The magnetic properties of myoglobin as studied by NMR spectroscopy

Deoxymyoglobin has been investigated by NMR spectroscopy to determine the magnetic anisotropy through pseudocontact shifts and the total magnetic susceptibility through Evans measurements. The magnetic anisotropy values were found to be Deltachi(ax)=-2.03+/-0.08 x 10(-32) m(3) and Deltachi(rh)=-1.02+/-0.09 x 10(-32) m(3). The negative value of the axial susceptibility anisotropy originates from the z tensor axis lying in the heme plane, unlike all other heme systems investigated so far. This magnetic axis is almost exactly orthogonal to the axial histidine plane. The other two axes lie essentially in the histidine plane, the closest to the heme normal being tilted by about 36 degrees from it, towards pyrrole A on the side of the proximal histidine. From the comparison with cytochrome c' it clearly appears that the position of the one axis lying in the heme plane is related to the axial histidine orientation. Irrespective of the directions, the magnetic anisotropy is smaller than that of the analogous reduced cytochrome c' and of the order of that of low-spin iron(III). The magnetic anisotropy of the system permits the measurement of residual dipolar couplings, which, together with pseudocontact shifts, prove that the solution structure is very similar to that in the crystalline state. Magnetic measurements, at variance with previous data, demonstrate that there is an orbital contribution to the magnetic moment, micro(eff)=5.5 micro(B). Finally, from the magnetic anisotropy data, the hyperfine shifts of iron ligands could be separated in pseudocontact and contact components, and hints are provided to understand the spin-delocalisation mechanism in S=2 systems by keeping in mind the delocalisation patterns in low-spin S=1/2 and high-spin S= 5/2 iron(III) systems.     

金华市各功能区表层土壤磁化率与重金属的相关性分析

对金华市不同功能区的59个表层土壤土样磁化率和重金属含量的相关关系进行了比较.结果表明,(1)居住区、文教区、商业区、果园和荒地的磁化率与重金属之间的相关性不显著;(2)重金属污染严重的功能区磁化率与重金属的相关性较为显著.以城市的工业区、绿化区和菜园最为典型,工业区土壤磁化率与Cu、Pb呈正相关关系,农业区(菜园)土...     

Diatropicity of tetraazanaphthalenes

Tetraazanaphthalenes are diatropic molecules, whose magnetic response to a magnetic field perpendicular to the molecular plane closely resembles that of naphthalene. The out-of-plane component of the magnetic susceptibility tensor and its strong anisotropy can be used as quantifiers of magnetic aromaticity. Maps showing streamlines and modulus of the current density field provide clear evidence for diatropicity of these systems. They also explain the strong anisotropy of carbon and nitrogen magnetic shielding, which is determined by the big out-of-plane component of the nuclear shielding tensor. The electronic ring currents observed in the map deshield the nuclei of ring hydrogens by enforcing the local magnetic field and diminishing the out-of-plane component of proton shielding.     

金华市土壤磁化率与重金属的空间变异特征

工业化、城市化的进程对城市土壤产生了巨大的环境压力。以浙江省金华市为典型区,采用地统计学方法对表层土壤的磁化率和Cr、Co、Ni、Cu、Pb等5种重金属结构特征和空间分布格局进行了分析,并从空间上寻找磁化率与重金属的关系。结果表明,(1)低频磁化率总体较低,频率磁化率总体偏高,都属于强变异,两者呈负相关。重金属Cu、Pb、Ni含量大多在土壤背景值之内,Cr、Co则有较多土样超过背景值。(2)从总体上看,磁化率与5种重金属相关性较弱。(3)低频磁化率、Pb、Co具有很强的空间相关性,频率磁化率、Ni、Cu具有中等的空间相关性,Cr的空间相关性较弱。(4)在空间上,低频磁化率与频率磁化率负相关明显;在城区西部和西北部,重金属Cr、Ni、Pb、Cu含量均相对较高,在城市中心,重金属Pb、Cu含量较高;Cr、Co与低频磁化率从空间上更多地表现出负相关,Co与频率磁化率在空间上正相关较明显。     

