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At least 19 recordsLinked to original sources

Innovative methods of energy transfer.

Energy is utilized in many forms for processing egg products and other foods. Energy in the form of heat has commonly been used to kill microorganisms and pasteurize eggs. Transfer of energy by convection and conduction is limited by the properties of the egg product. Energy transfer by radiation is being used to advantage in the development of innovative methods to kill or inactivate microorganisms. A review of the electromagnetic spectrum reveals underutilized forms of energy with unique properties. Specific frequencies and method of application are selected for their ability to focus energy toward the destruction of microorganisms and the production of safe food products for the public.

Animals↗

Energy imparted, energy transferred and net energy transferred.

The ICRU-defined non-stochastic quantity absorbed dose is related to the stochastic quantity energy imparted. In this paper the corresponding stochastic quantities energy transferred and net energy transferred are defined as precursors for kerma and collision kerma, respectively. This forms a rational fundamental framework for radiation dosimetry which facilitates its teaching and understanding.

Energy Transfer↗

Bioconjugated superstructures of CdTe nanowires and nanoparticles: multistep cascade Förster resonance energy transfer and energy channeling.

Nanoparticle/nanowire assemblies with a degree of radial organization were prepared around luminescent semiconducting CdTe nanowires using bioconjugation with streptavidin and D-biotin linkers. Red-emitting nanowires (6.62 +/- 1.55 nm diameter, 512 +/- 119 nm length) and green-emitting nanoparticles (3.2 +/- 0.7 nm diameter) were surface-modified with biotin, while orange-emitting nanoparticles (4.1 +/- 1.2 nm diameter) were decorated with streptavidin. CdTe nanocrystals produced two fuzzy layers around the nanowires in which the diameter of CdTe nanoparticles decreased with the distance from the nanowire axis. Förster resonance energy transfer (FRET) from the outside layer of nanoparticles to the central nanowire was observed for nanowires conjugated with 4.1 nm CdTe. Addition of 3.2 nm CdTe resulted in a red-orange-green optical progression with band gaps of CdTe decreasing toward the axis of the superstructure. In this case, 4-fold luminescence enhancement of the nanowire luminescence was observed and was attributed to multistep FRET. This observation indicated the accumulation of photogenerated excitons in the cascade terminal. A simple model of multiconjugated superstructure with cascade energy transfer is developed and used to describe and understand the experimental data. The experimental data and theoretical model suggest the possibility of utilization of the prepared superstructures with radial symmetry in several classes of optoelectronic devices including nanomaterials for energy collection. They can also be a convenient model object for the investigation of methods of energy funneling in nanoscale assemblies.

Biotin↗

Energy transfer between polyatomic molecules. 1. Gateway modes, energy transfer quantities and energy transfer probability density functions in benzene-benzene and Ar-benzene collisions.

We report collisional energy transfer, CET, quantities for polyatomic-polyatomic collisions and use excited benzene collisions with cold benzene bath, B-B, as our sample system and compare our results with the CET of excited benzene with Ar bath. We find that the gateway mode for both systems is the out-of-plane modes and that in B-B CET, vibration to vibration, V-V, is the dominant channel. Rotations play a mechanistic role in the CET but the net rotational energy transfer is small compared to V-V. The shape of the down side of the energy transfer probability density function, P(E,E'), is convex for B-B collisions and it becomes less so as the temperature increases. In Ar-B collisions, P(E,E') is concave and it becomes less so as the temperature decreases. We report average vibrational, rotational, and translational energy transferred, , as function of temperature for various initial conditions.

Journal Article↗

Monitoring receptor oligomerization using time-resolved fluorescence resonance energy transfer and bioluminescence resonance energy transfer. The human delta -opioid receptor displays constitutive oligomerization at the cell surface, which is not regulated by receptor occupancy.

