Synthesis, structures, and magnetic properties of dicopper(II) and dinickel(II) complexes with a new bis(macrocycle), 7,7-(2-hydoxypropane-1,3-diyl)bis{3,7,11,17-tetraazabicyclo[11.3.1]- heptadeca-1(17),13,15-triene}

A new bis(macrocycle) ligand, 7,7^′-(2-hydoxypropane-1,3-diyl)-bis{3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),13,15-triene} (HL), and its dicopper(II) ([Cu₂(HL)Cl₂](NO₃)₂ · 4H₂O (4a), [Cu₂(HL)I₂]I₂ · H₂O (4b)) and dinickel(II) ([Ni₂(L)(OH₂)](ClO₄)₃ (5a), [Ni₂(L)(OH₂)]I₃ · 2H₂O (5b), [Ni₂(L)N₃](N₃)₂ · 7H₂O (5c)) complexes have been synthesized. The alkoxide bridged face-to-face structure of the dinickel(II) complex 5c has been revealed by X-ray crystallography, as well as the “half-opened clamshell” form of the bis(macrocyclic) dicopper(II) complex 4b. Variable temperature magnetic susceptibility studies have indicated that there exists intramolecular antiferromagnetic coupling (J=−33.8 cm⁻¹ (5a), −32.5 cm⁻¹ (5b), and −29.7 cm⁻¹ (5c)) between the two nickel(II) ions in the nickel(II) complexes.     

Synthesis, magnetic properties and MCD spectra of a four coordinate copper(II) complex with two chelated phenolate-substituted imino nitroxides

A reaction of Cu(II) nitrate and 4,4,5,5-tetramethyl-2-(2-hydroxophenyl)imidazolin-1-oxyl (IM2PhOH) with potassium methoxide in methanol gave a homoleptic bis(imino nitroxide) complex of [Cu(IM2PhO)₂] (1). The single-crystal X-ray analysis of 1 showed that the imino nitroxide anion, IM2PhO⁻, chelated to a Cu^II ion via an imino-N and a phenoxide-O atoms to form a six-membered chelate ring. The coordination geometry around the Cu(II) ion was a distorted square-planar polygon; the dihedral angle between the two coordination planes, each of which was defined by Cu and two ligating atoms of IM2PhO⁻, was 40.81°. The temperature dependences of the magnetic susceptibility and the EPR spectra of 1 indicate that the magnetic interaction between Cu(II) and the imino nitroxide is ferromagnetic, while there is a moderate antiferromagnetic interaction between two coordinated imino nitroxides. A balance between these opposite interactions attains the lowest molecular doublet spin-state in 1. The variable temperature magnetic circular dichroism (MCD) spectrum of the complex 1 also showed two negative components with a large C term, which may be due to the charge-transfer (CT) transition originated from the d orbital to the SOMO π^* orbital in the spin-coupled IM2PhO⁻ radicals; resulting in the largely split doublet excited states with the spin singlet and triplet d⁸ configurations.     

D W I对脑转移瘤及胶质瘤的应用价值

目的：探讨弥散加权成像（DWI）对脑转移瘤与胶质瘤鉴别诊断的应用价值。方法：对常规MR扫描检出的42例颅内占位痛人行DWI扫描,对病人术后痛理随访后,将高级胶质瘤、低级胶质瘤及脑转移瘤各分成一组,并测定肿瘤区、水肿区、时侧正常脑组织的表观弥散系数（ADC）值及相时ADC（rADC）值。结果：低级胶质瘤与转移瘤的瘤灶rADC值比较存在差异;高级别胶质瘤与转移瘤瘤周水肿的rADC值相比较存在差异。结论：DWI及瘤灶、瘤周rADC值的定量测定对脑转移瘤与胶质瘤的鉴别诊断具有一定的临床应用价值。     

肝脏肿瘤的31P 磁共振波谱研究进展

磁共振渡谱（MRS）在基础医学和临床医学中起着越来越重要的作用,是目前对人体唯一无创的研究活体组织器官代谢、生化变化及化合物定量分析的方法,能显示肿瘤和正常组织之间的不同代谢。能在分子水平上反映病理情况。磷是能量代谢的重要要素,肝脏中许多化合物都含有31P,本文就31P磁共振渡谱在肝癌的研究及,临床应用方面的近况进行综述。     