磁场对乙基纤维素胆甾型液晶相的影响

高分子胆甾型液晶相是一个在高分子和液晶领域都引起广泛兴趣的课题,不仅因为自然界中的多种生物大分子,如纤维素,多肽,DNA等可以形成胆甾型液晶相;而且由于胆甾相具有特殊的螺旋结构(如图1所示),能产生一些特殊的光学性能,如强烈的旋光性,圆二色性和选择性反射光性能等;并带来相应的应用,正是由于高分子胆甾相材料的性能和应用,使得高分子胆甾相液晶的相态转变和结构变化也一直倍受关注。     

THE SYNTHESES AND PROPERTIES OF COBALT(II), NICKEL(II) AND COPPER(II) COMPLEXES WITH SOME 1,4-BENZODIAZEPINES

Abstract

The preparation and characterization of some cobalt(II), nickel(II) and copper(II) complexes with 7-chloro-2-methylamino-5-phenyl-3H-1, 4-benzodiazepin-4-oxide and 1, 3-dihydro-7-nitro-5-phenyl-2H-1, 4-benzodiazepin-2-one are reported. The complexes have been studied by means of magnetic susceptibility measurements, infrared and far infrared spectra, electronic spectra and conductivity measurements. Assignments for the metal-ligand and metal-halide bands have also been made. The evidence suggests that the cobalt(II) and nickel(II) complexes have a pseudotetrahedral symmetry, whereas the copper(II) complexes are octahedral.     

A LINEAR DICHROISM STUDY OF THE ORIENTATION OF AROMATIC PROTEIN RESIDUES IN MAGNETICALLY ORIENTED BOVINE ROD OUTER SEGMENTS

Abstract— Linear dichroism measurements using magnetic field oriented bovine visual rod outer segments have been made in the UV and visible spectral regions. The results indicate that the planes of the aromatic amino acid residues of rhodopsin tend to be oriented normal to the membrane plane both before and after bleaching. In contrast, the retinal chromophore which tends to be oriented with its absorption oscillator parallel to the membrane plane before bleaching is randomly oriented about 10min after bleaching whereas the membranes remain oriented. Estimates of the anisotropy in the diamagnetic susceptibility of rhodopsin aromatic residues indicate that the anisotropic magnetic properties of these protein residues are sufficient to account for the observed orientation of visual rod outer segments in a homogenous magnetic field.     

可控变色织物制备及颜色控制研究

基于聚苯胺电致变色高聚物、采用反射型电致变色器件结构模型,以柔性导电织物作为电极,构建了可控变色织物,可在-1.0～+1.0 V低电压范围内实现颜色变化显著的黄色和绿色的可逆响应.系统研究了变色织物在不同电压、不同弛豫时间及不同颜色工作电极下的L*a*b*,ΔE*值及反射率曲线,且讨论了透射型电致变色器件和电致变色织物的区别.随着正电压的增加,变色织物对应的a*b*依次减小,蓝绿色加深;随着负电压的增加,变色织物对应的a*b*依次增加,变色织物黄色加深.撤去电压后变色织物发生放电弛豫,慢慢回复到未加电压时的本征态.工作电极底色对电致变色织物也有显著的影响.变色织物的断电放电弛豫时间低于透射型电致变色器件.     

ANALYSIS AND CHARACTERIZATION OF MICROSCOPIC MORPHOLOGY AND ORIENTATION STRUCTURE OF POLYANILINE POLYMERIZED IN A CONSTANT MAGNETIC FIELD

Conductive polyaniline(PAn-_M and PAn-_O) doped with dodecylbenzene sulfonic acid(DBSA) was synthesized by using emulsion polymerization method in the presence of a constant magnetic field(0.4 T) and the absence of magnetic field, respectively.The effects of magnetic field on the microscopic morphology and orientation structure of PAn were generally analyzed and characterized by using transmission electron microscope(TEM),X-ray diffraction(XRD) and through the conductivity anisotropy of unit resistance o...     

