Designed iron carbonyls as carbon monoxide (CO) releasing molecules: rapid CO release and delivery to myoglobin in aqueous buffer, and vasorelaxation of mouse aorta

The physiological roles of CO in neurotransmission, vasorelaxation, and cytoprotective activities have raised interest in the design and syntheses of CO-releasing materials (CORMs) that could be employed to modulate such biological pathways. Three iron-based CORMs, namely, [(PaPy(3))Fe(CO)](ClO(4)) (1), [(SBPy(3))Fe(CO)](BF(4))(2) (2), and [(Tpmen)Fe(CO)](ClO(4))(2) (3), derived from designed polypyridyl ligands have been synthesized and characterized by spectroscopy and X-ray crystallography. In these three Fe(II) carbonyls, the CO is trans to a carboxamido-N (in 1), an imine-N (in 2), and a tertiary amine-N (in 3), respectively. This structural feature has been correlated to the strength of the Fe-CO bond. The CO-releasing properties of all three carbonyls have been studied in various solvents under different experimental conditions. Rapid release of CO is observed with 2 and 3 upon dissolution in both aqueous and nonaqueous media in the presence and absence of dioxygen. With 1, CO release is observed only under aerobic conditions, and the final product is an oxo-bridged diiron species while with 2 and 3, the solvent bound [(L)Fe(CO)](2+) (where L = SBPy(3) or Tpmen) results upon loss of CO under both aerobic and anaerobic conditions. The apparent rates of CO loss by these CORMs are comparable to other CORMs such as [Ru(glycine)(CO)(3)Cl] reported recently. Facile delivery of CO to reduced myoglobin has been observed with both 2 and 3. In tissue bath experiments, 2 and 3 exhibit rapid vasorelaxation of mouse aorta muscle rings. Although the relaxation effect is not inhibited by the soluble guanylate cyclase inhibitor ODQ, significant inhibition is observed with the BK(Ca) channel blocker iberiotoxin.     

Tractive performance of a tread design for improved flexibility

The tractive performance of an 18.4R38 radial-ply tractor tire with increased flexibility in the tread area was compared to that of a standard tread design. Normal soil-tire interface stresses were measured at four locations on the lug surfaces of both tires operating on Decatur clay loam and Norfolk sandy loam soils. There was a tendency for the increased flexibility in the tread area to provide a higher net traction ratio at the same tractive efficiency as the standard tread design, especially on Decatur clay loam soil. The more flexible tread design reduced the magnitude of peak normal contact stresses across the tire width, which may have implications for reducing soil compaction without compromising tractive performance. The more flexible tire reduced the average normal contact stress by approximately 15% in the sandy loam soil and 23% in the clay loam soil for the range of operating conditions investigated.     

Non-Gaussianities in New Ekpyrotic Cosmology

The new ekpyrotic model is an alternative scenario of the early Universe which relies on a phase of slow contraction before the big bang. We calculate the 3-point and 4-point correlation functions of primordial density perturbations and find a generically large non-Gaussian signal, just below the current sensitivity level of cosmic microwave background experiments. This is in contrast with slow-roll inflation, which predicts negligible non-Gaussianity. The model is also distinguishable from alternative inflationary scenarios that can yield large non-Gaussianity, such as Dirac-Born-Infeld inflation and the simplest curvatonlike models, through the shape dependence of the correlation functions. Non-Gaussianity therefore provides a distinguishing and testable prediction of New Ekpyrotic Cosmology.     

1616 supergravity coupled to matter: The low energy limit of the superstring

We analyze irreducible, N = 1 supergravity theories with 16 fermionic degrees of freedom. The lagrangians for pure $\text{16}\text{16}$ supergravity, and for $\text{16}\text{16}$ supergravity coupled to arbitrary chiral superfields are constructed. These theories are shown to have natural SU(1,1) non-compact symmetry. The low energy field theory limit of the superstring is conjectured to be of this type.     

A Monte Carlo method for finding important ligand fragments from receptor data

A simulated annealing method for finding important ligand fragments is described. At a given temperature, ligand fragments are randomly selected and randomly placed within the given receptor cavity, often replacing or forming bonds with existing ligand fragments. For each new ligand fragment combination, the bonded, nonbonded, polarization and solvation energies of the new ligand–receptor system are compared to the previous configuration. Acceptance or rejection of the new system is decided using the Boltzmann distribution , where E is the energy difference between the old and new systems, k is the Boltzmann constant and T is the temperature. Thus, energetically unfavorable fragment switches are sometimes accepted, sacrificing immediate energy gains in the interest of finding a system with minimum energy. By lowering the temperature, the rate of unfavorable switches decreases and energetically favorable combinations become more difficult to change. The process is terminated when the frequency of switches becomes too small. As a test, the method predicted positions and types of important ligand fragments for neuraminidase that were in accord with the known ligand, sialic acid.     