Oligomerization of the human delta-opioid receptor and its regulation by ligand occupancy were explored following expression in HEK293 cells using each of co-immunoprecipitation of differentially epitope-tagged forms of the receptor, bioluminescence resonance energy transfer and time-resolved fluorescence resonance energy transfer. All of the approaches identified constitutively formed receptor oligomers, and the time-resolved fluorescence studies confirmed the presence of such homo-oligomers at the cell surface. Neither the agonist ligand [d-Ala(2),d-Leu(5)]enkephalin nor the inverse agonist ligand ICI174864 were able to modulate the oligomerization status of this receptor. Interactions between co-expressed delta-opioid receptors and beta(2)-adrenoreceptors were observed in co-immunoprecipitation studies. Such hetero-oligomers could also be detected using bioluminescence resonance energy transfer although the signal obtained was substantially smaller than for homo-oligomers of either receptor type. Signal corresponding to the delta-opioid receptor-beta(2)-adrenoreceptor hetero-oligomer was increased in the presence of agonist for either receptor. However, substantial levels of this hetero-oligomer were not detected at the cell surface using time-resolved fluorescence resonance energy transfer. These studies demonstrate that, following transient transfection of HEK293 cells, constitutively formed oligomers of the human delta-opioid receptor can be detected by a variety of approaches. However, these are not regulated by ligand occupancy. They also indicate that time-resolved fluorescence resonance energy transfer represents a means to detect such oligomers at the cell surface in populations of intact cells.

Blotting, Western↗

Characterization of light-harvesting mutants of Rhodopseudomonas sphaeroides. I. Measurement of the efficiency of energy transfer from light-harvesting complexes to the reaction center.

Light-harvesting mutants of Rhodopseudomonas sphaeroides lacking either the B800-850 complex or the B875 complex have been characterized by their absorption spectra in the visible and near-infrared region, and by their ability to transfer energy from the light-harvesting complexes to the reaction center. A new method of measuring the relative efficiency of energy transfer from the light-harvesting complexes to the reaction center is described. The B875- mutant had absorption maxima in the near-infrared at 800 and 849 nm with no evidence of an 875-nm shoulder. The efficiency of energy transfer from the light-harvesting complexes to the reaction center in the B875- mutant was 24% of the value measured for the wild-type strain and the B800-850- mutant. Yet, despite the fact that the efficiency of energy transfer for the B800-850- mutant and the wild-type strain were the same, there was a large difference in their photosynthetic unit size. These results are discussed in the context of a model in which light energy captured by the B800-850 complexes is transferred through the B875 complexes to the reaction center.

Bacterial Proteins↗

Energy transfer between polyatomic molecules II: Energy transfer quantities and probability density functions in benzene, toluene, p-xylene, and azulene collisions.

Collisional energy transfer, CET, is of major importance in chemical, photochemical, and photophysical processes in the gas phase. In Paper I of this series (J. Phys. Chem. B 2005, 109, 8310) we have reported on the mechanism and quantities of CET between an excited benzene and cold benzene and Ar bath. In the present work, we report on CET between excited toluene, p-xylene, and azulene with cold benzene and Ar and on CET of excited benzene with cold toluene, p-xylene, and azulene. We compare our results with those of Paper I and report average vibrational, rotational, and translational energy quantities, , transferred in a single collision. We discuss the effect of internal rotation on CET and the identity of the gateway modes in CET and the relative role of vibrational, rotational, and translational energies in the CET process, all that as a function of temperature and excitation energy. Energy transfer probability density functions, P(E,E'), for the various systems are reported and the shape of the curves for various systems and initial conditions is discussed. The major findings for polyatomic-polyatomic collisions are: CET takes place mainly via vibration-to-vibration energy transfer assisted by overall rotations. Internal free rotors in the excited molecule hinder energy exchange while in the bath molecule they do not. Energy transfer at low temperatures and high temperatures is more efficient than that at intermediate temperatures. Low-frequency modes are the gateway modes for energy transfer. Vibrational temperatures affect energy transfer. The CET probability density function, P(E,E'), is convex at low temperatures and can be concave at high temperatures. A mechanism that explains the high values of and the convex shape of P(E,E') is that in addition to short impulsive collisions there are chattering collisions where energy is transferred in a sequence of short encounters during the lifetime of the collision complex. This also leads to the observed supercollision tail at the down wing of P(E,E'). Polyatomic-Ar collisions show mechanistic similarities to polyatomic-polyatomic collisions, but there are also many dissimilarities: internal rotations do not inhibit energy transfer, P(E,E') is concave at all temperatures, and there is no contribution of chattering collisions.

