O 1s excitation and ionization processes in the CO2 molecule studied via detection of low-energy fluorescence emission

Oxygen 1s excitation and ionization processes in the CO2 molecule have been studied with dispersed and non-dispersed fluorescence spectroscopy as well as with the vacuum ultraviolet (VUV) photon?photoion coincidence technique. The intensity of the neutral O emission line at 845 nm shows particular sensitivity to core-to-Rydberg excitations and core?valence double excitations, while shape resonances are suppressed. In contrast, the partial fluorescence yield in the wavelength window 300?650 nm and the excitation functions of selected O+ and C+ emission lines in the wavelength range 400?500 nm display all of the absorption features. The relative intensity of ionic emission in the visible range increases towards higher photon energies, which is attributed to O 1s shake-off photoionization. VUV photon?photoion coincidence spectra reveal major contributions from the C+ and O+ ions and a minor contribution from C2+. No conclusive changes in the intensity ratios among the different ions are observed above the O 1s threshold. The line shape of the VUV?O+ coincidence peak in the mass spectrum carries some information on the initial core excitation

Non-destructive optical characterisation of fruits with time-resolved reflectance spectroscopy.

Increasing attention is being paid to the possible development of non-invasive tests for the assessment of the quality of fruits We propose a novel non-destructive method for the measurement of the internal optical properties of fruits and vegetables by means of time resolved reflectance spectroscopy in the visible and NIR range. A fully automated instrumentation for time-resolved reflectance measurements was developed It is based on mode-locked laser sources and electronics for time-correlated single photon counting, and provides a time-resolution of 120-160 ps The system was used to probe the optical properties of several species and varieties of fruits and vegetables in the red and NIR range (650-1000 nm). In most fruits, the absorption line shape is dominated by the absorption peak of water, centred around 970 nm Generally, the absorption spectra also show the spectral features typical of chlorophyll, with maximum at 675 nm In particular, for what concerns apples, variations in peak intensity are observed depending on the variety, the degree of ripeness as well as the position on the apple. For all the species and varieties considered, the transport scattering coefficient decreases progressively upon increasing the wavelength.

Non-destructive optical characterization of fruits in the red and near infrared.

Increasing attention is being paid to the possible development of non-invasive tests for the assessment of the quality of Fruits. We propose a novel non-destructive method for the measurement of the internal optical properties of fruits and vegetables by means of lime-resolved reflectance spectroscopy in the visible and NIR range. A Fully automated instrumentation for time-resolved reflectance measurements was developed. It is based on mode-locked laser sources and electronics for time-correlated single photon counting, and provides a time-resolution of 120-160 ps. The system was used to probe the optical properties of several species and varieties of Fruits and vegetables in the red and NIR range (650-1000 nm). In most Fruits, the absorption line shape is dominated by the absorption peak of water, centred around 970 nm. Generally, the absorption spectra also show the spectral features typical of chlorophyll, with maximum at 675 nm. In particular, for what concerns apples, variations in peak intensity are observed depending on the variety, the degree of ripeness as well as the position on the apple. For all the species and varieties considered, the transport scattering coefficient decreases progressively upon increasing the wavelength.

Structural factors controlling ligand binding to myoglobin: A kinetic hole-burning study

Using temperature-derivative spectroscopy in the temperature range below 100 K, we have studied the dependence of the Soret band on the recombination barrier in sperm whale carbonmonoxy myoglobin (MbCO) after photodissociation at 12 K. The spectra were separated into contributions from the photodissociated species, Mb*CO, and CO-bound myoglobin. The line shapes of the Soret bands of both photolyzed and liganded myoglobin were analyzed with a model that takes into account the homogeneous bandwidth, coupling of the electronic transition to vibrational modes, and static conformational heterogeneity. The analysis yields correlations between the activation enthalpy for rebinding and the model parameters that characterize the homogeneous subensembles within the conformationally heterogeneous ensemble. Such couplings between spectral and functional parameters arise when they both originate from a common structural coordinate. This effect is frequently denoted as “kinetic hole burning.” The study of these correlations gives direct insights into the structure–function relationship in proteins. On the basis of earlier work that assigned spectral parameters to geometric properties of the heme, the connections with the heme geometry are discussed. We show that two separate structural coordinates influence the Soret line shape, but only one of the two is coupled to the enthalpy barrier for rebinding. We give evidence that this coordinate, contrary to widespread belief, is not the iron displacement from the mean heme plane.

