Carbazoledioxazines having long alkyl groups. 2. Synthesis of carbazoledioxazines with angular type structure

Carbazoledioxazines with an angular type structure (5,15-dialkyl-7,17-dialkyloxy-9,19-dichloro-5,15-dihydrodiindolo[2,3-c:2′,3′-n]triphenodioxazines) were selectively synthesized by electrochemical oxidative ring closure of precursors (2,5-bis(9-alkyl-2-alkyloxy-3-carbazolylamino)-3,6-dichloro-1,4-benzoquinones). The structure was confirmed by ¹H-nmr and other instrumental analyses. Their thermal properties and solubilities were investigated and were compared with those of carbazoledioxazines with a linear type structure.     

Controlled synthesis of amphiphilic block copolymers with pendant glucose residues by living cationic polymerization

Amphiphilic block copolymers of vinyl ethers (VEs) of the type —[CH₂CH(OCH₂CH₂OR)]_m—[CH₂CH(OiBu)]_n—were synthesized by living cationic polymerization, where R is a D-glucose residue, and m and n are the degrees of polymerization (m = 20–50; n = 11–89). To obtain them, sequential living block copolymerization of isobutyl vinyl ether (IBVE) and the vinyl ether carrying 1,2:5,6-diisopropylidene-D -glucose residue was conducted by using the HCl adduct of IBVE, CH₃CH(OiBu)Cl, as initiator in conjunction with zinc iodide. These precursor block copolymers had a narrow molecular weight distribution (M̄_w/M̄_n ∼ 1.1) and a controlled composition. Treatment of them with a trifluoroacetic acid/water mixture led to the target amphiphiles. The solubility of the amphiphilic block copolymers in various solvents depended strongly on composition or the m/n ratio. Their solvent-cast thin films were observed, under a transmission electron microscope, to exhibit various microphase-separated surface morphologies such as spheres, cylinders, and lamellae, depending on composition. © 1997 John Wiley & Sons, Inc.     

Coupling of numerical Green''s matrix and boundary integral equations for the elastodynamic analysis of inhomogeneous bodies on an elastic half-space

A coupled system of integral equations (of the domain and boundary types) is formulated for the elastodynamic response analysis of a locally inhomogeneous body on a homogeneous elastic half-space. The method uses the fundamental solution for homogeneous elastostatics in the inhomogeneous domain owing to the lack of a fundamental solution in inhomogeneous elastodynamics.

The integral representation of displacements in the inhomogeneous domain is formulated with the help of this elastostatic fundamental solution by considering the term induced by the inhomogeneity of materials and the acceleration term as the body force term. Then the Green's matrix is obtained numerically from this integral representation and combined with the ordinary boundary integral equations, which are valid in the exterior homogeneous half-space.

Some numerical examples show the efficiency and the versatility of this coupled method.     

On the convergence of finite element solutions to the interface problem for the Stokes system

The Stokes system with a discontinuous coefficient (Stokes interface problem) and its finite element approximations are considered. We firstly show a general error estimate. To derive explicit convergence rates, we introduce some appropriate assumptions on the regularity of exact solutions and on a geometric condition for the triangulation. We mainly deal with the MINI element approximation and then consider P1-iso-P2/P1 element approximation. Results are expected to give an instructive remark in numerical analysis for two-phase flow problems.     

Elongation and contraction of molecular springs. Synthesis, structures, and properties of bridged [7]thiaheterohelicenes

A series of bridged [7]thiaheterohelicenes 3a-c and 4 with a variety of helical pitches have been prepared from racemic and optical pure 2,13-bis(hydroxymethyl)dithieno[3,2-e:3',2'-e']benzo[1,2-b:4,3-b']bis[1]benzothiophene (1) in order to investigate the helical structures in solution. Recrystallizations of (PM)-3a, (PM)-3b, (PM)-3c, and (P)-4 from hexane-dichloromethane gave crystals suitable for X-ray crystallography, while recrystallization of (PM)-4 with benzene gave an inclusion complex with a stoichiometry of (PM-4)(4).(C(6)H(6)). X-ray analyses of (PM)-3a-c, (PM-4)(4).(C(6)H(6)), and (P)-4 indicate that the dihedral angles between terminal thiophene rings of the helical framework significantly vary from 22 degrees for 4 to 59 degrees for 3c. This represents as increase of 37 degrees or 168%. Although the (13)C NMR and UV absorption spectra of bridged helicenes 3a-c and unbridged helicene 5 are essentially the same, the molar rotation of 5 is very large compared with those of 3a-c and 4. A red shift (15 nm) in the circular dichroism (CD) spectrum is observed for 4, suggesting that this compound is more planar than 3a-c in solution. In the series of [7]thiaheterohelicenes studied, the minimum helical pitch is 2.70 A for 4.     

Homohelicity induction of propylene-linked zinc bilinone dimers by complexation with chiral amine and α-amino esters. Preorganization of structurally coupled homohelical subunits

Homohelicity induction of a series of propylene-linked zinc bilinone (ZnBL; linear tetrapyrrople-zinc(II) complex) dimers upon complexation with chiral amine and α-amino esters was investigated. Introduction of substituents such as dimethyl and diisobutyl to the central carbon of the propylene spacer gave rise to stabilization of the homohelical (PP and MM) conformers rather than the heterohelical (PM) conformer. As bulkiness of the substituent increased, stability of the homohelical conformers was raised. The preorganization of the homohelical structures led to significantly amplified homohelicity induction upon complexation with chiral amine and α-amino esters.     

Chemistry and antiproliferative activities of 3-methoxyflavones isolated from <Emphasis Type="Italic">Varthemia iphionoides</Emphasis>

A new isolated flavone, 4′-hydroxy-3,5,6,7-tetramethoxyflavone (6), together with seven known 3-O-methylated flavones isolated from the ethanol extract of the aerial parts of Varthemia iphionoides, were studied for DPPH free radical-scavenging and cytotoxic activities. Flavones 2, 3, 4, and 8 were the most active DPPH free-radical scavengers with inhibition percentage of 63.5, 42.9, 47.9, and 55.6, respectively, at a concentration of 100 μg/mL. Flavones 2 and 8 were the most active as inhibitor for human leukemia HL-60 cells; the IC₅₀ values after 48 h incubation were 20.5 and 23.9 μg/mL, respectively.