Weak Dipolar Interactions Research Articles

Regulating Interface Dipole Interaction between Ethers and Active Species toward Highly Stable Li-SPAN Batteries.

Sulfurized polyacrylonitrile (SPAN) is recognized as a promising organic cathode for long-lifespan lithium metal batteries. Nevertheless, the irreversible cleavage/formation of multiple sulfur-sulfur (S-S) bonds of SPAN within conventional ether-based electrolytes results in loss of active S species, severe capacity fading and shuttle effects. Herein, we propose a new electrolyte based on dipropyl ether (PE) solvent for Li-SPAN batteries. Benefiting from the particular chain-coordination structure and weak dipole interactions with Li+ and active species, the resulting electrolyte not only achieves low desolvation energy barrier and high Li+ transference number, but also displays stable electrolyte-electrode interface (EEI). Consequently, the full cells utilizing this electrolyte exhibit good cyclability, outstanding capacity retention and superior extreme-temperature (-50°C to 50 °C) performance. Furthermore, the Ah-scale pouch cell with lean electrolyte (2.5 g Ah-1) achieves record cycle stability with 96.5% capacity retention after 75 cycles, which deliver an initial specific energy density of 150 Wh kg-1 (based on the weight of the entire cell). Impressively, this strategy demonstrates universality in a series of organic electrodes employing with PE-based electrolytes. This work highlights the strategy for modulating the dipole interaction at EEI for long-lifespan Li-organic batteries at extreme conditions.

Regulating Interface Dipole Interaction between Ethers and Active Species toward Highly Stable Li‐SPAN Batteries

Sulfurized polyacrylonitrile (SPAN) is recognized as a promising organic cathode for long‐lifespan lithium metal batteries. Nevertheless, the irreversible cleavage/formation of multiple sulfur‐sulfur (S‐S) bonds of SPAN within conventional ether‐based electrolytes results in loss of active S species, severe capacity fading and shuttle effects. Herein, we propose a new electrolyte based on dipropyl ether (PE) solvent for Li‐SPAN batteries. Benefiting from the particular chain‐coordination structure and weak dipole interactions with Li+ and active species, the resulting electrolyte not only achieves low desolvation energy barrier and high Li+ transference number, but also displays stable electrolyte‐electrode interface (EEI). Consequently, the full cells utilizing this electrolyte exhibit good cyclability, outstanding capacity retention and superior extreme‐temperature (‐50°C to 50 °C) performance. Furthermore, the Ah‐scale pouch cell with lean electrolyte (2.5 g Ah‐1) achieves record cycle stability with 96.5% capacity retention after 75 cycles, which deliver an initial specific energy density of 150 Wh kg‐1 (based on the weight of the entire cell). Impressively, this strategy demonstrates universality in a series of organic electrodes employing with PE‐based electrolytes. This work highlights the strategy for modulating the dipole interaction at EEI for long‐lifespan Li‐organic batteries at extreme conditions.

High-Q plasmonic surface lattice resonance in the ultraviolet region

Surface lattice resonances (SLRs) arise from the long-range dipolar interaction in periodic plasmonic metallic nanostructures and exhibit higher quality factors (Q-factors) compared to plasmon resonances supported in isolated metallic nanostructures. In this Letter, we report a significant improvement in the Q-factor of SLR by a factor of three via modulating the efficiency of a long-range dipolar interaction, which can be achieved by varying the thickness or refractive index of the coating layer on the top of the metallic nanostructures. Under the condition of a weak long-range dipolar interaction, we observe a nascent state of SLR located directly at the Rayleigh cutoff wavelength. Due to the absence of an in-plane diffraction mode at shorter wavelengths, the nascent-SLR dip exhibits an asymmetric shape with a high Q-factor. We experimentally monitor the evolution trend at the onset of the SLR and demonstrate a plasmonic resonance reaching an experimental Q-factor exceeding 100 in the ultraviolet region, outperforming other resonance modes in metallic nanostructures. The reported nascent SLR holds promise for boosting the performance of nano-optic devices.

