Magnetochemistry, Volume 5, Issue 4 (December 2019) – 16 articles

Density functional theory (DFT) is used extensively for the first-principles calculation of hyperfine coupling constants in both main-group and transition metal systems. As with many other properties, the performance of DFT for hyperfine coupling constants is of variable quality, particularly for transition metal complexes, because it strongly depends on the nature of the chemical system and the type of approximation to the exchange-correlation functional. Recently, a meta-generalized-gradient approximation (mGGA) functional was proposed that obeys all known exact constraints for such a method, known as the Strongly Constrained and Appropriately Normed (SCAN) functional. In view of its theoretically superior formulation a benchmark set of complexes is used to assess the performance of SCAN for the challenging case of transition metal hyperfine coupling constants. In addition, two global hybrid versions of the functional, SCANh and SCAN0, are described and tested. The values computed with the new functionals are compared with experiment and with those of other DFT approximations. Although the original SCAN and the SCAN-based hybrids may offer improved hyperfine coupling constants for specific systems, no uniform improvement is observed. On the contrary, there are specific cases where the new functionals fail badly due to a flawed description of the underlying electronic structure. Therefore, despite these methodological advances, systematically accurate and system-independent prediction of transition metal hyperfine coupling constants with DFT remains an unmet challenge. Full article

The small amounts of gaseous ³He dissolved in low concentrated water solutions of NaCl, NaNO₃ and NaClO₄ were prepared and examined by ³He-, ²³Na-, ³⁵Cl- and ¹⁵N-NMR spectroscopy. This experimental data, along with new theoretical shielding factors, was used to measure the ²³Na nuclear magnetic moment against that of helium-3 μ(²³Na) = +2.2174997(111) in nuclear magnetons. The standard relationship between NMR frequencies and nuclear magnetic moments of observed nuclei was used. The nuclear magnetic shielding factors of ²³Na cation were verified against that of counter ions present in water solutions. Very good agreement between shielding constants σ(³He), σ(²³Na⁺), σ(³⁵Cl^‒), σ(³⁵ClO₄^‒), σ(¹⁵NO₃^‒) in water at infinite dilution and nuclear magnetic moments was observed for all magnetic nuclei. It can be used as a reference nucleus for calculating a few other magnetic moments of different nuclei by the NMR method. An analysis of new and former μ(²³Na) experimental data obtained by the atomic beam magnetic resonance method (ABMR) and other NMR measurements shows good replicability of all specified results. The composition of sodium water complexes was discussed in terms of chemical equilibria and NMR shielding scale. Full article

Hyperthermia is a noninvasive method that uses heat for cancer therapy where high temperatures have a damaging effect on tumor cells. However, large amounts of heat need to be delivered, which could have negative effects on healthy tissues. Thus, to minimize the negative side effects on healthy cells, a large amount of heat must be delivered only to the tumor cells. Magnetic hyperthermia (MH) uses magnetic nanoparticles particles (MNPs) that are exposed to alternating magnetic field (AMF) to generate heat in local regions (tissues or cells). This cancer therapy method has several advantages, such as (a) it is noninvasive, thus requiring surgery, and (b) it is local, and thus does not damage health cells. However, there are several issues that need to achieved: (a) the MNPs should be biocompatible, biodegradable, with good colloidal stability (b) the MNPs should be successfully delivered to the tumor cells, (c) the MNPs should be used with small amounts and thus MNPs with large heat generation capabilities are required, (d) the AMF used to heat the MNPs should meet safety conditions with limited frequency and amplitude ranges, (e) the changes of temperature should be traced at the cellular level with accurate and noninvasive techniques, (f) factors affecting heat transport from the MNPs to the cells must be understood, and (g) the effect of temperature on the biological mechanisms of cells should be clearly understood. Thus, in this multidisciplinary field, research is needed to investigate these issues. In this report, we shed some light on the principles of heat generation by MNPs in AMF, the limitations and challenges of MH, and the applications of MH using multifunctional hybrid MNPs. Full article

