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Magnetochemistry, Volume 6, Issue 1 (March 2020) – 16 articles

Cover Story (view full-size image): A possibility of the intramolecular ferromagnetic interaction in pyrazole-bridged dinuclear metal complexes was examined through DFT calculations. The antiferromagnetic interaction becomes very weak when acetate-bridging ligand is used. In the acetate-bridged complexes, an energy split of the frontier orbitals suggests the orbital counter-complementarity effect between the dxy orbital pair, which contributes to the ferromagnetic interaction; however, a significant overlap of other d-orbital pairs avoids the ferromagnetic interaction. In conclusion, the orbital counter-complementarity effect by the acetate-bridging ligand competes with the overlap of other d-orbital pairs. View this paper.
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Article
Structural Characterization of the S-glycosylated Bacteriocin ASM1 from Lactobacillus plantarum
Magnetochemistry 2020, 6(1), 16; https://doi.org/10.3390/magnetochemistry6010016 - 22 Mar 2020
Cited by 2 | Viewed by 1864
Abstract
In order to protect their environmental niche, most bacteria secret antimicrobial substances designed to target specific bacterial strains that are often closely related to the producer strain. Bacteriocins, small, ribosomally synthesised antimicrobial peptides, comprise a class of such substances and can either inhibit [...] Read more.
In order to protect their environmental niche, most bacteria secret antimicrobial substances designed to target specific bacterial strains that are often closely related to the producer strain. Bacteriocins, small, ribosomally synthesised antimicrobial peptides, comprise a class of such substances and can either inhibit (bacteriostatic) or kill (bactericidal) target cells. Glycocins are a class of bacteriocin that are post-translationally modified by one or more carbohydrate moieties that are either β-O-linked to either a serine or threonine and/or β-S-linked to a cysteine. The solution nuclear magnetic resonance structure (NMR) of the glycocin ASM1 (produced by Lactobacillus plantarum A-1), an orthologue of GccF, has been determined. In both structures, the disulfide bonds are essential for activity and restrict the mobility of the N-acetyl-glucosamine (GlcNAc) attached to Ser-18 (O-linked), compared to the much more flexible GlcNAc moiety on Cys-43 (S-linked). Interestingly, despite 88% sequence identity, the helical structure of ASM1 is less pronounced which appears to be consistent with the far ultra-violet circular dichroism (UV CD) spectra. Full article
(This article belongs to the Special Issue Nuclear Magnetic Resonance Spectroscopy in Biomedical Application)
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Review
Nano-Structured Dilute Magnetic Semiconductors for Efficient Spintronics at Room Temperature
Magnetochemistry 2020, 6(1), 15; https://doi.org/10.3390/magnetochemistry6010015 - 16 Mar 2020
Cited by 28 | Viewed by 2821
Abstract
In recent years, many efforts have been made to develop advanced metal oxide semiconductor nanomaterials with exotic magnetic properties for modern applications w.r.t traditional analogues. Dilute magnetic semiconductor oxides (DMSOs) are promising candidates for superior control over the charge and spin degrees of [...] Read more.
In recent years, many efforts have been made to develop advanced metal oxide semiconductor nanomaterials with exotic magnetic properties for modern applications w.r.t traditional analogues. Dilute magnetic semiconductor oxides (DMSOs) are promising candidates for superior control over the charge and spin degrees of freedom. DMSOs are transparent, wide band gap materials with induced ferromagnetism in doping, with a minor percentage of magnetic 3d cation to create a long-range antiferromagnetic order. Although significant efforts have been carried out to achieve DMSO with ferromagnetic properties above room temperature, it is a great challenge that still exists. However, TiO2, SnO2, ZnO and In2O3 with wide band gaps of 3.2, 3.6, 3.2 and 2.92 eV, respectively, can host a broad range of dopants to generate various compositions. Interestingly, a reduction in the size of these binary oxides can induce ferromagnetism, even at room temperature, due to the grain boundary, presence of defects and oxygen vacancies. The present review provides a panorama of the structural analysis and magnetic properties of DMSOs based on binary metal oxides nanomaterials with various ferromagnetic or paramagnetic dopants, e.g., Co, V, Fe and Ni, which exhibit enhanced ferromagnetic behaviors at room temperature. Full article
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Article
Effect of Terbium Ion Substitution in Inverse Spinel Nickel Ferrite: Structural and Magnetic Study
Magnetochemistry 2020, 6(1), 14; https://doi.org/10.3390/magnetochemistry6010014 - 10 Mar 2020
Cited by 9 | Viewed by 1712
Abstract
Doping rare-earth ions into spinel ferrites can alter their electrical and magnetic properties. The present study delineates the structure–property relationship of the effect of rare-earth terbium doping in NiFe2O4 ferrite. X-ray diffraction analysis (XRD) showed unit cell lattice expansion with [...] Read more.