Structural, optical, magnetic properties and energy-band structure of MFe2O4 (M = Co, Fe, Mn) nanoferrites prepared by co-precipitation technique.

MFe2O4 (M = Co, Fe, Mn) nanoparticles were successfully formed through the chemical co-precipitation technique. X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray analysis were used to investigate samples' structural properties. The investigated structural properties included phases formed, crystallite size, cation distribution, hopping length, bond length, bond angle, edge length, and shared and unshared octahedral edge length. Scanning electron micrographs of the prepared samples demonstrated well-defined crystalline nanoparticles. The grain diameter was 15, 9, and 34 nm for CoFe2O4, Fe3O4, and MnFe2O4, respectively. The energy-dispersive X-ray analysis confirmed the existence of every element (Co, Fe, and O) and no discernible impurities in the samples. The optical properties were studied in detail through photoluminescence (PL) spectroscopy and Raman spectroscopy. The presence of active modes in Raman spectra confirmed the spinel structure of the MFe2O4 nanoparticles. The direct bandgap energy estimated through UV-visible spectroscopy was about 2.59-2.64 eV, corresponding with the energy-band structures of the octahedral site (1.70 eV) and the tetrahedral site (0.9 eV). This result was further confirmed by PL emission spectra. Based on Mie theory and UV-visible and PL spectral data, the mechanism of photothermal characterization for MFe2O4 nanoparticles was determined. Investigating the changes in temperature of magnetic parameters including coercivity, squareness ratio, and saturation magnetization for MFe2O4 samples showed the dominant influence of ion distribution and A-A, A-B, and B-B exchange interactions. This study also showed that strong anisotropy and weak dipolar interaction tended to increase the coercivity and squareness ratio of CoFe2O4. Conversely, weaker anisotropy and stronger dipolar interaction corresponded with the small coercivity and squareness ratio of Fe3O4 and MnFe2O4 samples.

Ultrastable Super-Tonks-Girardeau Gases under Weak Dipolar Interactions.

The highly excited super-Tonks-Girardeau (sTG) gas was recently observed to be extremely stable in the presence of a weak dipolar repulsion. Here we reveal the underlying reason for this mysterious phenomenon. By exactly solving the trapped small clusters with both contact and dipolar interactions, we show that the reason lies in the distinct spectral responses between sTG gas and its decaying channel (bound state) when a weak dipolar interaction is present. Specifically, a tiny dipolar force can produce a visible energy shift for the localized bound state, but can hardly affect the extended sTG branch. As a result, the avoided level crossing between two branches is greatly modified in both location and width in the parameter axis of coupling strength, leading to a more (less) stable sTG gas for a repulsive (attractive) dipolar force. These results, consistent with experimental observations, are found to robustly apply to both bosonic and fermionic systems.

Excellent temperature stability of energy storage performance by weak dipolar interaction strategy

High-performance dielectric materials are widely used in energy storage applications, and temperature stability at extreme conditions is rarely considered yet. In this work, the Bi0.5Na0.5TiO3–Sr0.7Bi0.2□0.1TiO3–xNaNbO3 (x = 0, 0.05, and 0.15) system is designed with a room-temperature ergodic relaxor character to explore energy storage evolution with temperature. The addition of NaNbO3 increases tetragonal (P4bm) phase content and relaxor disorders and leads to a downshift of transition temperature, as verified by Rietveld refinement, dielectric analysis, and in situ Raman spectra. Superior temperature stability of recoverable energy storage density (WRec, change rate: δ ≤ 14%) and efficiency (η = 0.79–0.98) is found in x = 0.15 composition in a wide temperature range of 243–373 K, in contrast to a significant variation for x = 0 (δ ≤ 85%, η = 0.08–0.88) and 0.05 (δ ≤ 36%, η = 0.60–0.96) compositions. The dielectric relaxation speed is faster in x = 0.15, as characterized by on–off-electric field dielectric curves. This work demonstrates that the weak-dipolar-interaction system retards dipolar coalescence under cryogenic temperature and, thus, maintains high energy storage efficiency, which predicts their suitability in energy storage applications at an extreme condition.

