In a recent article (Hakala-Yatkin and Tyystjärvi BBA 1807 (2011) 243-250) it was reported that the singlet oxygen spin traps 2,2,6,6-tetramethylpiperidine (TEMP) and 2,2,6,6-tetramethyl-4-piperidone (TEMPD) inhibit Photosystem II (PSII), the water oxidizing enzyme. O₂ evolution, chlorophyll fluorescence and thermoluminescence were measured and were shown to be greatly affected by these chemicals. This work casts doubts over an earlier body of work in which these chemicals were used as spin traps for monitoring ¹O₂ production when PSII was inhibited by high light intensities. Here we show that these spin probes hardly affect PSII. We show that the commercial batches of TEMPD and TEMP used by Hakala-Yatkin and Tyystjärvi contained impurities and/or derivatives that inhibited PSII and caused the specific effects on fluorescence. Earlier work that used pure spin traps to measure ¹O₂ during photoinhibition, thus remains valid. However, concern must be expressed towards using these spin traps without proper controls.
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http://dx.doi.org/10.1016/j.bbabio.2011.09.009 | DOI Listing |
J Am Chem Soc
January 2025
Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China.
A small but growing set of radical SAM (-adenosyl-l-methionine) enzymes catalyze the radical mediated dehydration or dehydrogenation of 1,2-diol substrates. In some cases, these activities can be interchanged via minor structural perturbations to the reacting components raising questions regarding the relative importance of hyperconjugation, proton circulation and leaving group stability in determining the reaction outcome. The present work describes trapping and electron paramagnetic resonance (EPR) characterization of an α-hydroxyalkyl radical intermediate during dehydration and dehydrogenation of cytosylglucuronic acid and its derivatives catalyzed by the radical SAM enzyme BlsE and its Glu189Ala mutant from the blasticidin S biosynthetic pathway.
View Article and Find Full Text PDFEnviron Sci Technol
January 2025
State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, P. R. China.
The most well-known hydroxyl radical (OH)-generating system is the classic iron-mediated Fenton reaction. Thiourea has been considered as an efficient OH scavenger and is frequently used to study the role of OH in various biochemical and medical research studies. Here we found that the highly reactive OH can be produced from thiourea and HO through a metal-independent pathway, as measured by electron spin resonance (ESR) secondary radical spin-trapping and fluorescent methods.
View Article and Find Full Text PDFNat Commun
January 2025
Department of Optics and Optical Engineering, University of Science and Technology of China, Hefei, China.
The spin angular momentum (SAM) plays a significant role in light-matter interactions. It is well known that light carrying SAM can exert optical torques on micro-objects and drive rotations, but 3D rotation around an arbitrary axis remains challenging. Here, we demonstrate full control of the 3D optical torque acting on a trapped microparticle by tailoring the vectorial SAM transfer.
View Article and Find Full Text PDFSci Rep
January 2025
Centre for Molecular and Materials Science, TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3, Canada.
This paper describes muon spin spectroscopy studies of 12-phosphatetraphene stabilized by a peri-trifluoromethyl group and a meso-aryl substituent. Even though the prepared solution in tetrahydrofuran (THF) was quite dilute (0.060 M) for transverse-field muon spin rotation (TF-µSR) measurements, the π-extended heavier congener of tetraphene presented a pair of signals due to a muoniated radical from which the muon hyperfine coupling constant (hfc) was determined.
View Article and Find Full Text PDFSci Rep
January 2025
Department of Physics, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul, 03722, Republic of Korea.
Despite recent advancements in organic photovoltaics (OPVs), further improvements in power conversion efficiency (PCE) and device lifetime are necessary for commercial viability. Strategies such as optimizing the molecular orientation and minimizing the charge traps of organic films are particularly effective in enhancing photovoltaic performance. In this study, we successfully utilized vacuum electrospray deposition (VESD) to achieve favourable face-on stacking geometries while preserving the integrity of the interfaces in poly(3-hexylthiophene-2,5-diyl) (P3HT): [6,6]-phenyl-C-butyric acid methyl ester (PCBM) bulk heterojunction (BHJ) films.
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