Paramagnetic Spin Research Articles

Controlling Intramolecular Singlet Fission Dynamics via Torsional Modulation of Through-Bond versus Through-Space Couplings.

Covalent dimers, particularly pentacenes, are the dominant platform for developing a mechanistic understanding of intramolecular singlet fission (iSF). Numerous studies have demonstrated that a photoexcited singlet state in these structures can rapidly and efficiently undergo exciton multiplication to form a correlated pair of triplets within a single molecule, with potential applications from photovoltaics to quantum information science. One of the most significant barriers limiting such dimers is the fast recombination of the triplet pair, which prevents spatial separation and the formation of long-lived triplet states. There is an ever-growing need to develop general synthetic strategies to control the evolution of triplets following iSF and enhance their lifetime. Here, we rationally tune the dihedral angle and interchromophore separation between pairs of pentacenes in a systematic series of bridging units to facilitate triplet separation. Through a combination of transient optical and spin-resonance techniques, we demonstrate that torsion within the linker provides a simple synthetic handle to tune the fine balance between through-bond and through-space interchromophore couplings that steer iSF. We show that the full iSF pathway from femtosecond to microsecond timescales is tuned through the static coupling set by molecular design and structural fluctuations that can be biased through steric control. Our approach highlights a straightforward design principle to generate paramagnetic spin pair states with higher yields.

Complexation of AAPH (2,2′-azobis(2-methylpropionamidine) dihydrochloride) with cucurbit[7]uril enhances the yield of AAPH-derived radicals

AAPH (2,2′-azobis(2-methylpropionamidine) dihydrochloride), a water-soluble azo compound is widely employed to produce peroxyl radicals for chemical and biological studies. This compound is shown herein to form a stable inclusion complex with cucurbit[7]uril (CB7), a well-established supramolecular host. Competitive binding assays using berberine dye, isothermal titration calorimetry (ITC), and nuclear magnetic resonance (1H NMR) experiments, provided evidence for the inclusion of AAPH inside the CB7 cavity with a binding constant of 2.51 ± 0.76 × 105 M−1 (determined by ITC). Computational analysis at B3LYP-D3BJ/6-311G(d,p) of the complex (AAPH@CB7) showed interactions of the positively-charged amino groups of AAPH with carbonyl functions at the CB7 entrances. Photolysis of AAPH@CB7 by illumination at 365 nm, gave a higher yield of carbon-centered radicals when compared to the absence of CB7, as evidenced by electron paramagnetic resonance spin trapping using α-phenyl-N-t-butylnitrone. Enhanced radical formation was corroborated by increased consumption of pyrogallol red, free Trp and Trp-containing peptides when these were exposed to AAPH@CB7 in the presence of light. The increased yield of radicals generated by AAPH@CB7 is believed to arise from a pull effect of CB7 portals on initial AAPH-derived carbon-centered radicals generated by photolysis. It is proposed that these radicals are exposed and released to the bulk solution and react with O2 to give peroxyl radicals. These results suggest that the AAPH@CB7 complex can be used to generate high yields of peroxyl radicals for their use in studying these species in material, environmental and biomedical sciences amongst others.

The oxidation of fenamic acid NSAIDs by neutrophil myeloperoxidase produces toxic reactive metabolites that induce leukemic cell death

