Multiplicities of Maxwell sets of Pham singularities

A two-sided estimate of local multiplicities of Maxwell sets of isolated singularities of smooth functions is proved. This estimate is sharp for semi-homogeneous functions.     

Magneto-optical resonances in the field of counterpropagating waves

The resonance of the intersection of sublevels in a probe laser field resonant to the cyclic transition corresponding to the D ₂ ⁸⁷Rb line has been investigated in a zero magnetic field. The strong effect of an additional laser field acting on the adjacent transition has been revealed. In a cell without the buffer gas and antirelaxation coating, the amplitude of the probe-field absorption resonance can increase by more than an order of magnitude in the presence of a counterpropagating wave. The effect is observed at the laser frequency tuned to the cross resonance, when the counterpropagating waves simultaneously act on moving atoms at the cyclic and open transitions with the common lower level. The theoretical analysis of the effect of the additional field on the electromagnetically induced absorption resonance is in agreement with the experimental data.     

Pulsed and cw laser oscillations in LiF:F-2 color center crystal under laser diode pumping

Continuous-wave laser oscillations in LiF:F-2 crystal optically pumped by a laser diode at 970 nm were demonstrated for what is believed to be the first time. The slope efficiency of 14% and conversion efficiency of 5.5% were achieved for 80 micros pump pulse duration and 5 Hz pulse repetition rate. An efficiency twice as low was measured at a 6.25 kHz pulse repetition rate (50% off-duty factor) and in cw mode of laser operation.     

Redox-active tyrosine residues in pentapeptides

Tyrosyl radicals are important in long-range electron transfer in several enzymes, but the protein environmental factors that control midpoint potential and electron-transfer rate are not well understood. To develop a more detailed understanding of the effect of protein sequence on their photophysical properties, we have studied the spectroscopic properties of tyrosyl radicals at 85 K. Tyrosyl radical was generated by UV-photolysis of pentapeptides in polycrystalline samples. The sequence of the pentapeptides was chosen to mimic peptide sequences found in redox-active tyrosine containing enzymes, ribonucleotide reductase and photosystem II. From EPR studies, we report that the EPR line shape of the tyrosyl radical depends on peptide sequence. We also present the first evidence for a component of the tyrosyl radical EPR signal, which decays on the seconds time scale at 85 K. We suggest that this transient results from a spontaneous, small conformational rearrangement in the radical. From FT-IR studies, we show that amide I vibrational bands (1680-1620 cm(-1)) and peptide bond skeletal vibrations (1230-1090 cm(-1)) are observed in the photolysis spectra of tyrosine-containing pentapeptides. From these data, we conclude that oxidation of the tyrosine aromatic ring perturbs the electronic structure of the peptide bond in tyrosine-containing oligopeptides. We also report sequence-dependent alterations in these bands. These results support the previous suggestion (J. Am. Chem. Soc. 2002, 124, 5496) that spin delocalization can occur from the tyrosine aromatic ring into the peptide bond. We hypothesize that these sequence-dependent effects are mediated either by electrostatics or by changes in conformer preference in the peptides. Our findings suggest that primary structure influences the functional properties of redox-active tyrosines in enzymes.     

Long‐Lived Charge Separation in Novel Axial Donor–Porphyrin–Acceptor Triads Based on Tetrathiafulvalene,Aluminum(III) Porphyrin and Naphthalenediimide

Two self‐assembled supramolecular donor–acceptor triads consisting of Al^III porphyrin (AlPor) with axially bound naphthalenediimide (NDI) as an acceptor and tetrathiafulvalene (TTF) as a secondary donor are reported. In the triads, the NDI and TTF units are attached to Al^III on opposite faces of the porphyrin, through covalent and coordination bonds, respectively. Fluorescence studies show that the lowest excited singlet state of the porphyrin is quenched through electron transfer to NDI and hole transfer to TTF. In dichloromethane hole transfer to TTF dominates, whereas in benzonitrile (BN) electron transfer to NDI is the main quenching pathway. In the nematic phase of the liquid crystalline solvent 4‐(n‐pentyl)‐4′‐cyanobiphenyl (5CB), a spin‐polarized transient EPR spectrum that is readily assigned to the weakly coupled radical pair TTF^.+NDI^.? is obtained. The initial polarization pattern indicates that the charge separation occurs through the singlet channel and that singlet–triplet mixing occurs in the primary radical pair. At later time the polarization pattern inverts as a result of depopulation of the states with singlet character by recombination to the ground state. The singlet lifetime of TTF^.+NDI^.? is estimated to be 200–300 ns, whereas the triplet lifetime in the approximately 350 mT magnetic field of the X‐band EPR spectrometer is about 10 μs. In contrast, in dichloromethane and BN the lifetime of the charge separation is <10 ns.