Doping rare-earth ions into spinel ferrites can alter their electrical and magnetic properties. The present study delineates the structure–property relationship of the effect of rare-earth terbium doping in NiFe2O4 ferrite. X-ray diffraction analysis (XRD) showed unit cell lattice expansion with increased Tb3+ content. The Fourier transform infrared spectroscopy (FTIR) results indicate preferential occupancy of Tb3+ at the octahedral B site. The magnetic parameters derived from room temperature hysteresis loops where both the saturation magnetization, Ms, and coercivity, Hc, value decreased with the Tb3+ substitution and reached a minimum value of Ms ~30.6 emu/g at x = 0.1 and Hc ~102 Oe at x = 0.075. The temperature-dependent magnetocrystalline anisotropy derived from the magnetic isotherm was observed to be the highest for x = 0.1 at 5 K with the value K1 ~1.09 × 106 J/m3. The Tb3+ doping also resulted in the Curie temperature reduction from 938 K at x = 0.0 to 899 K at x = 0.1. Full article
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Review
Magnetic Nanoparticles as In Vivo Tracers for Alzheimer’s Disease
Magnetochemistry 2020, 6(1), 13; https://doi.org/10.3390/magnetochemistry6010013 - 04 Mar 2020
Cited by 4 | Viewed by 2202
Abstract
Drug formulations and suitable methods for their detection play a very crucial role in the development of therapeutics towards degenerative neurological diseases. For diseases such as Alzheimer’s disease, magnetic resonance imaging (MRI) is a non-invasive clinical technique suitable for early diagnosis. In this [...] Read more.
Drug formulations and suitable methods for their detection play a very crucial role in the development of therapeutics towards degenerative neurological diseases. For diseases such as Alzheimer’s disease, magnetic resonance imaging (MRI) is a non-invasive clinical technique suitable for early diagnosis. In this review, we will discuss the different experimental conditions which can push MRI as the technique of choice and the gold standard for early diagnosis of Alzheimer’s disease. Here, we describe and compare various techniques for administration of nanoparticles targeted to the brain and suitable formulations of nanoparticles for use as magnetically active therapeutic probes in drug delivery targeting the brain. We explore different physiological pathways involved in the transport of such nanoparticles for successful entry in the brain. In our lab, we have used different formulations of iron oxide nanoparticles (IONPs) and protein nanocages as contrast agents in anatomical MRI of an Alzheimer’s disease (AD) brain. We compare these coatings and their benefits to provide the best contrast in addition to biocompatibility properties to be used as sustainable drug-release systems. In the later sections, the contrast enhancement techniques in MRI studies are discussed. Examples of contrast-enhanced imaging using advanced pulse sequences are discussed with the main focus on important studies in the field of neurological diseases. In addition, T1 contrast agents such as gadolinium chelates are compared with the T2 contrast agents mainly made of superparamagnetic inorganic metal nanoparticles. Full article
(This article belongs to the Special Issue Nuclear Magnetic Resonance Spectroscopy in Biomedical Application)
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Article
Spontaneous Magnetization and Optical Activity in the Chiral Series {(L-proline)nV[Cr(CN)6]x} (0 < n < 3)
Magnetochemistry 2020, 6(1), 12; https://doi.org/10.3390/magnetochemistry6010012 - 03 Mar 2020
Cited by 3 | Viewed by 1579
Abstract
The incorporation of the natural amino acid L-proline in the synthesis to vanadium-chromium Prussian blue derivatives results in materials exhibiting magnetic ordering including chiral magnetic centers. Although the amorphous nature of these materials makes difficult to assess the structural features of these proline-containing [...] Read more.
