Alternating copolymers consisting of arylalkyl methacrylates. I. Fluorescence properties of poly(arylalkyl methacrylate-alt-styrene) in organic solution

Alternating and random copolymers of 9-phenanthrylmethyl methacrylate or 2-(9-carbazolyl)ethyl methacrylate with styrene were synthesized and their fluorescence properties were examined. There was no noticeable difference in the spectral features of the alternating and random copolymers in tetrahydrofuran (THF), demonstrating that this type of polymers have no quenching sites in the polymer chains. The fluorescence quenching studies indicated that the alternating copolymers permitted singlet-state energy migration as efficiently as the corresponding random copolymers but less efficiently than the random copolymers with higher chromophore contents. These results strongly suggest that to be chromophores close to each other is most important for facilitation of an intramolecular energy migration. © 1995 John Wiley & Sons, Inc.     

Enzymatic degradation of highly phenolic lignin-based polymers (lignophenols)

Enzymatic degradation of two lignin-based polymers (lignophenols), lignocatechol and lignocresol, prepared by selectively grafting catechol and p-cresol to C_α positions of lignin, respectively, were carried out in aqueous organic solvents. Both lignophenols showed high reactivity in the peroxidase-catalyzed oxidation. Structural analyses by NMR spectroscopies revealed that the degraded lignophenols contained aliphatic chain content, which might be mainly formed in the reduction of the intermediate initially generated by the aromatic ring cleavage. Lower amount of aromatic units in the lignophenols after degraded by peroxidase also indicted the cleavage of aromatic rings. Due to the substitution of phenols at C_α positions of lignin, the degraded lignophenols did not have carbonyl structure, which was abundant in the biodegradation products of native lignin. The two lignophenols were also degraded by Rhus vernicifera laccase. But the degree of degradation was lower than that of the degradation by peroxidase, which might be due to the low activity of laccase on the lignin moieties in lignophenols.     

Specific interaction between polyethylenimine and azo dyes carrying hydroxyl groups

The binding of acid azo dyes having phenolic hydroxyl groups such as orange I ( I ), orange II ( II ), chrome violet ( III ), 4-hydroxyazobenzene-4′-sulfonate ( IV ), and 2,4-dihydroxyazobenzene-4′-sulfonate ( V ) by polyethylenimine was studied by equilibrium dialysis and spectroscopic methods. The results obtained indicate that dyes ( III ) and ( V ) with two OH groups are bound much more strongly than dyes ( I ), ( II ), and ( IV ) with one OH group. Also polyethylenimine is far superior to any other polymers which have been examined, including bovine serum albumin, polyvinylpyrrolidone, and poly-L -lysine, in its ability to form complexes with these dyes ( III ) and ( V ). The OH groups involved participate preferentially in complex formation with polyethylenimine. The unusual affinity of polyethylenimine for the dyes carrying OH groups is discussed.     

Effects of added metal ions on the interaction between polyvinylpyrrolidone and azo dyes carrying hydroxyl groups

The extent of binding of chrome violet, which is a monoazo dye and involves two hydroxyl groups in o and o′ positions to azo group, by polyvinylpyrrolidone is markedly enhanced in the presence of Co²⁺ ion. The amount of binding in the presence of 1 × 10^?4 mol/L of Co²⁺ ion increases by a factor of about 10 compared to that in the absence of the metal ion. Ni²⁺ and Zn²⁺ ions do not perceptively influence the binding affinity of the dye. Cu²⁺ ion, in contrast, suppresses the binding. To investigate further the action of added metal ions, a cobalt–complex dye was prepared and its binding property for the polymer was compared to that of chrome violet in the presence of metal ions. Some possible mechanisms for the enhancement of chrome violet binding by the addition of Co²⁺ ion are described.     

