Structure-activity relationship in the ability of flavonols to inhibit chemiluminescence

Fourteen flavonoids were evaluated for their ability to inhibit chemiluminescence, either of neutrophils that had been briefly exposed to both luminol and phorbol-myristate acetate or to an enzymatic system with H2O2, luminol and horseradish peroxidase. Using chemiluminescence as the quantitative parameter, it can be concluded that the hydroxyl group in position 3 of the flavonols is vital for their inhibitory effect, and that two hydroxyl groups on the phenyl ring are optimal for such an effect. It was also noted that the C2-C3 double bond is essential for the flavonols' anti-oxidative effect. It is suggested that the ability of flavonols to suppress chemiluminescence is reciprocally correlated with their lipophilicity.     

Pure CuBi2O4 Photoelectrodes with Increased Stability by Rapid Thermal Processing of Bi2O3/CuO Grown by Pulsed Laser Deposition

A new method for enhancing the charge separation and photo‐electrochemical stability of CuBi₂O₄ photoelectrodes by sequentially depositing Bi₂O₃ and CuO layers on fluorine‐doped tin oxide substrates with pulsed laser deposition (PLD), followed by rapid thermal processing (RTP), resulting in phase‐pure, highly crystalline films after 10 min at 650 °C, is reported. Conventional furnace annealing of similar films for 72 h at 500 °C do not result in phase‐pure CuBi₂O₄. The combined PLD and RTP approach allow excellent control of the Bi:Cu stoichiometry and results in photoelectrodes with superior electronic properties compared to photoelectrodes fabricated through spray pyrolysis. The low photocurrents of the CuBi₂O₄ photocathodes fabricated through PLD/RTP in this study are primarily attributed to their low specific surface area, lack of CuO impurities, and limited, slow charge transport in the undoped films. Bare (without protection layers) CuBi₂O₄ photoelectrodes made with PLD/RTP shows a photocurrent decrease of only 26% after 5 h, which represents the highest stability reported to date for this material. The PLD/RTP fabrication approach offers new possibilities of fabricating complex metal oxides photoelectrodes with a high degree of crystallinity and good electronic properties at higher temperatures than the thermal stability of glass‐based transparent conductive substrates would allow.     

Image processing techniques for 3-D chromosome analysis

3-D karyotype analysis is developing rapidly due to the availability of confocal microscopes and CCD video cameras, and the development of 3-D processing techniques. Here, image enhancement and visualization techniques specifically designed for 3-D karyotype analysis are described. To facilitate a good comparison between the different techniques, the same 3-D image, obtained with a confocal scanning laser microscope (CSLM), of a mitotic prophase nucleus of a root-tip cell of Crepis capillaris was used throughout. Besides well-known stereoscopic presentation, another means of improving depth perception is shown, i.e. a solid modelling algorithm, which simulates the process of fluorescence. An interactive routine to dissect objects in the image is presented as an alternative for automated segmentation algorithms, which cannot be applied to closely apposed or merging objects. As an example of a convenient way to reduce the vast amount of data (2 Mbyte per image), a partly automated 3-D cursor is presented in detail. This cursor is used to trace the central axes of chromosomes and record them as strings of Cartesian coordinates. The advantages of a computer graphics display, which facilitates real-time rotation and hence is a powerful tool in studying 3-D features of chromosomes, are also shown.     

Frictional behaviour of oxygen diffusion hardened titanium in dry sliding against Co–28Cr–5W–4Fe–3Ni–1Si cobalt alloy

The results of conformal pin-on-disc tribological tests of a hard layer of the solid solution of oxygen in α-titanium sliding against a Co–28Cr–5W–4Fe–3Ni–1Si cobalt alloy counterspecimen are presented. The α-Ti(O) layer was diffusely produced over 2–8 h of oxidising in the superficial zone of a technical quality titanium specimen.The friction and wear responses of the system were recorded and the wear mechanisms were studied. Investigations of the material structure and chemical constitution in micro-areas of the titanium specimen, cobalt alloy counterspecimen and wear debris formed in dry sliding were performed with a Philips XL20 microscope equipped with an EDAX analyser. Crushing of the α-Ti(O) layer, lowering of the wear rate after comminution of the hard α-Ti(O) layer, local tack spots and fine powder wear particles, mostly Ti oxides, were detected at the beginning of each test. Gradual brittle fracture and decay by pulverising of the α-Ti(O) particles embedded in both mating surfaces, which occurred during the test, led to the increase of the wear rate of the couple and domination of microcutting and tack spots spalling after their partial oxidation. Finally, after the disappearance of the α-Ti(O) loose particles, adhesive junctions, metal transfer and smearing become leading wear mechanisms.     

