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Title: Structural characterization of synthetic and protein-bound porphyrins in terms of the lowest-frequency normal coordinates of the macrocycle

Abstract

The X-ray crystal structures of synthetic and protein-bound metalloporphyrins are analyzed using a new normal structural decomposition method for classifying and quantifying their out-of-plane and in-plane distortions. These distortions are characterized in terms of equivalent displacements along the normal coordinates of the D{sub 4h}-symmetric porphyrin macrocycle (normal deformations). It is shown that the macrocyclic structure is, even in highly distorted porphyrins, accurately represented by displacements along only the lowest-frequency normal coordinates. Accordingly, the macrocyclic structure obtained from just the out-of-plane normal deformations of the saddling (sad, B{sub 2u})-, ruffling (ruf, B{sub 1u})-, doming (dom, A{sub 2u})-, waving [wav(x), wav(y); E{sub g}]-, and propellering (pro, A{sub 1u})-type essentially simulates the out-of-plane distortion of the X-ray crystal structure. Similarly, the observed in-plane distortions are decomposed into in-plane normal deformations corresponding to the lowest-frequency vibrational modes including macrocycle stretching in the direction of the meso-carbon atoms (meso-str, B{sub 2g}), stretching in the direction of the nitrogen atoms (N-str, B{sub 1g}), x and y pyrrole translations [trn(x), trn(y); E{sub u}], macrocycle breathing (bre, A{sub 1g}), and pyrrole rotation (rot, A{sub 2g}). 71 refs., 9 figs., 4 tabs.

Authors:
; ;  [1]
  1. Sandia National Lab., Albuquerque, NM (United States)
Publication Date:
OSTI Identifier:
505187
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical
Additional Journal Information:
Journal Volume: 101; Journal Issue: 9; Other Information: PBD: 27 Feb 1997
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; 99 MATHEMATICS, COMPUTERS, INFORMATION SCIENCE, MANAGEMENT, LAW, MISCELLANEOUS; PORPHYRINS; STRUCTURAL CHEMICAL ANALYSIS; NUMERICAL DATA; PROTEINS; X-RAY DIFFRACTION; CRYSTAL STRUCTURE; ORGANOMETALLIC COMPOUNDS; MATHEMATICAL MODELS; CALCULATION METHODS

Citation Formats

Jentzen, W, Song, X Z, Shelnutt, J A, and Univ. of New Mexico, Albuquerque, NM. Structural characterization of synthetic and protein-bound porphyrins in terms of the lowest-frequency normal coordinates of the macrocycle. United States: N. p., 1997. Web. doi:10.1021/jp963142h.
Jentzen, W, Song, X Z, Shelnutt, J A, & Univ. of New Mexico, Albuquerque, NM. Structural characterization of synthetic and protein-bound porphyrins in terms of the lowest-frequency normal coordinates of the macrocycle. United States. https://doi.org/10.1021/jp963142h
Jentzen, W, Song, X Z, Shelnutt, J A, and Univ. of New Mexico, Albuquerque, NM. 1997. "Structural characterization of synthetic and protein-bound porphyrins in terms of the lowest-frequency normal coordinates of the macrocycle". United States. https://doi.org/10.1021/jp963142h.
@article{osti_505187,
title = {Structural characterization of synthetic and protein-bound porphyrins in terms of the lowest-frequency normal coordinates of the macrocycle},
author = {Jentzen, W and Song, X Z and Shelnutt, J A and Univ. of New Mexico, Albuquerque, NM},
abstractNote = {The X-ray crystal structures of synthetic and protein-bound metalloporphyrins are analyzed using a new normal structural decomposition method for classifying and quantifying their out-of-plane and in-plane distortions. These distortions are characterized in terms of equivalent displacements along the normal coordinates of the D{sub 4h}-symmetric porphyrin macrocycle (normal deformations). It is shown that the macrocyclic structure is, even in highly distorted porphyrins, accurately represented by displacements along only the lowest-frequency normal coordinates. Accordingly, the macrocyclic structure obtained from just the out-of-plane normal deformations of the saddling (sad, B{sub 2u})-, ruffling (ruf, B{sub 1u})-, doming (dom, A{sub 2u})-, waving [wav(x), wav(y); E{sub g}]-, and propellering (pro, A{sub 1u})-type essentially simulates the out-of-plane distortion of the X-ray crystal structure. Similarly, the observed in-plane distortions are decomposed into in-plane normal deformations corresponding to the lowest-frequency vibrational modes including macrocycle stretching in the direction of the meso-carbon atoms (meso-str, B{sub 2g}), stretching in the direction of the nitrogen atoms (N-str, B{sub 1g}), x and y pyrrole translations [trn(x), trn(y); E{sub u}], macrocycle breathing (bre, A{sub 1g}), and pyrrole rotation (rot, A{sub 2g}). 71 refs., 9 figs., 4 tabs.},
doi = {10.1021/jp963142h},
url = {https://www.osti.gov/biblio/505187}, journal = {Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical},
number = 9,
volume = 101,
place = {United States},
year = {Thu Feb 27 00:00:00 EST 1997},
month = {Thu Feb 27 00:00:00 EST 1997}
}