Magnetic relaxation in two dimensional assembly of dipolar interacting nanoparticles

We perform extensive kinetic Monte Carlo simulations to investigate the magnetic relaxation characteristics in a two-dimensional (Lx×Ly) assembly of magnetic nanoparticles (MNPs) as a function of dipolar interaction strength hd, aspect ratio Ar=Ly/Lx, and temperature T. The anisotropy axes are taken as randomly oriented in three-dimensional space. In the presence of small dipolar interaction (hd≤0.3) and substantial temperature, the magnetic relaxation follows the Néel Brown model as expected. Interestingly, the dipolar interaction of enough strength is found to induce antiferromagnetic coupling in the square arrangement of MNPs (Ar=1.0), resulting in the fastening of magnetic relaxation with hd. There is also a rapid increase in relaxation even with Ar<100 above a particular dipolar interaction strength hd⋆, which gets enhanced with Ar. Remarkably, magnetization relaxes slowly with hd for the highly anisotropic system, i.e. Ar>100. It is because the dipolar interaction induces ferromagnetic interaction in such a case. The temperature also affects relaxation drastically. For weak dipolar interaction, magnetization relaxes rapidly with T because of enhancement in thermal fluctuations. The effective Néel relaxation time τN also depends strongly on these parameters. In the presence of strong dipolar interaction (hd>0.3) and Ar=1.0, τN decreases with hd for a given temperature. On the other hand, there is an increase in τN with hd for huge Ar(>100). The comparison of relaxation behaviour and τN with aligned anisotropy cases also reveals a strong dependence of these characteristics on the anisotropy axes orientation. These results are beneficial in data storage and other spintronics based applications.

Anisotropic effect of dipolar interaction in ordered ensembles of nanoparticles

We implement extensive computer simulations to investigate the hysteresis characteristics in the ordered arrays (lx × ly) of magnetic nanoparticles as a function of aspect ratio Ar = ly/lx, dipolar interaction strength hd, and external magnetic field directions. We have considered the aligned anisotropy case, α is the orientational angle. It provides an elegant en route to unearth the explicit role of anisotropy and dipolar interaction on the hysteresis response in such a versatile system. The superparamagnetic character is dominant with weak dipolar interaction (hd ≤ 0.2), resulting in the minimal hysteresis loop area. Remarkably, the double-loop hysteresis emerges even with moderate interaction strength (hd ≈ 0.4), reminiscent of antiferromagnetic coupling. These features are strongly dependent on α and Ar. Interestingly, the hysteresis loop area increases with hd, provided Ar is enormous, and the external magnetic field is along the y-direction. The coercive field μoHc, remanent magnetization Mr, and the heat dissipation EH also depend strongly on these parameters. Irrespective of the external field direction and weak dipolar interaction (hd ≤ 0.4), there is an increase in μoHc with hd for a fixed α and Ar ≤ 4.0. The dipolar interaction also elevates Mr as long as Ar is huge and the field is along the y-direction. EH is minimal for negligible and weak dipolar interaction, irrespective of Ar, α, and the field directions. Notably, the magnetic interaction enhances EH if Ar is enormous and the magnetic field is along the long axis of the system. These results are beneficial in various applications of interest such as digital data storage and spintronics. (a) Schematic of the two-dimensional array of nanoparticles. The variation of heat dissipation EH as a function of dipolar interaction strength and anisotropy axis orientation is shown in (b)-(d). The magnetic field is applied along the x-direction in (b). In contrast, the magnetic field is applied along y-direction in (c) and (d).

P-glycoprotein (ABCB1) - weak dipolar interactions provide the key to understanding allocrite recognition, binding, and transport.

