Theoretical studies of structure and racemization mechanism of aspartate-intercalated hydrotalcite

Theoretical studies of structure and racemization mechanism of aspartate-intercalated hydrotalcite The structure and racemization mechanism of l-aspartic acid (l-ASP) and l-ASP-intercalated layered double hydroxide (l-ASP-LDH, with intercalated magnesium–aluminum hydrotalcite as the LDH), were theoretically studied using the B3LYP and PW91 method of density functional theory at 6-31G(d,p) and Lanl2dz level, respectively. The structural parameters obtained for l-ASP-LDH are in agreement with experimental data for materials, indicating that this theoretical method is appropriate for the hydrotalcite system. The computational results show that enantiomerism of l-ASP is difficult in the ground state due to high energy barriers, while in the excited state l-ASP can easily transform to d-ASP via proton transfer from the chiral carbon atom to the carbonyl oxygen atom, where the carbonyl oxygen atom plays a role as a medium for proton migration. In addition, hydrotalcite could inhibit racemization of l-ASP because the combination of the oxygen atom and hydrotalcite layers hindered proton movement. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Research on Chemical Intermediates Springer Journals

Theoretical studies of structure and racemization mechanism of aspartate-intercalated hydrotalcite

Loading next page...
 
/lp/springer_journal/theoretical-studies-of-structure-and-racemization-mechanism-of-xT54SiRYc0
Publisher
Springer Journals
Copyright
Copyright © 2016 by Springer Science+Business Media Dordrecht
Subject
Chemistry; Catalysis; Physical Chemistry; Inorganic Chemistry
ISSN
0922-6168
eISSN
1568-5675
D.O.I.
10.1007/s11164-015-2407-5
Publisher site
See Article on Publisher Site

Abstract

The structure and racemization mechanism of l-aspartic acid (l-ASP) and l-ASP-intercalated layered double hydroxide (l-ASP-LDH, with intercalated magnesium–aluminum hydrotalcite as the LDH), were theoretically studied using the B3LYP and PW91 method of density functional theory at 6-31G(d,p) and Lanl2dz level, respectively. The structural parameters obtained for l-ASP-LDH are in agreement with experimental data for materials, indicating that this theoretical method is appropriate for the hydrotalcite system. The computational results show that enantiomerism of l-ASP is difficult in the ground state due to high energy barriers, while in the excited state l-ASP can easily transform to d-ASP via proton transfer from the chiral carbon atom to the carbonyl oxygen atom, where the carbonyl oxygen atom plays a role as a medium for proton migration. In addition, hydrotalcite could inhibit racemization of l-ASP because the combination of the oxygen atom and hydrotalcite layers hindered proton movement.

Journal

Research on Chemical IntermediatesSpringer Journals

Published: Jan 21, 2016

References

You’re reading a free preview. Subscribe to read the entire article.


DeepDyve is your
personal research library

It’s your single place to instantly
discover and read the research
that matters to you.

Enjoy affordable access to
over 18 million articles from more than
15,000 peer-reviewed journals.

All for just $49/month

Explore the DeepDyve Library

Search

Query the DeepDyve database, plus search all of PubMed and Google Scholar seamlessly

Organize

Save any article or search result from DeepDyve, PubMed, and Google Scholar... all in one place.

Access

Get unlimited, online access to over 18 million full-text articles from more than 15,000 scientific journals.

Your journals are on DeepDyve

Read from thousands of the leading scholarly journals from SpringerNature, Elsevier, Wiley-Blackwell, Oxford University Press and more.

All the latest content is available, no embargo periods.

See the journals in your area

DeepDyve

Freelancer

DeepDyve

Pro

Price

FREE

$49/month
$360/year

Save searches from
Google Scholar,
PubMed

Create lists to
organize your research

Export lists, citations

Read DeepDyve articles

Abstract access only

Unlimited access to over
18 million full-text articles

Print

20 pages / month

PDF Discount

20% off