Synthesis and Characterization of a [Mn12O12(O2CR)16(H2O)4] Complex Bearing Paramagnetic Carboxylate Ligands. Use of a Modified Acid Replacement Synthetic Approach

Summary.  A new modified approach for the synthesis of Mn₁₂ clusters, based on the use of complex [Mn₁₂O₁₂(O₂C ^t Bu)₁₆(H₂O)₄] (2) as starting material to promote the acidic ligand replacement, is presented here. This new synthetic approach allowed us to obtain complex [Mn₁₂O₁₂(O₂CC₆H₄N(O^•) ^t Bu)₁₆(H₂O)₄] (3), whose preparation remained elusive by direct replacement of the acetate groups of Mn₁₂Ac (1). Complex 3 bearing open-shell radical units, was prepared to increase the total spin number of its ground state, and consequently, to increase T _B , with the expectation that the radical ligands may couple ferromagnetically with the Mn₁₂ core. Unfortunately, magnetic measurements of complex 3 revealed that the sixteen radical carboxylate ligands interact antiferromagnetically with the Mn₁₂ core to yield a S = 2 magnetic ground state. Corresponding author. E-mail: vecianaj@icmab.es Received March 27, 2002; accepted May 2, 2002     

Solvato Modulation of the Magnetic Memory in Isotopically Enriched Erbium Polyoxometalate

Single-Molecule Magnet (SMM) property is by essence molecular, while commonly measured in solid crystalline state. Solvent crystallization molecules are usually neglected in the analysis and interpretation of solid-state properties. The solvation/desolvation process in the polyoxometalate(POM)-based Na₉[Er(W₅O₁₈)₂] ⋅ 35 H₂O SMM demonstrates that the dehydrated form relaxes more than 1000 times faster than the initial state, while the rehydration process allows the quasi complete recovering of the initial magnetic behaviour. This dehydration process is monitored by thermogravimetric analysis (TGA) and temperature-dependent X-ray powder diffraction, and rationalized by periodic quantum chemical calculations evidencing the tremendous role of the labile water molecules in the stability of the edifice. Ab-initio calculations highlight that sodium ions localization in the structure drive the magnetic responses. Isotopic enrichment with nuclear spin free (¹⁶⁶Er, I=0) Er^III ions shows that the relaxation dynamics in the quantum regime depends on the nuclear spin.     

Application of pulsed-magnetic field enhances non-viral gene delivery in primary cells from different origins

Primary cell lines are more difficult to transfect when compared to immortalized/transformed cell lines, and hence new techniques are required to enhance the transfection efficiency in these cells. We isolated and established primary cultures of synoviocytes, chondrocytes, osteoblasts, melanocytes, macrophages, lung fibroblasts, and embryonic fibroblasts. These cells differed in several properties, and hence were a good representative sample of cells that would be targeted for expression and delivery of therapeutic genes in vivo. The efficiency of gene delivery in all these cells was enhanced using polyethylenimine-coated polyMAG magnetic nanoparticles, and the rates (17–84.2%) surpassed those previously achieved using other methods, especially in cells that are difficult to transfect. The application of permanent and pulsating magnetic fields significantly enhanced the transfection efficiencies in synoviocytes, chondrocytes, osteoblasts, melanocytes and lung fibroblasts, within 5 min of exposure to these magnetic fields. This is an added advantage for future in vivo applications, where rapid gene delivery is required before systemic clearance or filtration of the gene vectors occurs.     

HL-2M 磁体系统安装中的定位与测量

为提高磁体系统安装精度,在 HL-2M 集成大厅建立 63 个基准点构成测量基准网,并利用激光跟 踪仪等高精度测量设备建立每个磁体的局部坐标系,测量特征点的局部坐标;基于测量基准网和公共测量点,采 用最佳拟合得到坐标转换矩阵,以此得到特征点在测量基准网的位置,指导磁体安装。完成安装后的中心柱同支 撑基础的同轴度为∅2.03mm;PF1~PF4 线圈安装标高偏差为±0.5mm,与中心柱的同轴度为∅2.60mm;PF5/6/7/8 线圈与中心柱的同轴度偏差小于∅3.00mm,标高偏差在[−1mm, 1mm]区间内。基于以上方法所得到的线圈安装精 度都满足设计需求。     

