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.     

Nanopatterning in a compact setup using table top extreme ultraviolet lasers

The recent development of table top extreme ultraviolet (EUV) lasers have enabled new applications that so far were restricted to the use of large facilities. These compact sources bring now to the laboratory environment the capabilities that will allow a broader application of techniques related to nanotechnology and nanofabrication. In this paper we review the advances in the utilization of EUV lasers in nanopatterning. In particular we show results of the nanopatterning using a table-top capillary discharge laser producing 0.12-mJ laser pulses with 1.2-ns time duration at a wavelength λ = 46.9 nm. The nanopatterning was realized by interferometric lithography using a Lloyd’s mirror interferometer. Two standard photoresists were used in this work, polymethyl methacrylate (PMMA) and hydrogen silsesquioxane (HSQ). Pillars with a full width half maximum (FWHM) diameter of 60 nm and holes with FWHM diameter of 130 nm were obtained over areas in excess of 500×500 μm².     

Guiding of intense laser beams in highly ionized plasma columns generated by a fast capillary discharge

We have demonstrated the guiding of laser pulses with peak intensities up to 2.2 x 10(17) W/cm(2) in a 5.5 cm long plasma column containing highly charged Ar ions generated by a fast capillary discharge. A rapid discharge-driven hydrodynamic compression guides progressively lower order modes through a plasma with increasing density and degree of ionization, until the guide collapses on axis. The lowest order mode (FWHM approximately 50 microm) is guided with 75% transmission efficiency shortly before the plasma reaches the conditions for lasing in Ne-like Ar. The subsequent rapid plasma expansion forms a significantly leakier and more absorbent guide.     

Determination of organophosphorus pesticides in honeybees after solid-phase microextraction

The solvation parameter model has been applied to the characterization of micellar electrokinetic chromatographic (MEKC) systems with mixtures of lithium dodecyl sulfate and lithium perfluorooctanesulfonate as surfactant. The variation in MEKC surfactant composition results in changes in the coefficients of the correlation equation, which in turns leads to information on solute-solvent and solute-micelle interactions. Lithium perfluorooctanesulfonate is more dipolar and hydrogen bond acidic but less polarizable and hydrogen bond basic than lithium dodecyl sulfate. Therefore mixtures of lithium dodecyl sulfate and lithium perfluorooctanesulfonate cover a very wide range of polarity and hydrogen bond properties, which in turn results in important selectivity changes for analytes with different solute properties.     

Trends of volatile chlorinated hydrocarbons and trihalomethanes in Antarctica

In order to understand behaviour and environmental fate of manmade chemicals in remote and cold areas, during the XXVII Italian Expedition carried out in Antarctica throughout the austral summer 2011/2012, superficial snow and lake water were sampled along the Ross Sea's South coast and their content of some low-molecular weight volatile halogenated hydrocarbons was evaluated. In consideration of their important role in stratospheric ozone chemistry, some volatile chlorinated hydrocarbons (VCHCs) and trihalomethanes (THMs) were investigated. The analyses were realised with a dedicated system composed by a purge-and-trap injector coupled to a gas chromatograph with a mass spectrometer (PTI-GC-MS) operating in SIM mode. The investigated VCHCs (chloroform; 1,1,1-trichloroethane; tetrachloromethane; trichloroethylene and tetrachloroethylene) were present in all analysed samples, and concentration levels ranged from units to hundreds of ng L^?1 according to considered matrix. For the first time, THMs (bromoform; dibromochloromethane; bromodichloromethane), were measured in Antarctic lake waters and freshly deposited snow; their concentration levels ranged from units to tens of ng L^?1. In order to assess eventual temporal variations, VCHC content in aqueous Antarctic matrices was compared with levels occurring in the past Italian Antarctic expeditions: for some banned substances, a decrease in concentration was observed, probably due to worldwide use restrictions. Finally, current Antarctic and Italian VCHC and THM levels in snow and lake water samples were compared and were found to be quite similar, differing at most by one order of magnitude, corroborating the hypothesis of an accumulation of halogenated compounds in Antarctic aqueous matrices.     

Vibronic coupling calculation of the pre-resonance Raman intensities of naphthalene

The relative enhancement of the Raman intensities in the pre-resonance region has been computed for naphthalene, using the vibronic coupling expansion proposed by Albrecht. The relevant vibronic and transition moments have been computed in the CNDO/S approximation, while the normal coordinates of naphthalene have been evaluated using a MINDO/3 program. The experimental pattern of intensities is reproduced in a satisfactory way both for b_3g and a_g vibrations. The most important states and the main vibronic terms in the expansion are individuated and discussed with respect to the vibronic borrowing present in the Fluorescence spectrum of naphthalene.     

Combination of spectroscopic and computational methods to get an understanding of supramolecular chemistry of drugs: from simple host systems to biomolecules

Circular dichroism (CD) spectra of non-covalent ligand : biomolecule couples contain information on the equilibrium geometries of the associated structures that can be retrieved upon comparison of the sign and intensity of the experimental CD bands with the quantum mechanically calculated rotational strengths of low energy supramolecular complexes, obtained from molecular modelling methods. For both chiral and achiral ligands this approach proved useful to reach a structure based rationale of ground and excited state properties of the non-covalent ligand : protein associates. In this Perspective we illustrate the potential of this method focusing on the main achievements of our recent spectroscopic, conformational and photochemical studies on drug-albumin complexes and collocate it in the frame of current methodologies of molecular modelling and spectroscopic investigation of ligand : biomolecule binding.     

Aspects of nanometer scale imaging with extreme ultraviolet (EUV) laboratory sources

Imaging systems with nanometer resolution are instrumental to the development of the fast evolving field of nanoscience and nanotechnology. Decreasing the wavelength of illumination is a direct way to improve the spatial resolution in photon-based imaging systems and motivated a strong interest in short wavelength imaging techniques in the extreme ultraviolet (EUV) region. In this review paper, various EUV imaging techniques, such as 2D and 3D holography, EUV microscopy using Fresnel zone plates, EUV reconstruction of computer generated hologram (CGH) and generalized Talbot self-imaging will be presented utilizing both coherent and incoherent compact laboratory EUV sources. Some of the results lead to the imaging with spatial resolution reaching 50 nm in a very short exposure time. These techniques can be used in a variety of applications from actinic mask inspection in the EUV lithography, biological imaging to mask-less lithographic processes in nanofabrication.