Basic algebraic arguments demonstrate that the probability of radical pair recombination in low field for an arbitrary pair with Hamiltonian confined to Zeeman and isotropic hyperfine interactions contains two additive contributions linear with applied field with equal, but opposite in sign, proportionality factors. Their weights are determined by the probability of having all nuclear spins along the field in the initial electron-singlet state of the pair, and in the case of equilibrium with respect to nuclear spins, the two contributions completely compensate the field dependences of each other, producing an additive term in the singlet yield with zero derivative. However, if the nuclear set is polarized, a linear skew proportional to polarization appears, introducing anisotropy in the intrinsically spherically symmetric system. The key element in this derivation is guaranteed nondegeneracy of the eigenvalues of the "penultimate" (M - 1) block of the Hamiltonian for a radical with any number of distinct spin-1/2 nuclei in zero field, which leads to guaranteed applicability of the first-order nondegenerate perturbation theory with nonvanishing linear in field admixture of states, persisting all the way into the final expression for singlet yield for a pair with an arbitrary isotropic hyperfine structure. We argue that this behavior of the field dependence of recombination yield is representative of a radical pair of an arbitrarily complex hyperfine structure; this may be a possible mechanism for anisotropic response ("chemical compass") for an isotropic radical pair based system with isotropic-only internal interactions and anisotropy introduced via the initial state of nuclei, while such an approach may complement the usually needed numerical simulations.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1063/1.5127217 | DOI Listing |
Nat Chem
January 2025
SAMS Research Group, Université de Strasbourg, CNRS, Institut Charles Sadron UPR 22, Strasbourg, France.
Molecular spin qubits have the advantages of synthetic flexibility and amenability to be tailored to specific applications. Among them, chromophore-radical systems have emerged as appealing qubit candidates. These systems can be initiated by light to form triplet-radical pairs that can result in the formation of quartet states by spin mixing.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
University of Bari: Universita degli Studi di Bari Aldo Moro, Dept. of Pharmacy - Drug Sciences, via E. Orabona 4, 70125, Bari, ITALY.
Strained spiro-heterocycles (SSH) have gained significant attention within the medicinal chemistry community as promising (sp3)-rich bioisosteres for their aromatic and non-spirocyclic counterparts. We herein report access to an unprecedented spiro-heterocycle - 1,5-dioxaspiro[2.3]hexane.
View Article and Find Full Text PDFAdv Mater
January 2025
State Key Laboratory of Fine Chemicals, College of Materials Science and Engineering, Shenzhen University, Shenzhen, 518071, China.
Photodynamic therapy (PDT) using traditional type II photosensitizers (PSs) has been limited in hypoxic tumors due to excessive oxygen consumption. The conversion from type II into a less oxygen-dependent type I PDT pathway has shown the potential to combat hypoxic tumors. Herein, the design of a heterodimeric PS, NBSSe, by conjugating a widely used type I PS NBS and a type II PS NBSe via molecular dimerization, achieving the aggregation-regulated efficient type I photodynamic conversion for the first time is reported.
View Article and Find Full Text PDFBiomolecules
December 2024
Dipartimento di Chimica e Biologia "A. Zambelli", Università di Salerno, 84084 Fisciano, Italy.
In this review, we focus on the one-electron oxidation of DNA, which is a multipart event controlled by several competing factors. We will discuss the oxidation free energies of the four nucleobases and the electron detachment from DNA, influenced by specific interactions like hydrogen bonding and stacking interactions with neighboring sites in the double strand. The formation of a radical cation (hole) which can migrate through DNA (hole transport), depending on the sequence-specific effects and the allocation of the final oxidative damage, is also addressed.
View Article and Find Full Text PDFSci Rep
January 2025
Institute of Biochemistry and Biophysics, University of Tehran, Tehran, Iran.
Observing quantum mechanical characteristics in biological processes is a surprising and important discovery. One example, which is gaining more experimental evidence and practical applications, is the effect of weak magnetic fields with extremely low frequencies on cells, especially cancerous ones. In this study, we use a mathematical model of ROS dynamics in cancer cells to show how ROS oscillatory patterns can act as a resonator to amplify the small effects of the magnetic fields on the radical pair dynamics in mitochondrial Complex III.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!