Journal Article↗

Energy transfer between polyatomic molecules. 3. Energy transfer quantities and probability density functions in self-collisions of benzene, toluene, p-xylene and azulene.

This paper is the third and last in a series of papers that deal with collisional energy transfer, CET, between aromatic polyatomic molecules. Paper 1 of this series (J. Phys. Chem. B 2005, 109, 8310) reports on the mechanism and quantities of CET between an excited benzene and cold benzene and Ar bath. Paper 2 in the series (J. Phys. Chem., in press) discusses CET between excited toluene, p-xylene and azulene with cold benzene and Ar and CET between excited benzene colliding with cold toluene, p-xylene and azulene. The present work reports on CET in self-collisions of benzene, toluene, p-xylene and azulene. Two modes of excitation are considered, identical excitation energies and identical vibrational temperatures for all four molecules. It compares the present results with those of papers 1 and 2 and reports new findings on average vibrational, rotational, and translational energy, , transferred in a single collision. CET takes place mainly via vibration to vibration energy transfer. The effect of internal rotors on CET is discussed and CET quantities are reported as a function of temperature and excitation energy. It is found that the temperature dependence of CET quantities is unexpected, resembling a parabolic function. The density of vibrational states is reported and its effect on CET is discussed. Energy transfer probability density functions, P(E,E'), for various collision pairs are reported and it is shown that the shape of the curves is convex at low temperatures and can be concave at high temperatures. There is a large supercollision tail at the down wing of P(E,E'). The mechanisms of CET are short, impulsive collisions and long-lived chattering collisions where energy is transferred in a sequence of short internal encounters during the lifetime of the collision complex. The collision complex lifetimes as a function of temperature are reported. It is shown that dynamical effects control CET. A comparison is made with experimental results and it is shown that good agreement is obtained.

Journal Article↗

Energy transfer (deazaflavin-->FADH2) and electron transfer (FADH2-->T <> T) kinetics in Anacystis nidulans photolyase.

DNA photolyases catalyze the photocycloreversion of cyclobutane pyrimidine dimers. The enzyme from the cyanobacterium Anacystis nidulans contains two chromophores, 1,5-dihydroflavin adenine dinucleotide (FADH2) and 7,8-didemethyl-8-hydroxy-5-deazariboflavin (8-HDF). The photophysical/photochemical reactions leading to DNA repair were investigated by using time-resolved and steady-state fluorescence spectroscopy. It was found that the excited singlet state of 8-HDF transfers energy to FADH2 at a rate of 1.9 x 10(10) s-1 and a quantum yield of 0.98. Using the Forster equation for long-range energy transfer and assuming random orientations of the donor and acceptor the interchromophore distance was calculated to be 15 A. The excited singlet FADH2 which forms either by energy transfer from 8-HDF or by direct absorption of a photon has a lifetime of 1.8 ns in the absence of substrate and 0.14 ns in the presence of the photodimer indicating electron transfer from the FADH2 excited singlet state to the dimer at a rate of 6.5 x 10(9) s-1 and quantum efficiency of 92%.

Cyanobacteria↗

Correlations of structure and rates of energy transfer for through-bond energy-transfer cassettes.