翻转线圈系统在波荡器积分场测量中的应用

 为了更有效地测量用于上海同步辐射光源波荡器的积分场误差,在已有的伸展线磁测系统的基础上研制了一套翻转线圈磁测系统,该系统的运动控制、数据采集和数据分析处理均可自动完成。在利用这套磁测系统测量3.4×10^-6 T·m磁场积分时获得高于1×10^-6 T·m的测量精度,初步的实验结果表明这套波荡器积分磁场测量系统具有测量精度好、速度快的特点,与已有的伸展线磁测系统、平移线圈磁测系统和霍尔点测系统相比,它更适合于测量波荡器的一、二次场积分和多极场分量。     

Observing Confined Local Oxygen-induced Reversible Thiol/Disulfide Cycle with a Protein Nanopore

Disulfide bonds play an important role in thiol-based redox regulation. However, owing to the lack of analytical tools, little is known about how local O₂ mediates the reversible thiol/disulfide cycle under protein confinement. In this study, a protein-nanopore inside a glove box is used to control local O₂ for single-molecule reaction, as well as a single-molecule sensor for real-time monitoring of the reversible thiol/disulfide cycle. The results demonstrate that the local O₂ molecules in protein nanopores could facilitate the redox cycle of disulfide formation and cleavage by promoting a higher fraction of effective reactant collisions owing to nanoconfinement. Further kinetic calculations indicate that the negatively charged residues near reactive sites facilitate proton-involved oxygen-induced disulfide cleavage under protein confinement. The unexpectedly strong oxidation ability of confined local O₂ may play an essential role in cellular redox signaling and enzyme reactions.     

Synthesis and magnetic properties of La-substituted M-type Sr hexaferrites

Single-phase M-type hexagonal ferrites Sr_1−xLa_xFe₁₂O₁₉ (0≤x≤1) were prepared by a ceramic route. The stability limits of the ferrite phases were determined with a combination of various microscopy techniques, electron-probe micro-analysis, powder X-ray diffraction and thermal analysis. SrFe₁₂O₁₉ (x=0) is stable up to 1420 °C, whereas LaFe₁₂O₁₉ (x=1) exists between 1360 and 1400 °C only. The lattice parameters of Sr_1−xLa_xFe₁₂O₁₉ exhibit a linear variation with x, i.e. a₀ slightly increases and c₀ decreases with x, leading to a decrease of the unit cell volume with x. The saturation magnetization at T=5 K decreases with increasing La concentration. Room temperature Mössbauer analysis shows that the Fe³⁺/Fe²⁺ valence change occurs in the 2a sites for the whole composition range.     

先进超导导体测试装置设计分析

针对聚变工程大型超导导体样品在高场下的性能测试需求,设计了内径0.6m、磁场13T的背景磁体系统。磁体系统由6层12个分离式超导线圈组成,线圈采用常规的螺线管结构,由外至内分别使用NbTi、Nb₃Sn和YBCO三种超导材料绕制而成;在直径500mm的测试区域范围内产生最高达13.22T的背景磁场,均匀性不低于95%。介绍了磁体线圈主要设计参数,用有限元软件完成电磁、结构分析。结果表明,设计合理可靠,能够满足导体测试装置的需求。     

ITER 超导馈线系统的设计

ITER( 国际热核试验堆) 采用超导馈线系统传输磁体线圈所需电流、冷却液及数据信号, 并在失超等异常情况, 通过馈线转移磁体能量, 以保护整个磁体系统。介绍了国际热核试验堆超导馈线系统的结构及设计情况, 为同类型超导磁体的馈线设计提供了有益的参考。     

Enhancing Magnetic Communication between Metal Centres: The Role of s-Tetrazine Based Radicals as Ligands

Although 1,2,4,5-tetrazines or s-tetrazines have been known in the literature for more than a century, their coordination chemistry has become increasingly popular in recent years due to their unique redox activity, multiple binding sites and their various applications. The electron-poor character of the ring and stabilization of the radical anion through all four nitrogen atoms in their metal complexes provide new aspects in molecular magnetism towards the synthesis of new high performing Single Molecule Magnets (SMMs). The scope of this review is to examine the role of s-tetrazine radical ligands in transition metal and lanthanide based SMMs and provide a critical overview of the progress thus far in this field. As well, general synthetic routes and new insights for the preparation of s-tetrazines are discussed, along with their redox activity and applications in various fields. Concluding remarks along with the limitations and perspectives of these ligands are discussed.