Inhibition of lipid peroxidation in UVA‐treated skin fibroblasts by luteolin and its glucosides

Ultraviolet A (UVA) radiation causes oxidative damage to human skin cells. This damage may be reduced or prevented using plant compounds as photoprotectants. To investigate the relationship between chemical structure and UVA‐protective activity, three structurally related flavonoids, namely luteolin, luteolin‐7‐O‐glucoside (both present in artichoke) and luteolin‐4'‐O‐glucoside (present in wild carrot), were studied. Human skin fibroblasts exposed to UVA (250 and 500 kJ/m²) were treated with each flavonoid (30 µM) for 18 h prior to irradiation. The extent of lipid peroxidation in the cellular extracts was assessed as lipid peroxides and malondialdehyde (MDA). Luteolin and luteolin‐7‐O‐glucoside both prevented a significant increase in lipid peroxides at 250 kJ/m², but at 500 kJ/m² their effectiveness was clearly attenuated. Contrastingly, luteolin‐4'‐O‐glucoside was pro‐oxidant at both radiation doses. Measurements of MDA levels highlighted that luteolin was clearly more effective than the two glucosides at both 250 and 500 kJ/m². Overall, these results show clear differences between the three flavonoids and suggest that the B ring 3',4'‐dihydroxy group, lacking in luteolin‐4'‐O‐glucoside, may be particularly important. Flavonoid: transition metal ion chelation studies confirmed the influence of the 3',4'‐dihydroxy group, which is also relevant to the quenching of singlet oxygen. These features as well as the greater lipophilic nature of luteolin together explain the superior activity of this flavonoid which may be potentially useful as a supplement in photoprotective skin preparations.     

Microstructure and Microchemistry of Polymer-Derived Crystalline SiC Fibers

Stoichiometric and near-stoichiometric silicon carbide fibers, derived from the polymer polycarbosilane, have been characterized by scanning Auger and transmission electron microscope techniques. Excess carbon usually appeared in the fibers, but it could be eliminated by controlling processing conditions. The fibers consisted mainly of submicrometer-sized SiC microcrystals, with a considerably twinned and stacking-faulted β-SiC structure. Free carbon, which appeared in the form of graphite, was the only detectable intergranular phase in the nonstoichioinetric SiC fibers, while the stoichiometric SiC fibers contained no detectable second phase whatsoever.     

Ammoxidation of toluene over Y-Ba-Cu-Co-O perovskites

Ammoxidation of toluene over the perovskites YBa₂Cu₃O_6.1, YBa₂Cu₂CoO_6.7 and YBaCuCoO_4.9 was investigated at 400 °C. At low partial pressures of O₂ benzonitrile was selectively formed, while CO₂ was the main product at high pressures of O₂. Systematic differences in activity were observed for the three phases and are related to the crystal contents of Cu and Co. At low O₂ pressures, Cu-sites are active for nitrile formation, while Co-sites give CO₂. At high O₂ pressures, the activity for CO₂ of Cu-sites increases more than that of Co-sites due to filling of near-surface oxygen vacancies.     

Relationship between chemical degradation and thickness loss of an amine-cured epoxy coating exposed to different UV environments

The relationship between chemical degradation and thickness loss of an unpigmented, non UV-stabilized, crosslinked amine-cured epoxy coating exposed to three UV conditions was investigated. Spin-coated samples having a thickness of approximately 7 μm on an Si substrate were prepared from a stochiometric mixture of a bisphenol A epoxy resin and a tetra-functional amine curing agent. Samples were exposed outdoors and to two accelerated laboratory UV environments. Chemical degradation and thickness loss were measured by transmission Fourier transform infrared spectroscopy (FTIRS) and laser scanning confocal microscopy (LSCM), respectively. In addition, surface roughness and morphological changes were measured by atomic forcemicrosocopy (AFM) and LSCM. Substantial chemical degradation, thickness loss, and morpholocal changes occurred in the exposed films, and the rate of chemical degradation was greater than that due to the thickness loss. This additional chemical loss was attributed to an inhomogeneous degradation process in which nanoscale localized depressions initiate at certain sites on the surface, which then enlarge and deepen with exposure time. The results of this study provide a better understanding of the degradation mechanism and should lead to the development of scientific-based models for predicting the service life of crosslinked amine-cured epoxy coatings. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004, in Chicago, IL     

Ceramics for Prosthetic Hip and Knee Joint Replacement

The most commonly used bearing couple in prosthetic hip or knee joint replacements consists of a cobalt–chrome (CoCr) metal alloy articulating against ultrahigh-molecular-weight polyethylene. Ceramics have been used as an alternative to metal-on-polyethylene in joint replacement surgery of arthritic hips and knees since the 1970s. In prosthetic hip and knee bearings, ceramic surfaces offer a major benefit of drastically reduced wear rates and excellent long-term biocompatibility, which can increase the longevity of prosthetic hip and knee joints. This benefit is important clinically because hip and knee replacement has become a very common surgical procedure, particularly in the United States, and because these procedures are being increasingly performed in younger patients who place greater demands on the prosthetic bearings. However, ceramics are brittle and the risk of catastrophic bearing failure in vivo , while rare, is a major concern. Improvements in material quality, manufacturing methods, and implant design have resulted in a drastic reduction of the incidence of such failures, so that modern ceramic bearings are safe and reliable if used with components of proven design and durability. Future material improvements are actively being investigated to reduce the risk of ceramic-bearing failures even further. The purpose of this article is to review the structure, properties, applications, and limitations of the ceramics that have been used in orthopedic bearings, and to describe the new ceramic composite materials and surface treatments that will be available for joint replacement surgery in the near future.     

