Solid-phase syntheses of olefin-containing inhibitors for HTLV-1 protease using the Horner-Emmons reaction

[reaction: see text] The solid-phase Horner-Emmons reaction was successfully applied for the convenient syntheses of olefin-containing protease inhibitors. The isomerization during the solid-phase Horner-Emmons reaction can be minimized simply by the use of an appropriate amount of the base. The synthesized olefin peptides, which have an olefin gamma-amino acid at the scissile site, were found to act as effective inhibitors for the HTLV-1 protease for the first time.     

Kinetics of phase separation in polymer blends. Calculations based on nonlinear theory

Suzuki's scaling theory for transient phenomena is applied to the calculation of the kinetics of phase separation in the early-to-intermediate stage based on a nonlinear theory proposed by Langer, Bar-on, and Miller (LBM). Calculated results are compared with experimental data on light scattering from a polymer blend system. Deviations from predictions of Cahn's linearized theory in the early time range of phase separation can be explained well by the proposed method of calculation. Nonlinear effects are found to play an essential role in characterizing the light scattering behavior of phase separation in the intermediate stage. Time evolutions of the single-point distribution function of composition are calculated, and the results are in good agreement with those reported in digital imaging analysis experiments and computer simulations of the time-dependent Ginzburg-Landau equation. The influence of asymmetry of free-energy on the single-point distribution function is also investigated in this study. © 1993 John Wiley & Sons, Inc.     

A light-scattering study of deformation of liquid-crystalline spherulites of poly(γ-benzyl-L-glutamate) in an electric field

The deformation of liquid-crystalline spherulites of poly(γ-benzyl-L -glutamate) (PBLG) in an electric field was investigated by light scattering, polarized-light microscopy, and birefringence measurements. Under the polarizing microscope, the deformation was found to be dependent upon the field strength. The spherulites deformed perpendicular to the field. Above 75 V/cm in N,N-dimethylformamide or 120 V/cm in 1,1,2-trichloroethane, the deformed spherulites were transformed to rodlike textures. With increasing voltage, the rods gradually oriented parallel to the electric field. On the basis of the experimental results, models for affine deformation are proposed. With these models, light-scattering patterns are calculated. The calculated and experimental patterns agree semiquantitatively.     

Integrable coupled dispersionless equations

A new type of coupled dispersionless equations, which has a real dark type of soliton and a complex bright type of envelope soliton, is proposed and solved by the inverse scattering method. The N-soliton solution is given and one and two solitons are explicitly shown.     

Galois rigidity of pro- pure braid groups of algebraic curves

In this paper, Grothendieck's anabelian conjecture on the pro- fundamental groups of configuration spaces of hyperbolic curves is reduced to the conjecture on those of single hyperbolic curves. This is done by estimating effectively the Galois equivariant automorphism group of the pro- braid group on the curve. The process of the proof involves the complete determination of the groups of graded automorphisms of the graded Lie algebras associated to the weight filtration of the braid groups on Riemann surfaces.

     

Cutting Plane/Tabu Search Algorithms for Low Rank Concave Quadratic Programming Problems

In this paper, we will propose an efficient heuristic algorithm for solving concave quadratic programming problems whose rank of the objective function is relatively small. This algorithm is a combination of Tuy's cutting plane to eliminate the feasible region and a kind of tabu-search method to find a good vertex. We first generate a set of V of vertices and select one of these vertices as a starting point at each step, and apply tabu-search and Tuy's cutting plane algorithm where the list of tabu consists of those vertices eliminated by cutting planes and those newly generated vertices by cutting planes. When all vertices of the set V are eliminated, the algorithm is terminated. This algorithm need not converge to a global minimum, but it can work very well when the rank is relatively small (up to seven). The incumbent solutions are in fact globally optimal for all tested problems. We also propose an alternative algorithm by incorporating Rosen's hyperrectangle cut. This algorithm is more efficient than the combination of Tuy's cutting plane and tabu-search.     

Excellent chiralselectivity in sulfur-bridged CoIIIMCoIII (M = NiII and PdII) trinuclear complexes containing 1,2-cyclohexanediamine

The reaction of [Ni(aet)2] with [CoCl2(R,R-chxn)2]+ (aet = 2-aminoethanethiolate, R,R-chxn = 1R,2R-cyclohexanediamine) in water gave a CoIIINiIICoIII trinuclear complex, DeltaRRDeltaRR-[Ni(Co(aet)(2-)(R,R-chxn))2]4+ ([1a]4+), in which two cis(S)-[Co(aet)2(R,R-chxn)]+ units are linked by a central NiII ion through sulfur bridges. The two CoIII units in [1a]4+ uniformly adopt the Delta configuration, which is induced by the chirality of the terminal R,R-chxn ligands. The central NiII ion in [1a]4+ was replaced by a PdII ion to produce an analogous CoIIIPdIICoIII trinuclear complex, DeltaRRDeltaRR-[Pd(Co(aet)2(R,R-chxn))2]4+ ([2a]4+), with retention of the Delta configuration. When racemic R,R/S,S-chxn was employed instead of R,R-chxn, not only the chirality about two CoIII centers but also the chirality about two chxn ligands was unified in the S-bridged trinuclear structure, leading to the selective formation of a pair of enantiomers, DeltaRRDeltaRR/LambdaSSLambdaSS-[M(Co(aet)2(chxn))2]4+ (M = NiII ([1b]4+) and PdII ([2b]4+)). The stereochemical and spectroscopic features of these complexes are discussed on the basis of the electronic absorption, CD, and NMR spectroscopies, along with the crystal structures of [1a]4+ and [2a]4+.