Facile modifications of a polyimide via chloromethylation. I. Novel synthesis of a new photosensitive polyimide

A soluble aromatic polyimide was chloromethylated via a reaction with chloromethyl methyl ether in the presence of tin(IV) chloride to produce a new starting material for the modification of aromatic polyimides. The chemical structure of the resulting polymer was confirmed by ¹H NMR and Fourier transform infrared spectroscopy. The maximum number of chloromethyl groups per repeat unit was 1.81. The chloromethylated polyimide was stable up to 250 °C and soluble in both chloroform and tetrahydrofuran. So that its utilization for further modification could be demonstrated, cinnamic acid was reacted with the formed polyimide, and it produced a new photosensitive polyimide with a cinnamoyl side chain. The photosensitivity of the resulting polyimide was investigated with ultraviolet spectroscopic methods. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 22–29, 2003     

Ergodicity for the Dissipative Boussinesq Equations with Random Forcing

We study the stationary measure for the two-dimensional Boussinesq equation with random forcing. We prove the ergodicity for the two-dimensional stochastically forced Boussinesq equation. We also study the Galerkin truncations of the three-dimensional Boussinesq equations under degenerate stochastic forcing. We follow closely the previous results on the stochastically forced Navier–Stokes equations.     

Electrochemical and Electrochromic Properties of Ni Oxide Thin Films Prepared by a Sol–Gel Method

Nickel oxide thin films, which are well known anodic coloration materials that are used in electrochromic devices, were prepared by a sol–gel method, and their electrochemical and electrochromic properties were investigated. The sol was prepared from Ni(OH)₂ powder with an average size of 7 nm, in a mixture of ethylene glycol and absolute ethanol. The films were coated on an ITO substrate using the powder, dispersed in the solution. When additive materials, acetyl acetone and glycerol, were added to the sol its hardness and adhesion properties were improved. The optimized thin film formed an amorphous, porous structure, and showed a large current density during continuous potential and pulse potential cycling. The film also was transparent and had a high coloration efficiency (33.5 cm²/C) and a rapid response time (1.0–2.5 s) during the coloring/bleaching process.     

Soluble factor from tumor cells induces heme oxygenase-1 by a nitric oxide-independent mechanism in murine peritoneal macrophages

Tumor target-derived soluble secretary factor has been known to influence macrophage activation to induce nitric oxide (NO) production. Since heme oxygenase-1 (HO-1) is induced by a variety of conditions associated with oxidative stress, we questioned whether soluble factor from tumor cells induces HO-1 through NO-dependent mechanism in macrophages. We designated this factor as a tumor-derived macrophage-activating factor (TMAF), because of its ability to activate macrophages to induce iNOS. Although TMAF alone showed modest activity, TMAF in combination with IFN-gamma significantly induced iNOS expression and NO synthesis. Simultaneously, TMAF induced HO-1 and this induction was slightly augmented by IFN-gamma. Surprisingly, however, induction of HO-1 by TMAF was not inhibited by the treatment with the highly selective iNOS inhibitor, 1400 W, indicating that TMAF induces the HO-1 enzyme by a NO-independent mechanism. While rIFN-gamma alone induced iNOS, it had no effect on HO-1 induction by itself. Collectively, the current study reveals that soluble factor from tumor target cells induces HO-1 enzyme in macrophages. However, overall biological significance of this phenomenon remains to be determined.     

Spectroscopic characterization and preparation of low molecular,water‐soluble chitosan with free‐amine group by novel method

Low molecular, water‐soluble chitosan (LMWSC) with a free amine group was prepared by the novel salts‐removal method described in this study. A weight‐average molecular weight and degree of deacetylation (DDA) of LMWSC were determined by viscometry and Kina titration, resulting in 18,579 Da and 93% DDA, respectively. In the Fourier transform infrared spectroscopic, ¹H NMR, and ¹³C NMR spectra the absorption band by the carboxyl group derived from lactic acid and the impurities formed in the enzymatic process disappeared or were significantly lower than that of the control chitosan. Also, from the ¹H NMR and ¹³C NMR spectra the empirical value for the area ratio of the proton and carbon corresponds nearly to its theoretical values. The matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrum identified the difference in the two adjacent peaks as 161. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3796–3803, 2002     

Intermolecular alkyl/aryl exchange of 2-iminothiazoles with isothiocyanates and isocyanates: scopes and limitations

2-Iminothiazole, an isoform of 2-aminothiazole, is a scaffold of synthetic and medicinal significance. We have reported an efficient method by which alkyl group of 2-alkyliminothiazoles is changed into other alkyl groups by isothiocyanates. In this article, a detailed mechanistic aspect, and the scopes and limitations were disclosed. All the reactions were carried out in toluene at 105 °C without any additive. The reaction is a reversible process and the equilibrium is determined by the reactivity of both reactants, in which the more electron-withdrawing alkyl or aryl groups at the 2-imino group or isothiocyanate showed higher reactivities. With this simple method, we effectively altered the alkyl group attached on the imine nitrogen. A synthetic problem in 2-iminothiazole chemistry, synthesis of amino acid-derived 2-iminothiazole was solved in a very simple manner. Using suitably designed 2-iminothiazole substrate, the electrophilic reactivity of various isothiocyanates could be empirically compared by this exchange reaction. Moreover, successful exchange reaction using isocyanates instead of isothiocyanates broadened the utility of this reaction.     

Synthesis of polar block grafted syndiotactic polystyrenes via a combination of iridium‐catalyzed activation of aromatic C?H bonds and atom transfer radical polymerization

A combination of iridium‐catalyzed C H activation/borylation and atom transfer radical polymerization (ATRP) was used to generate polar graft copolymers of syndiotactic polystyrene (sPS). The borylation at aromatic C H bonds of sPS and subsequent oxidation of boronate ester proceeded without negatively affecting the molecular weight properties and the tacticity of sPS. A macroinitiator suitable for ATRP could be synthesized by the esterification of 2‐bromo‐2‐methylpropionyl bromide and hydroxy‐functionalized sPS. The graft polymerizations of methyl methacrylate and tert‐butyl acrylate from the macroinitiator using ATRP afforded polar block grafted sPS materials, syndiotactic polystyrene‐graft‐poly(methyl methacrylate) (sPS‐g‐PMMA) and syndiotactic polystyrene‐graft‐poly(tert‐butyl acrylate) (sPS‐g‐PtBA). The latter was hydrolyzed to yield an amphiphilic graft copolymer, syndiotactic polystyrene‐graft‐poly(acrylic acid) (sPS‐g‐PAA). The structures of the copolymers were characterized by NMR and FTIR spectroscopies. Size exclusion chromatography and ¹H NMR spectroscopy were used to study any changes in the molecular weight properties from the parent polymer. A decrease in the hydrophobicity of the graft copolymers was confirmed by water contact angle measurements. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6655–6667, 2009