Hydrogel of biodegradable cellulose derivatives. I. Radiation-induced crosslinking of CMC

Radiation crosslinking of carboxymethylcellulose (CMC) with a degree of substitution (DS) from 0.7 to 2.2 was the subject of the current investigation. CMC was irradiated in solid-state and aqueous solutions at various irradiation doses. The DS and the concentration of the aqueous solution had a remarkable affect on the crosslinking of CMC. Irradiation of CMC, even with a high DS, 2.2 in solid state, and a low DS, 0.7 in 10% aqueous solution, resulted in degradation. However, it was found that irradiation of CMC with a relatively high DS, 1.32, led to crosslinking in a 5% aqueous solution, and 20% CMC gave the highest gel fraction. CMC with a DS of 2.2 induced higher crosslinking than that with a DS of 1.32 at lower doses with the same concentration. Hence, it was apparent that a high DS and a high concentration in an aqueous solution were favorable for high crosslinking of CMC. It is assumed that; high radiation crosslinking of CMC was induced by the increased mobility of its molecules in water and by the formation of CMC radicals from the abstraction of H atoms from macromolecules in the intermediate products of water radiolysis. A preliminary biodegradation study confirmed that crosslinked CMC hydrogel can be digested by a cellulase enzyme. (C) 2000 John Wiley & Sons, Inc.

Effect of end substitution on optical properties and molecular orientation of distyrylbenzene derivatives in thin film

Three distyrylbenzene (DSB) derivatives were vacuum-evaporated on a (001) surface of KBr. DSB derivative molecules formed nuclei by interaction between the electron donative methoxyl group and Br- ion of the substrate crystal and oriented their longitudinal axis obliquely to the substrate surface. The peak shift between the emission peaks of solution and film decreased depending on the number of substituent. This phenomenon was originated to reduction of molecular interaction between neighboring molecules by steric hindrance of end substituents. (C) 2000 Elsevier Science S.A. All rights reserved.

Hydrogen-deuterium exchange reactions of cis- and trans-cyclopropane derivatives with D2O and CD3OD in the gas phase

Gas-phase hydrogen-deuterium (H/D) exchange reactions involving four isomeric cyclopropane derivatives were investigated under chemical ionization (CI) conditions, using D2O and CD3OD as reagent gases. There are abundant ions at [M + 1](+), [M + 2](+) and [M + 3](+) in the D2O and CD3OD positive-ion CI mass spectra of the two isomer pairs 1, 2 and 3, 4, Their CI mass spectra are identical with each pair, and so are the collision-induced dissociation (CID) spectra of ions [M + 1](+), [M + 2](+) and [M + 3](+) of each of the two isomer pairs. The CID spectra of [M + 1](+) ions indicate that they have common D/H exchange reactions within each pair, which take place between molecular ions and deuterium-labeling reagents to form the [M - H + D](+) ions. Those of their [M + 2](+) ions show that they have common D/H exchange reactions within each pair, which form the [M-d1 + H](+) ions. Those of their [M + 3](+) ions show that they have common D/H exchange reactions within each pair, which take place between the [M-d1] and deuterium-labeling reagents to produce [Md-2 + H](+) for the isomer pair 1, 2 and [M-d1 + D](+) for the Isomer pair 3, 4. The number and position, and active order of the active hydrogen atoms of the isomer pairs 1, 2 and 3, 4 were determined. Copyright (C) 2000 John Wiley & Sons, Ltd.

The research of cellulose derivatives as chiral stationary phases and high performance liquid chromatography with polarimeter as on-line detector

Three cellulose derivatives were synthesized and used as chiral stationary phases based on silica gel. The effects of adsorbances on the column numbers and stabilities have been investigated. These stationary phases exhibited high chiral recognition for various racemates. At the same time, the on-line curves of polarimeter were obtained by high performance liquid chromatography with polarimeter as on-line detector.

