有机磁合成化学研究进展

通过磁场对聚合反应、酯化反应、光还原反应和不对称合成等的影响，论述了有机磁化学的理论研究和应用进展。磁场在一定程度上影响有机反应的反应速率、产率、反应途径和产物构成。同时初步探讨了磁场影响化学反应速率的机理，并展望了磁化学的发展前景。     

Magnetic nano- and microparticles in biotechnology

Both synthetic and biologically produced magnetic nano- and microparticles exhibit several types of responses to external magnetic field which have been already employed in various areas of biosciences, biotechnology, medicine, environmental technology, etc. This short review shows selected important biotechnological applications of magnetic particles, and the biological processes leading to biogenic magnetic particles formation. Presented at the 1st Nanomaterials and Nanotechnology Meeting, Nano Ostrava, Ostrava, Czech Republic, 1–4 September 2008.     

Magnetic resonance in Cu(hfac)2LR heterospin chain polymer complexes

Cu(hfac)₂ chain polymer heterospin complexes with pyrazole-substituted nitronylnitroxides (L^R, where R = Me, Et) with a composition Cu(hfac)₂L^R, exhibiting structural rearrangements with magnetic effects in the solid state at reduced temperatures, were studied by magnetic resonance. The magnetic resonance spectrum changes substantially for substituents of different types. The results of this study are discussed in the context of the cluster approach in view of the specific crystal structure of the compounds.     

Physical Properties of Elongated Magnetic Particles: Magnetization and Friction Coefficient Anisotropies

Anisotropy counts: A brief review of the main physical properties of elongated magnetic particles (EMPs) is presented. The most important characteristic of an EMP is the additional contribution of shape anisotropy to the total anisotropy energy of the particle, when compared to spherical magnetic particles. The electron micrograph shows Ni‐ferrite microrods fabricated by the authors.

     

Floating Diamonds with Nanomagnetic Particles

In the diamond industry, ferrofluids are used in ferrohydrostatic separators for the density separation of diamonds from gangue material. The size of the magnetic core of the coated particles forming the ferrofluid suspension is vital in ensuring the stability of the fluid. The particle size must be small enough such that sedimentation does not occur in a magnetic field gradient and under the influence of a gravitational field and such that magnetic agglomeration can be overcome. This paper discusses the particle size requirements for fluid stability under the influence of these effects.     

A Novel Approach to Magnetic Nanoadsorbents with High Binding Capacity for Bovine Serum Albumin

Magnetic nanoadsorbents using Fe₃O₄ nanoparticles as cores and poly(methyl acrylic acid) (PMAA) as ionic exchange groups were prepared through our novel approach. Two steps were involved in this approach: the first was to functionalize the magnetic nanoparticles (MNPs) with methacrylate double bonds via the combination of ligand exchange and condensation of methacryloxypropyltrimethoxysilane(MPS); the second was to graft PMAA chains onto the surface of MNPs through radical polymerization. The success of the various surface functionalization steps was ascertained using FTIR and XPS. The as‐synthesized PMAA‐coated MNPs were effective in binding bovine serum albumin (BSA) with a high capacity of 1 300 mg · g⁻¹.

     

双层表面活性剂分散制备水基磁流体

Fe₃O₄ magnetic particles were synthesize by chemical co-precipitation. Sodium oleate and poly(ethylene glycol)-4000 were used as bilayer surfactants to envelope the ultra-fine Fe₃O₄ particles. Then stabilized water base magnetic fluid was obtained. Experiments indicated that surfactants and pH value of the solution had great effect on the stability and size of the magnetic fluid when Fe₃O₄ particles were synthesized and enveloped. It was the first time to employ this method to prepare magnetic fluid. Using laser diffraction particle size analyzer we found that the average diameter of magnetic fluid was lessen than 84 nanometer. Its magnetization was measured on magnetic balance and the result amounted to 3.84×10³A·m^-1. Further more， XRD and IR analysis measurements were employed to substantiate the existence of Fe₃O₄ and surfactant structure. The magnetic fluid can be used as tar-geted-part of nanometer targeted drug delivery system.     

