Synthesis and characterization of cobalt(III) complexes with sinambic amplector ligands

The synthesis of the hexadentate ligand 5,6-dimethyl-2,2,9,9-tetra(methyleneamine)-4,7-dithiadecane (1,2-Me(2)EtN(4)S(2)amp) is reported. The diastereiosomers were separated as cobalt(III) complexes using cation exchange chromatography. The rac and mesa isomers were characterized by NMR (C-13, H-1, Co-59), ESI-MS, UV-Vis spectroscopy and cyclic voltammetry. Single crystals of [Co(rac-1,2-Me(2)EtN(4)S(2)amp)] Cl-2(ClO4) (.) 2H(2)O were characterized by X-ray diffraction. The low-temperature (11 K) absorption spectra of the complexes have been measured in Nafion films and from the observed positions of both spin-allowed (1)A(1g) --> T-1(1g) and (1)A(1g) --> T-1(2g) and spin forbidden (1)A(1g) --> T-3(2g) bands, octahedral ligand-field parameters (10Dq, B and C) were determined. These results, in conjunction with the Co-59 NMR data, are used to further explore the relationship between the Co-59 magnetogyric ratio (gamma(Co)) and the product of the nephelauxetic ratio and the wavelength of the (1)A(1g) --> T-1(1g) transition (beta(DeltaE)(-1)) for complexes of mixed donor nitrogen-thioether ligands. (C) 2004 Elsevier Ltd. All rights reserved.

Embracing ligands. Synthesis, characterisation and the correlation between 59Co NMR and ligand field parameters of Co(III) complexes with a new class of nitrogen-thioether multidentate ligand

The syntheses of the hexadentate ligands 2,2,10,10-tetra(methyleneamine)-4,8-dithiaundecane (PrN(4)S(2)amp), 2,2,11,11-tetra(methyleneamine)-4,9-dithiadodecane (BuN(4)S(2)amp), and 1,2-bis(4,4-methyleneamine)-2-thiapentyl)benzene (XyN(4)S(2)amp) are reported and the complexes [Co(RN(4)S(2)amp)](3+) (R = Pr, Bu, Xy) characterised by single crystal X-ray study. The low-temperature (11 K) absorption spectra have been measured in Nafion films. From the observed positions of both spin-allowed (1)A(1g) --> T-1(1g) and (1)A(1g) --> T-1(2g) and spin forbidden (1)A(1g) --> T-3(1g) and (1)A(1g) --> T-3(2g) bands, octahedral ligand-field parameters (10D(q), B and C) have been determined. DFT calculations suggest that significant interaction between the d-d and CT excitations occurs for the complexes. The calculations offer an explanation for the observed deviations from linearity of the relationship between Co-59 magnetogyric ratio and beta(DeltaE)(-1) (beta = the nephelauxetic ratio; DeltaE the energy of the (1)A(1g) --> T-1(1g) transition) for a series of amine and mixed amine/thioether donor complexes.

The hydration of paper studied with solid-state magnetisation-exchange H-1 NMR spectroscopy

The wide-line H-1 nuclear magnetic resonance (NMR) spectrum of paper in equilibrium with ambient humidity consists of super-imposed relatively broad and narrow lines. The narrower line is of the order of 2 kHz wide at half the maximum height, while the broader line is of the order of 40 kHz in width at half height. On the basis of these line widths, the narrow line is assigned to water sorbed to the paper, and the broad line to the polymeric constituents of the paper. It was not possible to distinguish between the various polymeric components of paper contributing to the H-1 NMR spectra. A modified Goldman-Shen pulse sequence was used to generate a spatial magnetisation gradient between the polymer and water phases. The exchange of magnetisation between protons associated with water and those associated with the macromolecules in paper was observed. The exchange of magnetisation is discussed within a heat transfer model for homonuclear dipolar coupling, with exchange being characterised by a spin-diffusion coefficient. Consideration of the magnitude of the initial rate of the exchange process and estimates of the spin-spin relaxation times based on H-1 line widths indicate that some water must exist in a sufficiently immobile state as to allow homonuclear dipolar interactions between adjacent polymer and water protons. Thus, water sorbed onto paper must exist in at least two states in mass exchange with each other. This observation allows certain conclusions to be drawn about the ratio of free/bound water as a function of moisture content and the dispersal of water within the polymer matrix.