Fenamic acids are a group of non-steroidal anti-inflammatory drugs (NSAIDs) that are among the most common drugs prescribed globally. However, they have been associated with many adverse effects, such as agranulocytosis, neutropenia, hepatotoxicity, and nephrotoxicity. The interactions between peroxidase enzymes and fenamic acid-like NSAIDs cause the formation of reactive species, potentially involved in side effects. The aim of this study was to investigate the neutrophil myeloperoxidase (MPO)-mediated bioactivation of fenamic acids based on N-phenylanthranilic acid (NPA) and its four drug analogues: flufenamic acid (FFA), mefenamic acid (MFA), meclofenamic acid (MCFA), and tolfenamic acid (TFA). We hypothesized that the enzymatic oxidation of fenamic acids by MPO/hydrogen peroxide (H2O2) would produce reactive metabolites, cause oxidative damage and induce cytotoxicity. We utilized UV–Vis spectrophotometry, liquid chromatography-mass spectrometry (LC-MS), and electron paramagnetic spin resonance (EPR) spectroscopy using purified MPO from human neutrophils. In addition, in vitro studies were performed with MPO-containing human promyelocytic leukemia (HL-60) cells for cytotoxicity and immuno-spin trapping to detect protein-free radicals. UV–Vis spectrophotometry revealed that MPO oxidized the fenamic acids. LC-MS analyses revealed the formation of dimers, hydroxylated, and quinoneimine species, and glutathione (GSH) conjugates. EPR spin trapping with DMPO using GSH revealed that fenamic acids produced glutathionyl radicals in a concentration-dependent manner. We also detected the formation of protein-free radicals in HL-60 cells, which correlated with cytotoxicity. Despite the minor structural differences between the fenamic acids, there were variations in their oxidation potential. These findings revealed a correlation between pro-oxidant metabolite reactivity and cytotoxicity caused by fenamic acid NSAIDs.

Paramagnetic spin transport in a one-dimensional model

Paramagnetic spin transport in a one-dimensional model

Quantum Sensing of Paramagnetic Spins in Liquids with Spin Qubits in Hexagonal Boron Nitride

Quantum Sensing of Paramagnetic Spins in Liquids with Spin Qubits in Hexagonal Boron Nitride

Detection of Paramagnetic Spins with an Ultrathin van der Waals Quantum Sensor.

Detecting magnetic noise from small quantities of paramagnetic spins is a powerful capability for chemical, biochemical, and medical analysis. Quantum sensors based on optically addressable spin defects in bulk semiconductors are typically employed for such purposes, but the 3D crystal structure of the sensor inhibits sensitivity by limiting the proximity of the defects to the target spins. Here we demonstrate the detection of paramagnetic spins using spin defects hosted in hexagonal boron nitride (hBN), a van der Waals material that can be exfoliated into the 2D regime. We first create negatively charged boron vacancy (VB-) defects in a powder of ultrathin hBN nanoflakes (<10 atomic monolayers thick on average) and measure the longitudinal spin relaxation time (T1) of this system. We then decorate the dry hBN nanopowder with paramagnetic Gd3+ ions and observe a clear T1 quenching under ambient conditions, consistent with the added magnetic noise. Finally, we demonstrate the possibility of performing spin measurements, including T1 relaxometry using solution-suspended hBN nanopowder. Our results highlight the potential and versatility of the hBN quantum sensor for a range of sensing applications and make steps toward the realization of a truly 2D, ultrasensitive quantum sensor.

Isolated Spin-7/2 Species of Gadolinium (III) Chelate Complexes on the Surface of 5-nm Diamond Particles.

The magnetic characteristics of a system of triply charged gadolinium ions Gd3+ chelated with carboxyls on the surface of detonation nanodiamond (DND) particles have been studied. Gd3+ ions demonstrate almost perfect spin (S = 7/2) paramagnetism with negligible antiferromagnetic interaction between spins (Weiss temperature about -0.35 K) for a wide range of concentrations up to ~18 ions per 5 nm particle. The study of the concentration dependence of the electron paramagnetic resonance signal for DND intrinsic defects with spin ½ (g = 2.0027) shows that Gd3+ ions are located on average at a distance of no more than 1.4 nm from shallow subsurface defects with spin 1/2. At the same time, they are located (according to density functional theory calculations) at a distance of about or at least 0.28 nm from the particle surface. Magnetic studies also confirm the isolated nature of the gadolinium chelate complexes on the surface of DND particles. DND particles turn out to be an optimal carrier for high-spin 4f- ions (gadolinium) in a highly concentrated isolated state. This property makes DND-Gd particles a candidate for the role of a contrast agent for magnetic resonance imaging.