The incorporation of the natural amino acid L-proline in the synthesis to vanadium-chromium Prussian blue derivatives results in materials exhibiting magnetic ordering including chiral magnetic centers. Although the amorphous nature of these materials makes difficult to assess the structural features of these proline-containing compounds, magnetic and spectroscopic data confirms their multifunctionality. They exhibit high-temperature magnetic ordering (Tc < 255 K) and a circular dichroic signal, representing the molecule-based chiral magnets with the highest ordering temperatures reported to date. In addition, the presence of chiral L-proline (or D-proline) has additional benefits, including higher redox stability and the appearance of magnetic hysteresis. The latter was not observed in the parent compounds, the series of room temperature molecule-based magnets V[Cr(CN)6]x. Full article
(This article belongs to the Special Issue Feature Papers in Magnetochemistry)
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Review
A Review on the Optimal Design of Magnetic Nanoparticle-Based T2 MRI Contrast Agents
Magnetochemistry 2020, 6(1), 11; https://doi.org/10.3390/magnetochemistry6010011 - 28 Feb 2020
Cited by 26 | Viewed by 2281
Abstract
Relaxivity r2 and thus the contrast efficacy of superparamagnetic nanoparticles (NPs) can be enhanced via either NP’s magnetic properties or coating optimization. Numerous reports can be found about the investigation of the optimal iron oxide nanoparticles (IO NPs) size, shape, crystallinity and [...] Read more.
Relaxivity r2 and thus the contrast efficacy of superparamagnetic nanoparticles (NPs) can be enhanced via either NP’s magnetic properties or coating optimization. Numerous reports can be found about the investigation of the optimal iron oxide nanoparticles (IO NPs) size, shape, crystallinity and composition that yield high saturation magnetization (ms) values and, consequently, high r2 values. Although the use of an appropriate coating can boost up the NPs MRI contrast agent efficiency, this topic has been largely understudied. Therefore, in this review, the factors affording r2 enhancement of spherical magnetic NPs are discussed. Based on the literature, the requirements for an optimal surface coating that may increase r2 values and ensure stability and biocompatibility of NPs are listed. One of the best candidates that fulfil these requirements are liposomes with embedded magnetic NPs, so-called magneto-liposomes. The analysis of the literature elucidated the most appropriate phospholipid compositions for the relaxivity enhancement and for magneto-liposomes in vivo stability. Finally, the future directions in the development of NP-based contrast agents are given. For example, most of the synthetic NPs are recognized and eliminated as a foreign substance by the immune system. To overcome this issue, a design of a biomimetic, cell-membrane-based nanocarrier for contrast agents is proposed. Disguised with cell membranes, NPs or other active components can act as autogenous cells and thus ensure the inherent biocompatibility. Full article
(This article belongs to the Special Issue Magnetic Nanoparticles 2020)
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Article
Theoretical Study on Magnetic Interaction in Pyrazole-Bridged Dinuclear Metal Complex: Possibility of Intramolecular Ferromagnetic Interaction by Orbital Counter-Complementarity
Magnetochemistry 2020, 6(1), 10; https://doi.org/10.3390/magnetochemistry6010010 - 26 Feb 2020
Cited by 3 | Viewed by 1566
Abstract
A possibility of the intramolecular ferromagnetic (FM) interaction in pyrazole-bridged dinuclear Mn(II), Fe(II), Co(II), and Ni(II) complexes is examined by density functional theory (DFT) calculations. When azide is used for additional bridging ligand, the complexes indicate the strong antiferromagnetic (AFM) interaction, while the [...] Read more.
