Link to the University of Pittsburgh Homepage
Link to the University Library System Homepage Link to the Contact Us Form

UV resonance Raman studies of cis-to-trans isomerization of glycyglycine derivatives

Holtz, JSW and Li, P and Asher, SA (1999) UV resonance Raman studies of cis-to-trans isomerization of glycyglycine derivatives. Journal of the American Chemical Society, 121 (15). 3762 - 3766. ISSN 0002-7863

[img] Plain Text (licence)
Available under License : See the attached license file.

Download (1kB)

Abstract

We report kinetic UV resonance Raman measurements of the pH dependence of the activation barrier for the trans-cis isomerization of glycylglycine (Gly-Gly). We determined the charge-state dependence of the trans-cis ground- state energy difference, ΔG, and the trans-cis isomerization activation barrier, E(a). ΔG for zwitterionic Gly-Gly at pH 5.7 (3.0 ± 0.5 kcal/mol) is below that of pH 10.5 anionic Gly-Gly (4.4 ± 0.7 kcal/mol). The measured value of ΔG for cationic Gly-Gly at pH 3.0 (3.6 ± 0.4 kcal/mol) lies between the zwitterion and anion values. The measured trans-to-cis activation barriers of 13.3 ± 1.0, 12.6 ± 0.9, and 13.9 ± 1.1 kcal/mol for the cation, the zwitterion, and the anion, respectively, are identical within experimental error. However, the larger zwitterionic Gly-Gly (13 ± 1.9 s-1) cis-to-trans isomerization rate constant over those of the cation (3 ± 0.4 s-1) and anion (2 ± 0.3 s-1) suggests a ~1 kcal/mol decreased activation barrier. The small differences in energy and activation barriers are somewhat surprising since the zwitterionic form can uniquely form ion pairs, which should impact the trans, the cis, and the activated complex energies.


Share

Citation/Export:
Social Networking:
Share |

Details

Item Type: Article
Status: Published
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Holtz, JSW
Li, P
Asher, SAasher@pitt.eduASHER
Date: 21 April 1999
Date Type: Publication
Journal or Publication Title: Journal of the American Chemical Society
Volume: 121
Number: 15
Page Range: 3762 - 3766
DOI or Unique Handle: 10.1021/ja984003b
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Refereed: Yes
ISSN: 0002-7863
Date Deposited: 20 Mar 2013 16:41
Last Modified: 02 Feb 2019 16:55
URI: http://d-scholarship.pitt.edu/id/eprint/17809

Metrics

Monthly Views for the past 3 years

Plum Analytics

Altmetric.com


Actions (login required)

View Item View Item