Kinetics and mechanism of the comproportionation reaction between oxoammonium cation and hydroxylamine derived from cyclic nitroxides

Cyclic nitroxides demonstrate antioxidative activity in numerous in vitro and in vivo models, which frequently involves the participation of the reduced and oxidized forms of the nitroxide, namely, the hydroxylamine and oxoammonium cation. Generally, cellular reducing equivalents facilitate rapid enzymatic as well as nonenzymatic reduction of nitroxides in the tissue. On the other hand, the reaction of nitroxides with various radicals yields the highly oxidizing oxoammonium cation, which mediates the catalytic effect of nitroxides in selective oxidation of alcohols. Hence, nitroxides might act as both anti- and pro-oxidants. Therefore, the comproportionation reaction between the oxoammonium cation and the hydroxylamine might play a role in lowering the pro-oxidative activity of nitroxides. Although the comproportionation reaction has previously been studied, there is no agreement regarding its kinetic features. We investigated the reaction of the reduced forms of 2,2,6,6-tetramethylpiperidinoxyl (TPO) and 4-OH-2,2,6,6-tetramethylpiperidinoxyl (4-OH-TPO) with the oxoammonium cation derived from TPO at various pHs using rapid-mixing stopped-flow and EPR spectrometry. From the pH dependence of the reaction rate constants we determined the pK(1) of the respective hydroxylamines to be 7.5 and 6.9, respectively. The reduction potentials of the hydroxylamines were determined by cyclic voltammetry, and from their dependence on pH, we obtained the same pK(1) values. The rate constant of the comproportionation reaction does not exceed 20 M(-1) s(-1) in the physiological pH range and, therefore, cannot greatly contribute toward recycling of the nitroxides in the tissue.     

The role of nitric oxide in cancer

Nitric oxide (NO) is a pleiotropic regulator, critical to numerous biological processes, including va-sodilatation, neurotransmission and macrophage-mediated immunity. The family of nitric oxide synthases (NOS) comprises inducible NOS (iNOS), endothelial NOS (eNOS), and neuronal NOS (nNOS). Interestingly, various studies have shown that all three isoforms can be involved in promoting or inhibiting the etiology of cancer. NOS activity has been detected in tumour cells of various histogenetic origins and has been associated with tumour grade, proliferation rate and expression of important signaling components associated with cancer development such as the oestrogen receptor. It appears that high levels of NOS expression (for example, generated by activated macrophages) may be cytostatic or cytotoxic for tumor cells, whereas low level activity can have the opposite effect and promote tumour growth. Paradoxically therefore, NO (and related reactive nitrogen species) may have both genotoxic and angiogenic pro     

Measurement of the trunk musculature of active males using CT scan radiography: implications for force and moment generating capacity about the L4/L5 joint

The purpose of this study was to add to the growing database of cross-sectional areas and moment arm lengths of trunk musculature using the methods of computerized tomographic scanning. An attempt was also made to estimate muscle force and moment generating capacity under various reported values of muscle force per unit cross-sectional area. The data were obtained on 13 active men 40.5 +/- 11.9 years of age, 173.8 +/- 5.9 cm tall and 89.1 +/- 11.7 kg body mass. Transverse CT scans were taken at the level of the L4/L5 disc with the subjects supine. Muscle cross-sectional areas were measured from 35 mm slides of the scans using a planimeter and moment arm length in the transverse plane were taken from the centroid of the L4/L5 disc to the centroid of the muscle section. Prior to estimating force and moment generating capacity, areas were corrected, where necessary, for fibre pennation angle to produce a physiological cross-sectional area. The physiological cross-sectional areas (cm2) for one side of the body were (mean +/- S.D.): sacrospinalis (SS) 15.9 +/- 2.5; multifidus (Mu) 4.2 +/- 0.7; psoas (Ps) 17.6 +/- 4.0; rectus abdominis (RA) 7.9 +/- 2.5; external oblique (EO) 9.4 +/- 2.7; internal oblique (IO) 8.1 +/- 2.3; transverse abdominus (TA) 2.9 +/- 1.3. The anterior posterior moment arm lengths were: erector mass (SS and Mu combined) 5.90 +/- 0.52; Ps 0.58 +/- 0.40; R.A. 10.28 +/- 2.07; E.O. (anterior portion) 5.94 +/- 1.39; E.O. (posterior portion) 2.08 +/- 1.39; I.O. (anterior portion) 6.92 +/- 1.63; I.O. (posterior portion) 3.85 +/- 1.54. The corresponding lateral moment arm lengths were: 3.26 +/- 0.36; 4.88 +/- 0.36; 4.35 +/- 1.31; 12.86 +/- 1.93; 13.95 +/- 1.16; 10.77 +/- 2.02; 12.52 +/- 1.26. The maximum force per unit cross-section that human muscles are capable of generating is not well defined. However, assuming an intermediate value of 50 N cm-2 of physiological cross-section, the erector musculature observed at the L4/L5 level should be capable of generating an extensor moment of about 118 N.m. At a muscle stress of 30 or 90 N cm-2, values also reported on human muscle, the moment would be 71 and 213 Nm, respectively. It must be remembered, however, that muscles not observable at the L4/L5 level can create moments around that center of rotation.(ABSTRACT TRUNCATED AT 400 WORDS)     

Characterization of restricted area searching behavior following consumption of prey and non-prey food in a cursorial spider, Hibana futilis

Cursorial spiders are important predators of crop pests in a variety of agricultural systems. Their survivorship, growth, and fecundity can be enhanced by the consumption of extra‐floral nectar. We recently showed that Hibana futilis (Banks) (Araneae: Anyphaenidae) engages in restricted area search following contact with nectar, is stimulated by nectar aroma, and can learn to recognize novel aroma cues. Studies have shown that H. futilis is also responsive to solvent extracts of the eggs and scales of the corn earworm, Helicoverpa zea Boddie (Lepidoptera: Noctuidae), one of its primary prey insects in cotton. The arrestment behavior of cursorial spiders following consumption of prey and non‐prey food has not been characterized. In the present study, the responses of spiders were measured following consumption of prey (H. zea eggs) or non‐prey (droplets of dilute honey) food items and compared with individuals tested without food items. The food items were presented to the spiders in test arenas constructed from the top of an inverted glass Petri dish cover. A combination of real time and recorded observations were made via a video camera attached to a computer. The behaviors and movement patterns of individual spiders were analyzed with behavioral tracking software. Significant differences in the behaviors and motion paths of spiders tested in the different treatments were observed. Hibana futilis displayed significantly more dispersal behavior on a blank test arena, than on test arenas supplied with honey droplets or moth eggs. Likewise, spiders tested on the blank arena crawled faster and their motion paths were significantly less tortuous than those of spiders tested in the arenas with honey or moth eggs. Following consumption of both the honey droplets and moth eggs, spiders showed elevated levels of restricted area search and lowered levels of dispersal behavior. The analysis showed that these spiders could crawl rapidly for extended distances. Behaviors such as restricted area search and learned recognition of food‐based stimuli would facilitate efficient location of the food resources needed to maintain their high activity levels.