pH Effects on the Spectroscopic and Photochemical Behavior of Enoxacin: A Steady-State and Time-Resolved Study

The spectroscopic and photochemical behavior of Enoxacin (ENX), 1-ethyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-1,8-naphthyridine-3-carboxylic acid, has been investigated in aqueous solutions between pH 3.5 and pH 12. The absorption and emission properties of ENX are strongly affected by pH. The fluorescence quantum yield, 4 x 10⁻³ at pH 3.5, increases by a factor of two on going to neutral pH while a strong reduction is observed at alkaline pH. The photodegradation quantum yield also depends on pH, being maximum in neutral conditions ( ca 0.04). Nanosecond flash photolysis experiments confirm that the yield of absorbing transients is maximum at neutral pH while it decreases to zero at acid and alkaline pH. These results indicate that both the dissociation of the carboxylic group and the protonation of the piperazinyl residues are key steps for the formation of the photochemically active form of ENX. Loss of F⁻ by heterolytic cleavage of the C–F bond is proposed to occur from the triplet state of the zwitterion with formation of a carbocation. A path for the evolution of this intermediate to the final product is also proposed.     

Photophysical Properties of Rufloxacin in Neutral Aqueous Solution

The photophysical properties of rufloxacin, 9-fluoro-2_r3-dihydro-10-(4-methyl-l-pyrazinyl)-7-oxo-7-H-pyri-do[l,2,3-de]-l,4-benzothiazin-6-carboxylic acid, a fluoroquinolone antibacterial drug exhibiting photosensitizing action toward biological substrates, were studied in aqueous solutions at neutral pH. The lowest excited electronic states of the zwitterion were characterized by both experimental techniques and theoretical methods. Steady-state and time-resolved emission, triplet-state absorption and singlet oxygen production were investigated. The results indicate that the lowest excited singlet is a fluorescent, relatively long-lived state (φ_r= 0.075, T_r? 4.5 ns) with an efficient intersystem crossing to the triplet manifold (φ_isc? 0-⁷)- The lowest triplet is a long-lived state (T_T? 10 μs at 295 K in 0.01 M phosphate buffer), with properties that make it a good candidate for being the precursor of the photodecarboxylation of the drug. It is quenched by oxygen at a rate of 1.7 times 10⁹M^-1 s-¹ and singlet oxygen is formed with a quantum yield of 0.32 in air-saturated solutions.     

A Monte Carlo simulation of a stroboscopic laser diagnostics of ordered ion beams in a storage ring

A Monte Carlo code combined with a particle tracking program has been used to study a stroboscopic laser diagnostic system that is able to detect a string-like ordered ion beam. Different ion species have been studied to evaluate the diagnostics capability. This revised version was published online in July 2006 with corrections to the Cover Date.     

Substitutions in YBa2Cu3O7−y and their influence on the magnetic penetration depth,its anisotropy and T c: Muon spin rotation (μSR)

Il Nuovo Cimento D - Deterioration of the superconducting properties of HTC materials, induced by different substitutions, offers a key towards the understanding of the basic HTC interactions....     

A novel ultrasound instrument for investigation of arterial mechanics

The study of arterial mechanics concerns functional characteristics depending on wall elasticity and flow profile. Wall elasticity can be investigated through the estimation of parameters like the arterial distensibility, which is of high clinical interest because of its known correlation not only with the advanced atherosclerotic disease, but also with aging and major risk factors for cardiovascular disease. The flow velocity profile is also clinically relevant, because it modulates endothelial function and can be responsible for the development and distribution of atherosclerotic plaques. A clinically relevant variable extracted from the blood velocity profile is the wall shear rate (WSR), which represents the spatial velocity gradient near the vessel wall. This paper describes an integrated ultrasound system, capable of detecting both the velocity profile and the wall movements in human arteries. It basically consists of a PC add-on board including a single high-speed digital signal processor. This is dedicated to the analysis of echo-signals backscattered from 128 range cells located along the axis of the interrogating ultrasound (US) beam. Echoes generated from the walls (characterized by high amplitudes and low Doppler frequencies) and from red blood cells (characterized by low amplitudes and relatively high Doppler frequencies) are independently processed in real-time. Wall velocity is detected through the autocorrelation algorithm, while blood velocity is investigated through a complete spectral analysis of all signals backscattered by erythrocytes and WSR is extracted from the estimated velocity profile. Preliminary applications of the new system, including the simultaneous analysis of blood flow and arterial wall movement in healthy volunteers and in a diseased patient, are discussed, and first results are presented.     

Structural transformation induced by magnetic field and "colossal-like" magnetoresistance response above 313 K in MnAs

MnAs exhibits a first-order phase transition from a ferromagnetic, high-spin metal hexagonal phase to a paramagnetic, lower-spin insulator orthorhombic phase at T(C)=313 K. Here, we report the results of neutron diffraction experiments showing that an external magnetic field, B, stabilizes the hexagonal phase above T(C). The phase transformation is reversible and constitutes the first demonstration of a bond-breaking transition induced by a magnetic field. The field-induced phase transition is accompanied by an enhanced magnetoresistance of about 17% at 310 K. The phenomenon appears to be similar to that of the colossal magnetoresistance response observed in the Mn [corrected] perovskite family.     

Molecular structure of cyclopentadiene from its NMR spectrum in a nematic solvent

The NMR spectrum of cyclopentadiene partially oriented in a nematic phase has been measured and the proton geometry has been determined. The results are compared with those deduced from microwave spectroscopy.     

Effect of Fermi surface nesting on resonant spin excitations in Ba(1-x)K(x)Fe2As2

We report inelastic neutron scattering measurements of the resonant spin excitations in Ba(1-x)K(x)Fe(2)As(2) over a broad range of electron band filling. The fall in the superconducting transition temperature with hole doping coincides with the magnetic excitations splitting into two incommensurate peaks because of the growing mismatch in the hole and electron Fermi surface volumes, as confirmed by a tight-binding model with s(±)-symmetry pairing. The reduction in Fermi surface nesting is accompanied by a collapse of the resonance binding energy and its spectral weight, caused by the weakening of electron-electron correlations.     

Molecular Mechanism of Drug Photosensitization. IX. Effect of Inorganic Ions on DNA Cleavage Photosensitized by Naproxen

Abstract— Photocleavage of DNA induced by naproxen and the correlated protective effect by some inorganic ions have been considered. The presence of a DNA complex is suggested and only associated naproxen seems to be responsible for the cleavage, for which the quantum yield of single strand breaks was calculated. The inorganic ions I^-, Mn²⁺, Co²⁺ and Cu²⁺ decrease naproxen-photoin-duced DNA cleavage. Iodide acts by a heavy atom mechanism, thus inhibiting naproxen photolysis and decreasing the amount of free radicals responsible for the photocleavage both in aerobic and anaerobic conditions. Metallic ions protect only within a range of concentrations, as for higher amounts damaging processes are observed. The protective efficiency of cations decreases with the increase of free drug concentration in the bulk of the solution, due to their involvement in the scavenging of naproxen radicals generated by photolysis of the free drug. In the presence of EDTA the cations show a better protective action. The most likely hypothesis is an inhibiting effect on the damaging processes via a redox cycle. The different behaviors of copper and of the two other cations can be justified by the influence of redox potentials of free and complexed metals and by the superoxide dis-mutase-like activity of copper.