Magnetic nanoparticles became increasingly interesting in recent years as a result of their tailorable size-dependent properties, which enable their use in a wide range of applications. One of their emerging applications is biomedicine; in particular, bimetallic nickel/copper magnetic nanoparticles (NiCu MNPs) are gaining momentum as a consequence of their unique properties that are suitable for biomedicine. These characteristics include stability in various chemical environments, proven biocompatibility with various cell types, and tunable magnetic properties that can be adjusted by changing synthesis parameters. Despite the obvious potential of NiCu MNPs for biomedical applications, the general interest in their use for this purpose is rather low. Nevertheless, the steadily increasing annual number of related papers shows that increasingly more researchers in the biomedical field are studying this interesting formulation. As with other MNPs, NiCu-based formulations were examined for their application in magnetic hyperthermia (MH) as one of their main potential uses in clinics. MH is a treatment method in which cancer tissue is selectively heated through the localization of MNPs at the target site in an alternating magnetic field (AMF). This heating destroys cancer cells only since they are less equipped to withstand temperatures above 43 °C, whereas this temperature is not critical for healthy tissue. Superparamagnetic particles (e.g., NiCu MNPs) generate heat by relaxation losses under an AMF. In addition to MH in cancer treatment, which might be their most beneficial potential use in biomedicine, the properties of NiCu MNPs can be leveraged for several other applications, such as controlled drug delivery and prolonged localization at a desired target site in the body. After a short introduction that covers the general properties of NiCu MNPs, this review explores different synthesis methods, along with their main advantages and disadvantages, potential surface modification approaches, and their potential in biomedical applications, such as MH, multimodal cancer therapy, MH implants, antibacterial activity, and dentistry. Full article

When using single molecule magnets (SMMs) in spintronics devices, controlling the quantum tunneling of the magnetization (QTM) and spin-lattice interactions is important. To improve the functionality of SMMs, researchers have explored the effects of changing the coordination geometry of SMMs and the magnetic interactions between them. Here, we report on the effects of the octa-coordination geometry on the magnetic relaxation processes of dinuclear dysprosium(III) complexes in the low-temperature region. Mixed ligand dinuclear Dy³⁺ triple-decker complexes [(TPP)Dy(Pc)Dy(TPP)] (1), which have crystallographically equivalent Dy³⁺ ions, and [(Pc)Dy(Pc)Dy(TPP)] (2), which have non-equivalent Dy³⁺ ions, (Pc²⁻ = phthalocyaninato; TPP²⁻ = tetraphenylporphyrinato), undergo dual magnetic relaxation processes. This is due to the differences in the ground states due to the twist angle (φ) between the ligands. The relationship between the off-diagonal terms and the dual magnetic relaxation processes that appears due to a deviation from D_4h symmetry is discussed. Full article

Nanomaterial biosensors have revolutionized the entire scientific, technology, biomedical, materials science, and engineering fields. Among all nanomaterials, magnetic nanoparticles, microparticles, and beads are unique in offering facile conjugation of biorecognition probes for selective capturing of any desired analytes from complex real sample matrices (e.g., biofluids such as whole blood, serum, urine and saliva, tissues, food, and environmental samples). In addition, rapid separation of the particle-captured analytes by the simple use of a magnet for subsequent detection on a sensor unit makes the magnetic particle sensor approach very attractive. The easy magnetic isolation feature of target analytes is not possible with other inorganic particles, both metallic (e.g., gold) and non-metallic (e.g., silica), which require difficult centrifugation and separation steps. Magnetic particle biosensors have thus enabled ultra-low detection with ultra-high sensitivity that has traditionally been achieved only by radioactive assays and other tedious optical sources. Moreover, when traditional approaches failed to selectively detect low-concentration analytes in complex matrices (e.g., colorimetric, electrochemistry, and optical methods), magnetic particle-incorporated sensing strategies enabled sample concentration into a defined microvolume of large surface area particles for a straightforward detection. The objective of this article is to highlight the ever-growing applications of magnetic materials for the detection of analytes present in various real sample matrices. The central idea of this paper was to show the versatility and advantages of using magnetic particles for a variety of sample matrices and analyte types and the adaptability of different transducers with the magnetic particle approaches. Full article

