On the pH-Dependence of Greducing in the Radiation Chemistry of Aqueous Solutions

Alkaline N₂O-saturated solutions of 2-D-2-propanol and ferri-ferrocyanide mixtures were irradiated. The results indicate that G_red, which is the sum of G_eaq + G_H = 3.3, is pH-independent in the range 11 – 14. The results do not indicate that G_eaq and G_H are pH-dependent.     

One electron reduction of metmyoglobin and methemoglobin and the reaction of the reduced molecule with oxygen

We have used the pulse radiolysis technique to reduce with solvated electrons (see article) a single Fe(III) site in methemoglobin and metmyoglobin. The reduction process was followed spectrophotometrically and the reactions rate constants were measured: (see article) =6.5 +/- 1-10(10) M-1-S-1. (see article)=2.5 +/- 0.3-10(10) M-1-S-1. Approx. 60% of the (see article) have reacted with the hemin group, and the rest of the (see article) have probably reacted with the globin moiety. We followed the reaction of the reduced proteins to yield the oxyderivatives and measured the rate constants of the oxygenation process k reduced methemoglobin + O2 = 2.6 +/- 0.6-10(7) M-1-S-1 and k myoglobin + O2 = 1.8 +/- 0.2-10(7) M-1-S-1, all the rate constants were measured at pH = 6.8, I = 0.004, T = 22 +/- 2 degrees C. The high rate constant for reduced methemoglobin indicates that one-site-reduced methemoglobin is probably in the R state, as predicted for methemoglobin from X-ray analysis. The spectra of the reduced and oxygenated species were measured under similar conditions at gamma = 450-650 nm. We were able to follow slight changes in the micro-second time scale, these changes were attributed to conformational changes. We were not able to detect any reaction between the radical (see article) and the hemin group (which would result in a complex such as heme O-2). This may be due to kinetic reasons.     

Low-loss ring resonators fabricated from silicon based integrated optics technologies

The fabrication of low-loss ring resonators using silicon based integrated optics technologies is reported. Propagation losses of 0.028+or-0.009 dB/cm have been deduced from finesse measurements.<>     

The role of the reactions of .NO with superoxide and oxygen in biological systems: a kinetic approach

In this study we calculate the half-life of .NO in its reactions with superoxide and with oxygen under various conditions using the known rate constants for these reactions. The measured half-life of .NO in biological systems is 3-5 s, which agrees well with the calculated value for intracellular .NO, but not for extracellular .NO under normal physiological conditions. The autoxidation of .NO to yield NO2- as a final product cannot be responsible for such a short measured half-life under normal as well as pathologic conditions. Therefore, if there is direct evidence for the occurrence of the reaction of .NO with O2.- in the medium, one has to assume that the steady state concentrations of free .NO are much lower than those measured. The very low concentrations of free .NO in biological systems may result from its reversible strong binding to biological molecules. Simulation of the mechanism of the autoxidation of .NO indicates that the binding constants of .NO to O2 or to another .NO are too small to account for the very low concentration of free .NO in biological systems. Nevertheless, the reaction of .NO with oxygen cannot be neglected in biological systems if the intermediate ONOO. reacts rapidly with a biological target. The biological damage caused by ONOO. is expected to be due to the radical itself and to peroxynitrite, which is most probably formed via the reaction of ONOO. with the biological molecule.     

MCG simulations of myocardial infarctions with a realistic heart-torso model

Data from simulations of the anterior myocardial infarction (AMI) and inferior myocardial infarction (IMI) are presented. One infarct located in the anterior section of the left ventricle and a second one in the inferior wall of the left ventricle were modeled. A high-resolution finite element model of a heart and torso was used in this study. Differences in the normal and infarcted fields were computed. Our data suggest that the infarcted region contribution to the total magnetic field can be accounted for by an equivalent current dipole. It might also be possible to detect an infarct from these difference fields constructed for different cases of myocardial infarction. More simulations are needed to determine the relations between infarct sizes and locations and magnetic fields. These relations might then be used to detect various cases of myocardial infarction.     

The effect of heating conditions on losses and regeneration of betacyanins

Summary The losses of Betacyanins during heating at 90 °C and their regeneration after heating were investigated in red beet juice and solutions of pure betanin in different buffers. It was found that the regeneration of pigments during storage of heated samples is greater at 5 °C than at 20 °C. The time, in which the pigments reach the maximum concentration is different for juice and pure betanin solutions. The influence of the type of buffer and its concentration on heating in the absence of oxygen is insignificant, on the other hand the influence is distinctly marked when the betanin heated in the presence of oxygen. When heated in the presence of air, the betanin losses are influenced by the rate of diffusion of oxygen from the air.

