skip to main content

Title: Topology, Distance, and Orbital Symmetry Effects on Electronic Spin–Spin Couplings in Rigid Molecular Systems: Implications for Long-Distance Spin–Spin Interactions
Authors:
; ; ; ; ;
Award ID(s):
1900541
Publication Date:
NSF-PAR ID:
10334435
Journal Name:
The Journal of Physical Chemistry A
Volume:
124
Issue:
37
Page Range or eLocation-ID:
7411 to 7415
ISSN:
1089-5639
Sponsoring Org:
National Science Foundation
More Like this
  1. We demonstrate a host-guest molecular recognition approach to advance double electron-electron resonance (DEER) distance measurements of spin-labeled proteins. We synthesized an iodoacetamide (IA) derivative of 2,6-diazaadamantane nitroxide (DZD) spin label that could be doubly incorporated into T4 Lysozyme (T4L) by site-directed spin labeling (SDSL) with efficiency up to 50% per cysteine. The rigidity of the fused ring structure and absence of mobile methyl groups increase the spin echo dephasing time (Tm) at temperatures above 80 K. This enables DEER measurements of distances >4 nm in DZD labeled-T4L in glycerol/water at temperatures up to 150 K, with increased sensitivity compared to common spin label such as MTSL. Addition of β-cyclodextrin (β-CD) reduces the rotational correlation time of the label, slightly increases Tm, and most importantly, narrows (and slightly lengthens) the inter-spin distance distributions. The distance distributions are in good agreement with simulated distance distributions obtained by rotamer libraries. These results provide a foundation for developing supramolecular recognition to facilitate long-distance DEER measurements at near physiological temperatures.