Solid and liquid phase 59Co NMR studies of cobalamins and their derivatives

We describe the application of 59Co NMR to the study of naturally occurring cobalamins. Targets of these investigations included vitamin B12, the B12 coenzyme, methylcobalamin, and dicyanocobyrinic acid heptamethylester. These measurements were carried out on solutions and powders of different origins, and repeated at a variety of magnetic field strengths. Particularly informative were the solid-state central transition NMR spectra, which when combined with numerical line shape analyses provided a clear description of the cobalt coupling parameters. These parameters showed a high sensitivity to the type of ligands attached to the metal and to the crystallization history of the sample. 59Co NMR determinations also were carried out on synthetic cobaloximes possessing alkyl, cyanide, aquo, and nitrogenated axial groups, substituents that paralleled the coordination of the natural compounds. These analogs displayed coupling anisotropies comparable to those of the cobalamins, as well as systematic up-field shifts that can be rationalized in terms of their stronger binding affinity to the cobalt atom. Cobaloximes also displayed a higher regularity in the relative orientations of their quadrupole and shielding coupling tensors, reflecting a higher symmetry in their in-plane coordination. For the cobalamines, poor correlations were observed between the values measured for the quadrupole couplings in the solid and the line widths observed in the corresponding solution 59Co NMR resonances.

Femtosecond resolution of ligand-heme interactions in the high-affinity quinol oxidase bd: A di-heme active site?

Interaction of the two high-spin hemes in the oxygen reduction site of the bd-type quinol oxidase from Escherichia coli has been studied by femtosecond multicolor transient absorption spectroscopy. The previously unidentified Soret band of ferrous heme b595 was determined to be centered around 440 nm by selective excitation of the fully reduced unliganded or CO-bound cytochrome bd in the α-band of heme b595. The redox state of the b-type hemes strongly affects both the line shape and the kinetics of the absorption changes induced by photodissociation of CO from heme d. In the reduced enzyme, CO photodissociation from heme d perturbs the spectrum of ferrous cytochrome b595 within a few ps, pointing to a direct interaction between hemes b595 and d. Whereas in the reduced enzyme no heme d-CO geminate recombination is observed, in the mixed-valence CO-liganded complex with heme b595 initially oxidized, a significant part of photodissociated CO does not leave the protein and recombines with heme d within a few hundred ps. This caging effect may indicate that ferrous heme b595 provides a transient binding site for carbon monoxide within one of the routes by which the dissociated ligand leaves the protein. Taken together, the data indicate physical proximity of the hemes d and b595 and corroborate the possibility of a functional cooperation between the two hemes in the dioxygen-reducing center of cytochrome bd.

Theory of single-spin inelastic tunneling spectroscopy

I show that recent experiments of inelastic scanning tunneling spectroscopy of single and a few magnetic atoms are modeled with a phenomenological spin-assisted tunneling Hamiltonian so that the inelastic dI/dV line shape is related to the spin spectral weight of the magnetic atom. This accounts for the spin selection rules and dI/dV spectra observed experimentally for single Fe and Mn atoms deposited on Cu2N. In the case of chains of Mn atoms it is found necessary to include both first and second-neighbor exchange interactions as well as single-ion anisotropy.

Optical Bloch equations and enhanced decay of Rabi oscillations in strong driving fields

Optical Bloch equations are widely used for describing dynamics in a system consisting molecules, electromagnetic waves, and a thermal bath. We analyze applicability of these equations to a single molecule imbedded in a solid matrix. Classical Bloch equations and the limits of their applicability are derived from more general master equations. Simple and intuitively appealing picture based on stochastic Bloch equations shows that at low temperatures, contrary to common believes, a strong driving field can not only suppress but can also increase decay rates of Rabi oscillations. A physical system where predicted effects can be observed experimentally is suggested. (c) 2005 Elsevier B.V. All rights reserved.

Transmission Spectra of Rb 87 atoms near an Optical Nanofiber.

We present measurements of the transmission spectra of 87Rb atoms at 780 nm in the vicinity of a nanofiber. A uniform distribution of fixed atoms around a nanofiber should produce a spectrum that is broadened towards the red due to shifts from the van der Waals potential. If the atoms are free, this also produces an attractive force that accelerates them until they collide with the fiber which depletes the steady-state density of near-surface atoms. It is for this reason that measurements of the van der Waals interaction are sparse. We confirm this by measuring the spectrum cold atoms from a magneto-optical trap around the fiber, revealing a symmetric line shape with nearly the natural linewidth of the transition. When we use an auxiliary 750 nm laser we are able to controllably desorb a steady flux of atoms from the fiber that reside near the surface (less than 50 nm) long enough to feel the van der Walls interaction and produce an asymmetric spectrum. We quantify the spectral asymmetry as a function of 750 nm laser power and find a maximum. Our model, which that takes into account the change in the density distribution, qualitatively explains the observations. In the future this can be used as a tool to more comprehensively study atom-surface interactions.