P-glycoprotein (ABCB1) is the first discovered mammalian member of the large family of ATP binding cassette (ABC) transporters. It facilitates the movement of compounds (called allocrites) across membranes, using the energy of ATP binding and hydrolysis. Here, we review the thermodynamics of allocrite binding and the kinetics of ATP hydrolysis by ABCB1. In combination with our previous molecular dynamics simulations, these data lead to a new model for allocrite transport by ABCB1. In contrast to previous models, we take into account that the transporter was evolutionarily optimized to operate within a membrane, which dictates the nature of interactions. Hydrophobic interactions drive lipid-water partitioning of allocrites, the transport process's first step. Weak dipolar interactions (including hydrogen bonding, π-π stacking, and π-cation interactions) drive allocrite recognition, binding, and transport by ABCB1 within the membrane. Increasing the lateral membrane packing density reduces allocrite partitioning but enhances dipolar interactions between allocrites and ABCB1. Allocrite flopping (or reorientation of the polar part towards the extracellular aqueous phase) occurs after hydrolysis of one ATP molecule and opening of ABCB1 at the extracellular side. Rebinding of ATP re-closes the transporter at the extracellular side and expels the potentially remaining allocrite into the membrane. The high sensitivity of the steady-state ATP hydrolysis rate to the nature and number of dipolar interactions, as well as to the dielectric constant of the membrane, points to a flopping process, which occurs to a large extent at the membrane-transporter interface. The proposed unidirectional ABCB1 transport cycle, driven by weak dipolar interactions, is consistent with membrane biophysics.

On the roles of methionine and the importance of its microenvironments in redox metalloproteins.

The amino acid residue methionine (Met) is commonly thought of as a ligand in redox metalloproteins, for example in cytochromes c and in blue copper proteins. However, the roles of Met can go beyond a simple ligand. The thioether functional group of Met allows it to be considered as a hydrophobic residue as well as one that is capable of weak dipolar interactions. In addition, the lone pairs on sulphur allow Met to interact with other groups, inluding the aforementioned metal ions. Because of its properties, Met can play diverse roles in metal coordination, fine tuning of redox reactions, or supporting protein structures. These roles are strongly influenced by the nature of the surrounding medium. Herein, we describe several common interactions between Met and surrounding aromatic amino acids and how they affect the physical properties of both copper and iron metalloproteins. While the importance of interactions between Met and other groups is established in biological systems, less is known about their roles in redox metalloproteins and our view is that this is an area that is ready for greater attention.

Hysteresis in two dimensional arrays of magnetic nanoparticles

We perform computer simulations to probe the magnetic hysteresis in a two-dimensional (Lx×Ly) assembly of magnetic nanoparticles as a function of dipolar interaction strength hd, temperature T, aspect ratio Ar=Ly/Lx, and the applied alternating magnetic field’s direction. In the absence of magnetic interaction (hd≈0) and thermal fluctuations (T=0 K), the hysteresis follows the Stoner and Wohlfarth model, as expected. For weak dipolar interaction and substantial temperature, the hysteresis has the dominance of superparamagnetic behaviour, irrespective of the applied magnetic field’s direction and Ar. Interestingly, the hysteresis curve has all the characteristics of antiferromagnetic interaction dominance for Ar≤6 and considerable dipolar interaction strength (hd>0.2), independent of applied magnetic direction. When the magnetic field is applied along the system’s shorter axis (x-direction), a non-hysteresis straight line is observed with large hd. In the case of the magnetic field applied along the long axis of the sample (y-direction), ferromagnetic interaction dominates the hysteresis for large hd and Ar>6. Irrespective of hd and applied magnetic field’s direction, the coercive field μoHc and remanence Mr are minimal for Ar≤6 and significant temperature. They are found to increase with hd when Ar is enormous. There is a strong dependence of μoHc and Mr on temperature for weakly interacting MNPs. While for large hd, they depend weakly on temperature. Remarkably, the variation of hysteresis loop area EH as a function of these parameters is the same as that of the coercive field variation. We believe that the concepts presented in this work are relevant in various technological applications such as spintronics and magnetic hyperthermia, in which such self-assembled nanoparticle arrays are ubiquitous.

