Structural Relationships between the Hemiporphyrazine Macrocyclic Ligand and its Metal Complexes. II.: Planar Neutral Ligand,C26H16N8, and Four Isomorphous Metal Complexes, [M(C26H16N8)(H2O)], M=Mn(II), Co(II), Cu(II), Zn(II)

Crystal and molecular structures of the planar neutral ligand, C₂₆H₁₆N₈, and the four isomorphous five-coordinated metal complexes, [M(C₂₆H₁₆N₈)(H₂O)], M = Mn(II), Co(II), Cu(II), Zn(II), have been determined from three-dimensional X-ray diffraction data. The free ligand hpH₂, C₂₆H₁₆N₈, belongs to the P 2₁/c space group with Z=2, a=4.142(3), b=23.736(6), c=10.338(3) Ä, β=94.66(6)°. The metal complexes monohydrate Mhp-H₂O all belong to the orthorhombic Pcab space group with Z=8. The dimensions are roughly 8.8×19.3×23.7 ų. In each structure, the macrocyclic ligand has an almost planar conformation which differs from the saddle shaped ligand hydrate (hpH₂·H₂O) and the nickel complex [Nihp]⁵. The distances from the center of the macrocyclic ring to the nitrogen atom of the free ligand are 1.907(6) and 2.245(6)Å. The coordination geometry in these four complexes is square pyramidal with a water molecule as an axial ligand. The bond distances of M(II)-O(H₂O), M(II)-N1 (imine), M(II)-N3 (pyridine) are: 2.19(1), 2.00(2), 2.27(2)Å respectively for the manganese complex; 2.08(1), 1.97(1), 2.23(1)Å for the cobalt complex; 2.33(1), 1.92(3), 2.18(1)Å for the copper complex; 2.110(5), 1.964(6), 2.252(6)Å for the zinc complex. The variation of metal-ligand distances can be correlated to the metal d orbital occupancy. A comparison with similar ligands will be presented.     

Optimal Conditions for Existence of Vesicles Under Electric Field

Giant vesicles have been of intense interest as the model system for cell membranes. To bring numerous applications of the vesicles into full play, the existence time of the vesicles becomes particularly important. In this work, we explored the existence time of the vesicles in distilled water under four kinds of representative alternative current (AC) electric fields with different energizing time. When the application time of AC electric field reached 1 hour, the existence time of the vesicles reached the maximum value. As the applied electric field time increased, the existence time of the vesicles decreased. Thus, after obtaining the best vesicles on the carbon fiber electrode, disconnecting the external electric field is very necessary. Based on the in situ observation using inverted microscope, the disappearing phenomena of the vesicles were presented. In addition, it is found that vesicles in phosphate buffer solutions (PBSs) can last about 2–3 days when the electric field was applied for 1 hour, which was much longer than that in distilled water.     

Modified null field method for P- and SV-wave scattering from a partially debonded fiber

The modified null field approach to elastic P- and SV-wave scattering (in plane strain) from a partially debonded fiber has been developed. The debonded region on the fiber surface is subjected to traction free boundary conditions, whereas the fiber is assumed to be in welded contact with the host medium elsewhere. Additional null field equations for an elliptical extension of the actual surface of the scatterer are introduced which require additional expansions for the field in the region between the extended mathematical boundary and the actual boundary of the scatterer. The numerical accuracy of the modified null field method has been tested for the case of a perfectly bonded fiber for P- and SV-wave incidence. Scattering cross-section plots are presented for different degrees of debonding.     