Tuning Magnetic Anisotropy in a Class of Co(II) Bis(hexafluoroacetylacetonate) Complexes

Tuning the magnetic anisotropy of metal ions remains highly interesting in the design of improved single‐molecule magnets (SMMs). We herein report synthetic, structural, magnetic, and computational studies of four mononuclear Co^II complexes, namely [Co(hfac)₂(MeCN)₂] ( 1 ), [Co(hfac)₂(Spy)₂] ( 2 ), [Co(hfac)₂(MBIm)₂] ( 3 ), and [Co(hfac)₂(DMF)₂] ( 4 ) (MeCN=acetonitrile, hfac=hexafluoroacetylacetone, Spy=4‐styrylpyridine, MbIm=5,6‐dimethylbenzimidazole, DMF=N,N‐dimethylformamide), with distorted octahedral geometry constructed from hexafluoroacetylacetone (hfac) and various axial ligands. By a building block approach, complexes 2 – 4 were synthesized by recrystallization of the starting material of 1 from various ligands containing solution. Magnetic and theoretical studies reveal that 1 – 4 possess large positive D values and relative small E parameters, indicating easy‐plane magnetic anisotropy with significant rhombic anisotropy in 1 – 4 . Dynamic alternative current (ac) magnetic susceptibility measurements indicate that these complexes exhibit slow magnetic relaxation under external fields, suggesting field‐induced single‐ion magnets (SIMs) of 1 – 4 . These results provide a promising platform to achieve fine tuning of magnetic anisotropy through varying the axial ligands based on Co(II) bis(hexafluoroacetylacetonate) complexes.     

THE COMPARISON OF LANZHOU LOESS PROFILE WITH VOSTOK ICE CORE IN ANTARCTICA OVER THE LAST GLACIATION CYCLE

Loess near Lanzhou in the late Pleistocene is very sensitive to climatic fluctuations. The Beiyuan terrace profile in Linxia City, of which the curve of susceptibility tallies with the trend of isotopic curves of Vostok 2083 m ice core in Antarctica, is 35m thick. There are five layers of paleosols under Malan loess(L_1). Upper three layers (S_(1-a),S(1-b)and S_(1-c) correspond to three warm stages in last interglaciation, Interstadial of Last Glacial (C stage in Antarctic ice core)was clearly recorded in the Beiyuan profile, in which three layers of paleosols and two of loess were formed. The lowest section of the profile belongs to penultimate glaciation, in which fossils of cold-drought-resistant mammal and mollusc have been discovered.     

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.     

Anisotropy of the magnetic susceptibility of mesogeneous lanthanide complexes

Liquid crystalline adducts of lanthanide tris(β-diketonates) with 5,5′-diheptadecyl-2,2′-bipiridine forming a nematic mesophase were obtained. Molar constants of magnetic birefringence and the magnetic susceptibility anisotropy of synthesized complexes were determined according to the magnetic birefringence in solution. The values of magnetic susceptibility anisotropy are two orders of magnitude higher than those of organic liquid crystals.     

A DFT study of the Boulton-Katritzky rearrangement of (5R)-4-nitrosobenz[c]isoxazole and its anion: pseudopericyclic reactions with aromatic transition states

The nature of the Boulton-Katritzky rearrangement of (5R)-4-nitrosobenz[c]isoxazole and its anion was studied employing three methodologies: calculation of magnetic properties (magnetic susceptibility, magnetic susceptibility anisotropy, and the nucleus-independent chemical shifts), the natural bonding orbital analysis, and the ACID (anisotropy of the current-induced density) method. The deep analysis of the results indicates a pseudopericyclic character for these reactions despite the aromaticity of the transition states.     

Orientation of molecules by magnetic field as a new source of information on their structures

A complex procedure for quantitative allowance for small but significant effects of molecular orientation by strong static magnetic fields was elaborated. A series of high-resolution ¹H NMR spectra of 1,2,3-trichloronaphthalene recorded at magnetic field strength varied over a wide range was analyzed in the framework of a unified approach with high accuracy. The spin-spin coupling constants and the dipole-dipole coupling constants for all pairs of ¹H nuclei and the anisotropy and rhombicity parameters of the magnetic susceptibility tensor of the molecule were determined. Ab initio CSGT/RHF quantum chemical calculations of this property using a wide range of conventional diffuse and polarization basis set functions were carried out. Augmentation of the basis set with polarization functions affects the values of the calculated parameters to a lesser extent compared to augmentation with diffuse functions. The results of calculations using the 6-311G(df) and 6-311++G(df) basis sets are in good agreement with the experimental values of the magnetic susceptibility anisotropy for 1,2,3-trichloronaphthalene. The advantages of the method proposed and specific features of the effects of orientation by magnetic field as a new source of information on the structure of molecules in solution are discussed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1309–1317, August, 2006.     