Analysis of mussel standard reference material by inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry

A method for the analysis of mussel standard reference material by inductively coupled plasma atomic emission spectrometry( ICP-AES) and inductively coupled plasma mass spectrometry(ICP-MS) was developed. K, Na, Ca, Mg, P, Al, Fe, Zn, Mn and Sr were determined by ICP-AES and As, B, Cd, Co, Cr, Cu, Ga, Ge, Mn, Mo, Ni, Pb, Se, Sr, U and V by ICP-MS, The interference coefficients at the Mn-55, Se-78, Cu-63, Co-59, Ni-58, Ni-60, As-75, Se-77, V-51, Cr-53 and Cr-52 originating from polyatomic ion of the matrix elements (KO)-K-39-O-16, K-39(2), (ArNa)-Ar-40-Na-23, (CaO)-Ca-43-O-16, (CaO)-Ca-42-O-16, (CaO)-Ca-44-O-16, (PO2)-P-31-O-16, (ArCl)-Ar-40-Cl-35, (ArCl)-Ar-40-Cl-37, (ClO)-Cl-35-O-16, (ClO)-Cl-37-O-16 and (ArC)-Ar-40-C-12 were determined under the selected operation parameters. The major matrix elements, such as K, Na and Ca, result in the suppression of analytes signals. The apparent concentration at the significant biological element which was produced by the different digestion methods, (.) HNO3 + H2O2 (3 + 2), HNO3 + HClO4 (3 + 0.5) and HNO3 + H2SO4 (3 + 0.5),was determined. The sample digested by HNO3 + H2O2 did not give rise to interfere on the analyte, and the backgrounds of Se-77, Ga-69, Zn-67, As-75, V-51, Cr-53 and Cr-52 were increased by HNO3 + HClO4 digestion method, that affected the determination of these elements, especially the monoisotope As and V. Sample digested by HNO3 + H2SO4 increased the backgrounds at Cu-65, Zn-64 and Zn-67. Detection limits of ICP-AES are 0.001 similar to 0.75 mg/L and those of ICP-MS are 0.005 similar to 1.01 mu g/L. The relative standard derivations of ICP-AES and ICP-MS are 2.7% similar to 12.8%, 3.4% similar to 24.8%, respectively.

NONLOCAL EFFECTS IN THE NUCLEUS-NUCLEUS FUSION CROSS-SECTION

Effects of the nonlocality of factorizable potentials are taken into account in the calculation of nucleus-nucleus fusion cross section through an effective mass approach. This cross section makes use of the tunneling factor calculated for the nonlocal barrier, without the explicit introduction of any result coming from coupled channel calculation, besides the approximations of Hill-Wheeler and Wong. Its new expression embodies the nonlocal effects in a factor which redefines the local potential barrier curvature. Applications to different systems, namely O-16 + Co-59, O-16,O-18 + Ni-58,Ni-60,Ni-64, and O-16,O-18 + Cu-63,Cu-65 are presented, where the nonlocal range is treated as a free parameter.

~(59)Co~(2+)对~1H与~(35)Cl的NMR影响

<正> 在前文的基础上,用~(59)CO~2+Cl_2·6H_2O加D_2O作为样品,在200MHz谱仪上观察~1H,在400MHz谱仪上观察~(35)Cl,研究强顺磁离子~(59)Co~2+(s=3/2,I=7/2)在外加直流磁场H_0作用下,它对~1H与~(35)Cl的NMR影响。因为强顺磁离子~(59)Co~(2+)的电子自旋(s=3/2)是围绕着核旋转的,因此可以统计平均计算,

NMR investigation of certain hydrated fluorosilicates

Proton and fluorine NMR were investigated in the temperature range 90–425 °K in the hexahydrated fluorosilicates of Zn, Cu, Mn, Co, and Ni and in the tetrahydrated CuSiF6 to obtain information about the internal motions in these solids. Second moment transitions were observed at widely different temperatures for the different substances, and these are ascribed to the onset of reorientation of the M(H2O) and SiF octahedra. The correlation frequency and the potential barrier hindering the motion were calculated in all the cases. Apart from the narrowing taking place at higher temperatures, the Co salt showed a change in the line structure at 248 °K, where a phase transition was reported from magnetic susceptibility measurements. Studies on the single crystals of ZnSiF6 • 6H2O and NiSiF6 • 6H2O showed that there are three nonequivalent p-p vectors, and after the transition they all become equivalent, with the M(H2O) octahedron reorienting about the fourfold axes. ©1973 The American Institute of Physics

NMR investigation of certain hydrated fluorosilicates

Proton and fluorine NMR were investigated in the temperature range 90–425 °K in the hexahydrated fluorosilicates of Zn, Cu, Mn, Co, and Ni and in the tetrahydrated CuSiF6 to obtain information about the internal motions in these solids. Second moment transitions were observed at widely different temperatures for the different substances, and these are ascribed to the onset of reorientation of the M(H2O)₆²⁺ and SiF₆^2- octahedra. The correlation frequency and the potential barrier hindering the motion were calculated in all the cases. Apart from the narrowing taking place at higher temperatures, the Co salt showed a change in the line structure at 248 °K, where a phase transition was reported from magnetic susceptibility measurements. Studies on the single crystals of ZnSiF6 · 6H2O and NiSiF6 · 6H2O showed that there are three nonequivalent p-p vectors, and after the transition they all become equivalent, with the M(H2O)₆²⁺ octahedron reorienting about the fourfold axes.