Microbial Cells with a Fe3O4 Doped Hydrogel Extracellular Matrix: Manipulation of Living Cells by Magnetic Stimulus

This study aims to develop an effective method to control motile microorganisms and enable their manipulation as functional ‘live micro/nano robots'. A novel strategy based on Fe₃O₄ nanoparticle‐doped alginate hydrogel is developed to fashion an artificial extracellular matrix (ECM) for microbial cells (e.g., Saccharomyces cerevisiae and Flavobacterium heparinum). During this strategy, a single layer of alginate hydrogel is coated around the microbial cells doped with Fe₃O₄ nanoparticles to form the alg‐mag‐cells. Transmission electron microscopy shows that Fe₃O₄ nanoparticles are uniformly distributed in the hydrogel shell. Together with maintaining the cell activity and metabolism, the hydrogel coated microbial cells demonstrate high magnetic responsiveness in an external magnetic field and are able to form micro‐scaled patterns using the magnetic template designed in this study. This strategy provides a building block to fabricate advanced biological models, medical therapeutic products, and non‐medical biological systems using different microorganisms.

     

Polarized Neutron Diffraction as a Tool for Mapping Molecular Magnetic Anisotropy: Local Susceptibility Tensors in CoII Complexes

Polarized neutron diffraction (PND) experiments were carried out at low temperature to characterize with high precision the local magnetic anisotropy in two paramagnetic high‐spin cobalt(II) complexes, namely [Co^II(dmf)₆](BPh₄)₂ ( 1 ) and [Co^II₂(sym‐hmp)₂](BPh₄)₂ ( 2 ), in which dmf=N,N‐dimethylformamide; sym‐hmp=2,6‐bis[(2‐hydroxyethyl)methylaminomethyl]‐4‐methylphenolate, and BPh₄^?=tetraphenylborate. This allowed a unique and direct determination of the local magnetic susceptibility tensor on each individual Co^II site. In compound 1 , this approach reveals the correlation between the single‐ion easy magnetization direction and a trigonal elongation axis of the Co^II coordination octahedron. In exchange‐coupled dimer 2 , the determination of the individual Co^II magnetic susceptibility tensors provides a clear outlook of how the local magnetic properties on both Co^II sites deviate from the single‐ion behavior because of antiferromagnetic exchange coupling.     

Calculation of magnetic properties of HF,H2O,NH3, and CH4 molecules using a longitudinal gauge for the vector potential

A transformation of the transverse Coulomb vector potential was implemented to calculate molecular magnetic properties via the random-phase approximation (RPA) within the framework of a “longitudinal gauge.” In this gauge, the diamagnetic contribution to magnetic susceptibility is a tensor with equal diagonal components as in atoms, irrespective of molecular symmetry, whereas diagonal and average diamagnetic contributions to the nuclear magnetic shielding are the same as in the Coulomb gauge. Near-Hartree–Fock magnetic susceptibility and nuclear magnetic shielding tensors were evaluated for a set of small molecules, HF, H₂O, NH₃, and CH₄, employing extended Gaussian basis sets. The peculiar features of the longitudinal gauge, and the fulfillment of a series of sum rules involving the virial operator, which must be satisfied to guarantee gauge invariance of total magnetic tensors, were exploited to check the degree of convergence of theoretical values and to estimate the corresponding Hartree–Fock limit for the properties. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 66 : 31–45, 1998     

Effect of uniaxial strain on a molecule-based ferrimagnet with crystal chirality

Bimetallic ferrimagnet [Cr(CN)₆][Mn(R)-pnH(H₂O)]H₂O with crystallographical chirality of space group P2₁2₁2₁ exhibits a giant third-order harmonic susceptibility at around 38 K. This anomaly appears as precursory magnetic phenomenon of the magnetic ordering. In order to investigate the effect of lattice distortion on this giant nonlinear magnetic response (NLMR) and finally elucidate the correlation between the structural chirality and the giant NLMR, we performed the ac susceptibility measurement for the single crystal in the situation of bringing about lattice distortion along the direction parallel to the a-axis. This giant NLMR was drastically suppressed even by slight strain, whereas the traces could be confirmed in the region up to 3.7 kbar. We conclude that the appearance of the giant NLMR requires crystal chirality well-regulated over the crystal.     

Multimetal‐Substituted Epsilon‐Iron Oxide ϵ‐Ga0.31Ti0.05Co0.05Fe1.59O3 for Next‐Generation Magnetic Recording Tape in the Big‐Data Era

From the viewpoints of large capacity, long‐term guarantee, and low cost, interest in magnetic recording tapes has undergone a revival as an archive storage media for big data. Herein, we prepared a new series of metal‐substituted ?‐Fe₂O₃, ?‐Ga^III_0.31Ti^IV_0.05Co^II_0.05Fe^III_1.59O₃, nanoparticles with an average size of 18 nm. Ga, Ti, and Co cations tune the magnetic properties of ?‐Fe₂O₃ to the specifications demanded for a magnetic recording tape. The coercive field was tuned to 2.7 kOe by introduction of single‐ion anisotropy on Co^II (S=3/2) along the c‐axis. The saturation magnetization was increased by 44 % with Ga^III (S=0) and Ti^IV (S=0) substitution through the enhancement of positive sublattice magnetizations. The magnetic tape media was fabricated using an actual production line and showed a very sharp signal response and a remarkably high signal‐to‐noise ratio compared to the currently used magnetic tape.     