Tailoring Local Hysteresis in Small Clusters of Dipolar Interacting Magnetic Nanoparticles

Using first-principle calculations and kinetic Monte Carlo simulation, we study the local and averaged hysteresis in tiny clusters of [Formula: see text] magnetic nanoparticles (MNPs) or [Formula: see text]-mers. We also analyze the variation of local dipolar field acting on the constituent nanoparticles as a function of the external magnetic field. The dipolar interaction is found to promote chain-like arrangement in such a cluster. Irrespective of cluster size, the local hysteresis response depends strongly on the corresponding dipolar field acting on a nanoparticle. In a small [Formula: see text]-mer, there is a wide variation in local hysteresis as a function of nanoparticle position. On the other hand, the local hysteresis is more uniform for larger [Formula: see text]-mer, except for MNPs at the boundary. In the case of superparamagnetic nanoparticle and weak dipolar interaction, the local hysteresis loop area [Formula: see text] is minimal and depends weakly on the [Formula: see text]-mer size. While for ferromagnetic counterpart, [Formula: see text] is considerably large even for weakly interacting MNPs. The value of [Formula: see text] is found to be directly proportional to the dipolar field acting on the nanoparticle. The dipolar interaction and [Formula: see text]-mer size also enhance the coercivity and remanence. There is always an increase in [Formula: see text] with cluster size and dipolar interaction strength. Similarly, the averaged hysteresis loop area [Formula: see text] also depends strongly on the [Formula: see text]-mer size, particle size and dipolar interaction strength. [Formula: see text] and [Formula: see text] always increase with [Formula: see text]-mer size and dipolar interaction strength. Interestingly, the value of [Formula: see text] saturates for [Formula: see text] and considerable dipolar interaction irrespective of particle size. We believe that this work would help understand the intricate role of dipolar interaction on hysteresis and the organizational structure of MNPs and their usage in drug delivery and hyperthermia applications.

Thermal and dipolar interaction effect on the relaxation in a linear chain of magnetic nanoparticles

We perform computer simulations to study the relaxation in a one-dimensional chain of dipolar interacting magnetic nanoparticles (MNPs). Using the two-level approximation of the energy barrier, we perform kinetic Monte Carlo simulations to probe the relaxation mechanism as a function of dipolar interaction strength and temperature. The anisotropy axes of the MNPs are assumed to have random orientations. At high temperatures, the magnetization decay curve is exponential for weak dipolar interactions. It is found that dipolar interactions slow down the magnetic relaxation and increase the effective Néel relaxation time τN, which is affected by thermal fluctuations. In the weak dipolar limit, there is a perfect agreement between simulated and analytically evaluated values of τN for a wide range of temperatures. Microscopic analyses such as magnetic moments correlations and dynamic domain formation also suggest an increase in ferromagnetic coupling with an increase in dipolar interaction strength or decrease in thermal fluctuations. We believe that the concepts presented in this work are relevant in the context of applications such as data storage, digital data processing, and magnetic hyperthermia, in which the linear chain of MNPs are pervasive.

Topological phase diagrams of the frustrated Ising ferromagnet

The emergence of complex modulated structures in the magnetization pattern of thin films is a well-established experimental phenomenology caused by the frustrating effects of competing interactions. Using a coarse-grained version of the Ising ferromagnet with dipolar interactions, we develop a method that uses the information from the microscopic Hamiltonian to predict the specific topological phases present in the temperature-external magnetic field phase diagram. This is done by the combination of mean-field variational calculations and the renormalization group equations from the classical theory of two-dimensional melting. In this framework, we are able to distinguish when the orientational and translational symmetries are broken, discriminating between the ordered and disordered states of the system for all temperatures and fields. We observe that the reentrance developed by the $H$-$T$ phase diagrams in the regime of weak dipolar interactions is directly related with the appearance of anomalous topological transitions. These results motivate the realization of new experiments on magnetic thin films in order to explore the topological properties of the magnetic textures, allowing to identify new exotic phases in these materials.

Optimal diamagnetic dilution concentration for suppressing the dipole-dipole interaction in single-ion magnets.

