Synthesis and radical polymerization of styrene‐based monomer having a five‐membered cyclic carbonate structure

A styrene‐based monomer having a five‐membered cyclic carbonate structure, 4‐vinylbenzyl 2,5‐dioxoran‐3‐ylmethyl ether (VBCE), was prepared by lithium bromide‐catalyzed addition of carbon dioxide to 4‐vinylbenxyl glycidyl ether (VBGE). Radical polymerization of the obtained VBCE was carried out using 2,2′‐azobisisobutyronitrile as an initiator. PolyVBCE with number‐averaged molecular weight higher than 13,800 was obtained by a solution polymerization in N,N‐dimethylformamide, N,N‐dimethylacetamide, dimethyl sulfoxide, and methyl ethyl ketone. The glass transition temperature and 5 wt % decomposition temperature of the polyVBCE were determined to be 52 and 305 °C by differential scanning calorimetry and thermal gravimetry analysis, respectively. It was confirmed that a polymer consisting of the same VBCE repeating unit can be also obtained via chemical modification of polyVBGE, that is, a lithium‐bromide‐catalyzed addition of carbon dioxide to a polyVBGE prepared from a radical polymerization of VBGE. Further copolymerization of VBCE with styrene gave the corresponding copolymer in a high yield. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Supramolecular polymer gels from polystyrene bearing cyclic amidine Group and acrylic acid/n‐butyl acrylate copolymers

We have prepared supramolecular polymer gels by mixing solutions of a polystyrene bearing cyclic amidine pendant groups (Poly‐A) and copolymers of acrylic acid and n‐butyl acrylate (Poly‐C), followed by evaporation. FT‐IR analysis indicated that the gels were formed through three‐dimensional network of the amidinium‐carboxylate salt bridge. DSC study showed that the Poly‐A and the Poly‐C were miscible when the salt bridge content was high. On the other hand, the mixtures with small salt bridge content showed phase separation. Dynamic shear measurements showed that the gel prepared from Poly‐A and Poly‐C with acrylic acid unit content of 15% had G' higher than G″ over a temperature range of ?22 °C to 32 °C, in which the G' value reached almost 1 MPa. The gel had a crossover point of G' and G″ at 32 °C, very close to room temperature, which suggested facile processability. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 765–770     

Metallic conductivity and ferromagnetic interaction of iron(III) d spins in the needle crystals of (ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide)(2).FeBr(4) salt

The 2:1 charge-transfer (CT) salts (1(2).FeBr(4) and 1(2).GaBr(4)) of ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide (1) with FeBr(4)(-) and GaBr(4)(-) counteranions were obtained as needle crystals, whose structures are almost the same as each other. The 1 molecules form a one dimensionally stacked column with alternation of their molecular axis direction, while the counteranions are aligned in parallel with the 1-stacked columns with the direction of their distorted-tetrahedral geometry maintained. The room-temperature electrical conductivities measured on the single crystals of 1(2).FeBr(4) and 1(2).GaBr(4) were 4.6 and 2.1 S cm(-1), respectively. From the temperature dependences of their electrical conductivities in both cases the electrical conducting properties were metallic between ca. 170 and 300 K, but below ca. 170 K converted to be semiconducting and continued till 5 K, although the activation energies are very small (4-10 meV). For 1(2).FeBr(4) very weak and antiferromagnetic interaction occurred between the d spins of FeBr(4)(-) ions in the temperature range of ca. 1-300 K. However, below ca. 15 K the ferromagnetic interaction was reversely preferential possibly by participation of the pi spin of 1.     

Controlled monomer insertion into polymer main chain: synthesis of sequence ordered polystyrene containing thiourethane and trithiocarbonate units by the RAFT process

A polymer having a trithiocarbonate moiety in the main chain was applied as a polymeric precursor to the synthesis of a sequence ordered polymer by insertion polymerization of styrene into the main chain by a RAFT mechanism.     

Total synthesis of ecteinascidin 743

The total synthesis of ecteinascidin 743 (1), an extremely potent antitumor agent, has been accomplished. The synthesis features Ugi's 4CC reaction, intramolecular Heck reaction, phenol-aldehyde cyclization, and acid-induced intramolecular sulfide formation.     

