Epoxidation of alkenes and oxidation of alcohols with hydrogen peroxide catalyzed by a manganese(V) nitrido complex

The manganese(V) nitrido complex (PPh(4))(2)[Mn(N)(CN)(4)] is an active catalyst for alkene epoxidation and alcohol oxidation using H(2)O(2) as an oxidant. The catalytic oxidation is greatly enhanced by the addition of just one equivalent of acetic acid. The oxidation of ethene by this system has been studied computationally by the DFT method.     

Shake-up satellites in Hel photoelectron spectra: N2O4 and CH3O

Low-lying vacant molecular orbitals may lead not only to a breakdown of Koopmans' theorem but also to satellite structure in photoelectron spectra. This paper reports examples of the relatively infrequent appearance of shake-up satellites in Hel photoelectron spectra, namely those of N₂O₄ and CH₃NO. An extended version of the HAM/3 program was used to interpret these spectra.     

Flow behavior and deposition study of pollen-shape carrier particles in an idealized inhalation path model

Pollen-shape (spiked sphere) hydroxyapatite (HA) particles for drug carrier application are studied. The particle shape and size effect on flow characteristics and deposition are assessed. The pollen-shape HA particles are synthesized to have comparable size as typical carrier particles with mean diameter of 30-50 m and effective density less than 0.3 g/cm 3 . The flow behaviors of HA and commonly used lactose (LA) carrier particles are characterized by the Carr's compressibility index (CI). The HA particle...     

Preparation of poly(ethylene oxide)‐block‐poly(isoprene) by nitroxide‐mediated free radical polymerization from PEO macroinitiators

Amphiphilic poly(ethylene oxide)‐block‐poly(isoprene) (PEO‐b‐PI) diblock copolymers were prepared by nitroxide‐mediated polymerization of isoprene from alkoxyamine‐terminal poly(ethylene oxide) (PEO). PEO monomethyl ether (M_n ≈ 5200 g/mol) was functionalized by esterification with 2‐bromopropionyl bromide with subsequent copper‐mediated replacement of the terminal bromine with 2,2,5‐trimethyl‐4‐phenyl‐3‐azahexane‐3‐nitroxide. The resulting PEO‐alkoxyamine macroinitiator was used to initiate polymerization of isoprene in bulk and in solution at 125 °C to yield PEO‐b‐PI block copolymers with narrow molecular weight distributions (M_w/M_n ≤ 1.1). Polymerizations were first order in isoprene through 35% conversion. Micellar aggregates of PEO‐b‐PI in aqueous solution were crosslinked by treatment with a water‐soluble redox initiating system, and persistent micellar structures were observed in the dry state by AFM. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2977–2984, 2005     

Pricing and volume discounting for a dominant retailer with uncertain manufacturing cost information

A product costs the manufacturer c/unit to produce; the retailer sells it at p/unit to the consumers. The retail-market demand volume V varies with p according to a given demand curve D_p. How would or should the “players” (i.e., the manufacturer and the retailer) set their prices? In contrast to many studies that assume a dominant manufacturer implementing the “manufacturer-Stackelberg” (“[mS]”) game, this paper examines how a dominant retailer should operate when his knowledge of c is imperfect. We first derive optimal decisions (some of them counter-intuitive) for the dominant retailer when he is restricted to choosing between [rS] (retailer-Stackelberg) and [mS]. Second, we propose a “reverse quantity discount” scheme that the dominant retailer (i.e., the downstream player) can offer to the manufacturer (note that the standard discount scheme is offered by the upstream player). We show that this discounting scheme is quite effective compared to the considerably more complicated though nevertheless theoretically optimal “menu of contracts.” We also reveal a largely overlooked function of discounting; i.e., discounting enables an “ignorant” but dominant player to usurp the earnings attributable to the knowledge of the dominated player. Finally, we also show that discounting works well when the demand curve is linear, but becomes ineffective when the demand curve is iso-elastic – a result echoing the conclusions of some earlier related works.     

Piezoelectric PMN-PT fibre hydrophone for ultrasonic transducer calibration

A newly developed ceramic fibre hydrophone with an active element as small as 0.25 mm in diameter is described in this work. Lead magnesium niobate-lead titanate (PMN-PT) ceramic fibre with a nominal composition of 0.65Pb(Mg_1/3Nb_2/3)O₃-0.35PbTiO₃ was fabricated by an extrusion method. PMN-PT single crystals were ground to a powder form and then mixed with poly(acrylic) acid to form a homogenous slurry. The fibre was extruded by pressing the slurry through a spinneret and then sintering at 1250 °C for crystallization. The electrical characteristics of the PMN-PT fibre were evaluated by measuring the relative permittivity and the impedance spectrum. A piezoelectric PMN-PT fibre hydrophone was fabricated and its sensitivity, angular response, and spatial resolution were evaluated. The fibre hydrophone provides good spatial resolution, angular response and receiving sensitivity. PACS 43.58.+z; 77.84.Dy     

Two extensions of asymptotic methods in controlled Markov chains

The application of the Skorokhod representation of martingales and of the local asymptotic normality to derive limit inequalities for the cost in controlled finite state Markov chains is reviewed. The inequalities are usable in self-optimizing control. The methods are taken from the references listed but, with the exception of proposition 4, the results are formulated for Markov chains for the first time.     

Approximation of fixed points for amenable semigroups of nonexpansive mappings in Banach spaces

The purpose of this paper is to study iterative schemes of Browder and Halpern types for a semigroup of nonexpansive mappings on a compact convex subset of a smooth (and strictly convex) Banach space with respect to a sequence of strongly asymptotic invariant means defined on an appropriate space of bounded real valued functions of the semigroup. Various applications to the additive semigroup of nonnegative real numbers and commuting pairs of nonexpansive mappings are also presented.     

Vortex sound under the influence of a piecewise porous material on an infinite rigid plane

The vortex dynamics and the sound generation by an inviscid vortex in the presence of a finite length porous material on an otherwise rigid plane are studied numerically in the present study in an attempt to understand the sound generation near the surface of a wall lining in a lined duct. The combined effects of the effective fluid density and flow resistance inside the porous material, and the length and thickness of the porous material on the sound generation process are examined in detail. Results obtained demonstrate the sound pressure is longitudinal dipole and show how seriously the above-mentioned parameters are affecting the vortex sound pressure under the influence of the porous material.     

Many-body potential for point defect clusters in Fe-C alloys

Modeling the consequences of crystalline defects requires efficient interaction sampling. Empirical potentials can identify relevant pathways if the energetics and configurations of competing defects are captured. Here, we develop such a potential for an alloy of arbitrary point defect concentration, body-centered cubic alpha-Fe supersaturated in C. This potential successfully calculates energetically favored defects, and predicts formation energies and configurations of multicarbon-multivacancy clusters that were not attainable with existing potentials or identified previously via ab initio methods.