The Metallofullerene Field‐Induced Single‐Ion Magnet HoSc2N@C80

The low‐temperature magnetic properties of the endohedral metallofullerene HoSc₂N@C₈₀ have been studied by superconducting quantum interference device (SQUID) magnetometry. Alternating current (ac) susceptibility measurements reveal that this molecule exhibits slow relaxation of magnetization in a small applied field with timescales in the order of milliseconds. The equilibrium magnetic properties of HoSc₂N@C₈₀ indicate strong magnetic anisotropy. The large differences in magnetization relaxation times between the present compound and the previously investigated DySc₂N@C₈₀ are discussed.     

REACTIONS OF THE RHODIUM TRIFLUOROACETATE DIMER WITH NUCLEOSIDES AND NUCLEOTIDES

Abstract

Complexes of rhodium trifluoroacetate with adenosine (ado), adenosine-5′-momophosphate (AMP), cytidine (cyd), guanosine (guo) and inosine (ino) have been prepared from aqueous or methanolic solutions. They were characterized by elemental analysis, magnetic susceptibility measurements, mass spectra, infrared, visible and nuclear magnetic resonance spectroscopies. In some cases their formation was followed by NMR prior to isolation. They all proved to be diamagnetic and in every compound contain two ligand molecules per rhodium dimer except for the ado complex where the ratio is 1:1. In the solid state it was found that adenosine interacts with the metal via the N(1) and N(7) atoms, its nucleotide through N(7), whereas in the case of cyd, guo and ino their exocyclic oxygen atoms take part in coordination. Solution study seem highly interesting since in some cases more than one species appear.     

Synthesis and magnetic properties of liquid crystalline lanthanide complexes with alkylsulfate counterions

The reaction of Schiff"s base L with lanthanide alkylsulfates affords liquid crystalline complexes with the general formula L₃Ln(C_nH_2n+1OSO₃)₃. The liquid crystalline structure and magnetic properties are studied by polarization thermal microscopy, differential scanning calorimetry, X-ray diffraction, and measurement of magnetic susceptibility. The temperatures of the existence of the mesophase and magnetic anisotropy of the complexes with the same lanthanide depend on the chain length of the alkyl fragment in the sulfate anion.     

The magnetic behaviour of [NnBu4]4[Ni16Pd16(CO)40]: an even-electron homoleptic carbonyl-metal cluster anion displaying a J = 2 ground state

The magnetic behaviour of the even-electron [Ni16Pd16(CO)40]4- cluster, in its [NnBu4]+ salt, has been investigated by magnetometry and muon spin rotation/relaxation (muSR) spectroscopy. The susceptibility measurements show an exceptionally high magnetic moment corresponding to a total spin value J=2. This suggests a Hund filling of a quadruplet ground state, quite unique in carbonyl-metal clusters. SQUID magnetometry shows a departure from the Curie-Weiss law, for T>150 K, and strong deviation from a Brillouin behaviour of the magnetisation curves. muSR spectroscopy in zero applied field shows a temperature independent decay of the muon spin polarisation, similar to that of a purely paramagnetic system. The observed muon spin repolarisation in a moderate external longitudinal field, however, invalidates this simple picture and suggests the presence of a local anisotropy field acting on the cluster's magnetic moment. A consistent interpretation of magnetometry and muSR results implies the occurrence of an additional interaction of the cluster spin with an effective crystalline field. The inclusion of this interaction in a model Hamiltonian allows us to successfully reproduce both the susceptibility and magnetisation data.     

High-spin molecules with magnetic anisotropy toward single-molecule magnets

High-spin molecules with easy-axis magnetic anisotropy show slow magnetic relaxation of spin-flipping along the axis of magnetic anisotropy and are called single-molecule magnets (SMMs). SMMs behave as molecular-size permanent magnets at low temperature and magnetic relaxation occurs by quantum tunneling processes; such molecules are promising candidates for use in quantum devices. We first discuss intramolecular ferromagnetic interactions for preparing high-spin molecules. Second, we determine the magnetic anisotropy for single metal ions with d(n) configurations and discuss how molecular anisotropy arises from single-ion anisotropy of the assembled component metal ions.