Ferrimagnetic Oscillator Magnetometer

Quantum sensors based on solid-state spins have advanced rapidly over the prior decade, but deploying these sensors in real-world applications remains technically challenging. By introducing an innovative oscillator-based sensor architecture, and employing a ferrimagnetic material rather than the paramagnetic spin defects more commonly studied, this work details the construction of a compact magnetometer with a minimum sensitivity of 100 fT/\ensuremath{\surd}Hz. The sensor's architecture offers advantages in dynamic range, simplicity, and compactness---qualities that may enable widespread use of solid-state quantum sensors outside a laboratory environment.

Formation of free radicals in Chi-aroma Baijiu during aging process with fat pork

Soaking aged fat pork is a special aging process in the production of Chi-aroma Baijiu considered to involve the formation of free radicals. This study aimed to investigate the free radicals’ formation pathway in Chi-aroma Baijiu during aged fat pork soaking by using electron paramagnetic resonance (EPR) and spin trapping with 5,5-dimethyl-1-pyrrolin-n-oxide (DMPO). The alkyl radical adducts (DMPO-R) and hydroxyl radical adducts (DMPO-OH) were detected in Baijiu after soaking the fat pork for aging. During the preparation process of aged fat pork, alkoxy radicals adduct (DMPO-RO) were mainly detected since lipid oxidation. Oleic acid and linoleic acid, the two main unsaturated fatty acids in fat pork, produced alkoxy radicals in the oxidation process. The total amounts of spins in linoleic acid and oleic acid after 4-month oxidation treatment increased by 248.07 ± 26.65% and 34.17 ± 0.72% than 0-month. It indicated that the free radicals in aged Chi-aroma Baijiu were mainly derived from the two main unsaturated fatty acids in aged fat pork and linoleic acid had a stronger ability to produce free radicals than oleic acid. Alkoxy radicals (RO·) from fat pork reacted with ethanol in Baijiu to form alkyl radicals (R·). The peroxide bond of hydroperoxides from the oxidation of unsaturated fatty acid was cleaved to form hydroxyl radicals (·OH) that were transferred to Baijiu. The results provide theoretical guidance for the subsequent work of free radicals scavenging.

Heat conduction in herbertsmithite: Field dependence at the onset of the quantum spin liquid regime

We report thermal conductivity measurements on single crystals of herbertsmithite, over a wide range of temperatures (0.05-120 K) in magnetic fields up to 15 T. We also report measurements of the thermal Hall effect, found to be vanishingly small. At high temperatures, in the paramagnetic regime, the thermal conductivity has a negligible field dependence. Upon cooling and the development of correlations, the onset of a clear monotonic field dependence below about 20 K signals a new characteristic temperature scale that may reflect the subtle crossover towards the quantum spin liquid regime. Deconfined spinons, if present, are not detected and phonons, as the main carriers of heat, are strongly scattered by the intrinsic spin excitations and the magnetic defects. In view of the colossal fields required to affect the intrinsic spins, most of the field-induced evolution is attributed to the progressive polarization of some magnetic defects. By elaborating a phenomenological model, we extract the magnetization of these main scattering centers which does not resemble the Brillouin function for free spins 1/2, requiring to go beyond the paradigm of isolated paramagnetic spins. Besides, the onset of a nonmonotonic field dependence below about 2 K underlines the existence of another characteristic temperature scale, previously highlighted with other measurements, and sheds new light on the phase diagram of herbertsmithite down to the lowest temperatures.

