The main source of magnetic and electromagnetic effects in biological systems is now generally accepted and demonstrated in this paper to be radical pair mechanism which implies pairwise generation of radicals in biochemical reactions. This mechanism was convincingly established for enzymatic adenosine triphosphate (ATP) and desoxynucleic acid (DNA) synthesis by using catalyzing metal ions with magnetic nuclei ((25)Mg, (43)Ca, (67)Zn) and supported by magnetic field effects on these reactions. The mechanism, is shown to function in medicine as a medical remedy or technology (trans-cranial magnetic stimulation, nuclear magnetic control of the ATP synthesis in heart muscle, the killing of cancer cells by suppression of DNA synthesis). However, the majority of magnetic effects in biology remain to be irreproducible, contradictory, and enigmatic. Three sources of such a state are shown in this paper to be: the presence of paramagnetic metal ions as a component of enzymatic site or as an impurity in an uncontrollable amount; the property of the radical pair mechanism to function at a rather high concentration of catalyzing metal ions, when at least two ions enter into the catalytic site; and the kinetic restrictions, which imply compatibility of chemical and spin dynamics in radical pair. It is important to keep in mind these factors to properly understand and predict magnetic effects in magneto-biology and biology itself and deliberately use them in medicine.
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http://dx.doi.org/10.1002/bem.21947 | DOI Listing |
J Phys Chem Lett
January 2025
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China.
The photochemistry of nitrous acid (HONO) plays a crucial role in atmospheric chemistry as it serves as a key source of hydroxyl radicals (OH) in the atmosphere; however, our comprehension of the underlying mechanism for the photochemistry of HONO especially in the presence of water is far from being complete as the transient intermediates in the photoreactions have not been observed. Herein, we report the photochemistry of microsolvated HONO by water in a cryogenic N matrix. Specifically, the 1:1 hydrogen-bonded water complex of HONO was facially prepared in the matrix through stepwise photolytic O oxidation of the water complex of imidogen (NH-HO) via the intermediacy of the elusive water complex of peroxyl isomer HNOO.
View Article and Find Full Text PDFNat 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.
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