Magnetic nanoparticles (MNPs) have attracted growing interest as versatile materials for the development of analytical detection and separation platforms for food safety monitoring. This review discusses recent advances in the synthesis, functionalization and applications of MNPs in bioanalysis. A special emphasis is given to the use of MNPs as an immobilization support for biomolecules and as a target capture and pre-concentration to increase selectivity and sensitivity of analytical platforms for the monitoring of food contaminants. General principles and examples of MNP-based platforms for separation, amplification and detection of analytes of interest in food, including organic and inorganic constituents are discussed. Full article

Due to the expanding occurrence of marine toxins, and their potential impact on human health, there is an increased need for tools for their rapid and efficient detection. We give an overview of the use of magnetic beads (MBs) for the detection of marine toxins in shellfish and fish samples, with an emphasis on their incorporation into electrochemical biosensors. The use of MBs as supports for the immobilization of toxins or antibodies, as signal amplifiers as well as for target pre-concentration, is reviewed. In addition, the exploitation of MBs in Systematic Evolution of Ligands by Exponential enrichment (SELEX) for the selection of aptamers is presented. These MB-based strategies have led to the development of sensitive, simple, reliable and robust analytical systems for the detection of toxins in natural samples, with applicability in seafood safety and human health protection. Full article

Magnetic nanoparticles and magnetic nano-species of complex topology (e.g., nanorods, nanowires, nanotubes, etc.) are overviewed briefly in the paper, mostly giving attention to the synthetic details and particle composition (e.g., core-shell structures made of different materials). Some aspects related to applications of magnetic nano-species are briefly discussed. While not being a comprehensive review, the paper offers a large collection of references, particularly useful for newcomers in the research area. Full article

Extracellular vesicles (EVs) are essential tools for conveying biological information and modulating functions of recipient cells. Implantation of isolated or modulated EVs can be innovative therapeutics for various diseases. Furthermore, EVs could be a biocompatible drug delivery vehicle to carry both endogenous and exogenous biologics. Tracking EVs should play essential roles in understanding the functions of EVs and advancing EV therapeutics. EVs have the characteristic structures consisting of the lipid bilayer and specific membrane proteins, through which they can be labeled efficiently. EVs can be labeled either directly using probes or indirectly by transfection of reporter genes. Optical imaging (fluorescent imaging and bioluminescent imaging), single-photon emission computed tomography (SPECT)/positron emission tomography (PET), and magnetic resonance imaging (MRI) are currently used for imaging EVs. Labeling EVs with superparamagnetic iron oxide (SPIO) nanoparticles for MRI tracking is a promising method that can be translated into clinic. SPIO can be internalized by most of the cell types and then released as SPIO containing EVs, which can be visualized on T2*-weighted imaging. However, this method has limitations in real-time imaging because of the life cycle of SPIO after EV degradation. Further studies will be needed to validate SPIO labeling by other imaging modalities in preclinical studies. The emerging technologies of labeling and imaging EVs with SPIO in comparison with other imaging modalities are reviewed in this paper. Full article

In recent years, various reports related to sensing application research have suggested that combining the synergistic impacts of optical, electrical or magnetic properties in a single technique can lead to a new multitasking platform. Owing to their unique features of the magnetic moment, biocompatibility, ease of surface modification, chemical stability, high surface area, high mass transference, magnetic nanoparticles have found a wide range of applications in various fields, especially in sensing systems. The present review is comprehensive information about magnetic nanoparticles utilized in the optical sensing platform, broadly categorized into four types: surface plasmon resonance (SPR), surface-enhanced Raman spectroscopy (SERS), fluorescence spectroscopy and near-infrared spectroscopy and imaging (NIRS) that are commonly used in various (bio) analytical applications. The review also includes some conclusions on the state of the art in this field and future aspects. Full article

