Immobilization of dipyridyl complex to magnetic nanoparticle via click chemistry as a recyclable catalyst for Suzuki cross-coupling reactions

A magnetic nanoparticle (MNP)-supported di(2-pyridyl)methanol palladium dichloride complex was prepared via click chemistry. The MNP-supported catalyst was evaluated in Suzuki coupling reaction in term of activity and recyclability in DMF. It was found to be highly efficient for Suzuki coupling reaction using aryl bromides as substrates and could be easily separated by an external magnet and reused in five consecutive runs without obvious loss of activity.

磁性纳米颗粒负载催化剂的制备及其在有机合成中的应用

过去的几十年，纳米科学在材料、医药、生物、催化等领域得到极其广泛的应用。由于在尺寸上的优势，使用纳米材料作为催化剂载体，可以使异相催化剂均相化，从而提高催化剂的活性和选择性。近年来，磁性纳米颗粒由于其容易分离的特点而作为催化剂载体受到广泛关注。鉴于此，本论文着眼于设计合成一系列磁性纳米颗粒负载的催化剂并研究其在一些有机化学反应中的应用，并进一步研究其重复使用情况。 本论文的主要内容包括以下几个部分： 1．制备了一系列磁性纳米颗粒固载的季胺盐和季膦盐，并将其应用到由二氧化碳和环氧化合物制备环状碳酸酯的反应中，详细研究了温度、催化剂用量、压力等条件对反应的影响，并进一步研究了催化剂的分离和重复使用情况。 2. 合成了二（2－吡啶基）－甲醇，通过Click反应将其固载到磁性纳米颗粒表面并与Pd进行配位，并将其应用于Suzuki和Sonogashira交叉偶联反应中，研究了不同溶剂和反应条件对反应的影响，并讨论了该催化体系的重复利用性能。 3. 合成了一系列的树枝状大分子负载的Click型有机催化剂，并将其用于酮对芳香硝基乙烯化合物的不对称Michael加成反应中。分别研究了在水相和无溶剂条件下反应进行的情况，并研究了催化剂的重复使用情况。 4. 制备了一系列磁性纳米颗粒负载的树枝状大分子催化剂，并应用于环己酮对芳香硝基乙烯化合物的不对称Michael加成反应中。研究了树枝状大分子的代数对催化剂活性的影响，并讨论了催化剂的分离和重复使用情况。

Magnetic Properties of Mn-Implanted n-Type Ge

Mn+ ions were implanted into n-type Ge(111) single crystal at room temperature at an energy of 100 keV with a dose of 3 x 1016 cm-2. Subsequent annealing was performed on the samples at 400 °C and 600 °C in a flowing nitrogen atmosphere. The magnetic properties of the samples have been investigated by alternating gradient magnetometer at room temperature. The compositional properties of the annealed samples were studied by Auger electron spectroscopy and the structural properties were analyzed by X-ray diffraction measurements. Magnetization measurements reveal room-temperature ferromagnetism for the annealed samples. The magnetic analysis supported by compositional and structural properties indicates that forming the diluted magnetic semiconductor (DMS) MnxGe1-x after annealing may account for the ferromagnetic behavior in the annealed samples.

Magnetic properties of Mn-implanted n-type Ge

Mn+ ions were implanted into n-type Ge(1 1 1) single crystal at room temperature at an energy of 100 keV with a dose of 3 x 10(16) cm(-2). Subsequent annealing was performed on the samples at 400 degreesC and 600 degreesC in a flowing nitrogen atmosphere. The magnetic properties of the samples have been investigated by alternating gradient magnetometer at room temperature. The compositional properties of the annealed samples were studied by Auger electron spectroscopy and the structural properties were analyzed by X-ray diffraction measurements. Magnetization measurements reveal room-temperature ferromagnetism for the annealed samples. The magnetic analysis supported by compositional and structural properties indicates that forming the diluted magnetic semiconductor (DMS) MnxGe1-x after annealing may account for the ferromagnetic behavior in the annealed samples. (C) 2004 Elsevier B.V. All rights reserved.