The effect of screening the CoII moment of monomeric [CoIIL2(H2O)] (L = 8-hydroxyquinaldine), having a trigonal bipyramid coordination, by diamagnetic Zn in CoxZn1-x solid solutions on its magnetic relaxation was explored using ac-susceptibility, high-field electron-spin-resonance measurements and CASPT2 calculations. The retention of the crystal structure for all the solid solutions was demonstrated using single crystal diffraction. The dc-magnetization and theoretical fittings of the susceptibility for Co1 and Co0.1Zn0.9 gave a large zero-field-splitting (ZFS) D of 50 ± 6 cm-1, and very weak dipole interaction between the nearest neighbors, while EPR and calculations confirmed the positive sign of the axial component (D). Consistent parameters were obtained from experiments and theory. Importantly, only field-induced relaxation was observed for the samples with less than 50% Co and a gradual change in the barrier energy to moment reversal and relaxation times was observed between 11% and 20% Co, while both were enhanced for higher dilutions. The results establish a clear barrier for extending the longevity of the magnetism for this type of single-ion species by lowering the intramolecular interactions. The results suggest that the magnetic interaction persists up to the second sphere, that is, for a dilution of 1 in 9 (11% Co). Importantly, this method is applicable to all single-ion magnet systems, that is, the optimum dilution concentration to restrain the dipole field can be given only by the single crystal structure.

Addressing the Influence of Localized Plasmon Resonance on the Magneto-Optical Properties of Cobalt Ferrite Nanoparticles.

The optical and magneto-optical (MO) properties of magneto-plasmonic nanocomposite films made up of a transparent polymer with a dispersion of cobalt ferrite (CFO) nanoparticles (NPs) and different concentrations of Au NPs are investigated. The volumetric concentrations of CFO and Au NPs, around 3%, and below 7‰ respectively, are below the percolation limit, and hence the nanocom-posite films constitute models for investigating the influence of the electromagnetic field generated at the surface plasmon resonance of Au NPs on the magneto-optical properties of CFO NPs. The plasmon resonance is present in these magneto-plasmonic composites, red-shifted with respect to the bare Au NPs and covering the spectral region where charge-transfer and crystal field MO transitions can be excited. Moreover, the magneto-optical hysteresis loops were measured in the whole spectral region. We observe that the hysteresis loops shape is a fingerprint of the different MO transitions of the CFO NPs. The strength of the MO peak around 750 nm, corresponding to the Crystal Field transition is damped respect to the corresponding peak of the CFO NPs. The strength of this peak evolves non-monotonically with the Au NPs concentration. On the other hand, the MO band around 550 nm, excited by Charge Transfer transitions, changes sign when Au NPs are present. In addition, a second MO contribution is observed. Our results demonstrate that the interactions between plasmon resonance and MO effects are not only determined by the stronger local electromagnetic fields at the resonance but they depend on the type MO transition that is involved in these oxides. This study helps to understand and design the magneto plasmonic nano-structures and applications, for example in biomedicine and sensing, in which random and weak dipolar interparticle interactions between plasmonic and magnetic nanostructures are present.

Theoretical Aspects of the Cross Effect Enhancement of Nuclear Polarization under Static Dynamic Nuclear Polarization Conditions.

In this study, we perform quantum calculations of the spin dynamics of a small spin system that includes nine coupled electrons and one nucleus placed in an external magnetic field and exposed to microwave irradiation. This is an extension of a previous work in which we have demonstrated on a system of 11 coupled electron spins the dynamics of the electron polarizations composing the electron paramagnetic resonance (EPR) line during static dynamic nuclear polarization (DNP) experiments. There we have shown that the electron polarizations are determined by a spectral diffusion process, induced by the dipolar interaction and cross-relaxation. Additionally, we showed that a distinction had to be made between strong and weak dipolar-coupled systems relative to the inhomogeneity of the EPR line with only the first behaving according to the thermal mixing DNP (with two electron spin temperatures) description. The EPR spectra in the weak and strong dipolar interaction cases show different types of spectral features. In the extended spin system, we again make a distinction between weak and strong electron-electron interactions and show that the DNP spectra for the two cases are different in nature but that the DNP spectra can be derived in all cases from the EPR line shapes using the indirect cross effect.

