Separation and Enrichment of the Active Component of Carbon Based Paramagnetic Materials for Use in EPR Oximetry

Carbon based paramagnetic materials are frequently used for EPR oximetry, especiallyin vivo,but the EPR spectra of these materials often have more than one paramagnetic center and/or relatively low signal intensity. To determine whether the multi-components of carbon based materials could be separated and enriched in the active component, we used density gradient centrifugation to separate the materials into several fractions. We studied two types of coals, gloxy and Pocahontas, and found these materials to have large density distribution. The separated density fractions had very different EPR spectra and intensities. The active component from the coal material had a more homogeneous EPR signal and significantly increased EPR signal intensity, whereas for India ink, only slight changes were observed. This result can be very useful in the development of better probes for EPR oximetry.     

Synthesis of some 4-substituted-2-(o-halogenophenyl)-1,2,3-triazoles

Mesoaldehyde 1,3-dioxime was treated with either 2,4,6-trichlorophenyl- (a), o-fluorophenyl- (b), or o-bromophenyl- (c) hydrazine to give the corresponding mesoaldehyde 1,3-dioxime-2-halogenophenylhydrazones (1a,b,c). The latter were O-acetylated with acetic anhydride, and cyclized to triazole 4-oximes (3b, c) or triazole 4-O-acetyloximes ( 6a,b,c ) with cesium carbonate, then converted to nitriles ( 7a,b,c ) by refluxing with acetic anhydride followed by pyrolysis, or to aldehydes ( 4a,b,c ) by hydrolysis. The nitriles ( 7a,b,c ) were also converted to acids ( 9a,b,c ), esters ( 10a,b,c ), amides ( 8a,c ), an alcohol (11a), and an amine ( 12a ). In addition, tetrazoles of two types were prepared. The first ( 13d,e ) were obtained from the acid chlorides by the action of 5-aminotetrazole, whereas the second ( 14f ) was produced from the respective nitrile by the action of ammonium azide.     

Addition reaction of azido-exTTFs to C60: synthesis of fullerotriazoline and azafulleroid electroactive dyads

[structure: see text] The addition reaction of azido-exTTFs to C(60) affords electroactive fullerotriazoline and azafulleroid dyads, which behave as amphoteric redox systems. Fluorescence experiments and transient absorption spectroscopy reveal that excitation of the fullerene moiety leads to radical pair lifetimes that are 2 orders of magnitude higher than those previously reported for related fullerotriazolines.     

Pharmacokinetics of the nitroxide PCA measured by in vivo EPR

PCA (2,2,5,5-tetramethylpiperidine-1-oxyl-3-carboxylic acid) is a relatively stable free radical which has been shown to be useful as a contrast agent for nuclear magnetic resonance imaging and as an imaging/spectroscopy agent for EPR. In an effort to determine the role of the liver and kidney in the pharmacokinetics of PCA, using low frequency in vivo EPR spectroscopy, we followed the clearance of PCA after intravenous injection in mice: under normal conditions, with a restricted blood supply to the kidneys, after exposure to an acute hepatotoxin CCl₄, and after exposure to lipopolysaccharide (endotoxin). The observed pharmacokinetics fit a two-component model. The fast component was dramatically affected when the renal vessels were restricted, while CCl₄ and endotoxin had a smaller but significant effect. The half times of the slow components were not significantly different (p>0.05) in the groups treated by renal blood flow occlusion, CCl₄, or LPS, compared with the control group. In conclusion, we find that the pharmacokinetics of PCA need to be completely described in term of a two component model: the fast component of the decay is mainly due to the elimination by the kidneys and also is affected by the time for the initial distribution; the slow component is related to the bioreduction of the nitroxide. In addition to the liver other tissues can also effectively metabolize PCA. The effect of oxygen on the rate of metabolism is modest at most.     

An HPLC and EPR investigation on the stability of DMPO and DMPO spin adducts in vivo

Application of the spin trapping technique in intact animals requires an understanding of the stability and distribution of the spin traps and their spin adducts in vivo. We studied the stability of DMPO in vivo in mice using HPLC and the stability of spin adducts of DMPO by EPR in plasma, whole blood, peritoneal fluid, and homogenized heart tissue of the rat. At 15 minutes after intraperitoneal injection DMPO had similar concentrations in the liver, heart, and blood of the mice and 40% remained in the organs 2 hours after the injection. In contrast, the spin adduct DMPO-OH was short lived, with a half-life of 3.0 minutes in plasma, and was not detectable 1 minute after formation in whole blood and homogenized heart tissue. The carbon centered spin adduct DMPO-CH(OH)CH₃ was more stable, having half-lives of 16, 11, 3.6, and 0.79 minutes in plasma, peritoneal fluid, whole blood, and homogenized heart tissue, respectively. The spin adduct DMPO-SO₃ was sufficiently stable for the adduct to be observed directly from living mice.     

Homomorphisms of matrix algebras and constructions of Butson–Hadamard matrices

An $n\times n$ matrix $H$ is Butson–Hadamard if its entries are $k$th roots of unity and it satisfies $H{H}^1=n{I}_n$. Write $\mathrm{BH}(n,k)$ for the set of such matrices.Suppose that $k=p^{\alpha }{q}^{\beta }$ where $p$ and $q$ are primes and $\alpha \ge 1$. A recent result of Östergård and Paavola uses a matrix $H\in \mathrm{BH}(n,pk)$ to construct $H^{\prime }\in \mathrm{BH}(pn,k)$. We simplify the proof of this result and remove the restriction on the number of prime divisors of $k$. More precisely, we prove that if $k=mt$, and each prime divisor of $k$ divides $t$, then we can construct a matrix $H^{\prime }\in \mathrm{BH}(mn,t)$ from any $H\in \mathrm{BH}(n,k)$.     

Random Variable Generation Using Concavity Properties of Transformed Densities

Abstract

Algorithms are developed for constructing random variable generators for families of densities. The generators depend on the concavity structure of a transformation of the density. The resulting algorithms are rejection algorithms and the methods of this article are concerned with constructing good rejection algorithms for general densities.