Electrochemistry of P(CH2Fc)3 and derivatives

The oxidative electrochemistry of P(CH₂Fc)₃ and three of its derivatives was examined. The electrochemistry of these compounds is sensitive to the functionality added to the phosphorus lone pair and the supporting electrolyte used.     

Enhancement of epoxidation efficiencies for Ta-SBA15 catalysts. The influence of modification with -EMe3 (E = Si, Ge, Sn) groups

Site-isolated Ta(V) centers were introduced onto the surface of a mesoporous SBA-15 support via the thermolytic molecular precursor method. After thermal treatment under oxygen, the resulting Si-OH and Ta-OH sites of TaSBA15-O(2)were modified with a series of trimethyl group 14 species, Me(3)E-, by treatment with Me(3)E-NMe(2) (E = Si, Ge, Sn) reagents. The resulting surface-modified catalysts (Me(3)E)(cap)TaSBA15 exhibit a significantly increased rate of cyclohexene epoxidation with H(2)O(2) as an oxidant, and provided a decreased amount of allylic oxidation products with respect to the unmodified material, TaSBA15-O(2). The rate of nonproductive H(2)O(2) decomposition, as monitored via (1)H NMR spectroscopy, significantly decreased after the surface modification. The structure of the TaSBA15 catalysts and potential Ta(V) epoxidation intermediates (formed upon treatment of Ta(V) materials with H(2)O(2)) were probed using UV-visible absorbance and diffuse-reflectance UV-visible spectroscopy. A Ta(V)(η(2)-O(2)) intermediate species is proposed for the TaSBA15-O(2), (Me(3)Si)(cap)TaSBA15, and (Me(3)Ge)(cap)TaSBA15 catalysts, while intermediate species for the (Me(3)Sn)(cap)TaSBA15 catalysts could not be characterized.     

Magnetic levitating polymeric nano/microparticular substrates for three-dimensional tumor cell culture

Herein, we describe magnetic cell levitation models using conventional polymeric microparticles or nanoparticles as a substrate for the three-dimensional tumor cell culture. When the magnetic force originating from the ring-shaped magnets overcame the gravitational force, the magnetic field-levitated KB tumor cells adhered to the surface area of magnetic iron oxide (Fe(3)O(4))-encapsulated nano/microparticles and concentrated clusters of levitated cells, ultimately developing tumor cells to tumor spheroids. These simple cell culture models may prove useful for the screening of anticancer drugs and their formulations.     

Late-metal nitrosyl cations: synthesis and reactivity of [Ni(NO)(MeNO2)3][PF6

The reaction of [NO][PF(6)] with excess Ni powder in CH(3)NO(2), in the presence of 2 mol % NiI(2), results in the formation of [Ni(NO)(CH(3)NO(2))(3)][PF(6)] (1), which can be isolated in modest yield as a blue crystalline solid. Also formed in the reaction is [Ni(CH(3)NO(2))(6)][PF(6)](2) (2), which can be isolated in comparable yield as a pale-green solid. In the solid state, 1 exhibits tetrahedral geometry about the Ni center with a linear nitrosyl ligand [Ni1-N1-O1 = 174.1(8)°] and a short Ni-N bond distance [1.626(6) ?]. As anticipated, the weakly coordinating nitromethane ligands in 1 are easily displaced by a variety of donors, including Et(2)O, MeCN, and piperidine (NC(5)H(11)). More surprisingly, the addition of mesitylene to 1 results in the formation of an η(6)-coordinated nickel arene complex, [Ni(η(6)-1,3,5-Me(3)C(6)H(3))(NO)][PF(6)] (6). In the solid state, complex 6 exhibits a long Ni-C(cent) distance [1.682(2) ?], suggesting a relatively weak Ni-arene interaction, a consequence of the strong π-back-donation to the nitrosyl ligand. The addition of anisole to 1 also results in the formation of a η(6) nickel arene complex, [Ni(η(6)-MeOC(6)H(5))(NO)][PF(6)] (7). This complex also exhibits a long Ni-C(cent) distance [1.684(1) ?].     