Spin-Flop Transition in a Nickel–Octacyanidotungstate Chain Magnet

Crystal engineering of molecular magnetic materials often leads to novel magnetic functionalities. In this study, we synthesized an ionic chain magnet, i.e., [NiII(imi)6]{[NiII(imi)4][WV(CN)8]}2·4H2O (imi = imidazole; NiW) comprising anionic cyanido-bridged [NiII(imi)4WV(CN)8]nn– chains and cationic mononuclear [NiII(imi)6]2+ complexes. Ferromagnetic coupling between NiII and WV with S = 1 and 1/2, respectively, via a bridging cyanido ligand is found within the chain. However, the total magnetization of NiW is canceled out by a notable antiferromagnetic interchain interaction below a Néel temperature of 8.5 K. Such an antiferromagnetic interaction can be overcome by applying an external magnetic field of 0.9 T at 2 K, and a steep spin-flop transition is observed. From a crystal engineering perspective, we attribute this metamagnetic behavior to the isolated [NiII(imi)6]2+ complex that attracts the chains to be close to each other. Additionally, the complex operates as an independent paramagnetic spin source that offers an extra magnetization state of this compound.

Investigation of the Pauli paramagnetic effect in systematically tuned NbN thin films

Superconductivity and the normal-state properties of NbN films can be tuned in a wide range, supplying a suitable platform to investigate the systematical evolution of the superconducting performances. Herein, we report the upper critical field of NbN films in both the vertical (B⊥ film) and parallel (B∥ film) orientations over a wide temperature range. Eight samples with the superconducting critical temperature Tc ranging from 2.5 K to 9.8 K are studied. It is found that the magnitudes of the upper critical field in the parallel direction (Bc2∥) exceeds the paramagnetic limiting field Bp in the zero-temperature limit, while the perpendicular one (Bc2⊥) is closely approaching Bp. The temperature dependent Bc2⊥ can be described by the extended Werthamer–Helfand–Hohenberg (WHH) model considering the Pauli spin paramagnetism. Meanwhile, the Bc2∥−T data shows the feature of two-dimensional superconductivity in the temperature range near Tc. Our results show that the Pauli paramagnetic effect is greatly enhanced with the decrease of Tc. The evolution of the obtained Maki parameter with other parameters are discussed to reveal the characteristics of the Pauli paramagnetic effect in this system.

Mechanism of paramagnetic spin Seebeck effect

We have theoretically investigated the spin Seebeck effect (SSE) in a normal metal (NM)/paramagnetic insulator (PI) bilayer system. Through a linear response approach, we calculated the thermal spin pumping from PI to NM and backflow spin current from NM to PI, where the spin-flip scattering via the interfacial exchange coupling between conduction-electron spin in NM and localized spin in PI is taken into account. We found a finite spin current appears at the interface under the difference in the effective temperatures between spins in NM and PI, and its intensity increases by increasing the density of the localized spin $S$. Our model well reproduces the magnetic-field-induced reduction of the paramagnetic SSE in Pt/${\mathrm{Gd}}_{3}{\mathrm{Ga}}_{5}{\mathrm{O}}_{12}$ experimentally observed when the Zeeman energy is comparable to the thermal energy, which can be interpreted as the suppression of the interfacial spin-flip scattering. The present finding provides an insight into the mechanism of paramagnetic SSEs and the thermally induced spin-current generation in magnetic materials.

Enhancing quantum sensing performance by optimizing the concentration and dephasing time of the NV ensemble in CVD-diamond

The negatively charged nitrogen−vacancy (NV−) center ensembles in diamonds offer enormous potential for developing integrated sensors with an improved signal-to-noise ratio (SNR) and high sensitivity. However, the preparation and treatment of diamond samples with suitable NV− concentrations and dephasing time have remained challenging. This work provided insight into the NV− center formation mechanism and reconstruction via a comprehensive analysis of the concentration and dephasing time of a set of diamond samples treated by various parameters. By varying the electron irradiation dose and subsequent annealing duration, the conversion rate of nitrogen to NV− is up to 18.45%, and the corresponding maximum NV− concentration is 3.69 ppm. The dephasing time for all samples varies around 300 ns. The nitrogen-related NV− center ensemble dephasing rate per unit density is 146.4 (ppm·ms)−1, indicating that the treatment did not substantially alter the paramagnetic spin environment around the NV− center. This study not only offers support to exquisite sensitivities of NV-based sensors but also provides valuable experience for the preparation of unique properties of synthetic diamonds.