Rotational isomerism about the Ca-CO bond in proline derivatives. 1H and 13C NMR studies of benzyloxycarbonyl-Pro-N-methylamide and pivaloyl-Pro-N-methylamide

The 270 MHz 1H n.m.r. spectrum of benzyloxycarbonyl-Pro-N-methylamide in CDCl3 is exchange broadened at 293° K. Spectral lines due to two species are frozen out at 253° K and a dynamically averaged spectrum is obtained at 323° K. A selective broadening of the Cβ and Cγ resonances in the 13C n.m.r. spectrum is observed at 253° K, with a splitting of the Cβ and Cγ resonances into a pair of lines of unequal intensity. A similar broadening of Cβ and Cγ peaks is also detected in pivaloyl-Pro-N-methylamide where cis-trans interconversion about the imide bond is precluded by the bulky t-butyl group. The rate process is thus attributed to rotation about the Cα-CO bond (ψ) and a barrier (ΔG#) of 14kcal mol-1 is estimated. 13C n.m.r. data for pivaloyl-Pro-N-methylamide in a number of solvents is presented and the differences in the Cβ and Cγ chemical shifts are interpreted in terms of rotational isomerism about the Cα-CO bond.

94.5Mev ~(14)N+~(59)Co反应系统准弹及深度非弹研究

通过对94.5 Mev ~(14)N+~(59)Co反应数据的处理，得到了Li-Ne产物出射的wilczynski图、角分布、电荷分布，并对它们做了一些常规的分析工作。在Feldmeier模型框架下对该系统作了经典轨道动力学计算，给出了计算结果并对它们做了说明。本工作为轻系统低轰击能量下周边碰撞的系统性研究提供了一些参考数据

Studies of catalyzed reaction mechanism between co-polyether (THF/EO) and N-100 by NMR - Interaction and complex formation between reactants and catalysts

To elucidate the mechanism of the catalyzed reaction of co-polyether (EO/THF) with N-100, the interaction and complex formation between reactants and catalysts were investigated by means of NMR spectroscopy. It is shown that the resonance peak of isocyanate carbon splits into two parts when the solutions of N-100 and co-polyether were mixed. The disappearing of proton resonance peak of hydroxyl group in NMR spectra when dibutyltin dilaurate(DBTDL) were added to the copolyether(THF/EO) solution indicates the complex formation, This interaction appears to be a bonding of tin to the oxygen of hydroxyl and make the hydrogen of the hydroxyl group very mobile and active, then exchange with other protons, In the case of triphenyl bismuth(TPB), the high field shift and intensity enhancement of proton peak were observed, which suggest a nucleophilic attack of the bismuth to the hydroxyl hydrogen.

Co-acquisition of hyperpolarised 13C and 15N NMR spectra

Recent developments in dynamic nuclear polarisation now allow significant enhancements to be generated in the cryo solid state and transferred to the liquid state for detection at high resolution. We demonstrate that the Ardenkjaer-Larsen method can be extended by taking advantage of the properties of the trityl radicals used. It is possible to hyperpolarise 13C and 15N simultaneously in the solid state, and to maintain these hyperpolarisations through rapid dissolution into the liquid state. We demonstrate the almost simultaneous measurement of hyperpolarised 13C and hyperpolarised 15N NMR spectra. The prospects for further improvement of the method using contemporary technology are also discussed.

Projectile breakup dynamics for (6)Li+(59)Co: Kinematical analysis of alpha-d coincidences

A study of the kinematics of the alpha-d coincidences in the (6)Li + (59)Co system at a bombarding energy of E(lab) = 29.6MeV is presented. With exclusive measurements performed over different angular intervals it is possible to identify the respective contributions of the sequential and direct projectile breakup components. The angular distributions of both breakup components are fairly well described by the Continuum-Discretized Coupled-Channels framework (CDCC). Furthermore, a careful analysis of these processes using a semiclassical approach provides information on both their lifetime and their distance of occurrence with respect to the target. Breakup to the low-lying (near-threshold) continuum is delayed, and happens at large internuclear distances. This suggests that the influence of the projectile breakup on the complete fusion process can be related essentially to the direct breakup to the (6)Li high-lying continuum spectrum.

Reaction mechanisms in the (6)Li+(59)Co system

The reactions induced by the weakly bound (6)Li projectile interacting with the intermediate mass target (59)Co were investigated. Light charged particles singles and alpha-d coincidence measurements were performed at the near barrier energies E(lab) = 17.4, 21.5, 25.5 and 29.6 MeV. The main contributions of the different competing mechanisms are discussed. A statistical model analysis. Continuum-Discretized Coupled-Channels (CDCC) calculations and two-body kinematics were used as tools to provide information to disentangle the main components of these mechanisms. A significant contribution of the direct breakup was observed through the difference between the experimental sequential breakup cross section and the CDCC prediction for the non-capture breakup cross section. (C) 2009 Elsevier B.V. All rights reserved.