IR and theoretical studies of monocarbonyl Ni complexes formed by adsorption of CO at low pressure on silica-supported Ni(II) ions

This work reports on the reactivity of coordination vacancies of Ni(II) ions grafted onto the tridentate silica support (Ni(II)(3c) ions) with respect to CO used as a probe molecule. The adsorption of CO at 77 K in the 0.3 to 3.5 Pa CO pressure range is studied by FTIR on two samples differing in the dispersion of nickel. Quantum chemical calculations by the DFT method are performed to investigate, using a cluster approach, the binding of Ni to silica and, after CO adsorption, the geometry of the resulting carbonyl Ni complexes. Silica is modeled by using clusters composed of three types of monodentate ligands, SiO(-), SiOSi and/or SiOH, found on the surface of silica. This work is devoted to the monocarbonyl complexes. Whatever the sample, only one type of monocarbonyl is formed from Ni(II)(3c) ions. It is shown that the charge of the silica cluster is the major parameter influencing the CO IR frequency whereas the nature and the size of the silica cluster do not affect the CO bond length, confirming that local electrostatic interactions predominate. Only the 1- charged silica cluster Si(5)O(3)(-), composed of SiO(-), 2SiOSi fragments, respectively, reproduces the Ni[bond]O distances derived from EXAFS for the Ni(II)(3c) grafted site and gives CO frequencies in good agreement with the experimental values. It is shown that CO is stabilized by a magnetic transition from the (3)Ni(2+) triplet to the (1)Ni(2+) singlet state occurring upon adsorption.     

Molecular dynamics as studied by static-powder and magic-angle spinning 2H NMR

The 2H NMR magic-angle spinning (MAS) technique is compared to the static-powder quadrupole echo (QE) and Jeener-Brockaert (JB) pulse sequences for a quantitative investigation of molecular dynamics in solids. The linewidth of individual spinning sidebands of the one-dimensional MAS spectra are observed to be characteristic of the correlation time from approximately 10(-2) to approximately 10(-8) s so that the dynamic range is increased by approximately three orders of magnitude when compared to the QE experiment. As a consequence, MAS 2H NMR is found to be more sensitive to the presence of an inhomogeneous distribution of correlation times than the QE and JB experiments which rely upon lineshape distortions due to anisotropic T2 and T1Q relaxation, respectively. All these results are demonstrated experimentally and numerically using the two-site flip motion of dimethyl sulfone and of the nitrobenzene guest in the alpha-p-tert-butylcalix[4]arene-nitrobenzene inclusion compound.     

Compressing thin spheres in the complement of a link

Let L be a link in S³ that is in thin position but not in bridge position and let P be a thin level sphere with compressing disk D. We introduce the idea of alternating level spheres for D and show that all such spheres are thin and their widths are monotone decreasing. This allows us to generalize a result of Wu by giving a bound on the number of disjoint irreducible compressing disks P can have in terms of the width of P, including identifying thin spheres with unique compressing disks. We also give conditions under which P must be incompressible on some side or be weakly incompressible. In particular we show that the thin level sphere of second lowest width is weakly incompressible. If P is strongly compressible we describe how a pair of compressing disks must lie relative to the link.     

Synthesis of palladium nanoparticles by reaction of filamentous cyanobacterial biomass with a palladium(II) chloride complex

The interaction of cyanobacterial biomass (Plectonema boryanum UTEX 485) with aqueous palladium(II) chloride (PdCl2 degrees ) has been investigated at 25-100 degrees C for up to 28 days. We report that the release of organic materials from the cyanobacteria promoted the precipitation of Pd(0) as crystalline spherical and elongate nanoparticles (< or =30 nm), both in solution and as dispersed and encrusted nanoparticles on cyanobacterial cells. In contrast, under abiotic conditions at 100 degrees C, palladium hydride (PdHx) was the principal palladium phase precipitated, with only minor amounts of palladium metal.     