Fluorescent DNA-labeling cassettes are designed to have a common absorbing chromophore matched to a single exciting laser wavelength, but up to four different emitters. Experiments reported here have examined the energy-transfer rates and fluorescence polarization characteristics for two different types of cassette, involving three distinct relative orientations of the donor and acceptor transition moments and the axis of the rigid linker. Energy-transfer times range from <200 fs to approximately 20 ps, the fastest transfer times occurring when the transition moments of the donor and acceptor species are aligned parallel to the linker axis. Experimental evidence is presented that supports a through-bond energy-transfer mechanism, in contrast with a commercial DNA-labeling agent, which exhibits much slower transfer times controlled by FRET. These rigid cassettes also exhibit polarized fluorescence from the acceptor species, so that this particular type of DNA-labeling probe has some of the advantages of single-molecule probes such as rhodamine and coumarin dyes.

DNA Probes↗

CK flux or direct ATP transfer: versatility of energy transfer pathways evidenced by NMR in the perfused heart.

How the myocardium is able to permanently coordinate its intracellular fluxes of ATP synthesis, transfer and utilization is difficult to investigate in the whole organ due to the cellular complexity. The adult myocardium represents a paradigm of an energetically compartmented cell since 50% of total CK activity is bound in the vicinity of other enzymes (myofibrillar sarcolemmal and sarcoplasmic reticulum ATPases as well as mitochondrial adenine nucleotide translocator, ANT). Such vicinity of enzymes is well known in vitro as well as in preparations of skinned fibers to influence the kinetic properties of these enzymes and thus the functioning of the subcellular organelles. Intracellular compartmentation has often been neglected in the NMR analysis of CK kinetics in the whole organ. It is indeed a methodological challenge to reveal subcellular kinetics in a working organ by a global approach such as NMR. To get insight in the energy transfer pathway in the perfused rat heart, we developed a combined analysis of several protocols of magnetization transfer associated with biochemical data and quantitatively evaluated which scheme of energetic exchange best describes the NMR data. This allows to show the kinetic compartmentation of subcellular CKs and to quantify their fluxes. Interestingly, we could show that the energy transfer pathway shifts from the phosphocreatine shuttle in the oxygenated perfused heart to a direct ATP diffusion from mitochondria to cytosol under moderate inhibition of ATP synthesis. Furthermore using NMR measured fluxes and the known kinetic properties of the enzymes, it is possible to model the system, estimate local ADP concentrations and propose hypothesis for the versatility of energy transfer pathway. In the normoxic heart, a 3-fold ADP gradient was found between mitochondrial intermembrane space, cytosol and ADP in the vicinity of ATPases. The shift from PCr to ATP transport observed when ATP synthesis decreases might result from a balance in the activity of two populations of ANT, either coupled or uncoupled to CK. We believe this NMR approach could be a valuable tool to reinvestigate the control of respiration by ADP in the whole heart reconciling the biochemical knowledge of mitochondrial obtained in vitro or in skinned fibers with data on the whole heart as well as to identify the implication of bioenergetics in the pathological heart.

Adenosine Triphosphate↗

Determination of rates and yields of interchromophore (folate----flavin) energy transfer and intermolecular (flavin----DNA) electron transfer in Escherichia coli photolyase by time-resolved fluorescence and absorption spectroscopy.

