Conducting microfibers of poly(3,4‐ethylenedioxythiophene) doped with poly(4‐styrene sulfonate), having a diameter ranging between 4.6 and 16 μm, were fabricated by a wet‐spinning technique. The as‐spun microfiber had no notable orientation of polymer chains with poor crystallinity, and electrical conductivity was in the order of 10−1 S · cm−1 regardless of the diameter. Young's modulus, tensile strength, and elongation at break for the resulting microfiber were 1.1 ± 0.3 GPa, 17.2 ± 5.1 MPa, and 4.3 ± 2.3%, respectively.
SEM image of a PEDOT/PSS microfiber reported here.magnified imageSEM image of a PEDOT/PSS microfiber reported here.
The reactivity of flavonoids as radical scavengers was investigated under kinetic considerations using radical polymerization of methyl methacrylates initiated by benzoyl peroxide. The number of radicals which are trapped by each molecule of phenol (the stoichiometric factors, n values) decreased in the order of epigallocatechin-3-O-gallate (ECG) (5.5) > catechin (3.5) > resveratrol (2.4) > quercetin (1.9) > n-propylgallate (1.5) > hesperetin (1.0). The inhibition rate constants (k(inh)) (1-3 x 10(3) 1/(mol s)) for the flavonoids were not different from each other, and, therefore, the radical scavenging activity depend on n values. The n values of the fully oxidized flavonoids were estimated from the frontier orbital theory, using PM3 semiempirical molecular orbital calculation. The experimental n values were consistent with the calculated values.
The primary process for the influence of light on the Ru(bpy),"-catalyzed Belousov-Zhabotinskii reaction system was investigated. The wavelength dependence of the illumination effect on oscillations was found to be in good correlation with the absorption spectrum of Ru(bpy)?+. The dynamic behavior of bromide ion was measured simultaneously with that of Ru(bpy)?+ during illumination on the oscillatory reaction and the acidic bromate-Ru(bpy)?+ systems. The results suggest that the inhibitory effect of illumination results from the formation of bromide ion in the reaction of the excited state of Ru(bpy),2t with bromate.
To clarify the non-enzymatic radical-scavenging activity of beta-carotene-related compounds and other polyenes, we used differential scanning calorimetry to study the kinetics of radical polymerization of methyl methacrylate (MMA) by 2,2'-azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO) in the absence or presence of polyenes under nearly anaerobic conditions at 70 degrees C, and analyzed the results with an SAR approach. The polyenes studied were all-trans retinol, retinol palmitate, calciferol, beta-carotene and lycopene. Polyenes produced a small induction period. The stoichiometric factor (n) (i.e. the number of radicals trapped by each inhibitor molecule) of polyenes was close to 0. Tetraterpenes (beta-carotene, lycopene) suppressed significantly more of the initial rate of polymerization (R(inh)) than did diterpenes (retinol, retinol palmitate). The inhibition rate constants (k(inh)) for the reaction of beta-carotene with AIBN- or BPO-derived radicals were determined to be 1.2-1.6x10(5) l/mol s, similar to published values. A linear relationship between (k(inh)) and the kinetic chain length (KCL) for polyenes was observed; as (k(inh)) increased, KCL decreased. KCL also decreased significantly as the number of conjugated double bonds in the polyenes increased. Polyenes, particularly beta-carotene and lycopene, acted as interceptors of growing poly-MMA radicals.
Camphorquinone (CQ) is widely used as a photo-initiator in dental materials; however, its cytotoxicity against human pulp fibroblasts (HPF) and particularly the effects of 2-dimethylaminoethyl methacrylate (DMA), a reducing agent and visible light (VL) irradiation on it remain unknown. So we investigated the cytotoxic and reactive oxygen species (ROS)-producing effects of CQ with or without DMA, in the presence or absence of VL on HPF cells. The free-radical production activity of CQ was measured by two different methods [using diphenylpicryl hydrazyl and galvinoxyl]. The phase-transition properties of dipalmitoylphosphatidyl choline (DPPC) liposomes, as a model for biomembranes, induced by CQ were investigated by differential scanning calorimetry. These findings were compared with those of 9-fluorenone (9F), an aromatic photo-initiator with long conjugated groups. Camphorquinone with VL irradiation increased the radical production, whereas 9F with VL irradiation increased ROS production, as well as effecting changes in the DPPC phase-transition properties. The cytotoxicity of CQ towards HPF cells was smaller than that of 9F despite greater radical production. The addition of DMA to the photosensitizer enhanced the free-radical production without increasing the ROS level or the cytotoxicity. Camphorquinone/DMA is a valuable combination for the polymerization of dental resins.
To clarify the mechanism of methacrylate-induced toxicity, a total of 24 acrylates, methacrylates, and dimethacrylates were chosen for a structure-activity relationship (SAR) study in terms of NMR chemical shifts, semiempirical molecular descriptors, and reverse phase (RP)-HPLC log P. Molecular descriptors as well as bulk, electronic, and energy descriptors were calculated using the PM3/CONFLEX method. A significant multiple linear regression equation for methacrylates in mice was denoted as log 1/LD50 (which was function [-(EHOMO+ELUMO)/2, log P]). Besides, significant linear regression equations for methacrylates were denoted as log 1/ED50 in HeLa S3 and in HGF cells as function [EHOMO and/or log P]. Results showed that the 13 C NMR chemical shift of β-carbon for methacrylates was correlated with their EHOMO. Findings of this study thus suggested that it might be possible to predict methacrylate-induced toxicity using physicochemical properties.
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