Synthesis of Peptide Cysteine Dimedone Using Fmoc-Cys(Dmd)-OH: Glutathione Cysteine Dimedone as a Probe in Investigating the Sulfenic Acid Mediated Oxidation of Glutathione

Dimedone is the most widely used chemical probe for detection of cysteine sulfenic acid in peptides and proteins. The reaction of dimedone with cysteine sulfenic acid results in the formation of unique cysteine dimedone motif containing thioether bridge. Based on the structure of cysteine dimedone residue in polypeptide, a new building block of Fmoc-Cys(Dmd)-OH was developed for solid phase synthesis of peptide cysteine dimedone. Mass spectrometric sequencing of synthetic peptides have confirmed successful incorporation of cysteine dimedone in peptide chain using HBTU/HOBt as a coupling agent. The new method permits synthesis of peptides containing both cysteine thiol and cysteine dimedone in the same sequence which was difficult to achieve by conventional methods. The synthetic peptide of glutathione cysteine dimedone was used as a standard in probing the air-mediated oxidation of thiol to disulfide form of glutathione. The co-elution of standard peptide and reaction mixture of oxidation of glutathione in presence of dimedone using RP-HPLC have confirmed the formation of glutathione cysteine sulfenic as an intermediate in the air-mediated oxidation of glutathione. The synthetic peptides of cysteine dimedone may find application in the field of redox proteomics and generation of antibodies against modified cysteine residue.     

Coherent population trapping spectra in presence of ac magnetic fields

Experimental and theoretical investigations are reported on the effects induced by an alternating magnetic field on coherent population trapping resonances. We show that the ac magnetic field produces sidebands of these resonances in such a way that the spectrum observed is similar to those observed via the FM spectroscopic technique. Because of the very narrow linewidth of the resonances, sidebands are resolved even for ac field frequencies as low as a fraction of a kHz. The theoretical model developed, which takes into account a very simple atomic structure, fits the experimental data quite well.     

Ternary and binary copper(II) complexes: synthesis,characterization, ROS-inductive,proteasome inhibitory,and anticancer properties

Three ternary copper(II) complexes, [Cu(phen)(L-phe)Cl]·2H₂O, [Cu(phen)(L-leu)Cl]·4½H₂O, and [Cu(phen)(L-tyr)Cl]·3H₂O, and four binary copper(II) complexes, [Cu(phen)Cl₂]_, Cu(L-phe)₂·½H₂O, Cu(L-leu)₂·½H₂O, and Cu(L-tyr)₂·H₂O (where phen = 110-phenanthroline, L-phe = L-phenylalanine, L-tyr = L-tyrosine, L-leu = L-leucine and Cl^- = chloride), were synthesized and characterized by elemental analysis, spectroscopic techniques (FTIR, UV–visible, fluorescence spectroscopy), magnetic susceptibility, molar conductivity, and lipophilicity measurement. X-ray diffraction determination of a single crystal of [Cu(phen)(L-tyr)Cl] showed two independent molecules in the asymmetric unit, each with the same distorted square pyramidal geometry about copper(II). p-Nitrosodimethylaniline assay revealed that the three ternary complexes were better inducers of reactive oxygen species over time than binary complexes, CuCl₂, and free ligands. All the copper(II) complexes in this series inhibited the three proteolytic activities in the order Trypsin-like > Caspase-like > Chymotrypsin-like. In terms of anticancer properties, the copper(II)-phen complexes had GI50 values of less than 4 μM against MCF-7, HepG2, CNE1 and A549 cancer cell lines, more potent than cisplatin.     

Theory of frequency modulation spectroscopy of coherent dark resonances

The interaction of a three-level atom in the A configuration with a frequency-modulated (FM) field is analyzed theoretically for the first time. The two-frequency model for solving the problem of frequency modulation spectroscopy of coherent dark resonances is described and analyzed for a three-level A system. The effectiveness of the two-frequency model is demonstrated by comparing the results obtained using this model with the results of solving the exact problem of interaction of a A system with an FM field, which can be solved by the density matrix method. It is shown that the simple two-frequency model corresponds to the exact solution and is in qualitative agreement with experimental data.     

The Legnaro Francium Magneto-Optical Trap

Hyperfine Interactions - Laser cooling and trapping of radioactive atoms represent the new frontier in atomic physics and a new powerful tool in nuclear physics. We are setting up at the...     

Application of a very long cavity laser to atom slowing down and optical pumping

A method to slow down an atomic beam with a counter-propagating resonant laser beam is proposed. The laser radiates across the full Doppler profile of the atomic beam with a longitudinal mode separation which is slightly less than the homogeneous linewidth of the atoms. This allows the atoms to come to rest without the need for frequency tuning or laser chirping. The required mode separation can be obtained from a very long-cavity laser. The application to optical pumping will be also discussed.     

Molecule formation and energy transfer processes in a vapor with high density of 3P-excited sodium atoms

A rich fluorescence spectrum extending between 4000 and 8200 Å has been observed whenever sodium vapor is excited by dye laser light tuned to the 3²S → 3²P transition. Molecule formation due to collisions between excited and unexcited atoms is manifested by the presence of an emission band of sodium in the spectral range 4160–4570 Å.     

Laser photochemistry: The intramolecular cyclization of carvone to carvonecamphor

Kr-ion laser irradiation of carvone ($\text{1}$) at 350.7 and 356.4 nm gave carvonecamphor ($\text{2}$) in a much higher yield (88%) than in conventional photochemistry, while ($\text{3}$) was a primary photo-by-product.     

Optical relaxation effects on magnetic resonances in vapours oriented by broad-line laser excitation

Relaxation effects produced by the broad-band pumping laser light on magnetic resonances induced in oriented vapours are investigated. Experimental evidence of resonance bleaching by optical transverse relaxation in a sodium vapour pumped by multifrequency laser radiation is reported.     

Optical characterization and manipulation of alkali metal nanoparticles in porous silica

Rubidium and cesium metal nanoparticles were grown in nanoporous silica samples placed in alkali vapor cells. Their size and shape were investigated by measuring the sample optical transmittance. Spectral changes due to photodesorption processes activated by weak light were also analyzed. Alkali atoms photoejected from the silica walls diffuse through and out of the nanopores, modifying both the nanoparticle distribution in the silica matrix and the atomic vapor pressure in the cell volume. The number of rubidium and cesium atoms burst out of the samples was measured as a function of photon energy and fluence. The optical absorption measurements together with the analysis of the photodesorption yield give a complete picture of the processes triggered by light inside the nanopores. We show that atomic photodesorption, upon proper choice of light frequency and intensity, induces either growth or evaporation of nanosized alkali metal clusters. Cluster size and shape are determined by the host-guest interaction.