Relationship between apparent diffusion coefficient and signal intensity in endometrial and other pelvic cysts

We evaluated whether apparent diffusion coefficient (ADC) value is more useful than signal intensity for differentiating endometrial cysts from other pelvic cysts. In an in vitro study, signal intensity and diffusion coefficients were measured in whole blood phantoms in which blood oxidation was gradually increased and concentration subsequently diluted. Although both signal intensity and diffusion value were largely affected by blood concentration, diffusion value was almost independent of blood oxidation and red blood cell lysis-related diminution of magnetic nonhomogeneity, both factors greatly affecting signal intensity on T1- and T2-weighted images. In an in vivo study, differentiation between endometrial and other pelvic cysts was attempted by means of ADC values and signal ratios of cysts to muscles on T1- and T2-weighted images (T1- and T2-ratios). Endometrial cysts tended to show lower T2-ratios, higher T1-ratios, and lower ADC values than other pelvic cysts (p < 0.001). However, ADC values were not correlated with T1- and T2-ratios (p < /0.15/). The ability of ADC value to discriminate between these two groups (discriminant rate, 91.4%) was higher than that of T2-ratio (71.4%) or T1-ratio (88.6%). If combined, ADC and T1-ratio (or T2-ratio) showed higher discriminant rate (94.3%) than the combination of T1- and T2 ratios (88.6%). ADC value might be useful for evaluating the blood concentration of a cystic lesion, because diffusion value is more closely related to blood concentration and almost independent of blood oxidation and red blood cell lysis that largely affect signal intensity.     

Normal stress and shear stress in a viscoelastic liquid under steady shear flow: Effect of molecular weight heterogeneity

Under steady shear flow, the normal stress and the shear stress in both dilute and concentrated solutions of monodisperse poly-α-methylstyrenes and their blends were measured. It was confirmed that the molecular theories of Rouse and Zimm extended to concentrated solutions can explain the relation between the zero-shear normal stress coefficient and the zero-shear steady-flow viscosity for both monodisperse and polydisperse systems. Shear-rate dependence of steady-flow viscosity can be understood fairly well by the molecular entanglement concept proposed by Graessley so long as the polymer is monodisperse or the amount of the higher molecular weight component is high. However, zero-shear viscosity of blended systems cannot be explained quantitatively by the theory of Graessley. The shear-rate dependence of steady-state compliance of blended systems was also observed, and it can well be explained by the theory of Tanaka, Yamamoto, and Takano which interpreted the shear rate-dependent steady-state compliance in terms of the relaxation time spectrum and its variation with shear rate.     

Surface properties of styrene–ethylene oxide block copolymers

Hydrophobic–hydrophilic block copolymers were prepared by “living” anionic polymerization. They consist of polystyrene and poly(ethylene oxide) blocks, and are soluble in water. Their interfacial properties were investigated, employing aqueous solutions. The block copolymers lowered the surface tension of water in analogy with the low molecular weight surfactants such as sodium lauryl sulfate and heptaethylene oxide n-dodecyl ether. Their aqueous solutions exhibited solubilization properties differing from those of polyethylene glycol. Therefore, it is thought that the polystyrene blocks produce solubilization phenomena. In samples of the same styrene content, the precipitation temperature of a high molecular weight copolymer in water was lower than that of a low molecular weight copolymer at the same concentration in the same solvent. The surface tension and precipitation temperature of aqueous solutions seem to be influenced by molecular weight and composition.     

Application of pattern recognition to structure-activity problems: Use of minimal spanning tree

A graph-theoretical algorithm based on the minimal spanning tree (MST) is applied to structure—activity problems. The method is helpful in interpreting the results of cluster analysis, and becomes useful by combining with the mapping method that illustrates approximations of a multidimensional data structure. The antibacterial spectra of cephalosporins are analyzed by the MST approach and a linear mapping method. The main diameter obtained by MST gives the representative data set and clarifies the substituent effect on the antibacterial spectra. Relations between the central nervous system activity of benzodiazepine derivatives and their physicochemical parameters are also analyzed by MST and nonlinear mapping methods. These results for cephalosporins and benzodiazepines prove that MST is very useful in understanding the position of compounds in feature space and their activities.     

On the miscibility gap in liquid bismuth-bismuth tribromide system

We have determined the location of the miscibility gap in liquid Bi-BiBr₃ system in the concentration-temperature, x?T, plane from the measurement of the electrical conductivity. The measurements have been done in the concentration range between 30.5 and 92.5 mol.% Bi and in the temperature range between 300 and 600°C. It is found that the temperature dependence of the conductivity of the mixture changes near the retrograde solubility region.