山西耕作土壤样品磁性空间分异及其环境意义

本文分析了山西高原土壤耕作层(0-20cm)25个样品的磁性,用GIS空间分析方法,得出土壤磁化率平面分布等值线图和空间三维模型。磁化率空间分布机理如下:首先,强烈的人为影响使土壤中磁性矿物人为来源占有重要地位。第二,土壤磁性矿物以亚铁磁性的磁铁矿和磁赤铁矿为主导。第三,土壤磁化率极值差及其与母质之间的差异均受广泛而较均一的黄土母质的影响。第四,晋西北和晋中等区域出现土壤磁化率高值区域。第五,人为作用强烈影响掩盖了气温、降水等气候因子对土壤磁化率的作用。     

31P saturation transfer spectroscopy predicts differential intracellular macromolecular association of ATP and ADP in skeletal muscle

The kinetics of phosphoryl exchange involving ATP and ADP have been investigated successfully by in vivo ³¹P magnetic resonance spectroscopy using magnetization transfer. However, magnetization transfer effects seen on the signals of ATP also could arise from intramolecular cross-relaxation. This relaxation process carries information on the association state of ATP in the cell. To disentangle contributions of chemical exchange and cross-relaxation to magnetization transfer effects seen in ³¹P magnetic resonance spectroscopy of skeletal muscle, we performed saturation transfer experiments on wild type and double-mutant mice lacking the cytosolic muscle creatine kinase and adenylate kinase isoforms. We find that cross-relaxation, observed as nuclear Overhauser effects (NOEs), is responsible for magnetization transfer between ATP phosphates both in wild type and in mutant mice. Analysis of ³¹P relaxation properties identifies these effects as transferred NOEs, i.e. underlying this process is an exchange between free cellular ATP and ATP bound to slowly rotating macromolecules. This explains the β-ATP signal decrease upon saturation of the γ-ATP resonance. Although this usually is attributed to β-ADP ↔ β-ATP phosphoryl exchange, we did not detect an effect of this exchange on the β-ATP signal as expected for free [ADP], derived from the creatine kinase equilibrium reaction. This indicates that in resting muscle, conditions prevail that prevent saturation of β-ADP spins and puts into question the derivation of free [ADP] from the creatine kinase equilibrium. We present a model, matching the experimental result, for ADP ↔ ATP exchange, in which ADP is only transiently present in the cytosol.     

Structural Basis for Conformational Dynamics of GTP-bound Ras Protein

Ras family small GTPases assume two interconverting conformations, “inactive” state 1 and “active” state 2, in their GTP-bound forms. Here, to clarify the mechanism of state transition, we have carried out x-ray crystal structure analyses of a series of mutant H-Ras and M-Ras in complex with guanosine 5′-(β,γ-imido)triphosphate (GppNHp), representing various intermediate states of the transition. Crystallization of H-RasT35S-GppNHp enables us to solve the first complete tertiary structure of H-Ras state 1 possessing two surface pockets unseen in the state 2 or H-Ras-GDP structure. Moreover, determination of the two distinct crystal structures of H-RasT35S-GppNHp, showing prominent polysterism in the switch I and switch II regions, reveals a pivotal role of the guanine nucleotide-mediated interaction between the two switch regions and its rearrangement by a nucleotide positional change in the state 2 to state 1 transition. Furthermore, the ³¹P NMR spectra and crystal structures of the GppNHp-bound forms of M-Ras mutants, carrying various H-Ras-type amino acid substitutions, also reveal the existence of a surface pocket in state 1 and support a similar mechanism based on the nucleotide-mediated interaction and its rearrangement in the state 1 to state 2 transition. Intriguingly, the conformational changes accompanying the state transition mimic those that occurred upon GDP/GTP exchange, indicating a common mechanistic basis inherent in the high flexibility of the switch regions. Collectively, these results clarify the structural features distinguishing the two states and provide new insights into the molecular basis for the state transition of Ras protein.     