A possibility of the intramolecular ferromagnetic (FM) interaction in pyrazole-bridged dinuclear Mn(II), Fe(II), Co(II), and Ni(II) complexes is examined by density functional theory (DFT) calculations. When azide is used for additional bridging ligand, the complexes indicate the strong antiferromagnetic (AFM) interaction, while the AFM interaction becomes very weak when acetate ligand is used. In the acetate-bridged complexes, an energy split of the frontier orbitals suggests the orbital counter-complementarity effect between the dxy orbital pair, which contributes to the FM interaction; however, a significant overlap of other d-orbital pairs also suggests an existence of the AFM interaction. From those results, the orbital counter-complementarity effect is considered to be canceled out by the overlap of other d-orbital pairs. Full article
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Article
Effect of Ga and Zr Substitution on the Properties of Dy2Fe17−XZrX and Dy2Fe16Ga1−xZrx (0 ≤ x ≤ 1) Intermetallic Compounds Prepared via Arc Melting Process
Magnetochemistry 2020, 6(1), 9; https://doi.org/10.3390/magnetochemistry6010009 - 21 Feb 2020
Cited by 3 | Viewed by 1104
Abstract
The effects of substitution of Zr and Ga on the structural and magnetic properties of Dy2Fe17 intermetallic compound were investigated in this study. The Rietveld analysis confirmed that the crystalline system was a Th2Ni17 structure. Lattice parameters [...] Read more.
The effects of substitution of Zr and Ga on the structural and magnetic properties of Dy2Fe17 intermetallic compound were investigated in this study. The Rietveld analysis confirmed that the crystalline system was a Th2Ni17 structure. Lattice parameters a (Å) and c (Å), unit cell volume (Å3), and bonding distance (Å) were calculated using Rietveld analysis. The unit cell volume of Dy2Fe17−xZrx and Dy2Fe16Ga1−xZrx increased linearly with Zr and Ga substitution. The Curie temperature (Tc) of Dy2Fe17−xZrx and Dy2Fe16Ga1−xZrx was found to be Zr content-dependent. The maximum Curie temperatures were observed at 510 K (x = 0.75 Zr content) for Dy2Fe17−xZrx and 505.1 K (x = 0.5 Zr content) for Dy2Fe16Ga1−xZrx, which are 102 K and 97 K higher than the value found for Dy2Fe17, respectively. The room-temperature Mössbauer analysis showed a decrease in the average hyperfine field and increases in the isomer shift with Zr doping. The overall improvement in Curie temperature with the substitution strategy of Zr–Ga substitution in 2:17 intermetallic compounds could find potential use of these magnetic compounds in high-temperature applications. Full article
(This article belongs to the Special Issue Permanent Magnets)
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Article
Design, Characterization and Molecular Modeling of New Fluorinated Paramagnetic Contrast Agents for Dual 1H/19F MRI
Magnetochemistry 2020, 6(1), 8; https://doi.org/10.3390/magnetochemistry6010008 - 11 Feb 2020
Cited by 5 | Viewed by 1401
Abstract
One major goal in medical imaging is the elaboration of more efficient contrast agents (CAs). Those agents need to be optimized for the detection of affected tissues such as cancers or tumors while decreasing the injected quantity of agents. The paramagnetic contrast agents [...] Read more.
One major goal in medical imaging is the elaboration of more efficient contrast agents (CAs). Those agents need to be optimized for the detection of affected tissues such as cancers or tumors while decreasing the injected quantity of agents. The paramagnetic contrast agents containing fluorine atoms can be used for both proton and fluorine magnetic resonance imaging (MRI), and they open the possibility of simultaneously mapping the anatomy using 1H MRI and accurately locating the agents using 19F MRI. One of the challenges in this domain is to synthesize molecules containing several chemically equivalent fluorine atoms with relatively short relaxation times to allow the recording of 19F MR images in good conditions. With that aim, we propose to prepare a CA containing a paramagnetic center and nine chemically equivalent fluorine atoms using a cycloaddition reaction between two building blocks. These fluorinated contrast agents are characterized by 19F NMR, showing differences in the fluorine relaxation times T1 and T2 depending on the lanthanide ion. To complement the experimental results, molecular dynamics simulations are performed to shed light on the 3D-structure of the molecules in order to estimate the distance between the lanthanide ion and the fluorine atoms. Full article
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Editorial
Acknowledgement to Reviewers of Magnetochemistry in 2019
Magnetochemistry 2020, 6(1), 7; https://doi.org/10.3390/magnetochemistry6010007 - 04 Feb 2020
Viewed by 928
Abstract
Rigorous peer-review is the corner-stone of high-quality academic publishing [...] Full article
Editorial
Magnetic Nanoparticles
Magnetochemistry 2020, 6(1), 6; https://doi.org/10.3390/magnetochemistry6010006 - 15 Jan 2020
Cited by 16 | Viewed by 2169
Abstract
Magnetic nanoparticles are a class of nanoparticle that can be manipulated using magnetic fields [...] Full article
(This article belongs to the Special Issue Magnetic Nanoparticles)
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Perspective
False Chirality, Absolute Enantioselection and CP Violation: Pierre Curie’s Legacy
Magnetochemistry 2020, 6(1), 5; https://doi.org/10.3390/magnetochemistry6010005 - 15 Jan 2020
Cited by 14 | Viewed by 2112
Abstract
The 1884 suggestion of Pierre Curie (1859–1906) that the type of dissymmetry shown by collinear electric and magnetic fields may induce an enantiomeric excess, in a chemical reaction that would otherwise produce a racemic mixture, is explored in the context of fundamental symmetry [...] Read more.