A series of five new mononuclear pentagonal bipyramidal Co(II) complexes with the equatorial 2,6-diacetylpyridine bis(semicarbazone) ligand (H₂dapsc) and various axial pseudohalide ligands (SCN, SeCN, N(CN)₂, C(CN)₃, and N₃) was prepared and structurally characterizated: [Co(H₂dapsc)(SCN)₂]∙0.5C₂H₅OH (1), [Co(H₂dapsc)(SeCN)₂]∙0.5C₂H₅OH (2), [Co(H₂dapsc)(N(CN)₂)₂]∙2H₂O (3), [Co(H₂dapsc)(C(CN)₃)(H₂O)](NO₃)∙1.16H₂O (4), and {[Co(H₂dapsc)(H₂O)(N₃)][Co(H₂dapsc)(N₃)₂]}N₃∙4H₂O (5). The combined analyses of the experimental DC and AC magnetic data of the complexes (1–5) and two other earlier described those of this family [Co(H₂dapsc)(H₂O)₂)](NO₃)₂∙2H₂O (6) and [Co(H₂dapsc)(Cl)(H₂O)]Cl∙2H₂O (7), their theoretical description and the ab initio CASSCF/NEVPT2 calculations reveal large easy-plane magnetic anisotropies for all complexes (D = + 35 − 40 cm⁻¹). All complexes under consideration demonstrate slow magnetic relaxation with dominant Raman and direct spin–phonon processes at static magnetic field and so they belong to the class of field-induced single-ion magnets (SIMs). Full article

Numerical investigation of the effects of magnetic field strength, thermal radiation, Joule heating, and viscous heating on a forced convective flow of a non-Newtonian, incompressible power-law fluid in an axisymmetric stretching sheet with variable temperature wall is accomplished. The power-law shear-thinning viscosity-shear rate model for the anisotropic solutions and the Rosseland approximation for the thermal radiation through a highly absorbing medium is considered. The temperature-dependent heat sources, Joule heating, and viscous heating are considered to be the source terms in the energy balance. The non-dimensional boundary-layer equations are solved numerically in terms of similarity variable. A parameter study on the boundary value of chemical reaction and Nusselt number is performed as a function of thermal radiation parameter, Brinkman number, Prandtl number, Hartmann number, power-law index, heat source coefficient, Brownian parameter, thermophoresis parameter, and the chemical reaction parameter. The results show that the chemical reaction parameter has an increasing effect on the chemical reaction boundary while the magnetic, thermophoresis, and Brownian effects decrease the rate of the chemical reaction at the boundary. Full article

Two dinuclear lanthanide complexes [Dy₂(L¹)₆(L²)₂]·2EtOH (1) and [Tb₂(L¹)₆(L²)₂]·2EtOH (2) (HL¹ = phenoxyacetic acid and L² = 2,2′-bipyridine) were synthesized and the crystal structures were determined. In both complexes, the lanthanide centers are nine-coordinated and have a muffin geometry. Detailed magnetic study reveals the presence of field-induced single molecule magnet (SMM) behavior for complex 1, whereas complex 2 is non-SMM in nature. Further magnetic study with 1′, yttrium doped magnetically diluted sample of 1, disclosed the presence of Orbach and Raman relaxation processes with effective energy barrier, ∆E = 16.26 cm⁻¹ and relaxation time, τ_o = 2.42 × 10⁻⁸ s. Luminescence spectra for complexes 1 and 2 in acetonitrile were studied which show characteristic emission peaks for Dy^III and Tb^III ions, respectively. Full article

During the last few decades, magnetic nanoparticles have been evaluated as promising materials in the field of cancer detection, screening, and treatment. Early diagnosis and screening of cancer may be achieved using magnetic nanoparticles either within the magnetic resonance imaging technique and/or sensing systems. These sensors are designed to selectively detect specific biomarkers, compounds that can be related to the onset or evolution of cancer, during and after the treatment of this widespread disease. Some of the particular properties of magnetic nanoparticles are extensively exploited in cancer therapy as drug delivery agents to selectively target the envisaged location by tailored in vivo manipulation using an external magnetic field. Furthermore, individualized treatment with antineoplastic drugs may be combined with magnetic resonance imaging to achieve an efficient therapy. This review summarizes the studies about the implications of magnetic nanoparticles in cancer diagnosis, treatment and drug delivery as well as prospects for future development and challenges of magnetic nanoparticles in the field of oncology. Full article