Influence of crystallite size on acetone hydrogenation over copper catalysts

Acetone hydrogenation was studied over a family of Cu/SiO2 catalysts as well as UHP Cu powder and a Cu chromite catalyst. Oxygen chemisorption via dissociative N2O adsorption was used to count surface Cu atoms and calculate crystallite sizes, and a microwave absorption technique was used to measure the electrical conductivity of these Cu particles. Under differential reaction conditions at 423 K and 1 atm, all catalysts exhibited deactivation on stream and activities were typically 10-20% of their initial values after 3-4 h on stream. However, initial turnover frequencies (TOFs) varied from 0.056 s(-1) on the most highly dispersed Cu catalyst to 0.50 s(-1) on Cu powder, with the highest TOF of 2.4 s(-1) occurring on 110 nm crystallites. A similar trend with a broader (80-fold) variation was observed in the "steady-state" TOF values. Apparent activation energies varied between 11 and 14 kcal/mol. These initial TOF values are in good agreement with previous results, and a correlation exists between TOF and Cu crystallite size in this reaction, which appears to be structure sensitive. In addition, the electrical conductivity of these dispersed Cu nanoparticles, which was always less than that of bulk Cu, also increased with increasing Cu crystallite size; consequently, the change in this parameter may offer a possible explanation for the increase in TOF.     

Analysis of drug interactions with serum proteins and related binding agents by affinity capillary electrophoresis: A review

Biomolecules such as serum proteins can interact with drugs in the body and influence their pharmaceutical effects. Specific and precise methods that analyze these interactions are critical for drug development or monitoring and for diagnostic purposes. Affinity capillary electrophoresis (ACE) is one technique that can be used to examine the binding between drugs and serum proteins, or other agents found in serum or blood. This article will review the basic principles of ACE, along with related affinity-based capillary electrophoresis (CE) methods, and examine recent developments that have occurred in this field as related to the characterization of drug–protein interactions. An overview will be given of the various formats that can be used in ACE and CE for such work, including the relative advantages or weaknesses of each approach. Various applications of ACE and affinity-based CE methods for the analysis of drug interactions with serum proteins and other binding agents will also be presented. Applications of ACE and related techniques that will be discussed include drug interaction studies with serum agents, chiral drug separations employing serum proteins, and the use of CE in hybrid methods to characterize drug binding with serum proteins.     

Excimer emission from glassy films of some aromatic hydrocarbons

The fluorescence emission spectra and fluorescence decay times of amorphous films prepared by evaporation of a number of aromatic hydrocarbons on to a substrate cooled with liquid nitrogen were measured. The fluorescence of such films appears to originate from sites where the interaction between neighbouring molecules is of the same kind as that present in the well-known excimer state. The density of such sites is found to be so high as effectively to prevent energy migration. Some interesting exceptions to this behaviour are noted and comparisons drawn with experimental data reported for excimer formation in solution and in the crystalline phase.     

Laser intensity fluctuations when the photon number at threshold is small

Previous calculations of laser threshold statistics have described the radiation field with a Fokker-Planck equation that embodies the approximation that the photon number at threshold is large. Here, the magnitude and correlation time of intensity fluctuations are calculated directly from the Scully-Lamb equation of motion for the reduced density matrix of a single-mode laser. This model does not embody a restriction to large photon number at threshold. We delineate the regime in which the threshold photon number is sufficiently small to produce measurable differences from the results of the usual Fokker-Planck analysis.     