The 1884 suggestion of Pierre Curie (1859–1906) that the type of dissymmetry shown by collinear electric and magnetic fields may induce an enantiomeric excess, in a chemical reaction that would otherwise produce a racemic mixture, is explored in the context of fundamental symmetry arguments. Curie’s arrangement exhibits false chirality (time-noninvariant enantiomorphism), and so it may not induce absolute enantioselection (ae) in a process that has reached thermodynamic equilibrium, since it does not lift the degeneracy of chiral enantiomers. However, it may do so in far-from-equilibrium processes via a breakdown in microscopic reversibility analogous to that observed in elementary particle processes under the influence of CP violation, the associated force possessing false chirality with respect to CP enantiomorphism. In contrast, an influence like circularly polarized light exhibiting true chirality (time-invariant enantiomorphism) lifts the degeneracy of enantiomers, and so may induce ae in all circumstances. Although to date, ae has not been observed under the influence of Curie’s arrangement of collinear electric and magnetic fields, it is argued that two different experiments have now demonstrated ae under a falsely chiral influence in systems far from equilibrium, namely in a spinning sample under a gravitational field, and in the separation of enantiomers at a ferromagnetic surface. Full article
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Review
Hybrid Nanostructured Magnetite Nanoparticles: From Bio-Detection and Theragnostics to Regenerative Medicine
Magnetochemistry 2020, 6(1), 4; https://doi.org/10.3390/magnetochemistry6010004 - 10 Jan 2020
Cited by 16 | Viewed by 2556
Abstract
Nanotechnology offers the possibility of operating on the same scale length at which biological processes occur, allowing to interfere, manipulate or study cellular events in disease or healthy conditions. The development of hybrid nanostructured materials with a high degree of chemical control and [...] Read more.
Nanotechnology offers the possibility of operating on the same scale length at which biological processes occur, allowing to interfere, manipulate or study cellular events in disease or healthy conditions. The development of hybrid nanostructured materials with a high degree of chemical control and complex engineered surface including biological targeting moieties, allows to specifically bind to a single type of molecule for specific detection, signaling or inactivation processes. Magnetite nanostructures with designed composition and properties are the ones that gather most of the designs as theragnostic agents for their versatility, biocompatibility, facile production and good magnetic performance for remote in vitro and in vivo for biomedical applications. Their superparamagnetic behavior below a critical size of 30 nm has allowed the development of magnetic resonance imaging contrast agents or magnetic hyperthermia nanoprobes approved for clinical uses, establishing an inflection point in the field of magnetite based theragnostic agents. Full article
(This article belongs to the Special Issue Magnetic Nanoparticles)
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Review
Magnetic Nanoparticles for Nanomedicine
Magnetochemistry 2020, 6(1), 3; https://doi.org/10.3390/magnetochemistry6010003 - 09 Jan 2020
Cited by 24 | Viewed by 2441
Abstract
The field of nanomedicine has recently emerged as a product of the expansion of a range of nanotechnologies into biomedical science, pharmacology and clinical practice. Due to the unique properties of nanoparticles and the related nanostructures, their applications to medical diagnostics, imaging, controlled [...] Read more.
