Effect of Pd nanoparticle size on the catalytic hydrogenation of allyl alcohol

We report a particle size dependence for the rate of hydrogenation of allyl alcohol using 1.3-1.9 nm Pd dendrimer-encapsulated nanoparticle (DEN) catalysts. For particles with diameters of <1.5 nm and containing <147 Pd atoms, the modulation in catalytic activity is due to the electronic properties of the particle. For the larger particles, 1.5-1.9 nm in diameter and containing an average of 147-250 Pd atoms, the size effect is a result of geometrical constraints. Specifically, the hydrogenation reaction is shown to occur preferentially on the face atoms of the larger nanoparticles.     

Determining the time-frequency parameters of low-power bright picosecond optical pulses by using the interferometric technique

We present an approach to the characterization of low-power bright picosecond optical pulses with an internal frequency modulation simultaneously in both time and frequency domains in practically much used case of the Gaussian shape. This approach exploits the Wigner time-frequency distribution, which can be found for these bright pulses by using a novel interferometric technique under our proposal. Then, the simplest two-beam scanning Michelson interferometer is selected for shaping the field-strength auto-correlation function of low-power picosecond pulse trains. We are proposing and considering in principle the key features of a new experimental technique for accurate and reliable measurements of the train-average width as well as the value and sign of the frequency chirp of pulses in high-repetition-rate trains. This technique is founded on an ingenious algorithm for the advanced metrology, assumes using a specially designed supplementary semiconductor cell, and suggests carrying out a pair of additional measures with exploiting this semiconductor cell. Such a procedure makes possible constructing the Wigner distribution and describing the above-listed time-frequency parameters of low-power bright picosecond optical pulses. In the appendix, we follow one of possible avenues for deriving the joint Wigner time-frequency distribution via choosing the Weil's correspondence between classical functions and operators.     

Robust output synchronization of phase planar systems

We propose a technique to synchronize, under the master/slave synchronization scheme, two planar systems represented by phase state variables; we name them phase planar systems. The coupling signal has a discontinuous term that produces a closed-loop system having good characteristics of robustness with respect to bounded disturbances and parametric variations, and guarantees exponential convergence to the synchronization state. In general, the coupling signal needs the full state vector of both systems, but because we assume that only the system outputs are available, we include a robust observer. This observer also guarantees exponential convergence to the state of the plant in spite of the existence of bounded disturbances and parametric variations; this characteristic facilitates the stability analysis of the closed-loop system. The performance of the synchronization technique is illustrated with experimental results.     

Regioselective electrophilic additions to 2-alkoxy- and 2-alkoxymethyl-7-oxabicyclo [2.2.1] hept-5-ene derivatives

The influence of the stereochemistry at C-2 on the selectivity of the reaction between PhSeBr and 2-alkoxymethyl substituted oxanorbornenes has been studied. All endo isomers displayed complete regio- and stereocontrol with incorporation of the electrophile on C-5.     

Dispersion photopolymerization of styrene

Photopolymerization of styrene was carried out in a dispersed system to obtain 10 μm particles, using d-t-butylperoxide as initiator and poly(vinyl alcohol) as protective colloid. It was shown that particles typical for latex polymerization are also formed and interfere with the dispersion polymerization when excess protective colloid is used.     

Permanganate oxidation of α-amino acids: kinetic correlations for the nonautocatalytic and autocatalytic reaction pathways

The reactions of permanganate ion with seven α-amino acids in aqueous KH(2)PO(4)/K(2)HPO(4) buffers have been followed spectrophotometrically at two different wavelengths: 526 nm (decay of MnO(4)(-)) and 418 nm (formation of colloidal MnO(2)). All of the reactions studied were autocatalyzed by colloidal MnO(2), with the contribution of the autocatalytic reaction pathway decreasing in the order glycine > l-threonine > l-alanine > l-glutamic acid > l-leucine > l-isoleucine > l-valine. The rate constants corresponding to the nonautocatalytic and autocatalytic pathways were obtained by means of either a differential rate law or an integrated one, the latter requiring the use of an iterative method for its implementation. The activation parameters for the two pathways were determined and analyzed to obtain statistically significant correlations for the series of reactions studied. The activation enthalpy of the nonautocatalytic pathway showed a strong, positive dependence on the standard Gibbs energy for the dissociation of the protonated amino group of the α-amino acid. Linear enthalpy-entropy correlations were found for both pathways, leading to isokinetic temperatures of 370 ± 21 K (nonautocatalytic) and 364 ± 28 K (autocatalytic). Mechanisms in agreement with the experimental data are proposed for the two reaction pathways.     

Self-assembled 3D heterometallic Cu(II)/Fe(II) coordination polymers with octahedral net skeletons: structural features, molecular magnetism, thermal and oxidation catalytic properties

The new three-dimensional (3D) heterometallic Cu(II)/Fe(II) coordination polymers [Cu(6)(H(2)tea)(6)Fe(CN)(6)](n)(NO(3))(2n)·6nH(2)O (1) and [Cu(6)(Hmdea)(6)Fe(CN)(6)](n)(NO(3))(2n)·7nH(2)O (2) have been easily generated by aqueous-medium self-assembly reactions of copper(II) nitrate with triethanolamine or N-methyldiethanolamine (H(3)tea or H(2)mdea, respectively), in the presence of potassium ferricyanide and sodium hydroxide. They have been isolated as air-stable crystalline solids and fully characterized including by single-crystal X-ray diffraction analyses. The latter reveal the formation of 3D metal-organic frameworks that are constructed from the [Cu(2)(μ-H(2)tea)(2)](2+) or [Cu(2)(μ-Hmdea)(2)](2+) nodes and the octahedral [Fe(CN)(6)](4-) linkers, featuring regular (1) or distorted (2) octahedral net skeletons. Upon dehydration, both compounds show reversible escape and binding processes toward water or methanol molecules. Magnetic susceptibility measurements of 1 and 2 reveal strong antiferromagnetic [J = -199(1) cm(-1)] or strong ferromagnetic [J = +153(1) cm(-1)] couplings between the copper(II) ions through the μ-O-alkoxo atoms in 1 or 2, respectively. The differences in magnetic behavior are explained in terms of the dependence of the magnetic coupling constant on the Cu-O-Cu bridging angle. Compounds 1 and 2 also act as efficient catalyst precursors for the mild oxidation of cyclohexane by aqueous hydrogen peroxide to cyclohexanol and cyclohexanone (homogeneous catalytic system), leading to maximum total yields (based on cyclohexane) and turnover numbers (TONs) up to about 22% and 470, respectively.