Escherichia coli DNA photolyase, which photorepairs cyclobutane pyrimidine dimers, contains two chromophore cofactors, 1,5-dihydroflavin adenine dinucleotide (FADH2) and 5,10-methenyltetrahydrofolate (MTHF). Previous work has shown that MTHF is the primary photoreceptor which transfers energy to the FADH2 cofactor; the FADH2 singlet excited state then repairs the photodimer by electron transfer. In this study, we have determined the rate constants for these photophysical processes by time-resolved fluorescence and absorption spectroscopy. From time-resolved fluorescence, we find that energy transfer from MTHF to FADH2 and FADH degrees occurs at rates of 4.6 x 10(9) and 3.0 x 10(10) s-1, respectively, and electron transfer from FADH2 to a pyrimidine dimer occurs at a rate of 5.5 x 10(9) s-1. Using Förster theory for long-range energy transfer and assuming K2 = 2/3, the interchromophore distances were estimated to be 22 A in the case of the MTHF-FADH2 pair and 21 A for the MTHF-FADH degrees pair. Picosecond absorption spectroscopy identified an MTHF single state which decays to yield the first excited singlet state of FADH2. The lifetimes of MTHF and FADH2 singlets and the rates of interchromophore energy transfer, as well as the rate of electron transfer from FADH2 to DNA measured by time-resolved fluorescence, were in excellent agreement with the values obtained by picosecond laser flash photolysis. Similarly, fluorescence or absorption lifetime studies of the folate-depleted enzyme with and without photodimer suggest that FADH2, in its singlet excited state, transfers an electron to the dimer with 89% efficiency. The distance between FADH2 and the photodimer was calculated to be ca. 14 A.

Apoenzymes↗

Photoluminescence of europium(III) dithiocarbamate complexes: electronic structure, charge transfer and energy transfer.

For the first time, we observed photoluminescence in Eu(III) dithiocarbamate complexes at room temperature -- more specifically in [Eu(Et(2)NCS(2))(3)phen], [Eu(Et(2)NCS(2))(3)bpy] and the novel [Eu(Ph(2)NCS(2))(3)phen], where phen stands for 1,10-phenanthroline and bpy for 2,2'-bipyridine. Correlations between the electronic structure of the dithiocarbamate ligands on one hand, and covalency, intensity, and ligand field spectroscopic parameters on the other, could be established. Moreover, the relative values of the emission quantum efficiencies obtained for these complexes, as well as their dependence with temperature, could be satisfactorily described by a theoretical methodology recently developed.

Journal Article↗

Novel U-Shaped Systems Containing an Imide-Functionalized Cleft for the Study of Solvent-Mediated Electron Transfer and Energy Transfer: Synthesis and Binding Studies.

A solution to the vexing problem of investigating solvent-mediated electron transfer under conditions of frozen solvent motion may be at hand with the synthesis of novel U-shaped systems such as 1 (R=CO(2)Me) and 2 (R=CH(2)OMe), in which the imide-functionalized cleft provides the point of attachment of the "solvent" molecule, either covalently or by hydrogen bonding.

Journal Article↗

Photoinduced intramolecular electron transfer and triplet energy transfer in a steroid-linked norbornadiene-carbazole dyad.

Bichromophoric compound 3 beta-((2-(methoxycarbonyl)bicyclo[2.2.1]hepta-2,5-diene-3-yl)carboxy)androst-5-en-17 beta-yl-[2-(N-carbazolyl)acetate] (NBD-S-CZ) was synthesized and its photochemistry was examined by fluorescence quenching, flash photolysis, and chemically induced dynamic nuclear polarization (CIDNP) methods. Fluorescence quenching measurements show that intramolecular electron transfer from the singlet excited state of the carbazole to the norbornadiene group in NBD-S-CZ occurs with an efficiency (Phi SET) of about 14 % and rate constant (kSET) of about 1.6 x 10(7) s-1. Phosphorescence and flash photolysis studies reveal that intramolecular triplet energy transfer and electron transfer from the triplet carbazole to the norbornadiene group proceed with an efficiency (TET + TT) of about 52 % and rate constant (kTET + kTT) of about 3.3 x 10(5) s-1. Upon selective excitation of the carbazole chromophore, nuclear polarization is detected for protons of the norbornadiene group (emission) and its quadricyclane isomer (enhanced absorption); this suggests that the isomerization of the norbornadiene group to the quadricyclane proceeds by a radical-ion pair recombination mechanism in addition to intramolecular triplet sensitization. The long-distance intramolecular triplet energy transfer and electron transfers starting both from the singlet and triplet excited states are proposed to proceed by a through-bond mechanism.

