ASSESSING THE IMPACT OF BACKBONE LENGTH AND CAPPING AGENT ON THE CONFORMATIONAL PREFERENCES OF A MODEL PEPTIDE: CONFORMATION SPECIFIC IR AND UV SPECTROSCOPY.

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ASSESSING THE IMPACT OF BACKBONE LENGTH AND CAPPING AGENT ON THE CONFORMATIONAL PREFERENCES OF A MODEL PEPTIDE: CONFORMATION SPECIFIC IR AND UV SPECTROSCOPY OF 2- AMINOISOBUTYRIC ACID MG13 Adjust title? Joseph R. Gord, Daniel M. Hewett, Alicia O. Hernandez-Castillo, Karl N. Blodgett, Matthew A. Kubasik, and Timothy S. Zwier

Introduction Aib (U) vs Alanine (A) φ ψ (n) Aib (U) vs Alanine (A) Single methyl group a-aminoisobutyric Acid (Aib)n forms 310-helices (i → i+3) 3 residues/turn f and y angles are typically -60º and -30º, respectively Point out the group numbering… Timothy Zeko; Steven F. Hannigan; Timothy Jacisin; Matthew J. Guberman-Pfeffer; Eric R. Falcone; Melissa J. Guildford; Christopher Szabo; Kathryn E. Cole; Jessica Placido; Erin Daly; Matthew A. Kubasik; J. Phys. Chem. B 2014, 118, 58-68. DOI: 10.1021/jp408818g Copyright © 2013 American Chemical Society

Motivation Consider competition between a(3.613)- and 310- helices under solvent-free conditions Competing structures Look for earliest onset of 310-helix formation Crystal structure shows 310 with n=6 Identify spectroscopic signatures Clean up..

Methods R2PI RIDIRS IR-UV HB s0 sn Ion s0 sn Ion s0 sn Ion S0 A B C 1064 nm Graphite rod B C C A B A s0 sn Ion R2PI s0 sn Ion RIDIRS 200 ns IR-UV HB s0 sn Ion 200 ns B C A B C A B C A B B A A C C S0 A B C

Previous Data: Major Conformations Z-U-OH Z-U2-OH Z-U2-OMe C5 C5 C5 Add Dihedral angles…. Phi: -180 Psi: -180 Phi: 58, 172 Psi: 32, -178 Phi: -64, -174 Psi: -31, -174

Z-(Aib)4-OMe R2PI A B C A C B Fix the colors….

Z-U4-OMe A: C10/C10 NH (3)···O=C (0) NH (4)···O=C (1) C10 C10 Free (3) C10 (2, 3 in) C10 (0) C10 (1) Free (4) C10 (4) C10 (3) Free (2) Free (1) Fix the labels for the mid IR… lots of coupling. + 3 kJ/mol Phi: -61, -57, -57, -48 Psi: -27, -22, -35, -40 Clear 310-Helical structure is seen with only n = 4!

Z-U4-OMe B: C10/C7 Competing C10/C7 motif NH (3)···O=C (0) Freq Grp OMe cap C=O Z-cap C=O C=O(1) C=O(3) 1745 C=O(2) Free (4) C10 (0) Free (1) Free (3, 7-2 out) C7 (2, F3 in) C7 (4) C10 (3) Free (1 ,2) C7 C10 Note that the amide I fundamentals are spread over 90 cm-1. You can learn a lot from this. My guess is that the overtone of C=O(2) couples with NH(4) which is in a C7 H-bond with C=O(2), and that is why we have a doublet down in this region. + 4 kJ/mol Phi: 63, 58, -75, 52 Psi: 25, 30, 74, -143 Competing C10/C7 motif

Z-U4-OMe C Competing C7/C7/C14 motif + 24 kJ/mol C7 NH (1)···O=C (3, 4) NH (2)···O=C (0) NH (3)···O=C (1) C11 (3) C14 (4) C14/C11 (1) C7 (1) C7 (0) Free (2) Free (4) C7 (3) C7 (2) What makes C7(3) so low in frequency? The NH is bent out-of-plane a bit, which is interesting. Is this induced by the extra methyl group? The weak C7(2) is to the Z-cap C=O. Is it that C7(2) is so weak or the C7(3) is so strong? C7 + 24 kJ/mol Phi: -82, 68, -53, 43 Psi: 34, -79, 151, 49 Competing C7/C7/C14 motif C14 C7

Z-U4-OMe Assignments Major Conformer Minor Conformer Minor Conformer Conformer A +3 kJ/mol Phi: -61, -57, -57, -48 Psi: -27, -22, -35, -40 Conformer B +4 kJ/mol Phi: 63, 58, -75, 52 Psi: 25, 30, 74, -143 Conformer C +24 kJ/mol Phi: -82, 68, -53, 43 Psi: 34, -79, 151, 49

Z-(Aib)6-OMe A B Largest Structure Ever…in the Zwier Lab!

Z-(Aib)6-OMe B Clear 310 structure: Four C10s! + 0.0 kJ/mol Free (5) C10 C10 (1) C10 (3 & 4) C10 (6 & 5) C10 (3) C10 (0) Free (4) Free (6) Free (2) Free (1) C10 In the Z-U4’s, the only thing that gets us down well below 3300 is the low frequency C7 in conformers B and C of Z-U4-OMe. Remove the Fit from A and focus on B. Maybe don’t show A at all on this slide.. Clear 310 structure: Four C10s! + 0.0 kJ/mol Phi: -60, -54, -53, -55, -59, 50 Psi: -28, -28, -30, -30, -28, 40

Z-(Aib)6-OMe A

Z-(Aib)6-OH -OH is a more intrusive, natural cap +1 kJ/mol The assignments for this one are kinda funky. We should talk through them. I’ll put some additional slides together. Remove stick spectra Talk about regions Change the color scheme on this slide. Add shading for h-bonding regions. +1 kJ/mol Phi: 96, 53, 54, 49, 73, -57 Psi: 28, 29, 28, 39, -51, -39 -OH is a more intrusive, natural cap

Conclusions 310-helix seen at the earliest stages Full turn formed with only 4 residues More fully formed 310 seen with n =6 Multiple competing structures observed Aib is a clear 310 former! C10

Alicia O. Hernandez-Castillo Acknowledgements Prof. Timothy S. Zwier Prof. Matthew A. Kubasik Zwier Group Members Daniel Hewett Alicia O. Hernandez-Castillo Karl N. Blodgett