Studies on crude oil‐water biphasic mixtures by low‐field NMR

Low‐field ¹H NMR was used in this work for the analysis of mixtures involving crude oils and water. CPMG experiments were performed to determine the transverse relaxation time (T₂) distribution curves, which were computed by the inverse Laplace transform of the echo decay data. The instrument's ability of quantifying water and petroleum in biphasic mixtures following different methodologies was tested. For mixtures between deionized water and petroleum, one achieved excellent results, with root mean squared error of cross‐validation (RMSECV) of 0.8% for a regression between the water content (wt %) and the relative area of the water peak in the T₂ distribution curve, or a standard deviation of 0.9% for the relationship between the water content and the relative water peak area, corrected by the relative hydrogen index of the crude. In the case of biphasic mixtures of Mn²⁺‐doped water and crude oils, the best result of RMSECV = 1.6% was achieved by using the raw magnetization decay data for a partial least squares regression. Copyright © 2012 John Wiley & Sons, Ltd.     

Spectroscopic studies and crystal structure of a dimeric Zn(II) complex with diethyl (pyridin-2-ylmethyl)phosphate

The crystal structure of [Zn₂(2-pmOpe)₂Cl₄] (2-pmOpe?=?diethyl (pyridin-2-ylmethyl)phosphate) was determined by X-ray-diffraction method. The compound was also characterized by IR, far-IR, 1H, and ³¹P NMR spectroscopy. In this compound, 2-pmOpe is a bidentate N,O-bridging ligand and Zn(II) are slightly distorted tetrahedral ZnNOCl₂. Zn(II) ions are doubly bridged by the 2-pmOpe ligands, resulting in a dinuclear species. The structure is stabilized by intermolecular C–H?···?O and C–H?···?Cl hydrogen bonds. The spectral properties are in agreement with the structural data.     

Synthesis,structure and properties of aquabis(2,4′-bipyridine)di(propionato-O)copper(II)

The title complex has been synthesized and characterized by elemental and thermal analysis, IR and electronic spectroscopy, conductivity studies and X-ray crystallography. In the crystal, the complex has two-fold symmetry and the copper atom adopts square pyramidal coordination. Bond valences for Cu were computed. Cu–O_(propionate) bonds are slightly stronger than the Cu–N bonds, and the Cu–O_(water) bond is distinctly weaker. Molecules are linked by O–H···O hydrogen bonds to form infinite hydrogen-bonded chains along the y axis.     

Triphenyltin chloride complexes containing bidentate organodiimines as effective antitumor agents

Three triphenyltin chloride complexes, [(Ph₃SnCl)₂?·?(bpy)_1.5] (1), [(Ph₃SnCl)₂.tbpe] (2), and [(Ph₃SnCl)₂?·?bpe] (3), were synthesized by reaction of triphenyltin chloride with 4,4′-bipyridine (bpy), trans-1,2-bis(4-pyridyl)ethylene (tbpe), and 1,2-bis(4-pyridyl)ethane (bpe) in water/acetonitrile. Both 2 and 3 are binuclear; each consists of two Ph₃SnCl molecules bridged by the bidentate ligand. Complex 1 consists of two crystallographically independent and chemically different coordination complexes, mononuclear and binuclear in equal proportion. The structures of these complexes were investigated by single-crystal X-ray analysis, elemental analyses, NMR spectroscopy as well as electronic absorption and emission spectroscopy. The three complexes exhibit in vitro antitumor activity against human breast cancer cell line, MCF7.     

Fast vectorized algorithm for the Monte Carlo simulation of the random field Ising model

An algorithm for the simulation of the 3-dimensional random field Ising model with a binary distribution of the random fields is presented. It uses multi-spin coding and simulates 64 physically different systems simultaneously. On one processor of a Cray YMP it reaches a speed of 184 million spin updates per second. For smaller field strength we present a version of the algorithm that can perform 242 million spin updates per second on the same machine.     

Ising model in a quasiperiodic transverse field,percolation, and contact processes in quasiperiodic environments

Quantum Ising models in a transverse field are related to continuous-time percolation processes whose oriented percolation versions are contact processes. We study such models in the presence of quasiperiodic disorder and prove localization in the ground state, no percolation, and extinction, respectively, for sufficiently large disorder.