The electronic states of 1,2,3-triazole studied by vacuum ultraviolet photoabsorption and ultraviolet photoelectron spectroscopy, and a comparison with ab initio configuration interaction methods

The Rydberg states in the vacuum ultraviolet photoabsorption spectrum of 1,2,3-triazole have been measured and analyzed with the aid of comparison to the UV valence photoelectron ionizations and the results of ab initio configuration interaction (CI) calculations. Calculated electronic ionization and excitation energies for singlet, triplet valence, and Rydberg states were obtained using multireference multiroot CI procedures with an aug-cc-pVTZ [5s3p3d1f] basis set and a set of Rydberg [4s3p3d3f] functions. Adiabatic excitation energies obtained for several electronic states using coupled-cluster (singles, doubles, and triples) and complete active space self-consistent field procedures agree well with experimental values. Variations in bond lengths with the electronic state are discussed. The lowest energy UV band (～5.5-6.5 eV) is assigned to three electronically excited states and demonstrates the occurrence of a nonplanar upper state on the low energy side. A UV photoelectron spectrum with an improved resolution yielded adiabatic and vertical ionization energies and reorganization energies for several of the lowest cationic states. As well as excitations to the s, p, d-Rydberg states are the excitations consistent with an f-series.     

Theory of phonon-modulated electron spin relaxation time based on the projection reduction method

This paper introduces a new method for a formula for electron spin relaxation time of a system of electrons interacting with phonons through phonon-modulated spin-orbit coupling using the projection-reduction method. The phonon absorption and emission processes as well as the photon absorption and emission processes in all electron transition processes can be explained in an organized manner, and the result can be represented in a diagram that can provide intuition for the quantum dynamics of electrons in a solid. The temperature （T） dependence of electron spin relaxation times （T1） in silicon is T1 ∝ T-1.07 at low temperatures and T1 ∝ T-3.3 at high temperatures for acoustic deformation constant Pad = 1.4 × 10^7 eV and optical deformation constant Pod = 4.0 × 10^17 eV/m. This means that electrons are scattered by the acoustic deformation phonons at low temperatures and optical deformation phonons at high temperatures, respectively. The magnetic field （B） dependence of the relaxation times is T1 ∝ B-2.7 at 100 K and T1 ∝ B-2.3 at 150 K, which nearly agree with the result of Yafet, T1 ∝ B-3.0- B -2.5.     

Molecular motion in zinc hydrazone grid complexes

Four new grid forming hydrazone ligands substituted with methoxy and dimethylamino groups were synthesised. Combination of these ligands with zinc triflate in acetonitrile resulted in self-assembly to form grids as indicated by ¹H NMR and ES-MS. ¹H NMR also showed thermally induced rotation of the intercalated phenyl ring in both the new grids, and in three previously reported grid compounds. Of these seven, five were amenable to study by variable temperature ¹H NMR. Though the observed rates varied by more than an order of magnitude depending upon ligand structure and level of deprotonation, activation energies were similar (～60 kJ/mol) for all complexes studied. This suggests a model in which dissociation of the central pyrimidine ligand precedes phenyl group rotation with an enthalpy of dissociation near zero. The rate of rotation of the phenyl ring increases with an introduction of electron-donating substituents on the phenyl ring, possibly due to an increased repulsion between π systems.     

1D and 2D economical FIR filters generated by Chebyshev polynomials of the first kind

Christoffel–Darboux formula for Chebyshev continual orthogonal polynomials of the first kind is proposed to find a mathematical solution of approximation problem of a one-dimensional (1D) filter function in the z domain. Such an approach allows for the generation of a linear phase selective 1D low-pass digital finite impulse response (FIR) filter function in compact explicit form by using an analytical method. A new difference equation and structure of corresponding linear phase 1D low-pass digital FIR filter are given here. As an example, one extremely economic 1D FIR filter (with four adders and without multipliers) is designed by the proposed technique and its characteristics are presented. Global Christoffel–Darboux formula for orthonormal Chebyshev polynomials of the first kind and for two independent variables for generating linear phase symmetric two-dimensional (2D) FIR digital filter functions in a compact explicit representative form, by using an analytical method, is proposed in this paper. The formula can be most directly applied for mathematically solving the approximation problem of a filter function of even and odd order. Examples of a new class of extremely economic linear phase symmetric selective 2D FIR digital filters obtained by the proposed approximation technique are presented.     

Viskosität und Oberflächenspannung von Oelen

Ohne Zusammenfassung Deutsch von Luise Pieper (Leipzig).