Nitrogen vacancy defects in single-particle nanodiamonds sense paramagnetic transition metal spin noise from nanoparticles on a transmission electron microscopy grid.

Spin-active nanomaterials play a vital role in current and upcoming quantum technologies, such as spintronics, data storage and computing. To advance the design and application of these materials, methods to link size, shape, structure, and chemical composition with functional magnetic properties at the nanoscale level are needed. In this work, we combine the power of two local probes, namely, Nitrogen Vacancy (NV) spin-active defects in diamond and an electron beam, within experimental platforms used in electron microscopy. Negatively charged NVs within fluorescent nanodiamond (FND) particles are used to sense the local paramagnetic environment of Rb0.5Co1.3[Fe(CN)6]·3.7H2O nanoparticles (NPs), a Prussian blue analogue (PBA), as a function of FND-PBA distance (order of 10 nm) and local PBA concentration. We demonstrate perturbation of NV spins by proximal electron spins of transition metals within NPs, as detected by changes in the photoluminescence (PL) of NVs. Workflows are reported and demonstrated that employ a Transmission Electron Microscope (TEM) finder grid to spatially correlate functional and structural features of the same unique NP studied using NV sensing, based on a combination of Optically Detected Magnetic Resonance (ODMR) and Magnetic Modulation (MM) of NV PL, within TEM imaging modalities. Significantly, spin-spin dipole interactions were detected between NVs in a single FND and paramagnetic metal centre spin fluctuations in NPs through a carbon film barrier of 13 nm thickness, evidenced by TEM tilt series imaging and Electron Energy-Loss Spectroscopy (EELS), opening new avenues to sense magnetic materials encapsulated in or between thin-layered nanostructures. The measurement strategies reported herein provide a pathway towards solid-state quantitative NV sensing with atomic-scale theoretical spatial resolution, critical to the development of quantum technologies, such as memory storage and molecular switching nanodevices.

Oxygen vacancies at the origin of pinned moments in oxide interfaces: The example of tetragonal CuO/SrTiO3

Obtaining an accurate theoretical description of the emergent phenomena in oxide heterostructures is a major challenge. Recently, intriguing paramagnetic spin and pinned orbital moments have been discovered by x-ray magnetic circular dichroism measurements at the Cu ${L}_{2,3}$ edge of a tetragonal $\mathrm{CuO}/{\mathrm{SrTiO}}_{3}$ heterostructure. Using first-principles calculations, we propose a scenario that explains both types of moments, based on the formation of oxygen vacancies in the ${\mathrm{TiO}}_{2}$ interface layer. We show the emergence of a paramagnetic two-dimensional electron gas hosted in the interface CuO layer. It is invisible at the Ti ${L}_{2,3}$ edge since the valence of the Ti atoms remains unchanged. Strong structural distortions breaking both the local and global fourfold rotation ${C}_{4}$ symmetries at the interface lead to the in-plane pinning of the Cu orbital moment close to the vacancy. Our results, and in particular the pinning of the orbital moment, may have implications for other systems, especially monoxide/dioxide interfaces with similar metal-oxygen bond length and weak spin-orbit coupling.

Study of Tricalcium Phosphate Ceramics Doped with Gadolinium Ions with Various EPR Techniques

Tricalcium phosphate (TCP)-based materials, such as β-Ca3(PO4)2 doped with rare earth ions (RE), have shown applications as biomaterials, lighting emitting materials, scintillating materials, in vivo imaging probes, and thermoluminescent dosimeters. Their properties are found to be dependent on the distribution of RE3+ on Ca2+ sites that can be controlled by pulsed electron paramagnetic resonance (EPR) and electron spin echo envelop modulation (ESEEM) experiments. The main spectroscopic parameters (spin Hamiltonian values) of Gd3+ and nitrogen impurity centers are quantitatively determined (g-factor, the fine structure parameters D and E, the hyperfine constants A) as well as dynamic characteristics: spin–lattice T1 and spin–spin T2 relaxation times. Based on the analysis of the EPR datasets, the interatomic distance between Gd3+ and 31P was estimated in the dipole–dipole approximation. Two structurally nonequivalent Gd3+ positions in the β-TCP structure have been identified. The obtained valuable results demonstrate applicability of modern EPR techniques to characterize Gd-TCP systems despite the powder structure of the material and high electron spin S = 7/2 of Gd3+ ions.

