Novel Mechanism of Bioluminescence: Oxidative Decarboxylation of a Moiety Adjacent to the Light Emitter of Fridericia Luciferin

A novel luciferin from a bioluminescent Siberian earthworm Fridericia heliota was recently described. In this study, the Fridericia oxyluciferin was isolated and its structure elucidated. The results provide insight into a novel bioluminescence mechanism in nature. Oxidative decarboxylation of a lysine fragment of the luciferin supplies energy for light generation, while a fluorescent CompX moiety remains intact and serves as the light emitter.     

Flow in the zones of separation of a turbulent boundary layer in front of a subsonic jet injected through a circular nozzle

Flow taking place in the three-dimensional region of separation formed by the interaction of a subsonic stream with a single subsonic jet emerging from a circular hole in a plate perpendicular to the stream is considered. The aim of the investigation is to discover the physical characteristics of the flow in the three-dimensional separation zone in front of a subsonic jet obstacle and to determine the principal laws governing the geometrical and hydrodynamic characteristics of the flow as functions of the parameters of the driving stream and jet.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 3, pp. 34–41, May–June, 1973.     

Study of heat transfer in the separation zones formed in front of supersonic jets in a subsonic carrier flow

The heat transfer taking place between the gas and the surface of the plate in the zone of three-dimensional separation of the turbulent boundary layer in front of a set of supersonic jets injected perpendicularly to a subsonic carrier flow is considered. The aim of this investigation is to establish the main physical characteristics of heat transfer in the separation zones in front of jet obstacles and to obtain the distributions of the local heat-transfer coefficients and the temperature of the thermally insulating wall as functions of the parameters of the carrier flow and the injected jets. Analysis of the experimental results yields certain approximating relationships for the distribution of the local heat-transfer coefficients as functions of the Mach number of the carrier flow M, the Mach number of the jet M_j, the relative boundary-layer displacement thickness _s= _s ^* /d, and the degree of jet superheating T_ojT_o relative to the separation zones in front of supersonic jet obstacles.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 4, pp. 68–72, July–August, 1975.     

Combined frequency conversion and pulse compression in nonlinear tapered waveguides

We suggest an application of pump-degenerate four-wave mixing process in tapered waveguides for generation of ultrashort pulses with central frequency tunable over the material transparency range. Our method can produce strongly compressed frequency-converted pulses in presence of group-velocity mismatch and group-velocity dispersion. Additionally, the proposed technique does not require pulse phase synchronization and effectively operates for strongly chirped pump pulses, thus enabling the use of longer nonlinear media for high conversion efficiency.     

Metal-organic frameworks exhibiting strong anion-pi interactions

Coordination polymers offer a significant potential for applications in adsorption, guest and anion recognition and sensing. Their structure commonly provides binding sites for such specific interactions as pi-pi stacking and XH...pi hydrogen bonding. The latter reflects the ability of the pi-cloud to interact with positively polarized atoms. An electrostatic interaction between anionic species and electron deficient heterocycles, which parallels the above binding scheme, is also possible and very recently the existence of anion-pi interactions was proved in the solid state and in solution. This effect may be significant also for biomolecule/solution interfaces, as it occurs in protein structures. In fact, such interactions could be especially relevant for host-guest chemistry of coordination polymers, particularly for functionalization of hydrophobic crystal cavities and for the design of geometrically rigid anion receptors. However, typical electron deficient heterocycles such as 1,3,5-triazines and 1,2,4,5-tetrazines are very weak donors and they are hardly suitable for bridging metal ions and the generation of coordination frameworks. As a system that combines efficient donor properties towards transition metal ions and a pronounced ability for anion-pi interactions we have developed unsubstituted pyridazino[4,5-d]pyridazine, which was readily accessible by a novel one-pot synthesis involving inverse electron demand Diels-Alder cycloaddition (Scheme 1). Unusual anion binding properties of the ligand may be clearly related to its electron-deficiency (LUMO energy -1.591 vs. -0.288 eV for the parent pyridazine), influenced also by N-coordination to such Lewis acids as metal ions.     

Probing the decay coordinate of the green fluorescent protein: arrest of cis-trans isomerization by the protein significantly narrows the fluorescence spectra

The fluorescence spectra of the wild-type green fluorescence protein (wt-GFP) and the anionic form of p-hydroxybenzylidenedimethylimidazolone (p-HBDI), which models the protein chromophore, were obtained in the 80-300 K temperature range in glycerol/water solvent. The protein spectra have pronounced and well-resolved vibronic structure, at least at lower temperatures. In contrast, the chromophore spectra are very broad and structureless even at the lowest temperatures. Analysis of the spectra shows that the experimentally observed red-shift of the protein spectrum upon heating is apparently caused by quadratic vibronic coupling of the torsional deformation (TD) of the phenyl single bond of the chromophore to the electronic transition. The broad spectra of the chromophore manifest the contribution of different conformations in the glycerol/water solvent. In particular, the lowest-temperature spectrum reflects the distribution over the same TD coordinate in the excited electronic state, which essentially contributes to the asymmetry of the spectrum. Upon heating, motion along this coordinate leads to a configuration from which the radiationless transition takes place. This narrows the distribution along the TD coordinate, causing a more symmetric fluorescence spectrum. We were able to reconstruct the broad, structureless fluorescence spectra of p-HBDI in glycerol/water solutions at various temperatures by convoluting the original wt-GFP spectra with the function describing the distribution of the transition energies of the p-HBDI chromophore. Thus, both the fluorescence broadening and increase in radiationless transition upon removal of the protein chromophore to bulk solvent are consistent with decay by a barrierless TD of the phenyl single bond.     

Turning on Solid‐State Fluorescence with Light

A bioinspired fluorophore that is analogous to the substrate in the bioluminescence of fireflies was prepared and reacts when exposed to weak blue LED light. Upon excitation, this material is photodecarboxylated with a nearly 81‐fold enhancement of the solid‐state emission, the fluorescence quantum yield of the product in solution is approximately 90 %, and violent disintegrative effects occur as a result of the release of carbon dioxide. Crystallographic and computational results, together with global spectral analysis of the kinetics, confirmed that most of the emission observed in the decay‐associated spectra is intrinsic to the product molecule, with only a minor contribution from an excimer through π–π stacking of the molecules in the crystal.