Crystal chemistry peculiarities of Cs2Te4O12

The Raman and IR-absorption spectra of the Cs₂Te₄O₁₂ lattice are first recorded and interpreted. Extraordinary features observed in the structure and Raman spectra of Cs₂Te₄O₁₂ are analyzed by using ab initio and lattice-dynamical model calculations. This compound is specified as a caesium-tellurium tellurate Cs₂Te^IV(Te^VIO₄)₃ in which Te^IV atoms transfer their 5p electrons to [Te^VIO₄]₃⁶⁻ tellurate anions, thus fulfilling (jointly with Cs atoms) the role of cations. The Te^VI-O-Te^VI bridge vibration Raman intensity is found abnormally weak, which is reproduced by model treatment including the Cs⁺ ion polarizability properties in consideration.     

13C/15N distance determination by CPMAS NMR in uniformly 13C labeled molecules

The REDOR and CPMAS techniques are applied for measuring 13C-15N dipolar coupling constants in glycine. It is shown that the selective CP or SPECIFIC CP technique removes the coherent evolution of the spin system under homonuclear 13C-13C J couplings. While the large coupling constant (approximately 900 Hz) is readily determined because of the presence of large oscillations in the CPMAS dynamics, their absence precludes the measurement of the small coupling constant (approximately 200 Hz). The experimental results and numerical simulations demonstrate that the determination of 13C-15N coupling constants of medium size (<1 kHz) by the CPMAS technique is mainly limited by the strength of the 1H decoupling field and the size of the 13C and 15N chemical shift anisotropies.     

Biosynthesis of silver nanoparticles by filamentous cyanobacteria from a silver(I) nitrate complex

The biosynthesis of silver nanoparticles has been successfully conducted using Plectonema boryanum UTEX 485, a filamentous cyanobacterium, reacted with aqueous AgNO3 solutions (approximately 560 mg/L Ag) at 25-100 degrees C for up to 28 days. The interaction of cyanobacteria with aqueous AgNO3 promoted the precipitation of spherical silver nanoparticles and octahedral (111) silver platelets (of up to 200 nm) in solutions. The mechanisms of silver nanoparticles via cyanobacteria could involve metabolic processes from the utilization of nitrate at 25 degrees C and also organics released from the dead cyanobacteria at 25-100 degrees C.     

Batch Emulsion Polymerization of Styrene Stabilized by a Hydrophilic Macro‐RAFT Agent

Summary: A well‐defined homopolymer of 2‐(diethylamino)ethyl methacrylate has been synthesized by reversible addition‐fragmentation chain transfer (RAFT) polymerization using (4‐cyanopentanoic acid)‐4‐dithiobenzoate as a chain transfer agent. The corresponding protonated homopolymer with a very reactive dithiobenzoate end group has been used as a water‐soluble macromolecular chain transfer agent in the batch emulsion polymerization of styrene without any surfactant. The reaction leads to a stable latex, as a result of the in‐situ formation of an amphiphilic block copolymer stabilizer, via transfer reaction to the dithioester functions during the nucleation step. The work does not intend to apply controlled free‐radical polymerization in an aqueous dispersed system but takes advantage of the RAFT technique to create a well‐defined polyelectrolyte, with a high chain‐end reactivity.

Schematic of the formation of the stabilized latex by the in situ formation of an amphiphilic block copolymer stabilizer.     

Vibrational spectra of rhombohedral TeO3 compared to those of ReO3‐like proto‐phase and α‐TeO2 (paratellurite): lattice dynamic and crystal chemistry aspects

Vibrational spectra of rhombohedral TeO₃ (r‐TeO₃) are analyzed along with those of ReO₃‐like proto‐phase (c‐TeO₃) and α‐TeO₂ (paratellurite), emphasizing their lattice dynamic and crystal chemistry aspects. It is shown that (1) r‐TeO₃ can be regarded as resulting from the condensation of a particular R‐point soft phonon of c‐TeO₃; (2) the Raman spectra of r‐TeO₃ and α‐TeO₂ are indicative of the two fundamentally different (from the crystal chemistry point of view) types of crystalline oxides, namely, framework‐type and island‐type, respectively. Copyright © 2010 John Wiley & Sons, Ltd.