Characterization of palladium nanoparticles by using X-ray reflectivity, EXAFS, and electron microscopy

We compared the characteristics of dodecanethiolate palladium nanoparticles synthesized by two different techniques, a one-phase method and a two-phase method. From transmission electron microscopy (TEM), we determined that the particle sizes were 46 +/- 10 angstroms and 20 +/- 5 angstroms for the one- and two-phase particles, respectively. Electron diffraction confirmed that their structure was face-centered cubic (fcc). The lattice constant a0 was 3.98 +/- 0.01 angstroms and 3.90 +/- 0.01 angstroms for the one- and two-phase particles, respectively. High-resolution TEM (HRTEM) showed that the one-phase particles had an ordered core surrounded by a disordered shell structure, while the two-phase particles appeared to be crystalline throughout. The particles were also analyzed with extended X-ray absorption fine structure (EXAFS). A cuboctahedral fcc model was used to fit the data, which implied particle sizes of less than 10 angstroms for both the one- and two-phase particles. The discrepancy between the two techniques was attributed to the presence of a disordered phase, which we presumed was composed of Pd-S compounds. Compared with the bulk palladium, lattice expansion was observed in both one- and two-phase particles by electron diffraction, HRTEM, and EXAFS. At the air/water interface, a uniform film that produced surface pressure/area isotherms could only be obtained from the two-phase particles. The one-phase particles did not wet the water surface. X-ray reflectivity data indicated that the Langmuir monolayer of the two-phase particles was only 13 angstroms thick. TEM revealed the diameter of the particles in this layer to be 23 angstroms; hence the particles assumed an oblate structure after spreading. EXAFS examination of a stack of 750 Langmuir monolayers indicated far fewer Pd-S compounds, which may have dissolved in the water. The data were consistent with a model of a monolayer of truncated cuboctahedron Pd particles that were 7 angstroms thick and 19 angstroms in diameter.     

Novel asymmetric michael addition of alpha-cyanopropionates to acrolein by the use of a bis(oxazolinyl)phenylstannane-derived rhodium(III) complex as a chiral Lewis acid catalyst

The rhodium complex prepared in situ by simply mixing [[RhCl(c-octene)2]2] and [(Phebox)SnMe3] (1) (Phebox = 2,6-bis(oxazolinyl)phenyl) was found to serve as an efficient catalyst for the asymmetric Michael addition of alpha-cyanopropionates (4) to acrolein under mild and neutral conditions. In the present catalytic system, both the temperature of catalyst preparation and the order of the addition of the substrates were very important for the catalytic efficiency and enantioselectivity. Detailed mechanistic studies of this catalytic system revealed that the [(Phebox)RhIII(SnMe3)Cl] complex (9), generated by oxidative addition of [[RhCl(c-octene)2]2] to 1, is an active catalyst and the turnover number (TON) of the present actual catalyst existing in a reaction mixture is greater than 10,000. The obtained (R) stereochemistry of the Michael adducts 5 can be explained by N-bonded enol intermediates C', which are formed by enolization of 4 bound to the Lewis acidic rhodium complex 9. We also found that the active catalyst 9 gradually decomposed in the presence of the remaining [[RhCl(c-octene)2]2] in the reaction mixture to form the catalytically nonactive [(Phebox)RhCl2] fragment A, whose structure was characterized by an X-ray crystallographic study after converting to the tBuNC complex 10.     

Enright functors for Kac-Moody superalgebras

A simple generalization of the Enright functor associated with a non-isotropic simple root of Kac-Moody superalgebras is introduced. Two applications for a Kac-Moody superalgebra without isotropic simple root are given: the uniqueness (up to scalar) of homomorphisms between Verma modules and the Malikov-Feigin-Fuks type singular vector formula. The braid relations of the Enright functors are also discussed.     