Gold/platinum hybrid nanoparticles supported on multiwalled carbon nanotube/silica coaxial nanocables: Preparation and application as electrocatalysts for oxygen reduction

A simple approach combining sonication and sol-gel chemistry was employed to synthesize silica coated carbon nanotube (CNTs) coaxial nanocables. It was found that a homogeneous silica layer can be coated on the surface of the CNTs. This method is simple, rapid, and reproducible. Furthermore, gold nanoparticle supported coaxial nanocables were facilely obtained using amino-functionalized silica as the interlinker. Furthermore, to reduce the cost of Pt in fuel cells, designing a Pt shell on the surface of a noble metal such as gold or silver is necessary. High-density gold/platinum hybrid nanoparticles were located on the surface of I-D coaxial nanocables with high surface-to-volume ratios. It was found that this hybrid nanomaterial exhibits a high electrocatalytic activity for enhancing oxygen reduction (low overpotential associated with the oxygen reduction reaction and almost four-electron electroreduction of dioxygen to water).

Thiacalix[4]arene-Supported Planar Ln(4) (Ln = Tb-III, Dy-III) Clusters: Toward Luminescent and Magnetic Bifunctional Materials

This paper reports the syntheses, crystal structures, and luminescent and magnetic properties of four tetranuclear Tb-III (1 and 3) and Dy-III (2 and 4) complexes supported by p-phenylthiacalix[4]arene (H(4)PTC4A) and p-tert-butylthiacalix-[4]arene (H(4)TC4A). All four frameworks can be formulated as [Ln(4)(III)(PTC4A/TC4A)(2)(mu(4)-OH)Cl-3(CH3OH)(2)(H2O)(3)], and some methanol and water solvent molecules are occupied in the interstices. The compounds are featured with a sandwichlike unit constructed by two tail-to-tail calixarene molecules and a planar tetragonal (mu(4)-OH)Ln(4) cluster. The photoluminescent analyses suggest that there is an efficient ligand-to-Ln(III) energy transfer for compounds 1-3 and H(4)PTC4A is a more efficient "antenna" than H(4)TC4A.

Effects of Prenatal Exposure to a 50-Hz Magnetic Field on One-Trial Passive Avoidance Learning in 1-Day-Old Chicks

We investigated memory impairment in newly hatched chicks following in ovo exposure to a 50-Hz magnetic field (MF) of 2 mT (60 min/day) on embryonic days 12-18. Isolated and paired chicks were used to test the effect of stress during training, and memory retention was tested at 10, 30, and 120 min, following exposure to a bitter-tasting bead (100% methylanthranilate). Results showed that memory was intact at 10 min in both isolated and paired chicks with or without MF exposure. However, while isolated chicks had good memory retention levels at 30 and 120 min, those exposed to MF did not. The results suggest a potential disruption of memory formation following in ovo exposure to MF, with this effect only evident in the more stressed, isolated chicks. Bioelectromagnetics 31:150-155, 2010. (C) 2009 Wiley-Liss. Inc.

DTADH and quantum critical phenomena caused by anisotropy and external magnetic field for spin-1/2 Heisenberg diamond chains

Using the transfer matrix renormalization group (TMRG) method, we study the connection between the first derivative of the thermal average of driving-term Hamiltonian (DTADH) and the trace of quantum critical behaviors at finite temperatures. Connecting with the exact diagonalization method, we give the phase diagrams and analyze the properties of each phase for both the ferromagnetic and anti-ferromagnetic frustrated J(3) anisotropy diamond chain models. The finite-temperature scaling behaviors near the critical regions are also investigated. Further, we show the critical behaviors driven by external magnetic field, analyze the formation of the 1/3 magnetic plateau and the influence of different interactions on those critical points for both the ferrimagnetic and anti-ferromagnetic distorted diamond chains.

Structure and magnetic property of (Ga,Cr)As films with different Cr contents

We report variations in structure and magnetic property of (Ga,Cr) As films with increasing Cr content x. Due to phase segregation, a tendency towards inhomogeneous distribution with increasing x is confirmed. Barkhausen-like magnetization and large remanent magnetic moment were also clearly observed in the samples with x<5.3%. However, spin-glass-like behaviors were observed in both dc and ac magnetic measurements, which might originate from the competition between magnetic nucleation and frustration of long ferromagnetic order in this inhomogeneous system. All the samples exhibit characteristics of variable-range hopping conductivity at temperature below 150 K. Typical magnetic circular dichroism structure was observed in the sample with x=7.9%.

Magnetic silicon fullerene

A metal-encapsulating silicon fullerene, Eu@Si-20, has been predicted by density functional theory to be by far the most stable fullerene-like silicon structure. The Eu@Si-20 structure is a dodecahedron with D-2h symmetry in which the europium atom occupies the center site. The calculated results show that the europium atom has a large magnetic moment of nearly 7.0 Bohr magnetons. In addition, it was found that a stable "pearl necklace" nanowire, constructed by concatenating a series of Eu@Si-20 units, with the central europium atom, retains the high spin moment. The magnetic structure of the nanowire indicates potential applications in the fields of spintronics and high-density magnetic storage.