Syntheses, structures and magnetic properties of Mn(II), Co(II) and Ni(II) metal-organic frameworks constructed from 1,3,5-benzenetricarboxylate and formate ligands

Three compounds, [(CH₃)₂NH₂][M₃(BTC)(HCOO)₄(H₂O)]·H₂O (M = Mn (1), Co (2), Ni (3), H₃BTC = 1,3,5-benzenetricarboxylic acid), were synthesized under hydrothermal conditions and were characterized by single crystal and powder X-ray diffraction, IR spectra, elemental analysis, coupled TG-MS and magnetic measurements. Compounds 1-3 are isostructural analogues and crystallize in monoclinic space group P2₁/c. Each metal ion in these compounds connects to six oxygen atoms to form a MO₆ octahedron. Six MO₆ octahedra link to each other to form a corner-shared hexameric M₆ cluster, which is linked by BTC ligands to form two-dimensional layers. The two-dimensional layers are further connected by formic ions to form a three-dimensional network with channels, where (CH₃)₂NH₂⁺ ions and water molecular are located. Magnetic measurements indicate that anti-ferromagnetic ordering occurs at low temperature for these compounds.     

Structural and spectroscopic characterisation of the holmium double-decker partially oxidised and bi-radical phthalocyanine complexes with iodine

Two crystals of holmium(III) double-decker iodine doped phthalocyanines, HoPc₂I_5/3 (I) and HoPc₂I (II), were grown directly in the reaction of holmium chips with 1,2-dicyanobenzene under versatile quantity of iodine at 180-160 °C. The complex I crystallises in the P4/mcc space group of tetragonal system, while the complex II crystallises in the P2/c space group of monoclinic system. The space group of P4/mcc and z = 1 requires that the Ho(III) atom is statistically disordered in the HoPc₂I_5/3 structure. The iodine atoms form linear symmetrical triiodide ions in I, while the I⁻ ions in II. Assignment of iodine species as in the HoPc₂I_5/3 and I⁻ in HoPc₂I complexes point to the +5/9 and +1 oxidation state of the HoPc₂ unit in these complexes. Thus one Pc macrocycle of the double-decker HoPc₂ units has a non-integer oxidation state of −1.222 in I, while both Pc-rings are one-electron oxidised radical Pc⁻ in II. Magnetic susceptibilities of HoPc₂I_5/3 and HoPcI at room temperature are 4.56 × 10⁻² and 5.12 × 10⁻² emu/mol and the calculated magnetic moments are 10.46 and 11.08 μ_B, respectively. UV-Vis spectroscopic measurement of I and II in benzene solution were carried out and discussed.     

A series of inorganic-organic hybrid compounds constructed from bis(undecatungstophosphate) lanthanates and copper-organic units

A series of inorganic-organic hybrid compounds built from bis(undecatungstophosphate) lanthanates and copper-complexes, namely, H₈[Cu(en)₂H₂O]₄[Cu(en)₂]{[Cu(en)₂][La(PW₁₁O₃₉)₂]}₂·18H₂O (1), H₆[Na₂(en)₂(H₂O)₅][Cu(en)₂H₂O]₄[Cu(en)₂]{[Cu(en)₂][Ce(PW₁₁O₃₉)₂]}₂·16H₂O (2), H₆[Na₂(en)₂(H₂O)₅][Cu(en)₂H₂O]₄[Cu(en)₂]{[Cu(en)₂][Pr(PW₁₁O₃₉)₂]}₂·18H₂O (3), H₆[Na₂(en)₂(H₂O)₄][Cu(en)₂H₂O]₄[Cu(en)₂]{[Cu(en)₂][Nd(PW₁₁O₃₉)₂]}₂·14H₂O (4), H₆[Na₂(en)₂(H₂O)₅][Cu(en)₂H₂O]₄[Cu(en)₂]{[Cu(en)₂][Sm(PW₁₁O₃₉)₂]}₂·20H₂O (5), and H₇[Cu(en)₂]₂[Sm(PW₁₁O₃₉)₂]·10H₂O (6) (where en = 1,2-ethylenediamine), have been prepared. In these compounds, two lacunary [PW₁₁O₃₉]⁷⁻ anions sandwich an eight-coordinated Ln(III) cation to yield [Ln(PW₁₁O₃₉)₂]¹¹⁻ anion in a twisted square anti-prismatic geometry, which is further bridged by [Cu(en)₂]²⁺ fragments to generate a 1D zigzag-like chain. In 1-6, the coordination bond interactions and weak interactions between adjacent 1D chains play an important role in the zigzagging distances and angles of different 1D chains. The magnetic studies indicate that antiferromagnetic interactions exist in compounds 1, 2 and 4.