Effect of Ethylene Glycol on the Molecular Organization of H2O in Comparison with Methanol and Glycerol: A Calorimetric Study

Excess partial molar enthalpies of ethylene glycol, H ^E _EG, in binary ethylene glycol–H₂O, and those of 1-propanol, H ^E _IP, in ternary 1-propanol–ethylene glycol (or methanol)–H₂O were determined at 25°C. From these data, the solute–solute interaction functions, H ^E _EG–EG = N(H ^E _EG/n _EG) and H ^E _1P–1P = N(H ^E _1P/n _1P), were calculated by graphical differentiation without resorting to curve fitting. Using these, together with the partial molar volume data, the effect of ethylene glycol on the molecular organization of H₂O was investigated in comparison with methanol and glycerol. We found that there are three concentration regions, in each of which the mixing scheme is qualitatively different from the other regions. Mixing scheme III operative in the solute-rich region is such that the solute molecules are in a similar situation as in the pure state, most likely in clusters of its own kind. Mixing scheme II, in the intermediate region, consists of two kinds of clusters each rich in solute and in H₂O, respectively. Thus, the bond percolation nature of the hydrogen bond network of liquid H₂O is lost. Mixing scheme I is a progressive modification of liquid H₂O by the solute, but the basic characteristics of liquid H₂O are still retained. In particular, the bond percolation of the hydrogen bond network is still intact. Similar to glycerol, ethylene glycol participates in the hydrogen bond network of H₂O via-OH groups, and reduces the global average of the hydrogen bond probability and the fluctuations inherent in liquid H₂O. In contrast to glycerol, there is also a sign of a weak hydrophobic effect caused by ethylene glycol. However, how these hydrophobic and hydrophilic effects of ethylene glycol work together in modifying the molecular organization of H₂O in mixing scheme I is yet to be elucidated.     

Magnetic Temperature Standards for TG

Magnetic transition temperatures, Tc, are measured by simultaneous TM/DTA for Alumel, cobalt, nickel, and three alloys of Ni and Co. The observed values of Tc are corrected using the values for the melting temperatures of pure metals used to define the International Temperature Scale. These corrections are based on the simultaneous melting of these pure metals alongside, but separate from, the magnetic sample. Nine investigators, using a wide variety of instrumentation, have made these measurements utilizing a standard protocol. The results are compared for several heating rates. It is planned to make these same magnetic materials ultimately available to the public for calibration of temperature of their TG instruments. This revised version was published online in July 2006 with corrections to the Cover Date.     

A Non-aqueous H3PO4 Electrolyte Enables Stable Cycling of Proton Electrodes

A non-aqueous proton electrolyte is devised by dissolving H₃PO₄ into acetonitrile. The electrolyte exhibits unique vibrational signatures from stimulated Raman spectroscopy. Such an electrolyte exhibits unique characteristics compared to aqueous acidic electrolytes: 1) higher (de)protonation potential for a lower desolvation energy of protons, 2) better cycling stability by dissolution suppression, and 3) higher Coulombic efficiency owing to the lack of oxygen evolution reaction. Two non-aqueous proton full cells exhibit better cycling stability, higher Coulombic efficiency, and less self-discharge compared to the aqueous counterpart.     

Upper bounds to atomic electron densities in position and momentum spaces

Modified functions r ^–(r) and p ^–(p) of the spherically averaged electron densities (r) in position space and (p) in momentum space are found to be convex (i.e., the second derivatives are nonnegative everywhere) for all the 103 ground-state atoms from hydrogen (atomic number Z=1) to lawrencium (Z=103), if the parameters are chosen to be 0.6 and 1.4. The convex property of r ^–(r) and p ^–(p) is used to derive upper bounds to the density functions (r) and (p) in terms of their radial moments r ^s and p ^s or frequency moments ^t and ^t . In most cases, the present bounds are shown to be more general and more accurate than those reported in the literature.     

Linear integrability of wave functions

Finiteness is usually imposed as a condition for physical admissibility of a wave function. Examination of this condition in both position- and momentum-space shows that finiteness of the wave function at the origin in one space implies “linear” integrability in the reciprocal space, except in some pathological cases. Some implications of this result are discussed.