Heat-Induced Magnetic Transition for Water Electrolysis on NiFeN@NiFeOOH Core-Shell Assembly.

The overpotentials of electrochemical oxygen evolution reaction (OER) inherently originate from high electron transfer barriers of the redox couple driven water oxidation. Here, we propose a heat-induced magnetic transition strategy to reduce the spin-related electron transfer barriers. Coupling heat into electrochemical OER on a ferro-antiferromagnetic core-shell NiFeN@NiFeOOH, the heat-induced ferro-to-paramagnetic transition for NiFeN core at 55 °C and antiferro-to-paramagnetic transition for NiFeOOH shell at 70 °C significantly accelerate and accordingly achieve a cascaded Ni2+/Ni3+ driven water oxidation reaction. In addition, paramagnetic Niδ+ (δ ≥ 3) in NiFeN@NiFeOOH can thermochemically react with water to produce oxygen. The heat-induced magnetic transition concomitantly triggers the electrochemical redox couple driven water oxidation and the thermochemical water oxidation due to that heat-induced paramagnetic spin reduces the barriers of electricity driving the spin flipping. Our findings offer new insights into constructing the heat-electricity coupling water splitting.

Properties of CuFeS2/TiO2 Nanocomposite Prepared by Mechanochemical Synthesis.

CuFeS2/TiO2 nanocomposite has been prepared by a simple, low-cost mechanochemical route to assess its visible-light-driven photocatalytic efficiency in Methyl Orange azo dye decolorization. The structural and microstructural characterization was studied using X-ray diffraction and high-resolution transmission electron microscopy. The presence of both components in the composite and a partial anatase-to-rutile phase transformation was proven by X-ray diffraction. Both components exhibit crystallite size below 10 nm. The crystallite size of both phases in the range of 10–20 nm was found and confirmed by TEM. Surface and morphological properties were characterized by scanning electron microscopy and nitrogen adsorption measurement. Scanning electron microscopy has shown that the nanoparticles are agglomerated into larger grains. The specific surface area of the nanocomposite was determined to be 21.2 m2·g−1. Optical properties using UV-Vis and photoluminescence spectroscopy were also investigated. CuFeS2/TiO2 nanocomposite exhibits strong absorption with the determined optical band gap 2.75 eV. Electron paramagnetic resonance analysis has found two types of paramagnetic ions in the nanocomposite. Mössbauer spectra showed the existence of antiferromagnetic and paramagnetic spin structure in the nanocomposite. The CuFeS2/TiO2 nanocomposite showed the highest discoloration activity with a MO conversion of ~ 74% after 120 min irradiation. This study has shown the possibility to prepare nanocomposite material with enhanced photocatalytic activity of decoloration of MO in the visible range by an environmentally friendly manner

Spin Seebeck effect at low temperatures in the nominally paramagnetic insulating state of vanadium dioxide

The low temperature monoclinic, insulating phase of vanadium dioxide is ordinarily considered nonmagnetic, with dimerized vanadium atoms forming spin singlets, though paramagnetic response is seen at low temperatures. We find a nonlocal spin Seebeck signal in VO2 films that appears below 30 K and that increases with a decrease in temperature. The spin Seebeck response has a nonhysteretic dependence on the in-plane external magnetic field. This paramagnetic spin Seebeck response is discussed in terms of prior findings on paramagnetic spin Seebeck effects and expected magnetic excitations of the monoclinic ground state.