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Einflu der Erhitzungsbedingungen auf Verluste und Regeneration der Betacyanine

Zusammenfassung Die Verluste an Betacyaninen während der Erhitzung auf 90 °C und ihre Regeneration nach dem Erhitzen wurden in Rote-Beete-Saft und in verschieden gepufferten reinen Betanin-Lösungen untersucht. Bei 5 °C ist die Regeneration der Farbstoffe besser als bei 20 °C. Die Zeit bis zur maximalen Regeneration der Farbstoffe ist für den Saft und für die Betanin-Lösungen unterschiedlich. Pufferart und -konzentration sind unter sauerstofffreien Bedingungen unwesentlich; bei Anwesenheit von Sauerstoff üben sie indessen einen merklichen Einflu aus. Beim Erhitzen in Gegenwart von Sauerstoff werden die Betanin-Verluste von der Diffusionsgeschwindigkeit des Luftsauerstoffs beeinflußt.

     

Heat stability of betacyanins in red beet juice and in betanin solutions

Summary The losses of red pigments during heating and their regeneration after heating were investigated in red beet juice and pure betanin solutions. The experiments were carried out with equal access of oxygen and a similar level of the initial content of the pigment. The presence of heavy metal ions in trace amounts had a great destructive influence on the pigment in solutions of pure betanin. In red beet juice compounds which decrease and compounds which increase the retention of betanin both occured during heating and regeneration. The group of compounds that decrease betanin stability included some metal ions, e.g. Cu(II) and Fe(III), along with certain amino acids. The negative influence of the metal ions in beet juice decreased probably due to the presence of metal-complexing agents.

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Stabilität der Betacyane während der Erhitzung des Rote-Beete-Saftes und der Betanin-Lösungen

Zusammenfassung Es wurden die Verluste an rotem Farbstoff im Rote-Beete-Saft und in Betanin-Lösungen während der Erhitzung mit der Regeneration des Farbstoffes in den erhitzten Proben verglichen. Die Versuche wurden bei gleichem Sauerstoffdruck und bei vergleichbarer Menge des Farbstoffes zu Beginn durchgeführt. Die Anwesenheit von Spuren an Schwermetallen in den Lösungen von reinem Betanin wirkt zerstörend auf den Farbstoff. Im Rote-Beete-Saft treten sowohl Verbindungen auf, die die Betanin-Retention während der Erhitzung und die Regeneration vermehren, wie auch solche, die sie vermindern. Zur Gruppe der Verbindungen, die die Stabilität von Betanin verringern, gehören die Ionen einiger Schwermetalle wie Cu(II) und Fe(III) und einige Aminosäuren. Die negative Wirkung der Metallionen im Saft wird wahrscheinlich durch Anwesenheit metallkomplexierender Verbindungen vermindert.

     

Flash Photolysis of the Oxybromine Anions

The flash photolysis of BrO₃^?, BrO₂^? and BrO^? in strongly alkaline solutions was investigated. The formation of O₃^? in oxygen containing solutions indicates that the three oxybromine anions undergo the primary photochemical process . The decay rate of O₃^? is enhanced by the oxybromine anions; this is ascribed to the reactions of BrO_n^? with O^? and OH. From the study of the ozonide decay rate as a function of BrO_n^? concentration and pH, the rate constants for the reactions of BrO_n^? with O^? and OH could be determined. The production of BrO₂ from BrO₃^?, in amount equal to that of O^?, was demonstrated. BrO₂ is also produced from BrO₂^?, presumably by secondary reactions of BrO and O^? with BrO₂^?.     

The effect of remodelling and contractility of the actin cytoskeleton on the shear resistance of single cells: a computational and experimental investigation

The biomechanisms that govern the response of chondrocytes to mechanical stimuli are poorly understood. In this study, a series of in vitro tests are performed, in which single chondrocytes are subjected to shear deformation by a horizontally moving probe. Dramatically different probe force–indentation curves are obtained for untreated cells and for cells in which the actin cytoskeleton has been disrupted. Untreated cells exhibit a rapid increase in force upon probe contact followed by yielding behaviour. Cells in which the contractile actin cytoskeleton was removed exhibit a linear force–indentation response. In order to investigate the mechanisms underlying this behaviour, a three-dimensional active modelling framework incorporating stress fibre (SF) remodelling and contractility is used to simulate the in vitro tests. Simulations reveal that the characteristic force–indentation curve observed for untreated chondrocytes occurs as a result of two factors: (i) yielding of SFs due to stretching of the cytoplasm near the probe and (ii) dissociation of SFs due to reduced cytoplasm tension at the front of the cell. In contrast, a passive hyperelastic model predicts a linear force–indentation curve similar to that observed for cells in which the actin cytoskeleton has been disrupted. This combined modelling–experimental study offers a novel insight into the role of the active contractility and remodelling of the actin cytoskeleton in the response of chondrocytes to mechanical loading.