Benzylic triflates prepared in‐situ: novel initiators for mono‐, bi‐ and trifunctional living poly(THF)s

Mono‐, bis‐, and tris(trifluoromethanesulfonate ester)s ((triflate ester)s) were prepared by the reaction of benzyl alcohol ( 1 ), 1,4‐bis(hydroxymethyl)benzene ( 2 ) and 1,3,5‐tris(hydroxymethyl)benzene ( 3 ) with trifluoromethanesulfonic anhydride in the presence of 2,6‐di‐tert‐butylpyridine. These benzylic triflate esters were applied in‐situ for the living polymerization of tetrahydrofuran (THF). The subsequent end‐capping reaction with a suitable nucleophile proceeded quantitatively to produce mono, bi‐ and, in particular, novel trifunctional telechelic poly(THF)s, respectively.     

Synthesis and isolation of a monoamine having a thermodynamically stabilized pseudo-chirotopic nitrogen

We have synthesized a tricyclic monoamine, (1S,4R)-(E)-7,3′-heptenylene-2,3:5,6-dibenzo-7-azabicyclo[2.2.1]heptane (1), by applying a ring-closing metathesis reaction in the key step of the synthetic route and by using preparative chiral HPLC for the separation. The X-ray crystallographic analysis of its salt with (1R)-camphor-10-sulfonic acid showed that the geometry and absolute configuration are (E) and (1S,4R), respectively. The theoretical calculations revealed that the inversion of the nitrogen atom at the 7-position of (1S,4R)-(E)-1 thus isolated takes place through a very slow process and that the configuration of the N(7) is highly biased to (R), indicating that (1S,4R)-(E)-1 is a thermodynamically controlled N-pseudo-chirotopic compound ((1S,4R,7R): (1S,4R,7S) = 99.68:0.32 at 120 °C).     

On the Lp–Lq maximal regularity for the linear thermoelastic plate equation in a bounded domain

This paper is concerned with the thermoelastic plate equations in a domain Ω: subject to the boundary condition: u|=D_νu|=θ|=0 and initial condition: (u, u_t, θ)|_t=0=(u₀, v₀, θ₀). Here, Ω is a bounded domain in ?ⁿ(n≧2). We assume that the boundary ?Ω of Ω is a C⁴ hypersurface. We obtain an L_p–L_q maximal regularity theorem. Copyright © 2008 John Wiley & Sons, Ltd.     

In situ and ex situ observations of the growth dynamics of single perylene nanocrystals in water

The growth dynamics of fluorescent perylene nanocrystals, which are fabricated by the reprecipitation method, was investigated using in situ and ex situ single-particle fluorescence measurements. A red shift in the emission maxima as the aging time increased was observed by single-particle fluorescence spectral measurements. The number and size of the nanocrystals increased with the increasing aging time in water. It was concluded that the metastable intermediates, such as clusters and initial nanoparticles, are relevant for the early stages of nucleation and growth of the perylene nanocrystals.     

Acceleration of laser-induced formation of gold nanoparticles in a poly(vinyl alcohol) film

Gold nanoparticles (AuNps) were fabricated in a poly(vinyl alcohol) (PVA) film using the photochemically generated benzophenone ketyl radical and PVA radical by laser irradiation as a reducing agent. The measurements of the surface plasmon band of AuNps indicated that AuNps continued growing in the PVA film for several hours or days after the laser irradiation. The formation process of AuNps in the PVA film was investigated by using laser flash photolysis and UV-vis absorption spectroscopy. Additive doping (formic acid or sodium 2-mercaptoethanesulfonate) in the PVA film dramatically accelerated or inhibited the formation rate of the AuNps, respectively. The doping of formic acid accelerated the formation rate of the AuNps by a factor of 10-20. On the contrary, doping of 2-mercaptoethanesulfonate inhibited the formation of AuNps. The mechanisms of the acceleration and inhibition were investigated by using laser flash photolysis. The effects of additives on the formation process of AuNps are discussed.     

Two significantly different conformations in crystal: formation of a molecular dimer governed by cation-π interactions

Two significantly different conformations were observed in crystal of 1, which form an unsymmetrical molecular dimer governed by cation-π interactions between a pyridinium cation and a phenyl ring, whereas compound 2 forms a head-to-tail type of dimer.     

Emission from charge recombination during the pulse radiolysis of 9-cyano-10-phenylethynylanthracenes with donor and acceptor substituents

Emission from 9-cyano-10-phenylanthracene and 9-cyano-10-phenylethynylanthracenes having donor and acceptor substituents (RA = PA, PEA, OEA, NEA, and DEA) was studied with the time-resolved fluorescence measurement during the pulse radiolysis of RAs in benzene (Bz). PA and DEA showed only monomer emission, while other RAs (PEA, OEA, and NEA) showed both monomer and excimer emissions with much lower intensities. On the basis of the steady-state and transient absorption and emission measurements, the formation of RA in the singlet excited state ((1)RA*) can be attributed to the charge recombination between RA radical cation and anion (RA*+ and RA*-, respectively) which are initially generated from the radiolytic reaction in Bz. It is expected that for PA with a twisted geometry, the charge recombination between PA*+ and PA*- occurs to give (1)PA* during the pulse radiolysis in Bz. For PEA and OEA, pi-stacking interaction is possible for the formation of an encounter complex during the charge recombination between RA*+ and RA*-. For NEA, it is expected that NEA*+ and NEA*- collide neck-to-neck to generate the excimer due to the twisted geometry. For DEA, a considerably twisted structure is assumed to give (1)DEA* with strong ICT character but not (1)(DEA)2* because of the bulky donor substituent.     

Properties of hadron and quark matter studied with molecular dynamics

We study the hadron-quark phase transition in a molecular dynamics (MD) of quark degrees of freedom. The hadron state at low density and temperature, and the deconfined quark state at high density and temperature are observed in our model. We investigate the equations of state and draw the phase diagram at wide baryon density and temperature range. We also discuss the transport property, e.g. viscosity, of $q\bar q$ matter. It is found that the ratio of the shear viscosity to the entropy density is less than one for quark matter.     

Fractality and degree correlations in scale-free networks

Fractal scale-free networks are empirically known to exhibit disassortative degree mixing. It is, however, not obvious whether a negative degree correlation between nearest neighbor nodes makes a scale-free network fractal. Here we examine the possibility that disassortativity in complex networks is the origin of fractality. To this end, maximally disassortative (MD) networks are prepared by rewiring edges while keeping the degree sequence of an initial uncorrelated scale-free network. We show that there are many MD networks with different topologies if the degree sequence is the same with that of the (u,v)-flower but most of them are not fractal. These results demonstrate that disassortativity does not cause the fractal property of networks. In addition, we suggest that fractality of scale-free networks requires a long-range repulsive correlation, in the sense of the shortest path distance, in similar degrees.     

Facile synthesis of biphenyl-fused BODIPY and its property

A biphenyl-fused BODIPY was synthesized through a facile oxidative cyclization of peripheral aryl-substituents at the β-position of the BODIPY unit. The extended π-system of the fused BODIPY induces near-infrared (NIR) absorption and strong π-π interactions in the solid state. These features are beneficial for the application of the dye as a functional material. The biphenyl-fused BODIPY dye was demonstrated to exhibit photocurrent conversion ability on the basis of its n-type semiconducting property.