Multilayer nanoencapsulation. New approach for immune protection of human pancreatic islets

Immune protection of artificial tissue by means of pancreatic islet microencapsulation is a very ambitious new approach to avoid life-long immune suppression. But the success in the utilization of the alginate-beads with incorporated islets is unfortunately limited. Some of the problems cannot be solved by a two-component system, so polymer encapsulation of the microbeads was tested to improve the properties. In the present paper a pure nanoencapsulation multilayer approach was tested in order to reduce the size of the capsule and possibly apply in the future a multilayer capsule with individual properties in each layer or region of the capsule. Different polycations were attached in a self-assembly process. The advantage in using the surface charge of islets as binding site for the polyions is the guarantee of complete coverage after the second layer. Release of insulin was determined to characterize the function of the islets after encapsulation as well as the permeability of the capsule. Fluorescence microscopy was used to visualize the polyelectrolyte layers. Finally by means of an immune assay, the protection capability of the capsule was proved. In these first measurements the encapsulation with a multilayer nanocapsule was shown to be a possible alternative to the more space-consuming and random islet-trapping microencapsulation.     

Effect of ascorbate and ascorbyl palmitate on lipid oxidation in semi-dry saugages manufactured from pork materials differing in stability towards oxidation

Semi-dry fermented sausages were manufactured from three batches of pork slightly differing in their polyenoic fatty acid levels and α-tocopherol contents. The sausage doughs were treated as follows: (1) control, (2) ascorbate, (3) ascorbyl palmitate and (4) a combination of ascorbate and ascorbyl palmitate. After brine fermentation, products ripened at 15°C were evaluated for rancidity by peroxide values and TBA numbers. During ripening important differences in stability towards oxidation were generally not observed. Both peroxide and TBA values gradually increased linearly with time. For the TBA values, gradients for the products derived from the three diet groups differed considerably. Only two of six batches containing increased levels of α-tocopherol and product antioxidants exhibited slightly improved stability towards oxidation, as judged by peroxide and TBA values. Sensory evaluations, performed only on the product series containing ascorbate, failed to reveal any positive effect in favour of the increased α-tocopherol content. Thus, for semi-dry sausages manufactured from pork materials with a slightly increased sensitivity towards oxidation, results indicated with there was little advantage to increasing the levels of α-tocopherol in the meat by dietary means or to changing the current commercial practice of adding ascorbate to the sausage doughs.     

Redesign of V Belts

Russian Engineering Research - Redesign of V belts is considered: configurations where the belt cross section forms a convex or concave arc are proposed. With the same belt width, the new design...     

Bioreductive activation of catechol estrogen-ortho-quinones: aromatization of the B ring in 4-hydroxyequilenin markedly alters quinoid formation and reactivity

There is a clear association between excessive exposure to estrogens and the development of cancer in several tissues including breast and endometrium. The risk factors for women developing these cancers are all associated with longer estrogen exposure, as may be facilitated by early menses, late menopause and long-term estrogen replacement therapy. Equilenin (1,3,5(10),6,8-estrapentaen-3-ol-17-one) or its 17-hydroxylated analogs make up 15% of the most widely prescribed estrogen replacement formulation, Premarin, and yet there is very little information on the human metabolism of these estrogens. In this study, we synthesized the catechol metabolite of equilenin, 4-hydroxyequilenin, and examined how aromatization of the B ring affects the formation and reactivity of the o-quinone (3,5-cyclohexadien-1,2-dione). 4-Hydroxyequilenin-o-quinone is much more redox-active and longer-lived than the endogenous catechol estrone-o-quinones, which suggests that the mechanism(s) of toxicity of the former could be quite different. Interestingly, the rate of reduction of the 4-hydroxyequilenin-o-quinone is increased at least 13-fold in the presence of NAD(P)H:quinone oxidoreductase (DT-diaphorase). Once NADH is consumed however, the catechol auto-oxidized rapidly to the o-quinone. NADH consumption was accompanied by dicumarol-sensitive oxygen uptake both with the purified enzyme and with cytosol from human melanoma cells with high levels of DT-diaphorase activity. P450 reductase and rat liver microsomes also catalyzed NADPH consumption and oxygen uptake. 4-Hydroxyestrone-o-quinone was also rapidly reduced by NAD(P)H; however, this o-quinone does not auto-oxidize and once the o-quinone is reduced the reaction terminates. Including oxidative enzymes in the incubation completes the redox couple and 4-hydroxyestrone-o-quinone behaves like 4-hydroxyequilenin-o-quinone. These data suggest that reduction of estrogen-o-quinones may not result in detoxification. Instead this could represent a cytotoxic mechanism involving consumption of reducing equivalents (NADH/NADPH) as well as formation of superoxide and other reactive oxygen species leading to oxidative stress. Finally, we have compared the cytotoxicity of 4-hydroxyequilenin with that of the estrone catechols in human melanoma cells. 4-Hydroxyequilenin is 5-fold more toxic in these cells compared with 4-hydroxyestrone (ED50 = 7.8 versus 38 microM, respectively) suggesting that formation of the longer-lived redox-active 4-hydroxyequilenin-o-quinone was responsible for the cytotoxic differences. These results substantiate the conclusion that the involvement of quinoids in catechol estrogen toxicity depends on a combination of the rate of formation of the o-quinone, the lifetime of the o-quinone, and the electrophilic/redox reactivity of the quinoids.