Back to Search
Start Over
Key Building Block of Photoresponsive Biomimetic Systems
- Source :
- Journal of Physical Chemistry B, Journal of Physical Chemistry B, American Chemical Society, 2011, 115 (5), pp.1232-1242. ⟨10.1021/jp108341a⟩, Recercat. Dipósit de la Recerca de Catalunya, instname, UPCommons. Portal del coneixement obert de la UPC, Universitat Politècnica de Catalunya (UPC)
- Publication Year :
- 2011
- Publisher :
- American Chemical Society (ACS), 2011.
-
Abstract
- The conformational, electrical, and optical intrinsic properties of L-phenylazophenylalanine (L-PAP), a nonproteinogenic photoresponsive amino acid used to modulate the binding affinity and activity of peptides and proteins, have been systematically investigated using quantum mechanical calculations, with special emphasis being put on the trans-to-cis isomerization of the azobenzene side group. Analyses of the conformational maps and the minimum-energy conformations, which were obtained using density functional theory calculations at the B3LYP/6-311þþG(d, p) level, indicate that the semiextended β is the most favored conformation for both the trans and cis isomers in the gas phase. However, water tends to stabilize the helical backbone arrangement, but only for the cis isomer since this is a sterically forbidden conformation for the trans one. On the other hand, time-dependent density functional theory calculations at the BMK/6-311þG(d,p) level indicate that the peptide backbone does not induce significant changes in the optical properties of the chromophore. This feature was evidenced by both the small dependence of the πfπ* and nfπ* transition wavelengths with the backbone dihedral anglesjandψand the resemblance between the transition wavelengths determined for L-PAP and free azobenzene. In contrast, the dipole moment has been identified as a key property for this photoresponsive amino acid because of its large dependence on both the peptide backbone and the isomerization state.
- Subjects :
- Steric effects
Stereochemistry
Phenylalanine
Biomimètica
010402 general chemistry
01 natural sciences
chemistry.chemical_compound
Enginyeria química [Àrees temàtiques de la UPC]
Isomerism
Biomimetic Materials
Biomimetics
Materials Chemistry
Physical and Theoretical Chemistry
Pendant group
chemistry.chemical_classification
010405 organic chemistry
Block (periodic table)
0104 chemical sciences
Surfaces, Coatings and Films
Amino acid
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
Azobenzene
chemistry
Thermodynamics
Density functional theory
Gases
Azo Compounds
Isomerization
Cis–trans isomerism
Subjects
Details
- ISSN :
- 15205207 and 15206106
- Volume :
- 115
- Database :
- OpenAIRE
- Journal :
- The Journal of Physical Chemistry B
- Accession number :
- edsair.doi.dedup.....f281e1f2774dbb15240fca146750b598