Oxidation of Butane to Maleic Anhydride using Vanadium Phosphate Catalysts: Comparison of Operation in Aerobic and Anaerobic Conditions using a Gas-gas Periodic Flow Reactor

The use of a periodic flow reactor is described for the oxidation of butane to maleic anhydride to compare the catalytic performance of vanadium phosphate catalysts operating under aerobic and anaerobic conditions. It is found that for the catalyst prepared via a standard VPO method, operation in the absence of oxygen leads to a very small enhancement in selectivity when butane concentrations in the range 0.9–2.9% are used. Operation in the absence of oxygen leads to very small differences in conversion such that the overall yield is enhanced and this effect is maximised for reactor feeds containing 1.5% butane. However, the enhancement is negligible when the catalyst is operated at high conversion required for commercial operation, indicating that reactors operating with continuous flow with aerobic conditions are preferred. Similar experiments are conducted for a catalyst prepared by the VPD method and, in contrast, this catalyst gives lower butane conversion and maleic anhydride selectivity when operated in the absence of oxygen.     

Two-dimensional correlation relaxometry studies of cement pastes performed using a new one-sided NMR magnet

We present preliminary results of the first NMR T₁-T₂ two-dimensional relaxation correlation experiments performed using a one-sided NMR system in cement based materials. Two-dimensional correlation relaxometry has itself only recently been demonstrated in cement paste where it proved to be a particularly sensitive probe of pore-water dynamics providing direct information on exchange of water between the gel and capillary pore networks. Further to this we have observed differences in the structural development of a selection of cement pastes throughout the early stages of hydration and verified the theoretical frequency dependence of the ratio T₁ / T₂. When coupled with instrumentation developments in one-sided NMR magnets the way is opened to detailed, spatially resolved studies of the development of hydration and porosity in the surface layers (top 50 mm) of cementitious materials. A new magnet, suitable for such applications, is discussed.     

Terpolymers. II. Mechanical properties and transition temperatures of terpolymers of vinyl stearate,vinyl acetate,and vinyl chloride

Vinyl stearate was studied as a major internal plasticizer in terpolymers containing vinyl acetate and vinyl chloride. The terpolymers were prepared by systematically replacing vinyl acetate by close increments of vinyl stearate starting with combinations of vinyl acetate and vinyl chloride, in increments, over all compositions. For comparison of properties, a complete range of copolymers of vinyl stearate and vinyl chloride, as well as mixtures of poly(vinyl chloride) and di-2-ethylhexyl phthalate (DOP) were also made. The external plasticizer was more efficient in reducing the glass temperature than was vinyl stearate. The decline in T_g with weight fraction of plasticizer was linear for the copolymers and terpolymers but concave downward with the liquid diluent. The linear decline was shown to involve mere additivity of the free volume contributed by each side-chain methylene (or methyl) group in both vinyl esters to reducing T_g. The mechanism of the diluent system was more complex. However, the magnitude of the reduction of tensile modulus at a given weight fraction of DOP could be equaled or exceeded by the same amount of vinyl stearate, by increasing the vinyl acetate content of the base copolymer to 40 mole-% or more. Unfortunately, the ultimate strengths and elongations of internally plasticized systems were reduced more than those of the mixtures at comparable compositions. Vinyl stearate was found to markedly retard photolytic degradation compared to both vinyl acetate and the external plasticizer in unstabilized samples having nearly the same thermal treatment. The effect was greater than could be ascribed to dilution by the long alkyl group. The production of a stearoyl radical more stable than the radicals initiating dehydrochlorination is suggested as a possible mechanism.     

The role of the automation development group in analytical research and development at Dupont Merck

Laboratory robotics has been firmly established in many non-QC laboratories as a valuable tool for automating pharmaceutical dosage form analysis. Often a single project or product line is used to justify an initial robot purchase thus introducing robotics to the laboratory for the first time. However, to gain widespread acceptance within the laboratory and to justify further investment in robotics, existing robots must be used to develop analyses for existing manual methods as well as new projects beyond the scope off the original purchase justification. The Automation Development Group in Analytical Research and Development is a team of analysts primarily devoted to developing new methods and adapting existing methods for the robot. This team approach developed the expertise and synergy necessary to significantly expand the contribution of robotics to automation in the authors'' laboratory.