Optimal successive overrelaxation iterative methods for P-cyclic matrices

Summary We consider linear systems whose associated block Jacobi matricesJ _p are weakly cyclic of indexp. In a recent paper, Pierce, Hadjidimos and Plemmons [13] proved that the block two-cyclic successive overrelaxation (SOR) iterative method is numerically more effective than the blockq-cyclic SOR-method, 2<qp, if the eigenvalues ofJ _p ^p are either all non-negative or all non-positive. Based on the theory of stationaryp-step methods, we give an alternative proof of their theorem. We further determine the optimal relaxation parameter of thep-cyclic SOR method under the assumption that the eigenvalues ofJ _p ^p are contained in a real interval, thereby extending results due to Young [19] (for the casep=2) and Varga [15] (forp>2). Finally, as a counterpart to the result of Pierce, Hadjidimos and Plemmons, we show that, under this more general assumption, the two-cyclic SOR method is not always superior to theq-cyclic SOR method, 2<qp.Dedicated to R. S. Varga on the occasion of his 60th birthdayResearch supported in part by the Deutsche Forschungsgemeinschaft     

Plant calorimetry. Part 2. Modeling the differences between apples and oranges

In a previous review we discussed calorimetric methods for the study of plant metabolism. Since that review, a number of papers describing calorimetric measurements examining plant growth, stress responses and effects of temperature have appeared. This recent work is reviewed here.

In addition to the experimental work, a mechanistic model linking respiration rates to growth has been published. This model is derived from both mass and enthalpy balance equations. It describes specific growth rate and substrate carbon conversion efficiency as functions of the metabolic heat rate, the rate of CO₂ production, the mean oxidation state of the substrate carbon produced by photosynthesis, and enthalpy changes for conversion of photosynthate to biomass and CO₂. Application of this model to understanding the basis for variation in growth rates among individual genotypes in plants is reviewed.

The effects of environment on the plant respiration-growth relation has been an important focus for plant calorimetry studies. Climatic temperature is one of the most important variables determining growth. Extremes of temperature determine limits of growth, and diurnal variation and mean temperature have a major influence on growth rate. Calorimetric measurements of respiratory rates as a function of temperature can be used to relate the temperature influence on respiratory metabolism to the temperature influence on growth rate. These studies have also discovered the existence of an isokinetic point within the range of normal growth temperatures. Studies of temperature dependence are reviewed and the results analyzed in terms of the recently published mechanistic model.     

Quantum yield of photoenhanced currents in crystalline tetracene

A study of photoenhanced currents (PEC) in crystalline tetracene has been made. Using the well-established theory of space-charge controlled currents in insulators, it is shown that the quantum yield for the release of trapped carriers by triplet excitons is less than unity.     

A characterization of best complex rational approximants in a fundamental case

Necessary conditions for a given complex rational approximantR= p/q, degp, degq, to be a local best uniform approximation of a continuous complex-valued functionf defined on a compact subset of the plane are obtained. These conditions are used to characterize when a givenR is a best uniform complex rational approximant off in the special case where the extremal set off?R contains exactly max {n+degp,m+degq}+2 points.     

Correlative atomic scale characterisation of secondary carbides in M50 bearing steel

Correlative atom probe tomography (APT) and transmission electron microscopy (TEM) are used to characterise the microstructure and chemistry of carbide precipitation in M50 bearing steel. This is a prerequisite in establishing relationships between the microstructure and hydrogen embrittlement (HE) resistance. Secondary carbides are the focus of this study, as they play a major role in improving HE-resistance. Secondary carbides are observed in APT, with compositions close to M₄C_3, M₂C and M₃C. Correlative TEM measured orientation relationships between the martensite matrix and carbides, enabling the confirmation of M₃C cementite precipitates in the corresponding APT reconstruction. Additionally, other precipitates observed in TEM were correlated to the M₂C carbides in APT data. The M₄C₃ carbides are found to have a significantly lower volume fraction than the M₂C carbides.     

Plant calorimetry: A window to plant physiology and ecology

The use of calorespirometry in developing models for biological growth is discussed. The relationships between respiratory heat, CO₂, and O₂ rates and physiological parameters such as substrate carbon conversion efficiency, and substrate and biomass carbon oxidation states are presented and discussed. A biochemical model relating ratios of the respiratory rates to the physiological parameters and biochemical pathways in plants is presented. Examples of applications of these models and equations to plant physiology and ecology are given.