Resonance Raman analysis of nonlinear solvent dynamics: betaine-30 in ethanol

Resonance Raman profiles for 14 vibrational modes of betaine-30 in ethanol at room temperature were measured at wavelengths within the first charge-transfer absorption band. The absorption spectrum and resonance Raman profiles were analyzed using time-dependent theory and a Brownian oscillator model modified to account for nonlinear solvent response; i.e., dependence of the solvent reorganization energy on the electronic state of the solute. As in our previous study of betaine-30 in acetonitrile, the solvent reorganization energy for the excited electronic state, determined from resonance Raman spectroscopy, was found to be smaller than that for the ground electronic state, determined from the absorption spectrum. The mode-dependent internal reorganization energies of betaine-30 in ethanol were found to be slightly larger than those of betaine-30 in acetonitrile. Temperature-dependent solvent reorganization energies for the ground electronic state were determined from analysis of the absorption line shape from 279 to 332 K and were found to decrease with increasing temperature. The influence of hydrogen bonding on the solvent and internal reorganization energy of betaine-30 is considered, and the physical basis for nonlinear solvent response is discussed.     

High-performance liquid chromatographic analysis of oxytetracycline in chinook salmon following administration of medicated feed.

A high-performance liquid chromatographic assay was developed to detect oxytetracycline (OTC) in chinook salmon muscle tissue. A solid-phase extraction protocol was used to recover OTC and the internal standard, epitetracycline hydrochloride, from the salmon tissue samples. OTC was analyzed using a mobile phase of methanol-0.02 M phosphate buffer, pH 2.25 (60:190), an ultraviolet detection wavelength of 365 nm and 250 mm x 4.6 mm I.D. Ultrasphere ODS column. A linear calibration curve (r2 = 0.999) of OTC in salmon muscle tissue from 0.05 to 3.0 ppm was obtained. Using a signal-to-noise ratio of 5:1, the OTC detection limit was 0.5 ppm in salmon muscle tissue. OTC recovery (74.4%) and intra-assay variability (2.3%) were optimized for salmon muscle tissue. An in vivo feeding study was performed by administrating OTC-medicated feed for a period of 10 days, followed by a 42-day sampling period. The half-life for the elimination of OTC in chinook salmon muscle tissue was found to be 5.4 days.     

PHOTOSENSITIZATION BY DRUGS IN SURFACTANT SOLUTIONS

Abstract— Chlorpromazine, promazine, anthracene and furosemide were tested as photosensitizers using 365 nm UV light in micellar solutions of cationic, anionic and nonionic surfactants. In all cases, micelles enhanced the ability of these compounds to photosensitize the oxidation of 2,5-dimethylfuran and the free radical polymerization of acrylamide. pH variation showed that the base form of chlorpromazine and the acid form of furosemide are the principal photosensitizing forms of these compounds. Rate differences between cationic and anionic surfactant media indicate the cation radical to be the major photochemical species formed from chlorpromazine and promazine in micellar media. Photodechlorination of chlorpromazine accounted for a significantly higher reactivity of chlorpromazine over promazine. Anthracene was found to be a very active photosensitizer by the singlet oxygen mechanism but also yielded a small concentration of cation radicals in micellar solution. In its neutral form, furosemide reacted strongly in both photooxidation and photopolymerization systems.
The implications of this study to drug-induced photosensitivity are that (i) free radical reactions may play a major role, and (ii) these sensitizers are more reactive in a hydrophobic environment, suggesting that the cellular membrane or the hydrophobic surfaces of proteins or DNA are more important sites of action in photosensitivity.     

Entangled and disentangled evolution for a single atom in a driven cavity

For an atom in an externally driven cavity, we show that special initial states lead to near-disentangled atom-field evolution, and superpositions of these can lead to near maximally entangled states. Somewhat counterintutively, we find that (moderate) spontaneous emission in this system actually leads to a transient increase in entanglement beyond the steady-state value. We also show that a particular field correlation function could be used, in an experimental setting, to track the time evolution of this entanglement.