scholarly journals Coherent electric field manipulation of Fe3+ spins in PbTiO3

2021 ◽  
Vol 7 (10) ◽  
pp. eabf8103
Author(s):  
Junjie Liu ◽  
Valentin V. Laguta ◽  
Katherine Inzani ◽  
Weichuan Huang ◽  
Sujit Das ◽  
...  
Keyword(s):  
Electric Field ◽  
Degrees Of Freedom ◽  
Coherent Control ◽  
Polar Axis ◽  
Ferric Ion ◽  
Paramagnetic Resonance ◽  
Time Resolved ◽  
Spin Charge Coupling ◽  
Electron Paramagnetic ◽  
Field Manipulation

Magnetoelectrics, materials that exhibit coupling between magnetic and electric degrees of freedom, not only offer a rich environment for studying the fundamental materials physics of spin-charge coupling but also present opportunities for future information technology paradigms. We present results of electric field manipulation of spins in a ferroelectric medium using dilute ferric ion–doped lead titanate as a model system. Combining first-principles calculations and electron paramagnetic resonance (EPR), we show that the ferric ion spins are preferentially aligned perpendicular to the ferroelectric polar axis, which we can manipulate using an electric field. We also demonstrate coherent control of the phase of spin superpositions by applying electric field pulses during time-resolved EPR measurements. Our results suggest a new pathway toward the manipulation of spins for quantum and classical spintronics.

scholarly journals Photoreactivity of Hair Melanin from Different Skin Phototypes—Contribution of Melanin Subunits to the Pigments Photoreactive Properties

2021 ◽  
Vol 22 (9) ◽  
pp. 4465
Author(s):  
Krystian Mokrzynski ◽  
Shosuke Ito ◽  
Kazumasa Wakamatsu ◽  
Theodore G. Camenish ◽  
Tadeusz Sarna ◽  
...  
Keyword(s):  
Chemical Composition ◽  
Singlet Oxygen ◽  
Near Infrared ◽  
Paramagnetic Resonance ◽  
Time Resolved ◽  
W Band ◽  
Epr Oximetry ◽  
X Band ◽  
Hair Samples ◽  
Electron Paramagnetic

Photoreactivity of melanin has become a major focus of research due to the postulated involvement of the pigment in UVA-induced melanoma. However, most of the hitherto studies were carried out using synthetic melanin models. Thus, photoreactivity of natural melanins is yet to be systematically analyzed. Here, we examined the photoreactive properties of natural melanins isolated from hair samples obtained from donors of different skin phototypes (I, II, III, and V). X-band and W-band electron paramagnetic resonance (EPR) spectroscopy was used to examine the paramagnetic properties of the pigments. Alkaline hydrogen peroxide degradation and hydroiodic acid hydrolysis were used to determine the chemical composition of the melanins. EPR oximetry and spin trapping were used to examine the oxygen photoconsumption and photo-induced formation of superoxide anion, and time-resolved near infrared phosphorescence was employed to determine the singlet oxygen photogeneration by the melanins. The efficiency of superoxide and singlet oxygen photogeneration was related to the chemical composition of the studied melanins. Melanins from blond and chestnut hair (phototypes II and III) exhibited highest photoreactivity of all examined pigments. Moreover, melanins of these phototypes showed highest quantum efficiency of singlet oxygen photogeneration at 332 nm and 365 nm supporting the postulate of the pigment contribution in UVA-induced melanoma.

scholarly journals Copper Complexes of Benzoylacetone Bis-Thiosemicarbazones: Metal and Ligand Based Redox Reactivity

2021 ◽  
Vol 74 (1) ◽  
pp. 34 ◽  
Author(s):  
Jessica K. Bilyj ◽  
Jeffrey R. Harmer ◽  
Paul V. Bernhardt
Keyword(s):  
Electron Paramagnetic Resonance ◽  
Cyclic Voltammetry ◽  
Copper Complexes ◽  
Atmospheric Oxygen ◽  
The Other ◽  
Oxidation Reactions ◽  
Paramagnetic Resonance ◽  
Time Resolved ◽  
Vis Spectroscopy ◽  
Electron Paramagnetic

Bis-thiosemicarbazones derived from the β-diketone benzoylacetone (H3banR, R=Me, Et, Ph) are potentially tetradentate N2S2 ligands whose coordination chemistry with copper is reported. In the absence of oxygen and in the presence of base they form anionic CuII complexes of the fully deprotonated ligands [CuII(banR)]–. Upon exposure to atmospheric oxygen they undergo a complex series of reactions leading to two types of products; one a ligand oxidised ketone complex [CuII(banRO)] and the other an unprecedented dimeric di-CuIII complex [(CuIII(banR))2] depending on the R substituent. Time-resolved UV-vis spectroscopy, cyclic voltammetry, spectroelectrochemistry, and electron paramagnetic resonance (EPR) spectroscopy have been used to identify intermediates on the way to stable products formed under both anaerobic and aerobic conditions. It is found that both ligand-centred and Cu-centred oxidation reactions are occurring in parallel leading to this unusually complicated mixture of products.

scholarly journals Observing 3-hydroxyanthranilate-3,4-dioxygenase in action through a crystalline lens

2020 ◽  
Vol 117 (33) ◽  
pp. 19720-19730 ◽  
Author(s):  
Yifan Wang ◽  
Kathy Fange Liu ◽  
Yu Yang ◽  
Ian Davis ◽  
Aimin Liu
Keyword(s):  
Conformational Changes ◽  
Quinolinic Acid ◽  
De Novo ◽  
Crystalline Lens ◽  
Paramagnetic Resonance ◽  
Time Resolved ◽  
X Ray Crystallography ◽  
Protein Conformational Changes ◽  
Catalytic Intermediates ◽  
Electron Paramagnetic

The synthesis of quinolinic acid from tryptophan is a critical step in the de novo biosynthesis of nicotinamide adenine dinucleotide (NAD+) in mammals. Herein, the nonheme iron-based 3-hydroxyanthranilate-3,4-dioxygenase responsible for quinolinic acid production was studied by performing time-resolvedin crystalloreactions monitored by UV-vis microspectroscopy, electron paramagnetic resonance (EPR) spectroscopy, and X-ray crystallography. Seven catalytic intermediates were kinetically and structurally resolved in the crystalline state, and each accompanies protein conformational changes at the active site. Among them, a monooxygenated, seven-membered lactone intermediate as a monodentate ligand of the iron center at 1.59-Å resolution was captured, which presumably corresponds to a substrate-based radical species observed by EPR using a slurry of small-sized single crystals. Other structural snapshots determined at around 2.0-Å resolution include monodentate and subsequently bidentate coordinated substrate, superoxo, alkylperoxo, and two metal-bound enol tautomers of the unstable dioxygenase product. These results reveal a detailed stepwise O-atom transfer dioxygenase mechanism along with potential isomerization activity that fine-tunes product profiling and affects the production of quinolinic acid at a junction of the metabolic pathway.

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