Spontaneous alternating copolymerization of isobutoxyallene with 4-phenyl-1,2,4-triazoline-3,5-dione

The spontaneous copolymerization of isobutoxyallene ( 1 ) with 4-phenyl-1,2,4-triazoline-3,5-dione ( 2 ) was carried out to afford a copolymer with a number-average molecular weight of 5900–10,300. The copolymer consisted of a 2,3-polymerization unit of 1 and a  NN polymerization unit of 2 , maintaining an alternating character regardless of the monomer feed ratio. The corresponding copolymerization of 1 with 2 in the presence of methanol afforded the adduct of the compounds without the polymer, indicating the generation of a zwitterion of 1 and 2 . © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1564–1571, 2001     

Hydrofluoroarylation of alkynes with fluoroarenes

A combination of Ni(cod)(2) and PCyp(3) is found to be an effective catalyst for chemoselective activation of the C-H bond of fluoroarenes over C-F bonds followed by insertion of alkynes to allow direct alkenylation of the electron-deficient arenes. The characteristics of the reactions are: a C-H bond ortho to a fluorine substituent is selectively activated; the reactivity of fluorobenzenes is roughly proportional to the number of fluorine atoms. The reaction conditions tolerate a broad range of both alkynes and fluoroarenes containing both electron-withdrawing and -donating groups, thus allowing efficient synthesis of a variety of substituted ethenes containing a fluoroaryl motif in high regio- and stereoselective manners. Mechanistic studies including both labeling experiments and stoichiometric reactions reveal that oxidative addition of C-H bonds in fluoroarenes to nickel(0) is kinetically highly facile whereas that of C-F bonds is thermodynamically favoured.     

Peierls mechanism of the metal-insulator transition in ferromagnetic hollandite K2Cr8O16

Synchrotron x-ray diffraction experiment shows that the metal-insulator transition occurring in a ferromagnetic state of a hollandite K(2)Cr(8)O(16) is accompanied by a structural distortion from the tetragonal I4/m to monoclinic P112(1)/a phase with a √2×√2×1 supercell. Detailed electronic structure calculations demonstrate that the metal-insulator transition is caused by a Peierls instability in the quasi-one-dimensional column structure made of four coupled Cr-O chains running in the c direction, leading to the formation of tetramers of Cr ions below the transition temperature. This provides a rare example of the Peierls transition of fully spin-polarized electron systems.     

Predicted radiolysis yield in a Fricke solution irradiated with various heavy ions

Experimental data on the spatial distribution of the energy deposited around an energetic heavy ion, from 1 MeV proton to 5.9 MeV/n uranium ion, which have been reported in the literature were documented to obtain a scaled radial dose distribution; (β/Z*)² D(Z*, β,t)=200 (for t=0–1), 200/t² (for t=1t_c), and 200 t_c/t³ (for t>t_c) where Z* and β are the effective charge and velocity relative to c, the velocity of light, of the incident ion, respectively, D the dose in unit of Gy, t the radial distance in unit of nm, t_c the critical distance empirically determined.

Then, if we know the yield of any chemical reaction as a function of dose from the results of experiments using γ-radiations or fast electrons or theoretical calculations, we can calculate the probability for the yield of the chemical reaction in the system bombarded with a heavy ion of the effective charge Z* and velocity β. The results of the present calculation of the LET-values and of G(Fe³⁺) in the ferrous sulfate acidic solution are presented and compared with reported experimental results.     

On computational proofs of the existence of solutions to nonlinear parabolic problems

This paper is an extension of the preceding study (Nakao, this journal, 1991) in which we described a numerical verification method of the solution for one-space dimensional parabolic problems, to the several-space dimensional case. Here, numerical verification means the automatic proof of the existence of solutions to the problems by some numerical techniques on a computer. We reformulate the verification condition for nonlinear parabolic initial boundary value problems using the fixed-point problem of a compact operator on certain function spaces. As in the preceding study based upon a simple C⁰ finite-element approximation and its constructive a priori error estimates, a numerical verification procedure is presented with some numerical examples.     

Some functional inequalities on non-reversible Finsler manifolds

We continue our study of geometric analysis on (possibly non-reversible) Finsler manifolds, based on the Bochner inequality established by Ohta and Sturm. Following the approach of the \(\Gamma \)-calculus of Bakry et al (2014), we show the dimensional versions of the Poincaré–Lichnerowicz inequality, the logarithmic Sobolev inequality, and the Sobolev inequality. In the reversible case, these inequalities were obtained by Cavalletti and Mondino (2015) in the framework of curvature-dimension condition by means of the localization method. We show that the same (sharp) estimates hold also for non-reversible metrics.     

Silicon-based cross-coupling reaction: an environmentally benign version

Much attention has been paid to the cross-coupling reaction of organosilicon compounds due to their stability, non-toxicity, and natural abundance of silicon. In addition, the silicon-based cross-coupling has many advantages over other cross-coupling protocols. Successful examples of the silicon-based cross-coupling reaction are reviewed, focusing especially on the advances made in the last decade. Having had a number of highly effective palladium catalysts developed mainly for other cross-coupling reactions, the development of the silicon-based protocol owes heavily to the design of organosilicon reagents which effectively undergo transmetalation, a key elemental step of the silicon-based cross-coupling reaction. This tutorial review thus classifies various organosilicon reagents depending on substituents on silicon and surveys their cross-coupling reactions with various electrophiles.     

Remark on the global existence and large time asymptotics of solutions for the quadratic NLS

We study the global in time existence of small solutions to the nonlinear Schrödinger equation with quadratic interactions (0.1) We prove that if the initial data u₀ satisfy smallness conditions in the weighted Sobolev norm, then the solution of the Cauchy problem (0.1) exists globally in time. Furthermore, we prove the existence of the usual scattering states and find the large time asymptotics of the solutions.     

Synthesis and pharmacological evaluation of 1-isopropyl-1,2,3,4-tetrahydroisoquinoline derivatives as novel antihypertensive agents

A series of 1-isopropyl-1,2,3,4-tetrahydroisoquinoline derivatives were synthesized and their bradycardic activities were evaluated in isolated guinea pig right atria. Structure-activity relationship studies revealed that the introduction of an appropriate substituent and its position on the 1,2,3,4-tetrahydroisoquinoline ring are essential for potent in vitro activity. Furthermore, the tether between the piperidyl moiety and the terminal aromatic ring is important for potent antihypertensive activity. Oral administration of 6-fluoro-1-isopropyl-2-{[1-(2-phenylethyl)piperidin-4-yl]carbonyl}-1,2,3,4-tetrahydroisoquinoline (3b) to spontaneously hypertensive rats (SHR) elicited antihypertensive effects without inducing reflex tachycardia, which is often caused by traditional L-type Ca2? channel blockers.     

Reinvestigation of the synthesis of isoliquiritigenin: application of Horner-Wadsworth-Emmons reaction and Claisen-Schmidt condensation

Isoliquiritigenin [ILG, (E)-1] was readily prepared via the Horner-Wadsworth-Emmons reactions using β-ketophosphonates 5a, b. An improved protocol for the synthesis of (E)-1 via the Claisen-Schmidt condensation was also presented.