The field of nanomedicine has recently emerged as a product of the expansion of a range of nanotechnologies into biomedical science, pharmacology and clinical practice. Due to the unique properties of nanoparticles and the related nanostructures, their applications to medical diagnostics, imaging, controlled drug and gene delivery, monitoring of therapeutic outcomes, and aiding in medical interventions, provide a new perspective for challenging problems in such demanding issues as those involved in the treatment of cancer or debilitating neurological diseases. In this review, we evaluate the role and contributions that the applications of magnetic nanoparticles (MNPs) have made to various aspects of nanomedicine, including the newest magnetic particle imaging (MPI) technology allowing for outstanding spatial and temporal resolution that enables targeted contrast enhancement and real-time assistance during medical interventions. We also evaluate the applications of MNPs to the development of targeted drug delivery systems with magnetic field guidance/focusing and controlled drug release that mitigate chemotherapeutic drugs’ side effects and damage to healthy cells. These systems enable tackling of multiple drug resistance which develops in cancer cells during chemotherapeutic treatment. Furthermore, the progress in development of ROS- and heat-generating magnetic nanocarriers and magneto-mechanical cancer cell destruction, induced by an external magnetic field, is also discussed. The crucial roles of MNPs in the development of biosensors and microfluidic paper array devices (µPADs) for the detection of cancer biomarkers and circulating tumor cells (CTCs) are also assessed. Future challenges concerning the role and contributions of MNPs to the progress in nanomedicine have been outlined. Full article
(This article belongs to the Special Issue Magnetic Nanoparticles)
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Review
Magnetic Nanoparticle Systems for Nanomedicine—A Materials Science Perspective
Magnetochemistry 2020, 6(1), 2; https://doi.org/10.3390/magnetochemistry6010002 - 02 Jan 2020
Cited by 41 | Viewed by 3481
Abstract
Iron oxide nanoparticles are the basic components of the most promising magneto-responsive systems for nanomedicine, ranging from drug delivery and imaging to hyperthermia cancer treatment, as well as to rapid point-of-care diagnostic systems with magnetic nanoparticles. Advanced synthesis procedures of single- and multi-core [...] Read more.
Iron oxide nanoparticles are the basic components of the most promising magneto-responsive systems for nanomedicine, ranging from drug delivery and imaging to hyperthermia cancer treatment, as well as to rapid point-of-care diagnostic systems with magnetic nanoparticles. Advanced synthesis procedures of single- and multi-core iron-oxide nanoparticles with high magnetic moment and well-defined size and shape, being designed to simultaneously fulfill multiple biomedical functionalities, have been thoroughly evaluated. The review summarizes recent results in manufacturing novel magnetic nanoparticle systems, as well as the use of proper characterization methods that are relevant to the magneto-responsive nature, size range, surface chemistry, structuring behavior, and exploitation conditions of magnetic nanosystems. These refer to particle size, size distribution and aggregation characteristics, zeta potential/surface charge, surface coating, functionalization and catalytic activity, morphology (shape, surface area, surface topology, crystallinity), solubility and stability (e.g., solubility in biological fluids, stability on storage), as well as to DC and AC magnetic properties, particle agglomerates formation, and flow behavior under applied magnetic field (magnetorheology). Full article
(This article belongs to the Special Issue Magnetic Nanoparticles)
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Article
Magnetoelectrochemistry and Asymmetric Electrochemical Reactions
Magnetochemistry 2020, 6(1), 1; https://doi.org/10.3390/magnetochemistry6010001 - 18 Dec 2019
Cited by 6 | Viewed by 1925
Abstract
Magnetoelectrochemistry is a branch of electrochemistry where magnetic fields play a vital role in the oxidation and reduction process of the molecules. When it comes to spin-dependent electrochemistry (SDE), becomes a new paradigm. This work presents electrochemical response during the “chiral imprinting” on [...] Read more.
Magnetoelectrochemistry is a branch of electrochemistry where magnetic fields play a vital role in the oxidation and reduction process of the molecules. When it comes to spin-dependent electrochemistry (SDE), becomes a new paradigm. This work presents electrochemical response during the “chiral imprinting” on working electrodes and the effects of potentiostatic and galvanostatic methods. We explore the use of the SDE concept, which is implemented for chiral-ferromagnetic (CFM) hybrid working electrodes, and we compare various electrochemical parameters affecting the quality of deposition. We electrochemically co-deposited nickel (Ni) with a chiral compound (tartaric acid) in its enantiopure forms (L and D), which allows us to obtain a chiral co-deposited nickel-tartaric acid (Ni-LTA or Ni-DTA) working electrode. Full article
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