Influence of Si doping on magnetic properties of (Ga,Mn)As

We have systematically investigated the magnetic properties of Si-doped (Ga,Mn)As films. When the Si content is low, both Curie temperature (T-C) and carrier density (p) decrease compared with undoped (Ga,Mn)As, whereas a monotonic increase of T-C and p is observed with further increase in the doping content of Si. We discuss the possible mechanism for the changes obtained by different Si doping contents and attribute the results to a competition between the existence of Si-Ga (Si substitutes for Ga site) that acts as a donor and Si-I (Si interstitials) which is in favor of the improvement of ferromagnetism. (C) 2008 Elsevier B.V. All rights reserved.

Spin states in semiconductor quantum dot with a single magnetic ion

We investigate theoretically CdTe quantum dots containing a single Mn2+ impurity, including the sp-d exchange interaction between carriers and the magnetic ion and the short-range exchange interaction between electron and hole. We find anticrossing behaviors in the energy spectrum of the electron-hole (e-h) pair that arise from the interplay between exchange interactions and the magnetic field. In addition to the s-d exchange interaction, we find that other mechanisms inducing the anticrossings become important in the strong heavy hole-light hole (hh-lh) mixing regime. The transition strengths between the states with spin projection of Mn2+ ion S-z not equal -5/2 (S-z = -5/2) decrease (increase) with increasing magnetic fields due to the alignment of the Mn2+ spin. The spin splitting of the e-h pair states depends sensitively on the external magnetic and electric field, which reveals useful information about the spin orientation and position of the magnetic ion. Meanwhile, the manipulation of the position of the magnetic ion offers us a way to control the spin splitting of the carriers. (C) 2008 Elsevier B.V. All rights reserved.

Structure and magnetic characteristics of nonpolar a-plane GaN : Mn films

Diluted magnetic nonpolar GaN:Mn films have been fabricated by implanting Mn ions into unintentionally doped nonpolar a-plane (1 1 (2) over bar 0) GaN films with a subsequent rapid thermal annealing (RTA) process. The structure, morphology and magnetic characteristics of the samples were investigated by means of high-resolution x-ray diffraction (XRD), atomic force microscopy (AFM) and a superconducting quantum interference device (SQUID), respectively. The XRD analysis shows that the RTA process can effectively recover the crystal deterioration caused by the implantation process and that there is no obvious change in the lattice parameter for the as-annealed sample. The SQUID result indicates that the as-annealed sample shows ferromagnetic properties and magnetic anisotropy at room temperature.

Magnetic coupling properties of rare-earth metals (Gd, Nd) doped ZnO: First-principles calculations

The electronic structure and magnetic coupling properties of rare-earth metals (Gd, Nd) doped ZnO have been investigated using first-principles methods. We show that the magnetic coupling between Gd or Nd ions in the nearest neighbor sites is ferromagnetic. The stability of the ferromagnetic coupling between Gd ions can be enhanced by appropriate electron doping into ZnO Gd system and the room-temperature ferromagnetism can be achieved. However, for ZnO Nd system, the ferromagnetism between Nd ions can be enhanced by appropriate holes doping into the sample. The room-temperature ferromagnetism can also be achieved in the n-conducting ZnO Nd sample. Our calculated results are in good agreement with the conclusions of the recent experiments. The effect of native defects (V-Zn, V-O) on the ferromagnetism is also discussed. (C) 2009 American Institute of Physics. [DOI 10.1063/1.3176490]

Room-temperature ferromagnetism and in-plane magnetic anisotropy characteristics of nonpolar GaN:Mn films

Diluted magnetic nonpolar GaN Mn films have been fabricated by implanting Mn ions into nonpolar aplane (1 1 (2) over bar 0) p-type GaN films and a subsequent rapid thermal annealing process. The ferromagnetism properties of the films were studied by means of superconducting quantum interference device (SQUID). Clearly in-plane magnetic anisotropy characteristics of the sample at 10 K were revealed with the direction of the applied magnetic field rotating along the in-plane [0 0 0 1]-axis. Moreover, obvious ferromagnetic properties of the sample up to 350 K were detected by means of the temperature-dependent SQUID. (C) 2009 Elsevier B.V. All rights reserved.