NDLI: Vibrational circular dichroism measurements of ligand vibrations in haem and non-haem metalloenzymes

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Faraday Discussions Vol -197

Faraday Discussions Vol -99

Front cover

Contents pages

Introductory lecture. The theoretical background to vibrational optical activity

Comparison of IR and Raman forms of vibrational optical activity

Recent developments in Raman optical activity instrumentation

Intramolecular energy transfer and vibrational redistribution in chiral molecules: experiment and theory

Vibrational circular dichroism of the OH-stretching vibration in 2,2′-dihydroxy-1,1′-binaphthyl

General discussion ( Faraday Discussions Vol -99 )

Theoretical calculation of vibrational circular dichroism spectra

Basis set convergence and correlation effects in vibrational circular dichroism calculations using London atomic orbitals

Vibrational circular dichroism in ephedra molecules. Experimental measurement and ab initio calculation

Structural determinations using vibrational Raman optical activity: from a single peptide group to β-turns

Vibrational Raman optical activity calculations using London atomic orbitals

Understanding normal modes of proteins

General discussion ( Faraday Discussions Vol -99 )

Vibrational Raman optical activity of biopolymers

IR circular dichroism of turns in small peptides

Contributions of tryptophan side chains to the circular dichroism of globular proteins: exciton couplets and coupled oscillators

Empirical studies of protein secondary structure by vibrational circular dichroism and related techniques. α-Lactalbumin and lysozyme as examples

Quantitative analysis of vibrational circular dichroism spectra of proteins. Problems and perspectives

General discussion ( Faraday Discussions Vol -99 )

Vibrational circular dichroism measurements of ligand vibrations in haem and non-haem metalloenzymes

Consequences of chirality in second-order non-linear spectroscopy at surfaces

Reflective optical activity

Electric-field optical activity, Rayleigh optical activity and the measurement of superpositions of chiral amplitudes

Two-group Raman optical activity revisited

General discussion ( Faraday Discussions Vol -99 )

Summary and forward look

List of posters

List of participants

Index of contributors

General Discussions of the Faraday Society/Faraday Discussions of the Chemical Society

Vibrational circular dichroism measurements of ligand vibrations in haem and non-haem metalloenzymes

Content Provider	Royal Society of Chemistry (RSC)
Author	Asher, Sanford A. Smith, Gregory D. Kurtz, Donald M. Bormett, Richard W. Barrick, Doug
Copyright Year	1994
Abstract	We have measured the vibrational circular dichroism (VCD) spectra of the stretching vibrations of azide and cyanide ligated to the Fe3+ atoms of haemoglobin (Hb) and myoglobin (Mb). The antisymmetric azide-stretch of the low-spin haems have an anomalously large g-value of ca.–1 × 10–3. In contrast, CN– has a g-value of ca.+2.4 × 10–3. We also show, for the first time, that a significant VCD occurs for the azide ligand antisymmetric stretches of non-haem proteins; we measure a g-value of ca.–1 × 10–4 for azide bound to haemerythrin. We have examined the mechanism of the VCD phenomenon by: (1) reconstituting Mb with haems substituted such that they insert differently in the haem pocket; (2) replacing the Fe3+ with Mn3+; (3) examining proteins where replacements occur for E-7 His and E-11 Val distal amino acids close to the haem and (4) examining an Mb mutant where the proximal F-8 His is replaced by Gly, and where an imidazole ligand inserts into the resulting crevice and binds to the haem in a way similar to that of the proximal histidine in the native protein. The VCD anisotropy appears insensitive to the haem substituent replacements used in this study. Exchange of the E-7 distal His or the E-11 Val has a dramatic effect on the g-value. Exchange of the F-8 proximal His reverses the sign of the g-value for the azide complex, but not for the cyanide complex. The work to date indicates that VCD has the potential to become a sensitive technique for examining the structure of metalloenzymes. Work is needed to determine the mechanism giving rise to the large g-values and to correlate the VCD spectrum with the metalloenzyme structure at the active site.
Starting Page	327
Ending Page	339
Page Count	13
File Format	PDF
ISSN	13596640
Volume Number	99
Journal	Faraday Discussions
DOI	10.1039/FD9949900327
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Vibrational circular dichroism Video CD Azide Cyanide Hemoglobin Myoglobin Ligand Hemerythrin Heme Mutation Vought F-8 Crusader Imidazole Histidine Protein Anisotropy Substituent Metalloprotein Active site
Content Type	Text
Resource Type	Article
Subject	Physics and Astronomy Physical and Theoretical Chemistry

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Faraday Discuss., 1994,99,327-339 Vibrational Circular Dichroism Measurements of Ligand Vibrations in Haem and Non-haem Metalloenzymes

Characterization of haem disorder by circular dichroism.

Selective Examination of Heme Protein Azide Ligand-Distal Globin Interactions by Vibrational Circular Dichroism

MD Simulations of Carbonmonoxy Myoglobin and Calculations of Heme CD

Unusual flexibility of distal and proximal histidine residues in the haem pocket of Drosophila melanogaster haemoglobin

Significantly enhanced heme retention ability of myoglobin engineered to mimic the third covalent linkage by nonaxial histidine to heme (vinyl) in synechocystis hemoglobin.

Assignment of the heme axial ligand(s) for the ferric myoglobin (h93g) and heme oxygenase (h25a) cavity mutants as oxygen donors using magnetic circular dichroism† (1998).

Assignment of the heme axial ligand(s) for the ferric myoglobin (H93G) and heme oxygenase (H25A) cavity mutants as oxygen donors using magnetic circular dichroism. Biochemistry (1999)

Vibrational dephasing of carbonmonoxy myoglobin (2001).

Vibrational circular dichroism measurements of ligand vibrations in haem and non-haem metalloenzymes

Similar Documents

Faraday Discuss., 1994,99,327-339 Vibrational Circular Dichroism Measurements of Ligand Vibrations in Haem and Non-haem Metalloenzymes

Characterization of haem disorder by circular dichroism.

Selective Examination of Heme Protein Azide Ligand-Distal Globin Interactions by Vibrational Circular Dichroism

MD Simulations of Carbonmonoxy Myoglobin and Calculations of Heme CD

Unusual flexibility of distal and proximal histidine residues in the haem pocket of Drosophila melanogaster haemoglobin

Significantly enhanced heme retention ability of myoglobin engineered to mimic the third covalent linkage by nonaxial histidine to heme (vinyl) in synechocystis hemoglobin.

Assignment of the heme axial ligand(s) for the ferric myoglobin (h93g) and heme oxygenase (h25a) cavity mutants as oxygen donors using magnetic circular dichroism† (1998).

Assignment of the heme axial ligand(s) for the ferric myoglobin (H93G) and heme oxygenase (H25A) cavity mutants as oxygen donors using magnetic circular dichroism. Biochemistry (1999)

Vibrational dephasing of carbonmonoxy myoglobin (2001).

Vibrational circular dichroism measurements of ligand vibrations in haem and non-haem metalloenzymes