FTIR microspectroscopy of melanocytic skin lesions: a preliminary study

Fourier transform infrared (FTIR) microspectroscopy has been employed to investigate benign (ordinary dermal and Reed nevi), dysplastic and malignant (invasive melanoma) skin lesions through the analysis of spectral changes of melanocytes as well as in the evaluation of the presence of melanin. Hierarchical cluster analysis and principal component analysis led to a satisfactory separation of malignant from dysplastic and normal melanocytes. Also, on enlarging the clustering with spectra from Reed and dermal nevi, the multivariate analysis segregated well the spectral data into discrete clusters, allowing the obtaining of reliable average spectra for analysis at the molecular level of the main groups or components responsible for the biological and biochemical changes. The most significant spectral characteristics appear to be related to differences in secondary protein structures, in nucleic acid conformation, in intra- and intermolecular bonding. In all cases, supervised and unsupervised spectral analyses resulted in satisfactory agreement with histopathological findings.     

Synthesis of epoxy and aziridino malonyl peptidomimetics

Short malonyl dehydro peptides have been epoxidized using H₂O₂/Na₂WO₄ dihydrate. The obtained diastereomeric epoxides were separated by HPLC and successfully tested in the ring opening reaction with N-Boc l-cysteine methyl ester, to indicate their electrophilic behavior. Moreover, by a simple two-step reaction, the epoxy malonyl peptides can be converted into the corresponding aziridino malonyl peptides.     

Full-dimensional quantum dynamics of vibrationally highly excited NHD2

We report on full-dimensional vibrational quantum dynamics of the highly excited ammonia isotopologue NHD(2) using a newly developed potential energy surface and the MCTDH program package. The calculations allow to realistically simulate an infrared laser induced stereomutation reaction at the pyramidal nitrogen atom in the femtosecond time domain. Our results allow for a thorough qualitative and quantitative understanding of infrared photoinduced stereomutation kinetics, the underlying quantum dynamics, and the reaction mechanisms. Comparison is made with a previous, reduced dimensionality study of the same reaction [R. Marquardt, M. Quack, I. Thanopulos, and D. Luckhaus, J. Chem. Phys. 118, 643 (2003)], and it is shown that slight variances of reduced spaces lead to significantly different kinetics. Because the quantum dynamics depends subtly on variances of reduced spaces, reduced dimensionality treatments are not reliable even for qualitative predictions of the stereomutation kinetics. The first direct comparison between the Multiconfigurational Time Dependent Hartree [M. H. Beck, A. Ja?ckle, G. A. Worth et al., Phys. Rep. 324, 1 (2000)] and Unimolecular Reactions Induced by Monochromatic Infrared Radiation [M. Quack and E. Sutcliffe, QCPE Bulletin 6, 98 (1986)] program packages on a specific, four dimensional quantum dynamical problem allows for their full validation in the present work.     

Search for direct photons from S-Au collisions at 200 GeV/nucleon

The CERES experiment has measured inclusive photon production in S-Au collisions of 200 GeV/nucleon at the CERN SPS. No evidence for direct emission of photons was found. For the kinematic region 2.1<y<2.65 and 0.4 GeV/c<p??<2.0 GeV/c the yield andp??-dependence of the observed photons are well reproduced by hadron decays. Furthermore, their production rate is found to be proportional to the charged particle density. The systematic errors comparing the measured and expected photon yield result in an upper limit of 14% for the emission of direct photons in central S-Au collisions. For a photon source with a yield depending quadratically on the charged particle density the limit can be reduced to 7%.     

Absolute frequency spectroscopy of CO2 lines at around 2.09 μm by combined use of an Er:fiber comb and a Ho:YLF amplifier

The low-frequency tail of an octave-spanning supercontinuum (SC) generated by an Er:fiber comb is enhanced by a multipass Ho:YLF amplifier and used in a sum-frequency-generation scheme to obtain absolute referencing of a single-mode Tm-Ho:YAG laser tunable around 2.09 μm. By tuning the comb repetition frequency, the probing laser is scanned across the absorption lines of a CO(2) gas sample and highly accurate absorption profiles are measured. This approach can be readily scaled to any wavelength above ~2 μm.     

A class of quasi-variational inequalities for adaptive image denoising and decomposition

We introduce a class of adaptive non-smooth convex variational problems for image denoising in terms of a common data fitting term and a support functional as regularizer. Adaptivity is modeled by a set-valued mapping with closed, compact and convex values, that defines and steers the regularizer depending on the variational solution. This extension gives rise to a class of quasi-variational inequalities. We provide sufficient conditions for the existence of fixed points as solutions, and an algorithm based on solving a sequence of variational problems. Denoising experiments with spatial and spatio-temporal image data and an adaptive total variation regularizer illustrate our approach.     

Multimode squeezed states produced by a confocal parametric oscillator

We investigate the spatial behaviour of the quantum-noise-reduction spectrum of the vacuum state emitted by a degenerate optical parametric oscillator below threshold. In view of possible experimental implementations, we consider a mode-degenerate resonator and two matching lenses and show that, for the realistic case of a finite-width pump, significant level of squeezing can be observed in a very small region of the beam. Received 25 September 2002 Published online 11 February 2003     

Chemical insight into electron density and wave functions: software developments and applications to crystals, molecular complexes and materials science

This paper overviews the work made by our group during the past 10–15 years on crystalline systems, semiconductor surfaces, molecular complexes and on materials of interest for technological applications, such as the defective silicon or the novel generation thermoelectric materials. Our main aim of extracting chemical insight into the analysis of electron densities and computed wave functions is illustrated through a number of examples. The recently proposed Source Function analysis is reviewed and a few of its more interesting applications are summarized. Software package developments, motivated by the need of a direct comparison with experiment or by the help these packages can provide for interpreting complex experimental outcomes, are described and future directions outlined. A particular emphasis is given to the TOPOND and TOPXD programs, which enable one to analyze theoretical and experimental crystalline densities using the rigorous framework of the Quantum Theory of Atoms in Molecules, due to Bader.