Variable selection by orthogonal descriptors and prediction of R-f value of phenol and aniline derivatives

Orthogonal descriptors is a viable method for variable selection, but this method strongly depend on the orthogonalisation ordering of the descriptors. In this paper, we compared the different methods used for order the descriptors. It showed that better results could be achieved with the use of backward elimination ordering. We predicted R-f value of phenol and aniline derivatives by this method, and compared it with classical algorithms such as forward selection, backward elimination, and stepwise procedure. Some interesting hints were obtained.

H/D exchange reaction of cyclopropane derivatives in the ion system of CD3OD

The fragmentation properties of the product ions [M + 1](+), [M + 2](+) and [M + 3](+) formed by ion-molecule reaction of four cyclopropane derivatives with the ion system of CD3OD were investigated by using collision-induced dissocation technique. The experiment results indicated that the product ions were produced via the H/D exchange reaction between reactants and reactive reagent ions of CD3OD. There are two exchangable hydrogen atoms on the ring of compounds 1 and 2, and only one for compound 3 and 4.

Synthesis and properties of three tris(1,10-phenanthroline) ruthenium (II) derivatives

Three new asymmetrical ruthenium (II) complexes: [Ru(phen)(2){phen-NHCO(CH2)(4)Br}](PF6)(2), [Ru(phen)(2){phen-NHCO(CH2)(5)Br}](PF6)(2) and [Ru(phen)(2){phen-NHCO(CH2)(10)Br}](PF6)(2) were synthesized, which were confirmed by the technique of FT-IR, H-1 NMR and ESI-MS. The electrochemical and fluorescent properties of three Ru (II) complexes were investigated with cyclic voltammetry and fluorometry.

Synthesis, electrochemistry and fluorescence of four new Ru(phen)(3)(2+) derivatives

Four typical LB monolayer film materials, Ru(phen)(3)(2+) complexes with one ligand attached to different long chain alkyl amides, were designed and synthesized. Their chemical structures were identified by the techniques of FT-IR, H-1 NMR and ESI-MS. Also, UV-Vis, electrochemistry and fluorescence of these complexes are reported.

Four novel screw-like tris(1,10-phenanthroline) ruthenium(II) bishexafluorophosphate derivatives

Four novel screw-like Ru(II) complexes, tris(5-lauramide-1,10-phenanthroline)Ru(II) bishexafluorophosphate, tris(5-myristamide-1,10-phenanthroline)Ru(II) bishexafluorophosphate, tris(5-palmitamide-1,10-phenanthroline)Ru(II) bishexafluorophosphate and tris (5-stearamide-1,10-phenanthroline)Ru(II) bishexafluorophosphate have been efficiently synthesized. They are confirmed by the techniques of IR, H-1 NMR, H-1-H-1 COSY and ES-MS. Also, their electrochemistry, fluorescence and electrochemiluminescence are reported.

Fabrication and characterization of orientation-controlled thin films of distyryl benzene derivatives

Distyryl benzene derivatives (DSB-1 and DSB-2) were deposited on a KBr (001) surface. DSB-1 molecules took two kinds of orientations depending on the substrate temperature. On the other hand, DSB-2 grew epitaxially. The longitudinal axes of DSB-2 molecules were oriented parallel to the substrate surface.

Synthesis and characterization of soluble polyimides from 2,2-bis(4-aminophenyl)cycloalkane derivatives

New aromatic diamines [(1) and (2)] containing polycycloalkane structures between two benzene rings were synthesized by HCl-catalyzed condensation reaction of aniline hydrochloride and corresponding polycycloalkanone derivatives. The structures of diamines were identified by H-1-NMR, C-13-NMR, FTIR spectroscopy, and elemental analysis. The polyimides were synthesized from the obtained diamines with various aromatic dianhydrides by one-step polymerization in m-cresol. The inherent viscosities of the resulting polyimides were in the range of 0.34-1.02 dL/g. The polyimides showed good thermal stabilities and solubility. All the polymers were readily soluble in N-methyl-2-pyrrolidone, m-cresol, tetrachloroethane, etc. Some of them were soluble even in chloroform at room temperature. The glass transition temperatures were observed in the range of 323-363 degrees C, and all of the polymers were stable up to 400 degrees C under nitrogen atmosphere. (C) 1999 John Wiley & Sons, Inc.

