4-6), and [Cu(RL)(NO(3))(2)] (7-9), have been explored in the solid state and in solution to gain some insights into modulation of the copper coordination structures by bridgehead alkyl groups (CH, CMe, and CEt). The crystal structures of 1-9 show that RL binds a copper ion in a tridentate facial-capping mode, except for 3, where EtL chelates in a bidentate mode with two pyridyl nitrogen atoms. To avoid the steric repulsion between the bridgehead alkyl group and the 3-H(py) atoms, the pyridine rings in Cu(I) and Cu(II) complexes of MeL and EtL shift toward the Cu side as compared to those in Cu(I) and Cu(II) complexes of HL, leading to the significant differences in the nonbonding interatomic distances, H.H (between the 3-H(py) atoms), N.N (between the N(py) atoms), and C.C (between the 6-Me carbon atoms), the Cu-N(py), Cu-N(MeCN), and Cu-O bond distances, and the tilt of the pyridine rings. The copper coordination geometries in 4-6, where a SO(4) ligand chelates in a bidentate mode, are varied from a square pyramid of 4 to distorted trigonal bipyramids of 5 and 6. Such structural differences are not observed for 7-9, where two NO(3) ligands coordinate in a monodentate mode. The structures of 1-9 in solution are investigated by means of the electronic, (1)H NMR, and ESR spectroscopy. The (1)H NMR spectra show that the structures of 1-3 in the solid state are kept in solution with rapid coordination exchange of the pyridine rings. The electronic and the ESR spectra reveal the structural changes of 5 and 6 in solution. The bridgehead alkyl groups and 6-Me groups in the sterically hindered tripyridine ligand play important roles in modulating the copper coordination structures.     

An efficient 1,3-dipolar cycloaddition between aromatic selenoaldehydes and nitrile oxides or nitrile imines: an easy access to selenium-containing five-membered heterocyclic ring system

1,3-Dipolar cycloaddition between aromatic selenoaldehydes, generated by thermal retro Diels-Alder reaction of anthracene cycloadducts, and nitrile oxides or nitrile imines proceeded efficiently to give the corresponding [3+2] cycloadducts as a single isomer in good yields, being 1,4,2-oxaselenazoles or 1,3,4-selenadiazoles, respectively.     

Air-Segmented Continuous-Flow Analysis for Molybdenum in Various Geochemical Samples

 An air-segmented continuous-flow method has been developed for the determination of molybdenum at ultra trace levels using the catalytic effect of molybdate during the oxidation of L-ascorbic acid by hydrogen peroxide. Incorporation of an on-line ion exchange column improved the tolerance limit for various ions. The detection limits with and without the column were 64 pmol L⁻¹ and 17 pmol L⁻¹, and the reproducibilities at 10 nmol L⁻¹ were 2.1% and 0.2%, respectively. The proposed method was applied to the determination of molybdenum in seawater and lake water as well as in rock and sediment samples. This method has the highest sensitivity among the available literature to our knowledge, and is also convenient for routine analysis of molybdenum in various natural samples. Author for correspondence. E-mail: masahito.sugiyama@ sojin0206.mbox.media.kyoto-u.ac.jp Received October 23, 2002; accepted January 28, 2003 Published online May 19, 2003