Androstenes↗

Energy transfer in artificial membrane systems. Singlet-singlet energy transfer from alloxazines to isolloxazines in dipamitoyl phosphatidylcholine liposomes and dialkylammonium chloride vesicles.

The singlet-singlet energy transfer from alloxazines to isoalloxazines has been investigated in dialmitoyl phosphatidylcholine (DPPC) liposomes and dioctadecyltrimethylammonium chloride (2C18NC) vesicles to clarify the role of the artificial membranes in the energy transfer phenomenon. The structures of the artificial membranes were divided into two types: the single-walled (sonicated DPPC) and the multi-compartment vesicles (unsonicated DPPC and sonicated 2C18NC). In the DPPC single-walled liposomes, the energy of the donor lost by quenching is efficiently transferred to the acceptor via the Förster-type dipoledipole interaction. In the case of multi-compartment liposomes of DPPC, the mean distance between donor and acceptor is so small because the external surface of a bilayer is in the vicinity of the internal surface of another bilayer. As a consequence, efficiencies both of energy transfer and of energy loss were greater than those in single-walled liposomes. The fluid property of the 2C18NC bilayer allowed the preferential collisional quenching. The marked reduction in the efficiencies of both energy transfer and energy loss were attributed to the elongation of donor-acceptor distances due to the increase of the size of liposome.

Energy Transfer↗

Luminescence energy transfer using a terbium chelate: improvements on fluorescence energy transfer.

We extend the technique of fluorescence resonance energy transfer (FRET) by introducing a luminescent terbium chelate as a donor and an organic dye, tetramethylrhodamine, as an acceptor. The results are consistent with a Förster theory of energy transfer, provided the appropriate parameters are used. The use of lanthanide donors, in general, and this pair, in particular, has many advantages over more conventional FRET pairs, which rely solely on organic dyes. The distance at which 50% energy transfer occurs is large, 65 A; the donor lifetime is a single exponential and long (millisecond), making lifetime measurements facile and accurate. Uncertainty in the orientation factor, which creates uncertainty in measured distances, is minimized by the donor's multiple electronic transitions and long lifetime. The sensitized emission of the acceptor can be measured with little or no interfering background, yielding a > 25-fold improvements in the signal-to-background ratio over standard donor-acceptor pairs. These improvements are expected to make distances > 100 A measurable via FRET. We also report measurement of the sensitized emission lifetime, a measurement that is completely insensitive to total concentration and incomplete labeling.

Base Sequence↗

Alpha-crystallin/lens lipid interactions using resonance energy transfer.

Resonance energy transfer was used to study the interaction of alpha-crystallin with lens cortex lipid vesicles. The binding of alpha-crystallin to cortex lipid vesicles and the preincubation temperature dependence of the binding were confirmed. In this study, the tryptophan of alpha-crystallin was used as the energy donor, and the fluorescence probe N-(5-dimethylaminonaphthalene-1-sulfonyl)-1, 2-dihexadecanoyl-sn-glycero-3-phosphoethanolamine triethylammonium salt (dansyl DHPE) was chosen as the energy acceptor. Lens cortex lipid vesicles were preincorporated with dansyl DHPE. Energy transfer from the tryptophan of alpha-crystallin to dansyl DHPE was found and the energy transfer efficiency was calculated. There was a higher energy transfer efficiency between alpha-crystallin and dansyl DHPE when alpha-crystallin was preincubated at 65 degrees C compared to 22 degrees C. Data confirmed the binding of alpha-crystallin to lens cortex lipid and showed that alpha-crystallin bound more closely to the surface of cortex vesicles when it was preincubated at a higher temperature. This is probably due to the exposure of hydrophobic surfaces when alpha-crystallin is preincubated at a higher temperature.

Absorption↗