Characteristics of signal propagation in multiferroic majority logic gates subjected to thermal noise

The error rates of multiferroic majority logic gate (MLG) in the presence of thermal noise fluctuation are evaluated via solving the Landau–Lifshitz–Gilbert equations. It is found that in the pre-stress condition, magnetisation orientations of nanomagnets in the MLG denote an initial 4°–10° departure from the easy axis direction due to random thermal noise field. This phenomenon may be the main origin of switching errors of multiferroic logic gates at high temperature. Specifically, in the post-stress condition, it has been seen that larger spacing between nanomagnets leads to a high error rate, up to 50%, which arises from weak dipolar coupling interactions and strong thermal fluctuations. However, opposed to their expected, small spacing between nanomagnets leads to a higher error rate, up to 90%, which mainly arises from spontaneous magnetisation reversal induced by weak stress anisotropy energy. Therefore, moderate spacing is very important to MLG switching at room temperature, for example the optimal spacing is 250–310 nm for MLG constructed with nanomagnets having shape anisotropy energy of 623 kT. These findings can provide guides on multiferroic logic circuit design.

Controlled surface/interface structure and spin enabled superior properties and biocompatibility of cobalt ferrite nanoparticles

High quality, crystalline, well-dispersed, and stable magnetic oxide nanoparticles (NPs) of inverse spinel cobalt ferrite (CoFe2O4; CFO) were prepared by a facile, reproducible, and simple hydrothermal route. The transmission electron microscopy, small-angle scattering and X-ray diffraction analyses demonstrate the structural quality of CFO NPs with a controlled size of ∼12 nm. Small-angle scattering experiments demonstrate that the pristine CFO NPs have the individual size ∼8.5 nm and spherical shape. The Raman and infrared spectroscopic measurements further confirm their high chemical quality and cubic symmetry. CFO NPs exhibit a remarkable, maximum coercivity (HC) value of 18.92 kOe, which is the highest value achieved to date. Surface spins and spins canting along with a weak dipolar interaction accounts for the giant HC and large effective anisotropy (11.45 × 106 erg/cm3) of these CFO NPs. The magnetic grain size of NPs reveals that the canted surface spins exist around the magnetic particles. Reorientation of surface spins and interparticle interaction causes the jumping behaviour in M-H hysteresis loops at H = 0. The cell viability of CFO NPs against the cancer (cisplatin resistant ovarian cancer – A2780/CP70) was evaluated to determine their potential application in biomedicine and health science. The mild response of CFO NPs in terms of their anti-proliferative nature against cancer cells and negligible cytotoxicity suggests their human-safe-and-friendly nature which makes them suitable for biomedical/health-related applications. Assessment of toxicity toward human red blood cells (RBC) revealed that hemolysis is less than 5% compared to the positive control confirming the potential applications of CFO NPs targeting human cells and making relevant for adopting them in biomedicine.

Exploring Exchange Bias Coupling in Fe3−δO4@CoO Core–Shell Nanoparticle 2D Assemblies

AbstractCore‐shell ferro(i)magnetic@antiferromagnetic (F(i)M@AFM) nanoparticles exhibiting exchange bias coupling are very promising to push back the superparamagnetic limits. However, their intrinsic magnetic properties can be strongly affected by interparticle interactions. This work reports on the collective properties of Fe3–dO4@CoO core‐shell nanoparticles as function of the structure of their assembly. The structure of nanoparticle assembly is controlled by a copper (I) catalyzed alkyne–azide cycloaddition (CuAAC) “click” reaction between complementary functional groups located at the surface of both substrates and nanoparticles. 2D arrays of nanoparticles with tunable sizes ranging from clusters of few nanoparticles to a dense and homogenous monolayer were prepared. The spatial arrangement of nanoparticles strongly influences the exchange bias coupling which is significantly enhanced for large 2D nanoparticle assemblies and, even more in 3D assemblies such as powder, which favour weak and random dipolar interactions.