A cyclic hexacopper(II) fluoro complex that encapsulates two fluoride anions

The complex [[Cu3(HpztBu)4(mu-pztBu)2(mu-F)2(mu 3-F)]2]F2 (HpztBu = 3[5]-tert-butylpyrazole) has a cyclic, C2v-symmetric hexacopper core. The two non-coordinated F- anions are encapsulated within cavities formed by three HpztBu ligands.     

Novel generation of an o-quinone methide from 2-(2'-cyclohexenyl)phenol by excited state intramolecular proton transfer and subsequent C-C fragmentation

Formation of an o-quinone methide via C-C fragmentation of a zwitterion formed by intramolecular excited state proton transfer from an o-allylphenol derivative is reported for the first time.     

A high statistics measurement of the Lambda(+)(c) lifetime

A high statistics measurement of the Lambda(+)(c) lifetime from the Fermilab fixed-target FOCUS photoproduction experiment is presented. We describe the analysis technique with particular attention to the determination of the systematic uncertainty. The measured value of 204.6 +/- 3.4 (stat) +/- 2.5 (syst) fs from 8034 +/- 122 Lambda(+)(c)-->pK(-)pi(+) decays represents a significant improvement over the present world average.     

Application of high-resolution magic-angle spinning NMR spectroscopy to define the cell uptake of MRI contrast agents

A new method, based on proton high-resolution magic-angle spinning ((1)H HR-MAS) NMR spectroscopy, has been employed to study the cell uptake of magnetic resonance imaging contrast agents (MRI-CAs). The method was tested on human red blood cells (HRBC) and white blood cells (HWBC) by using three gadolinium complexes, widely used in diagnostics, Gd-BOPTA, Gd-DTPA, and Gd-DOTA, and the analogous complexes obtained by replacing Gd(III) with Dy(III), Nd(III), and Tb(III) (i.e., complexes isostructural to the ones of gadolinium but acting as shift agents). The method is based on the evaluation of the magnetic effects, line broadening, or induced lanthanide shift (LIS) caused by these complexes on NMR signals of intra- and extracellular water. Since magnetic effects are directly linked to permeability, this method is direct. In all the tests, these magnetic effects were detected for the extracellular water signal only, providing a direct proof that these complexes are not able to cross the cell membrane. Line broadening effects (i.e., the use of gadolinium complexes) only allow qualitative evaluations. On the contrary, LIS effects can be measured with high precision and they can be related to the concentration of the paramagnetic species in the cellular compartments. This is possible because the HR-MAS technique provides the complete elimination of bulk magnetic susceptibility (BMS) shift and the differentiation of extra- and intracellular water signals. Thus with this method, the rapid quantification of the MRI-CA amount inside and outside the cells is actually feasible.     

Photobinding of carprofen to protein

Carprofen is a non-steroidal antiinflammatory drug with marked photosensitising properties. In order to elucidate the mechanisms underlying the phenomenon of drug-protein photobinding, mixtures of the drug and human serum albumin were irradiated under different experimental conditions. After irradiation and subsequent gel-filtration chromatography of the photomixture, the eluting protein fraction was analysed by means of fluorescence spectroscopy. The formation of drug-protein photoadducts could be evidenced by the characteristic emission properties of the carbazole chromophore. The photobinding of the drug to human serum albumin appears to involve the formation of aryl radicals resulting from carbon-halogen photocleavage. This mechanistic interpretation is supported by the observed variations in the intensity of the fluorescence spectra, which can be correlated with the lower quantum yield emission of chlorocarbazoles as compared to non-halogenated analogues. The results from laser flash photolysis studies are also in agreement with this proposal.     

Optical Single-Sideband Modulators and Their Applications

We review our recent work in the implementation of optical single-sideband (OSSB) modulation and in the application of this modulation format to microwave photonics and optical testing systems. We have developed an enhanced OSSB modulator for wide-band operation, the so-called bidirectional OSSB modulator, and a simplification of this scheme for narrow-band applications. These OSSB modulators are based on the use of a standard single-electrode Mach-Zehnder electro-optic modulator (MZ-EOM) and passive fiber-optic components. In both designs, the OSSB operation is shown to be independent of the MZ-EOM bias. Therefore, the optical modulation depth at the output of the device can be enhanced using minimum transmission biasing to provide suppression of the optical carrier. Finally, we demonstrate the application of OSSB modulators to the improvement of microwave/millimeter-wave subcarrier multiplexing fiber-optic links and to narrow-band fiber radio systems. In addition, we analyzed the feasibility and the limitations of an optical vector network analysis technique based on OSSB modulation that can provide sub-picometer wavelength resolution.     

Electronic structure of a cobalt monolayer on Cu(100)

Angular resolved photoemission spectra using synchrotron radiation have been measured for different amounts of cobalt evaporated on Cu(100). At room temperature cobalt grows layer-bylayer forming well-ordered layers in registry with the substrate, as judged by AES, LEED and UPS measurements. The energy position and linewidth of the Cu peaks remain unchanged when cobalt is deposited onto the surface, suggesting a rather weak interaction between the d-bands of Co and Cu. The two-dimensional band structure of the monolayer of cobalt has been determined. We have obtained a value for the magnetic exchange splitting of ΔE_exch = 0.80 ± 0.15 eV, which is nearly identical to the bulk value. A shift in the energy positions of the critical points for the monolayer versus bulk of cobalt is interpreted in terms of a narrower 2D density of states in the monolayer as compared to the bulk. A resonant valence-band two-electron satellite has been found. The correlation energy and screening effects of the two d-holes are very similar to the corresponding bulk values, while the decreased intensity of the satellite at resonance compared to the one for Co(0001) suggests that there are more d-states relative to s-states in the monolayer than in a bulk cobalt single crystal, in agreement with recent models of the valence band electronic structure at surfaces.     

Stimulated spin-flip emission from magnetic semiconductors

We show that by inverting the spin state population in a s-d model one might get a temperature tunable stimulated spin-flip emission line in ferromagnetic semiconductors.