MOLECULAR MECHANISM OF DRUG PHOTOSENSITIZATION–II. PHOTOHEMOLYSIS SENSITIZED BY KETOPROFEN

Red blood cell lysis photosensitized by ketoprofen (KPF) was investigated. The photohemolysis was inhibited by butylated hydroxyanisole, reduced glutathione, superoxide dismutase and mannitol, and was unaffected by sodium azide; the presence of oxygen markedly enhanced the lysis. Photohemolysis was also observed under anaerobic conditions. Ketoprofen, irradiated in aqueous buffer solution at pH 7.4, underwent a decarboxylation process via intermediate radicals, leading to the compounds (3-benzoylphenyl)ethane, (3-benzoylphenyl)ethyl hydroperoxide, (3-benzoylphenyl)ethanol and (3-benzoylphenyl)ethanone under aerobic conditions and only to the compound (3-benzoylphenyl)ethane under anaerobic conditions. The four photoproducts showed lytic activity, particularly high for the alcohol and hydroperoxide. The overall results suggest for KPF-photosensitized hemolysis a molecular mechanism involving free radicals, superoxide anion and sensitizer photodegradation products.     

High-efficiency beam extraction and collimation using channeling in very short bent crystals

A silicon crystal was used to channel and extract 70 GeV protons from the U-70 accelerator with an efficiency of 85.3+/-2.8%, as measured for a beam of approximately 10(12) protons directed towards crystals of approximately 2 mm length in spills of approximately 2 s duration. The experimental data follow very well the prediction of Monte Carlo simulations. This demonstration is important in devising a more efficient use of the U-70 accelerator in Protvino and provides crucial support for implementing crystal-assisted slow extraction and collimation in other machines, such as the Tevatron, RHIC, the AGS, the SNS, COSY, and the LHC.     

Velocity magnitude estimation with linear arrays using Doppler bandwidth

The dependence of pulsed wave Doppler bandwidth on parameters typical of linear transducer arrays used in commercial Duplex and color flow mapping systems is investigated experimentally. For a single flow line it is observed that this bandwidth generally depends not only on the scatterer velocity and the beam-to-flow angle, but also on the flow line range and orientation. This is due to the fact that in Duplex and color flow systems the transducer is differently focused in the scan and elevation planes and its aperture and focal lengths are often made to vary, depending on the distance of the flow line from the transducer. It is however experimentally demonstrated that, at points where the ultrasound beamwidths in the scan and elevation planes are both comparable to the sample volume length, the Doppler bandwidth is independent of the beam-to-flow angle. It is also shown that this invariance can be extended to other ranges by appropriately modifying the array aperture. Finally, as an application of this independence, the flow-line velocity magnitude in these beam regions is estimated with better than 5% uncertainty through a simple bandwidth measurement.     

Experimental study for the feasibility of a crystalline undulator

We present an idea for creation of a crystalline undulator and report its first realization. One face of a silicon crystal was given periodic microscratches (grooves) by means of a diamond blade. The x-ray tests of the crystal deformation due to a given periodic pattern of surface scratches have shown that a sinusoidal-like shape is observed on both the scratched surface and the opposite (unscratched) face of the crystal; that is, a periodic sinusoidal-like deformation goes through the bulk of the crystal. This opens up the possibility for experiments with high-energy particles channeled in a crystalline undulator, a novel compact source of radiation.     

Macroscopic evidence of quantum coherent oscillations of the total spin in the Mn-[ \mathsf{3\times3}] molecular nanomagnet

Molecular nanomagnets, besides promising to open new frontiers in technology, have attracted huge interest in the scientific community because they can exhibit the phenomenon known as quantum tunnelling of the magnetization, i.e. coherent fluctuations of the direction of the total spin vector. In this paper we study a different quantum phenomenon involving fluctuations of the magnitude of the total spin vector. These fluctuations are related to the mixing between states with different spin quantum number, and imply new macroscopic effects, which we theoretically investigated in the Mn-[ grid.Received: 9 October 2003, Published online: 8 December 2003PACS: 75.45. + j Macroscopic quantum phenomena in magnetic systems - 75.50.Xx Molecular magnets - 52.70.Ds Electric and magnetic measurements     

Determination of specific volatile organic compounds synthesised during Tuber borchii fruit body development by solid-phase microextraction and gas chromatography/mass spectrometry

Fruit body development is a particular phase of the Tuber life cycle, characterised by the aggregation of different types of hyphae, i.e., vegetative hyphal cells and highly specialised reproductive hyphae (asci). In order to identify the volatile organic compounds (VOCs) produced in different stages of the Tuber borchii ripening fruit body, solid-phase microextraction with gas chromatography and mass spectrometry was used. The volatile organic compounds were extracted using a DVB/CAR/PDMS 50/30 microm fiber placed for 10 min at room temperature in the truffle headspace. The results obtained reveal 49 compounds each of which was present only in a particular stage of maturation. 1-octen-3-ol, aromadendrene, alpha-farnesene and other terpenoid compounds were of particular interest, and their possible biological roles are discussed. The production of aromadendrene in the completely unripe fruit body suggests the existence of communication events in the early stage of ascomata formation between the fungus and the host plant. alpha-Farnesene could represent a chemotactic attractant to saprophytic organisms in order to disperse the fungal spores in the environment. The identification of the VOCs produced by truffles during their maturation could give information about the processes underlying this phase of Tuber life cycle.     

A way to manage the thermal flexibility of ligand candidates for bioassays

An original way to manage both stereochemistry and conformational constraints in ligand candidates for bioassays is presented with reference to a group of model N,N′-tetrasubstituted o-phthalamides and thioamides. The study shows that a scale of thermal flexibility in solution can be envisaged, the divisions of which are represented by compounds sharing quite similar geometrical features. NMR spectroscopy and powder X-ray analysis were used for the physical chemical investigation. An attempt to exploit the conformational instability of a model thioamide in the medium of a bioassay was also performed.     

Photoinduced N-demethylation of rufloxacin and its methyl ester under aerobic conditions

Irradiation of rufloxacin (RF) under aerobic conditions gives rise to N-demethylation of the piperazinyl ring, which is enhanced in aerated D2O. Two primary processes seem to be involved in RF N-demethylation: photoionization from 1RF and singlet oxygen generation from 3RF. Both processes may lead to the same key intermediates, namely, RF*+ and superoxide radical anion; coupling of these intermediates explains N-demethylation of RF via an iminium cation. Formation of the hydrated electron by a monophotonic process (with a quantum yield of 0.09) is detected along with 3RF (with a intersystem-crossing quantum yield phiISC = 0.36) by laser flash photolysis. Studies performed on RF methyl ester give qualitatively similar results.     

Polarized electron sources

We review current methods for production of polarized electron beams. Major focus is devoted to photoemission from GaAs, which is the way that current facilities rely on. Some aspects of this kind of technology such as the physics behind generation of polarized beams and its advantages and limitations are considered. Finally, the perspectives for implementation of a GaAs photocathode in a RF gun are discussed. This revised version was published online in August 2006 with corrections to the Cover Date.