Time-Resolved Single Tryptophan Fluorescence in Photoactive Yellow Protein Monitors Changes in the Chromophore Structure during the Photocycle via Energy Transfer†

Biochemistry ◽  
2005 ◽  
Vol 44 (51) ◽  
pp. 16804-16816 ◽  
Author(s):  
Harald Otto ◽  
Daniel Hoersch ◽  
Terry E. Meyer ◽  
Michael A. Cusanovich ◽  
Maarten P. Heyn
Keyword(s):  
Energy Transfer ◽  
Tryptophan Fluorescence ◽  
Photoactive Yellow Protein ◽  
Time Resolved

scholarly journals Time-Resolved Measurements and Master Equation Modelling of the Unimolecular Decomposition of CH3OCH2

2020 ◽  
Vol 234 (7-9) ◽  
pp. 1233-1250 ◽  
Author(s):  
Arrke J. Eskola ◽  
Mark A. Blitz ◽  
Michael J. Pilling ◽  
Paul W. Seakins ◽  
Robin J. Shannon
Keyword(s):  
Energy Transfer ◽  
Master Equation ◽  
Rate Coefficient ◽  
Zero Point ◽  
Buffer Gas ◽  
Unimolecular Decomposition ◽  
Time Resolved ◽  
Point Energy ◽  
Wide Range ◽  
Transfer Parameters

AbstractThe rate coefficient for the unimolecular decomposition of CH3OCH2, k1, has been measured in time-resolved experiments by monitoring the HCHO product. CH3OCH2 was rapidly and cleanly generated by 248 nm excimer photolysis of oxalyl chloride, (ClCO)2, in an excess of CH3OCH3, and an excimer pumped dye laser tuned to 353.16 nm was used to probe HCHO via laser induced fluorescence. k1(T,p) was measured over the ranges: 573–673 K and 0.1–4.3 × 1018 molecule cm−3 with a helium bath gas. In addition, some experiments were carried out with nitrogen as the bath gas. Ab initio calculations on CH3OCH2 decomposition were carried out and a transition-state for decomposition to CH3 and H2CO was identified. This information was used in a master equation rate calculation, using the MESMER code, where the zero-point-energy corrected barrier to reaction, ΔE0,1, and the energy transfer parameters, ⟨ΔEdown⟩ × Tn, were the adjusted parameters to best fit the experimental data, with helium as the buffer gas. The data were combined with earlier measurements by Loucks and Laidler (Can J. Chem.1967, 45, 2767), with dimethyl ether as the third body, reinterpreted using current literature for the rate coefficient for recombination of CH3OCH2. This analysis returned ΔE0,1 = (112.3 ± 0.6) kJ mol−1, and leads to $k_{1}^{\infty}(T)=2.9\times{10^{12}}$ (T/300)2.5 exp(−106.8 kJ mol−1/RT). Using this model, limited experiments with nitrogen as the bath gas allowed N2 energy transfer parameters to be identified and then further MESMER simulations were carried out, where N2 was the buffer gas, to generate k1(T,p) over a wide range of conditions: 300–1000 K and N2 = 1012–1025 molecule cm−3. The resulting k1(T,p) has been parameterized using a Troe-expression, so that they can be readily be incorporated into combustion models. In addition, k1(T,p) has been parametrized using PLOG for the buffer gases, He, CH3OCH3 and N2.

Synthesis and Photophysical Properties of a Conformationally Flexible Mixed Porphyrin Star-Pentamer

2009 ◽  
Vol 62 (7) ◽  
pp. 692 ◽  
Author(s):  
Toby D. M. Bell ◽  
Sheshanath V. Bhosale ◽  
Kenneth P. Ghiggino ◽  
Steven J. Langford ◽  
Clint P. Woodward
Keyword(s):  
Energy Transfer ◽  
Photophysical Properties ◽  
Fluorescence Decay ◽  
High Yield ◽  
Free Base ◽  
Time Resolved ◽  
Zinc Porphyrin ◽  
Relative Contribution ◽  
Synthetic Strategy ◽  
Decay Times

The synthesis of a porphyrin star-pentamer bearing a free-base porphyrin core and four zinc(ii) metalloporphyrins, which are tethered by a conformationally flexible linker about the central porphyrin’s antipody, is described. The synthetic strategy is highlighted by the use of olefin cross metathesis to link the five chromophores together in a directed fashion in high yield. Photoexcitation into the Soret absorption band of the zinc porphyrin chromophores at 425 nm leads to a substantial enhancement of central free-base porphyrin fluorescence, indicating energy transfer from the photoexcited zinc porphyrin (outer periphery) to central free-base porphyrin. Time-resolved fluorescence decay profiles required three exponential decay components for satisfactory fitting. These are attributed to emission from the central free-base porphyrin and to two different rates of energy transfer from the zinc porphyrins to the free-base porphyrin. The faster of these decay components equates to an energy-transfer rate constant of 3.7 × 109 s–1 and an efficiency of 83%, whereas the other is essentially unquenched with respect to reported values for zinc porphyrin fluorescence decay times. The relative contribution of these two components to the initial fluorescence decay is ~3:2, similar to the 5:4 ratio of cis and trans geometric isomers present in the pentamer.

scholarly journals Horizontal versus vertical charge and energy transfer in hybrid assemblies of semiconductor nanoparticles

2012 ◽  
Vol 3 ◽  
pp. 629-636 ◽  
Author(s):  
Gilad Gotesman ◽  
Rahamim Guliamov ◽  
Ron Naaman
Keyword(s):  
Energy Transfer ◽  
Charge Transfer ◽  
Horizontal Plane ◽  
Quartz Substrate ◽  
Vertical Direction ◽  
Time Resolved ◽  
Transfer Processes ◽  
Donor And Acceptor ◽  
Hybrid Assemblies ◽  
Time Resolved Photoluminescence

We studied the photoluminescence and time-resolved photoluminescence from self-assembled bilayers of donor and acceptor nanoparticles (NPs) adsorbed on a quartz substrate through organic linkers. Charge and energy transfer processes within the assemblies were investigated as a function of the length of the dithiolated linker (DT) between the donors and acceptors. We found an unusual linker-length-dependency in the emission of the donors. This dependency may be explained by charge and energy transfer processes in the vertical direction (from the donors to the acceptors) that depend strongly on charge transfer processes occurring in the horizontal plane (within the monolayer of the acceptor), namely, parallel to the substrate.

Time-resolved studies of state-to-state vibrational energy transfer: I2(B3IIou+:v′ = 19) + He

2010 ◽  
Vol 9 (2) ◽  
pp. 102-108 ◽  
Author(s):  
Tian-Xiang Xiang ◽  
Sheng Sun ◽  
Shun-Sheng Gong ◽  
Jia-Min Wang
Keyword(s):  
Energy Transfer ◽  
Vibrational Energy ◽  
Vibrational Energy Transfer ◽  
Time Resolved

Luminescence and Time-Resolved Infrared Study of Dyads Containing (Diimine)Ru(4,4′-diethylamido-2,2′-bipyridine)2and (Diimine)Ru(CN)4Moieties: Solvent-Induced Reversal of the Direction of Photoinduced Energy-Transfer

2009 ◽  
Vol 48 (18) ◽  
pp. 8759-8770 ◽  
Author(s):  
Timothy L. Easun ◽  
Wassim Z. Alsindi ◽  
Nina Deppermann ◽  
Michael Towrie ◽  
Kate L. Ronayne ◽  
...  
Keyword(s):  
Energy Transfer ◽  
Infrared Study ◽  
Time Resolved
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