Translation Lattices by R.S. Pierce

By R.S. Pierce

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By R.S. Pierce

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The core of the macrocycle expands upon photoexcitation due to population of the 3 d x2-y2 , , orbital in the B,ig state, which would favor a planar conformation of the porphyrin in the excited state. The spectral evolution could then be accounted for by the conversion of ruffled conformers to the favored planar form in the excited state. A key experiment to test this suggestion is to monitor the excited state position v.. on the time scale of the spectral evolution observed by time-resolved absorption.

X. ■= 470 nm) and Hb('A ) (X. 2 ps, respectively. max Identical kinetics were observed with 307 nm or 580 nm pump pulses. It is unlikely that the broadening of o. arises from scattering contributions by herae electronic excited states. The yield of excited states is critically dependent on the absolute number of photons in the laser pulse relative to the number of molecules 1n the interrogated sample volume. In the 13 experiments with high laser fluence at 436 nm, -2 x 10 photons per 30 ps 12 pulse irradiated -5 x 10 molecules.

Experimentally observed the broadening and shifting of a heme vibrational mode subsequent to CO photolysis using 350 fs laser pulses. This behavior was attributed, in part, to vibrational heating of the heme. The recent experiments in our lab began in an attempt to use time-resolved resonance 43 Raman (RR) spectroscopy with -30 ps laser pulses to further examine this putative heating phenomenon in deoxy-Hb. , Classical molecular dynamics simulations have been conducted by Henry et 81 to predict the rate at which excess vibrational energy in the heme is dissipated into the protein matrix for myoglobin and cytochrome c.

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