Binding of metal ions by polyethylenimine and its derivatives

Measurements have been made of the binding of divalent metal ions, Cu²⁺, Ni²⁺, Co²⁺, and Zn²⁺ ions, by polyethylenimine (PEI) and its acetyl or alkyl derivatives by the equilibriumdialysis technique. These metal ions, in particular the Cu²⁺ ion, exhibited tremendously remarkable binding affinity toward PEI. The extent of complexation of the polymer with the metal ions was decreased markedly by acetylation or alkylation of the polymer. PEI with no primary amine showed an appreciable decrease in its affinity for the metal ion. These results indicate the participation of the primary amine of the polymer in the formation of the complex. A cooperative binding isotherm was observed in PEI–metal ion complex formation, suggesting swelling or conformational change of the polymer induced by this coordination process. Binding of the Cu²⁺ ion by PEI was found to be essentially independent of temperature over the range 5–35°C.     

INVESTIGATIONS ON THE MECHANISM OF CHLORPROMAZINE PHOTOTOXICITY: EFFECTS ON LYSOSOMES OF CULTURED HUMAN FIBROBLASTS

Abstract The effect of chlorpromazine (CPZ) and UVA on lysosomes of cultured normal human fibroblasts has been investigated. Acid phosphatase (ACPase) activity in 12 000 g pellet of cells treated with CPZ (10 μg/m l ) and UVA (6 × 10⁴ J/m²) was found to be decreased as compared with non-treated, CPZ or UVA treated control cells. This decrease, however, was not accompanied by a concomitant increase in ACPase activity in the 12 000 g supernatant. The addition of Triton X-100 to cells pretreated with CPZ + UVA resulted in only a moderate increase in ACPase activity of the 12 000 g supernatant. ACPase activity of the cells incubated in media containing preirradiated CPZ was also found to he decreased. These results indicate that CPZ + UVA directly inactivate lysosomal enzymes, possibly without affecting the membrane.     

Effect of solvent on the cation-sensitive fluorescence of polyanions bearing 4′-acryloylbenzo-18-crown-6 Units

Changes in the fluorescence intensity of polyanions bearing 4-acryloylbenzo-18-crown-6 units on the addition of cations were studied in a mixed solvent of methanol and water at 30°C. The sensitivity of the change in fluorescence intensities of the polymers toward cations was strongly enhanced compared to that of the corresponding model compound. When alkali metal cations were added, the fluorescence intensity of the polymers decreased in the orders Li⁺>Na⁺>Cs⁺>Rb⁺>K⁺ in a methanol-water (19) mixture and Li⁺>Na⁺>Rb⁺>K⁺Cs⁺ in a methanol-water (91) mixture. Alkaline earth metal cations and alkylamine hydrochlorides decreased the fluorescence intensity of the polymers in a methanol-water (19) mixture. The cation-dependent decrease in the fluorescence intensity of the polymers was affected by the water fraction in a mixed solvent of methanol and water.     

QUATERNARY STRUCTURE OF PEA PHYTOCHROME I DIMER STUDIED WITH SMALL-ANGLE X-RAY SCATTERING and ROTARY-SHADOWING ELECTRON MICROSCOPY

Abstract— The quaternary structure of pea phytochrome type I (PI) dimer in the red-light-absorbing form was studied by small-angle X-ray scattering (SAXS) technique and rotary-shadowing electron microscopy. Structural parameters for PI 114 kDa chromopeptide dimer and its tryptically digested N-terminal 59 kDa chromopeptide monomer, such as average electron density, molecular volume and the second moment of electron density distribution, were determined in terms of SAXS using the contrast variation method. Furthermore, by means of model simulation for the scattering profiles of the chromopeptides, most plausible structural models for both peptides were constructed. The distance between the chromophoric domains was estimated to be about 70 A in the resultant model for 114 kDa chromopeptide dimer. Furthermore, the model was consistent with the electron-micrographic images of both the intact PI dimer and the PI 114 kDa chromopeptide dimer, so that the N-terminal 7 kDa fragment did not significantly contribute the low-resolution images of the dimer.