Magnetic Behavior at Low Temperatures of Ti Oxide Polycrystalline Samples

Ti-oxide polycrystalline samples have been synthesized by the Pechini method and their low temperature magnetic properties have been characterized. The synthesis procedures allow the preparation of high-quality samples ensuring that the observed low temperature magnetic behavior is intrinsic to the system, not due to the polycrystalline nature of the samples. Magnetic susceptibility measurements showed that the anatase and rutile TiO₂ exhibit a paramagnetic behavior. For the CoTiO₃ samples, a totally reversible antiferromagnetic transition at 38 K is reported.     

磁性液体的合成及生物医学应用

本文综述了纳米磁粉的化学合成及磁性液体的一般制备方法及其磁性、磁流变性和磁熵热效应等在靶向给药、栓塞治疗、温热治疗上的应用。     

On Approaching the Limit of Molecular Magnetic Anisotropy: A Near‐Perfect Pentagonal Bipyramidal Dysprosium(III) Single‐Molecule Magnet

We report a monometallic dysprosium complex, [Dy(O^tBu)₂(py)₅][BPh₄] ( 5 ), that shows the largest effective energy barrier to magnetic relaxation of U_eff=1815(1) K. The massive magnetic anisotropy is due to bis‐trans‐disposed tert‐butoxide ligands with weak equatorial pyridine donors, approaching proposed schemes for high‐temperature single‐molecule magnets (SMMs). The blocking temperature, T_B , is 14 K, defined by zero‐field‐cooled magnetization experiments, and is the largest for any monometallic complex and equal with the current record for [Tb₂N₂{N(SiMe₃)₂}₄(THF)₂].     

Magnetic nanoparticles supported copper catalysts: Synthesis of heterocyclic scaffolds

Abstract

Heterocyclic scaffolds are important components in the structure of many drugs and natural products. They are well-known compounds because of their broad spectrum of pharmaceutical and biological activities. In this paper, we provide an overview of the utilization of copper complexes immobilized on magnetic nanoparticles as economical and efficient catalytic systems for the synthesis of heterocyclic molecules.     

五磷酸铕的摩尔磁化率与其光谱的关联

在三价镧系顺磁离子中,由于Eu~(3+)的基态(~1F_0)的总量子数J为0,如按Hund公式μ_(cff)=g(J(J+1))~(1/2)计算,其有效磁矩μ_(cff)=0,此结果与实验不符,表明,Hund公式不适     

The induced magnetic field in cyclic molecules

The response of a molecule to an applied external magnetic field can be evaluated by a graphical representation of the induced magnetic field. We have applied this technique to four representative, cyclic organic molecules, that is, to aromatic (C(6)H(6), D(6h)), anti-aromatic (C(4)H(4), D(2h)) and non-aromatic (C(4)H(8), D(4h), and C(6)H(12), D(3d)) molecules. The results show that molecules that contain a pi system possess a long-range magnetic response, while the induced magnetic field is short-range for molecules without pi systems. The induced magnetic field of aromatic molecules shields the external field. In contrast, the anti-aromatic molecules increase the applied field inside the ring. Aromatic, anti-aromatic, and non-aromatic molecules can be characterized by the appearance of the magnetic response. We also show that the magnetic response is directly connected to nucleus-independent chemical shifts (NICS).     

Ultraparamagnetic Cells Formed through Intracellular Oxidation and Chelation of Paramagnetic Iron

Making cells magnetic is a long‐standing goal of chemical biology, aiming to enable the separation of cells from complex biological samples and their visualization in vivo using magnetic resonance imaging (MRI). Previous efforts towards this goal, focused on engineering cells to biomineralize superparamagnetic or ferromagnetic iron oxides, have been largely unsuccessful due to the stringent required chemical conditions. Here, we introduce an alternative approach to making cells magnetic, focused on biochemically maximizing cellular paramagnetism. We show that a novel genetic construct combining the functions of ferroxidation and iron chelation enables engineered bacterial cells to accumulate iron in “ultraparamagnetic” macromolecular complexes, allowing these cells to be trapped with magnetic fields and imaged with MRI in vitro and in vivo. We characterize the properties of these cells and complexes using magnetometry, nuclear magnetic resonance, biochemical assays, and computational modeling to elucidate the unique mechanisms and capabilities of this paramagnetic concept.