The reactions of a TTQ model compound [1, 3-methyl-4-(3'-methylindol-2'-yl)indole-6,7-dione] with several amines have been investigated in organic media to obtain mechanistic information on the action of quinoprotein methylamine and aromatic amine dehydrogenases. It has been found that compound 1 acts as an efficient catalyst for the autorecycling oxidation of benzylamine by molecular oxygen in CH(3)OH. In order to evaluate the oxidation mechanism of amines by 1, the product analyses and kinetic studies have been carried out under anaerobic conditions. In the first stage of the reaction of 1 with amines, 1 is converted into an iminoquinone-type adduct (so-called substrateimine), which was isolated and characterized by using cyclopropylamine as a substrate. The observed NOE of the isolated product indicates clearly that the addition position of the amine is C-6 of the quinone. The molecular orbital calculations suggest that the thermodynamic stability of the carbinolamine intermediate is a major factor to determine such regioselectivity; the C-6 carbinolamine is more stable than the C-7 counterpart by 2.9 kcal/mol. The reactivity of several primary amines and the electronic effect of the p-substituents of benzylamine derivatives in the iminoquinone formation suggest that the addition step of the amine to the quinone is rate-determining. When amines having an acidic alpha-proton such as benzylamine derivatives are employed as substrates, formation of the iminoquinone adduct was followed by rearrangement to the productimine. The kinetic analysis has revealed that this rearrangement consists of noncatalyzed and general base-catalyzed processes. Large kinetic isotope effects of 7.8 and 9.2 were observed for both the noncatalyzed and general base-catalyzed processes, respectively, since these steps involve a proton abstraction from the alpha-position of the substrate. In the reaction with benzhydrylamine, the product imine was isolated quantitatively and well characterized by several spectroscopic data. In the case of benzylamine, the product imine is further converted into the aminophenol derivative by the imine exchange reaction with excess benzylamine. These results indicate clearly that the amine oxidation by compound 1 proceeds via a transamination mechanism as suggested for the enzymatic oxidation of amines by TTQ cofactor.
Photodynamic diagnosis is used during glioma surgery. Although some studies have shown that the spectrum of fluorescence was efficient for precise tumor diagnosis, previous methods to characterize the spectrum have been problematic, which can lead to misdiagnosis. In this paper, we introduce a comparison technique to characterize spectrum from pathology and results of preliminary measurement using human brain tissues. We developed a spectrum scanning system that enables spectra measurement of raw tissues. Because tissue preparations retain the shape of the device holder, spectra can be compared precisely with pathological examination. As a preliminary analysis, we measured 13 sample tissues from five patients with brain tumors. The technique enabled us to measure spectra and compare them with pathological results. Some tissues exhibited a good relationship between spectra and pathological results. Although there were some false positive and false negative cases, false positive tissue had different spectra in which intensity of short-wavelength side was also high. The proposed technique provides an accurate comparison of quantitative fluorescence spectra with pathological results. We found that spectrum analysis may reduce false positive errors. These results will increase the accuracy of tumor tissue identification.
Evaluation of the intravascular blood volume is an important assessment in emergency and critical care medicine. Measurement of the inferior vena cava (IVC) respiratory variation by ultrasound echography is useful, but it entails subjective problems. We have hypothesized that IVC cardiac variation is also correlated with intravascular blood volume and analyzed it automatically using computer software of two kinds, later comparing the results. Snakes, software to track boundaries by curve line continuity, and template matching software were incorporated into a computer with an ultrasound machine to track the short-axis view of IVC automatically and analyze it with approximation by ellipse. Eight healthy volunteers with temporary mild hypovolemia underwent echography before and after passive leg raising and while wearing medical anti-shock trousers. IVC cardiac variation was visually decreased by both leg raising and medical anti-shock trousers. The collapse index (maximum - minimum/maximum) of area during three cardiac beats was decreased showing a good relationship to fluid load simulations; 0.24 ± 0.03 at baseline versus 0.11 ± 0.01 with leg raising and 0.12 ± 0.01 with medical anti-shock trousers. In conclusion, IVC cardiac variation has the potential to provide an evaluation of water volume. It presents some advantages in mechanical analysis over respiratory variation. At the very least, we need to exercise some caution with cardiac variation when evaluating respiratory variation.
This study proposed a new algorithm, which was based on snake and speckle tracking models, for dynamic extraction of IJV in ultrasound images. In addition to algorithm validation, it was suggested that some indices the ultrasound image of IJV could be used for the evaluation of the circulating blood volume.
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