FRET experiments enable studies of the chemical and physical properties of individual molecules, which has long been a dream of chemists. However, these modern experimental techniques are still limited by the lack of information about the dynamic behavior of the fluorescent labels as well as by the use of dipole-dipole approximation even at short donor-to-acceptor distances. Our results help to suggest that these assumptions need to be carefully considered when designing experiments. We show that at short donor-acceptor separation, dipole-dipole approximation breaks down and Forster theory fails and cannot be used to obtain correct distances. We also explicitly demonstrate that dyes' linkers allow for a lot of flexibility in the fluorescent label orientation and position resulting in distances much shorter than assumed earlier.
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http://dx.doi.org/10.1021/jp811395r | DOI Listing |
Chem Sci
January 2025
Departament de Farmàcia i Tecnologia Farmacèutica, i Fisicoquímica, Facultat de Farmàcia i Ciències de l'Alimentació, Universitat de Barcelona (UB) Barcelona Spain
Förster resonance energy transfer (FRET) is a powerful technique used to investigate the conformational preferences of biosystems, and molecular simulations have emerged as an ideal complement to FRET due to their ability to provide structural models that can be compared with experiments. This synergy is however hampered by the approximations underlying Förster theory regarding the electronic coupling between the participating dyes: a dipole-dipole term attenuated by a simple dielectric screening factor 1/ that depends on the refractive index of the medium. Whereas the limits of the dipole approximation are well-known, detailed insights on how environment effects deviate from the 1/ assumption and modify the distance dependence that characterizes FRET as a spectroscopic ruler are still not well understood, especially in biosystems characterized by significant structural disorder.
View Article and Find Full Text PDFJ Magn Reson
January 2025
NMR Research Unit, University of Oulu, P.O. Box 3000, FI-90014, Finland. Electronic address:
Spin relaxation is modelled using the so-called relaxation superoperator Γˆˆ. Analytic forms of Γˆˆ have been derived in the literature in the simplest cases of one- or two-spin systems, with S=12 nuclei and no more than two different simultaneous relaxation mechanisms involved. Beyond that, for systems of more than two spins, with S>12 and/or multiple relaxation mechanisms at play, the derivations become notoriously complicated, which is why analytic relaxation theory has mostly been considered a dead end.
View Article and Find Full Text PDFJ Fluoresc
December 2024
Department of Applied Physics, Delhi Technological University, Bawana Road, Delhi, 110042, India.
In the present research work, a solid-state reaction method was employed to synthesize a series of CaGdSbWO:SmEu (x = 1, 1.5, 2, 3 and 4 mol%) phosphors. The phase purity, crystallinity, morphological and compositional studies were analysed via X-ray diffraction (XRD), scanning electron microscopy (SEM) imaging, and energy dispersive spectroscopy (EDS) analysis.
View Article and Find Full Text PDFJ Chem Phys
December 2024
Novosibirsk State University, Novosibirsk 630090, Russia.
Determining the stability constant of the complex formed by an organic ligand with a protein is the first stage in the screening of new drugs. Nuclear spin long-lived states, in particular the singlet state, can be used to study the reversible binding of ligands to proteins. In a complex with a protein, the spins of the ligand interact with the spins of the protein, the system of protein and ligand nuclei can relax by a dipole-dipole mechanism, and the lifetime of the singlet state is strongly reduced.
View Article and Find Full Text PDFPhys Rev E
September 2024
Department of Theoretical and Mathematical Physics, Institute of Natural Sciences and Mathematics, Ural Federal University, 51 Lenin Avenue, Ekaterinburg 620000, Russia.
Information about the nonlinear magnetic response of dispersions of magnetic particles is the basis for biomedical applications. In this paper, using analytical and numerical methods, the third harmonic of the dynamic susceptibility of an ensemble of moving magnetic particles in an ac magnetic field with an arbitrary amplitude is studied, taking into account interparticle interactions. A simple approximation formula is proposed to predict the third harmonic as a function of two parameters: the Langevin susceptibility χ_{L}, which is used to estimate the particle dipole-dipole interactions, and the Langevin parameter ξ, which represents the ratio of the energy of the magnetic moment interacting with the magnetic field to the thermal energy.
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