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101.
Different structures have been found for poly(α-tetrathiophene) [poly(α-4TF)] electrosynthesized on Pt by anodic oxidation of 1.0 mM monomer solutions in media such as 45:35:20 (v/v/v) acetonitrile/THF/DMF, 45:35:20 (v/v/v) acetonitrile/ethanol/DMF and 72:28 (v/v) acetonitrile/DMF containing 0.1 M LiClO4; as well as 72:28 (v/v) acetonitrile/DMF with 0.1 M NaClO3, under dynamic and static conditions at 25 °C. In all cases the polymer was generated by chronoamperometry at 1.000 V vs. Ag∣AgCl, corresponding to the first oxidation peak detected by cyclic voltammetry. Uniform, adherent, insoluble and black polymer films were obtained under these conditions. The resulting structures have been elucidated by combining the information of their IR spectrum, nox-value and doping level of the counterion. The degree of crosslinking of every polymer has been quantified and related to the molecular flow of monomer on the Pt electrode. A monomer concentration flow between 4 × 10−6 and 5 × 10−6 mmol cm−2 s−1 was determined as the limiting value below which the polymer grows with crosslinking. This value corresponds to the electropolymerization rate of α-4TF by Pt area unit at 25 °C. 相似文献
102.
Krishna Bisetty Francesc J. Corcho Josep Canto Hendrik G. Kruger Juan J. Perez 《Journal of Molecular Structure》2006,770(1-3):221-228
In this paper, we report on the conformational profile of the pentacyclo-undecane (PCU) cage tripeptide carried out by molecular dynamics (MD) simulation using water as an explicit solvent. The MD solution phase studies carried on the model peptide analogues (A)=Ac–Ala–Ala–Ala–NHMe; (B)=Ac–Cage–Cage–Cage–NHMe; (C)=Ac–Ala–Cage–Ala–NHMe and (D)=Ac–Ala–Pro–Ala–NHMe, are used as a complimentary technique to the corresponding gas phase simulated annealing (SA) study previously carried out in our laboratory. No significant structural changes were observed over the MD trajectories. However, the results reported here provide further evidence that the (PCU) cage amino acid exhibits C7eq, C7aq, R and L conformations, and the theoretical results suggest that the PCU cage amino acid is a strong β-turn inducer. These results support the prediction that when the PCU cage residues are in the (i) and (i+2) positions, the β-turn can be extended in either direction to form anti-parallel β-pleated sheets, thereby forming the basis of the mechanism for the folding back of the chain in a cross-β-turn structure. 相似文献
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107.
Radiative corrections to low-energy ππ scattering are calculated. A chiral SU(2) × SU(2) Lagrangian is used to describe low-energy scattering. This strong interaction Lagrangian is modified in the presence of the electromagnetic field in a gauge invariant way. It is found that photons do not probe the strong vertex. Corrections to the cross sections are calculated to O(α). All the ultra-violet divergences cancel, and the results are independent of cut-off parameters. Corrections to the Weinberg scattering lengths of the order of 1% are defined by removal of the Coulomb pole terms. The field theoretic calculation is compared with a potential theory approach. It is argued that the potential theory calculation of radiative corrections is more reliable. 相似文献
108.
Both bilirubin and biliverdin, their cesium salts, have been covalently attached to an insoluble polystyrene matrix (the so-called Nbb-resin), some chemical transformations have been carried out upon the supported pigments, and the resulting products have been detached by alkaline methanol. 相似文献
109.
Two new phenylmalonate-bridged copper(II) complexes with the formulas [Cu(4,4'-bpy)(Phmal)](n).2nH(2)O (1) and [Cu(2,4'-bpy)(Phmal)(H(2)O)](n)() (2) (Phmal = phenylmalonate dianion, 4,4'-bpy = 4,4'-bipyridine, 2,4'-bpy = 2,4'-bipyridine) have been synthesized and characterized by X-ray diffraction. Complex 1 crystallizes in monoclinic space group P2(1), Z = 4, with unit cell parameters of a = 9.0837(6) Angstroms, b = 9.3514(4) Angstroms, c = 11.0831(8) Angstroms, and beta = 107.807(6) degrees , whereas complex 2 crystallizes in orthorhombic space group C2cb, Z = 8, with unit cell parameters of a = 10.1579(7) Angstroms, b = 10.3640(8) Angstroms, and c = 33.313(4) Angstroms. The structures of 1 and 2 consist of layers of copper(II) ions with bridging bis-monodentate phenylmalonate (1 and 2) and 4,4'-bpy (1) ligands and terminal monodentate 2,4'-bpy (2) groups. Each layer in 1 contains rectangles with dimensions of 11.08 x 4.99 Angstroms(2), the edges being defined by the Phmal and 4,4'-bpy ligands. The intralayer copper-copper separations in 1 through the anti-syn equatorial-apical carboxylate-bridge and the 4,4'-bpy molecule are 4.9922(4) and 11.083(1) Angstroms, respectively. The anti-syn equatorial-equatorial carboxylate bridge links the copper(II) atoms in complex 2 within each layer with a mean copper-copper separation of 5.3709(8) Angstroms. The presence of 2,4'-bpy as a terminal ligand accounts for the large interlayer separation of 15.22 Angstroms. The copper(II) environment presents a static pseudo-Jahn-Teller disorder which has been studied by EPR and low-temperature X-ray diffraction. Magnetic susceptibility measurements of both compounds in the temperature range 2-290 K show the occurrence of weak antiferromagnetic [J = -0.59(1) cm(-1) (1)] and ferromagnetic [J = +0.77(1) cm(-1) (2)] interactions between the copper(II) ions. The conformation of the phenylmalonate-carboxylate bridge and other structural factors, such as the planarity of the exchange pathway in 1, account for the different nature of the magnetic interaction. 相似文献