EXTRARETINAL PHOTORECEPTION IN LIZARDS

Abstract— In lizards both photoperiodic photoreception and entrainment (synchronization) of the biological clock by environmental light cycles can be accomplished by extraretinal photoreceptors. Testicular size and spermatogenic activity in the green anole, Anolis carolinensis , is maintained under long (14 h) photoperiods in the summer in both sighted and blinded lizards whereas short days (6h) cause testicular regression. In the fall, long photoperiods cause testicular recrudescence and maturation in blinded and blinded-parietalectomized anoles as well as in sighted anoles.
Extraretinal photoreceptors can mediate entrainment of the circadian locomotor rhythm in every lizard species examined to date (8 species). The photosensory pineal complex in lizards (pineal organ and parietal eye) may not be involved in entrainment; in any case, its removal does not prevent entrainment of blinded lizards. Localization experiments have shown that the brain is the site of the extraretinal receptors mediating entrainment. The lateral eyes can also contribute to entrainment. In some species, but not all, blinding alters the pattern of the entrained activity rhythm. The free-running activity rhythms of two species of lizards exposed to continuous illumination respond very differently to blinding; these experiments yield insight into the mechanisms of entrainment in the two species as well as showing that caution must be observed when generalizing about the role of retinal and extraretinal receptors not only among different vertebrate classes but also among species of the same class.     

Is the McLafferty rearrangement of ketones concerted or stepwise? The application of kinetic isotope effects

Intramolecular ¹³C and ²H isotope effects have been measured for unimolecular losses of ethene (the McLafferty rearrangement) from metastable molecular ions of 2-ethyl-1-phenylbutanl-1-one, 3-ethylpentan-2-one and heptan-4-one. Primary and secondary deuterium isotope effects are observed at the γ-(terminal) and β-positions, respectively. Large primary ¹³C isotope effects occur at β-positions and for the y positions of γ-ethylpentan-2-one and heptan-4-one. The carbon isotope effects in the cases of the doubly isotopically labelled CH₃COCH(C₂H₅)(¹³CH₂CH₃) and CD₃COCD(C₂D₅)(¹³CD₂CD₃) are 1.17 (±0.01) and 1.04 (±0.01), respectively. All of these isotope effects are consistent with a stepwise mechanism in which more than one step is rate determining.     

Reactivity of electrochemically generated rhenium (II) Tricarbonyl alpha-diimine complexes: a reinvestigation of the oxidation of luminescent Re(CO)3(alpha-Diimine)Cl and related compounds

The oxidative electrochemistry of luminescent rhenium (I) complexes of the type Re(CO) 3(LL)Cl, 1, and Re(CO) 3(LL)Br, 2, where LL is an alpha-diimine, was re-examined in acetonitrile. These compounds undergo metal-based one-electron oxidations, the products of which undergo rapid chemical reaction. Cyclic voltammetry results imply that the electrogenerated rhenium (II) species 1 ( + ) and 2 ( + ) disproportionate, yielding [Re(CO) 3(LL)(CH 3CN)] (+), 7, and additional products. Double potential step chronocoulometry experiments confirm that 1 ( + ) and 2 ( + ) react via second-order processes and, furthermore, indicate that the rate of disproportionation is influenced by the basicity and steric requirements of the alpha-diimine ligands. The simultaneous generation of rhenium (I) and (III) carbonyl products was detected upon the bulk oxidation of 1 using infrared spectroelectrochemistry. The rhenium (III) products are assigned as [Re(CO) 3(LL)Cl 2] (+), 5; an inner-sphere electron-transfer mechanism of the disproportionation is proposed on the basis of the apparent chloride transfer. Chemically irreversible two-electron reduction of 5 yields 1 and Cl (-). No direct spectroscopic evidence was obtained for the generation of rhenium (III) tricarbonyl bromide disproportionation products, [Re(CO) 3(LL)Br 2] (+), 6; this is attributed to their relatively rapid decomposition to 7 and dibromine. In addition, the 17-electron radical cations, 7 ( + ), were successfully characterized using infrared spectroelectrochemistry.     

Service-simulation tests to determine the fatigue life of outside-diameter-notched thick-wall cylinders

Simulation specimens were used to model the fatigue behavior of outside-diameter-notched internally pressurized cylinders of alloy steel. Results from continuum mechanics and finite-element analyses are described for use in selection of simulation-test conditions. The effects of notch depth and residual stress on fatigue life are determined from the simulation tests.     

Measurements of the total cross-section difference and the parameter CLL in pp scattering with longitudinally-polarized beam and target

We have measured the difference between the pp total cross-sections for parallel and anti-parallel longitudinal spin states at beam momenta of 3 and 6 GeV/c. These results, combined with our previous measurements, at lower momenta, are useful in clarifying a striking structure appearing at around 1.5 GeV/c. We have also measured for the first time, the spin-spin correlation parameter C_LL (t) in pp elastic scattering at 6 GeV/c. We observe evidence for an exchange with A₁-like quantum-numbers.