Study of the effect of hydrogen bonding on the phase behaviour of p-nitro azobenzene derivatives with hydrophilic tails

The infrared spect ra of N-n-(4-nitrophenyl)azophenyloxyalkyldiethanolamines (Cn) are examined in the range of 4000-400 cm(-1) at different temperatures and the assignment of the fundamental vibrations given. Based on (1) the localization of the broad absorption band at 3456 cm(-1), and (2) attribution of the associated OH bands centred at 1410-1390, 1100, and 650-634 cm(-1) to, respectively delta OH deformation, nu C-O stretching and gamma OH out-of-plane bending, intermolecular hydrogen bonding between OH groups in the crystalline, liquid crystalline and isotropic states is proposed. By considering the results of FTIR, WAXD and DSC measurements, the molecular arrangement of C10 in its smectic A phase as consisting of hydrogen bonding and strong interaction between dipolar groups (NO,) is proposed. This may explain the high stability and high orientational ordering property of Cn compounds in the liquid crystalline state compared with that of n-bromo-1-[4-(4-nitrophenyl)azophenyl]oxyalkanes (Bn).

Preparation and characterization of self-assembled monolayers of trichlorogermanyl propanoic acid and its derivatives

Self-assembled monolayers(SAMs) of trichlorogermanyl propanoic acid derivatives on hydroxylated silicon substrates are prepared for the first time. Contact angle measurement, ellipsometry and X-ray photoelectron spectrometry(XPS) are used to characterize these SAMs, It is demonstrated that a quasi-2D network is formed on the surface of the substrate after molecules adsorbed on it. The molecular chains have certain tilt angles to the substrate surface, The wettabilities of the SAMs are various,because the molecules adsorbed and liquids used in the experiments are different. It can be concluded that trichlorogermanes have similar self-assembly behavior as trichlorosilanes, Four SAMs are studied together: they are acid, ethyl, butyl and hexyl surfaces whose results are of good consistency.

Studies on quantitative structure-activity relationship between the structures of derivatives of benzamide and their antiallergic activities

Molecular connectivity index and comparative molecular field analysis (CoMFA) have been applied to the studies of the correlation of the derivatives of benzamide and their antiallergic activities. The results achieved by using CoMFA based on 3D factors are much better than that obtained by using multiple regression analysis based on majorly 2D structural information. The CoMFA results show that the dominant factor which affects activity is steric, whereas electrostatic effect only plays an unimportant role.

Ion-molecule reactions of cis- and trans-cyclopropane derivatives with methane, acetone and vinyl acetate under chemical ionization conditions

Ion-molecule reactions of four isomeric cyclopropane derivatives were investigated under chemical ionization(CI) conditions, using methane, acetone and vinyl acetate as reagent gases, The methane positive-ion CI mass spectra of each of two isomer pairs 1,2 and 3,4 are identical, and so are the collision-induced dissociation (CTD) spectra of the protonated molecules of each of the two isomer pairs, The protonation reactions for the isomer pairs 1,2 and 3,4 occurred on the sites of the carboxyl groups and the R groups, respectively, Differences between isomers 1 and 2 are observed in their acetone (A) positive-ion CI mass spectra and in the CID spectra of their adduct ions ([M+H+A](+)), The adduct ions of compounds 2, 3 and 4 with protonated acetone and with protonated acetone dimer are observed in their CI mass spectra, However, only the adduct ions of compound 1 with protonated acetone appear in its CI mass spectrum, The protonated dimers of each of the four compounds are found in their vinyl acetate positive-ion CI mass spectra, and the CID spectra of these dimers for isomers 1 and 2 can also reflect their stereostructural difference. (C) 1998 John Wiley & Sons, Ltd.