Morphology-based model for predicting osteocyte-like cell line (MLO-Y4) growth process

This work has led to the development of empirical mathematical models to quantitatively predicate the changes of morphology in osteocyte-like cell lines (MLO-Y4) in culture. MLO-Y4 cells were cultured at low density and the changes in morphology recorded over 11 hours. Cell area and three dimensional shape features including aspect ratio, circularity and solidity were then determined using widely accepted image analysis software (ImageJTM). Based on the data obtained from the imaging analysis, mathematical models were developed using the non-linear regression method. The developed mathematical models accurately predict the morphology of MLO-Y4 cells for different culture times and can, therefore, be used as a reference model for analyzing MLO-Y4 cell morphology changes within various biological/mechanical studies, as necessary.

How distributional preferences shape incentives on (experimental) markets for credence goods

Credence goods markets suffer from inefficiencies caused by superior information of sellers about the surplus-maximizing quality. While standard theory predicts that equal mark-up prices solve the credence goods problem if customers can verify the quality received, experimental evidence indicates the opposite. We identify a lack of robustness of institutional design with respect to heterogeneity in distributional preferences as a possible cause and design new experiments that allow for parsimonious identification of sellers’ distributional types. Our results indicate that less than a fourth of the subjects behave according to standard theory’s assumption, the rest behaving either in line with non-standard selfish or in accordance with non-trivial other-regarding preferences. We discuss consequences of our findings for institutional design and agent selection.

Word order and tonal shape in the production of focus in short Finnish utterances

This paper presents results from a study on the production of Finnish prosody. The effect of word order and the tonal shape in the production of Finnish prosody was studied as produced by 8 native Finnish speakers. Predictions formulated with regard to results from an earlier study pertaining to the perception of promi- nence were tested. These predictions had to do with the tonal shape of the utterances in the form of a flat hat pattern and the effect of word order on the so called top-line declination within an adver- bial phrase in the utterances. The results from the experiment give support to the following claims: the temporal domain of prosodic focus is the whole utterance, word order reversal from unmarked to marked has an effect on the production of prosody, and the pro- duction of the tonal aspects of focus in Finnish follows a basic flat hat pattern. That is the prominence of a word can be produced by an f 0 rise or a fall, depending on the location of the word in an utterance. The basic accentual shape of a Finnish word is then not a pointed rise/fall hat shape as claimed before since it can vary depending on the syllable structure and the position within an ut- terance.

Study of forging design using slip-line fields

The main purpose of forging design is to ensure cavity filling with minimum material wastage, minimum die load and minimum deformation energy. Given the desired shape of the component and the material to be forged, this goal is achieved by optimising the initial volume of the billet, the geometrical parameters of the die and the process parameters. It is general industrial practise to fix the initial billet volume and the die parameters using empirical relationships derived from practical experience. In this paper a basis for optimising some of the parameters for simple closed-die forging is proposed. Slip-line field solutions are used to predict the flow, the load and the energy in a simple two-dimensional closed-die forging operation. The influence of the design parameters; flash-land width, excess initial workpiece area and forged cross-sectional size; on complete cavity filling and efficient cavity filling are investigated. Using the latter as necessary requirements for forging, the levels of permissable design parameters are determined, the variation of these levels with the size of the cross-section then being examined.

New Concepts for Three-Dimensional Shape Analysis

A new approach to machine representation and analysis of three-dimensional objects is presented. The representation, based on the notion of "skeleton" of an object leads to a scheme for comparing two given object views for shape relations. The objects are composed of long, thin, rectangular prisms joined at their ends. The input picture to the program is the digitized line drawing portraying the three-dimensional object. To compare two object views, two characteristic vertices called "cardinal point" and "end-cardinal point," occurring consistently at the bends and open ends of the object are detected. The skeletons are then obtained as a connected path passing through these points. The shape relationships between the objects are then obtained from the matching characteristics of their skeletons. The method explores the possibility of a more detailed and finer analysis leading to detection of features like symmetry, asymmetry and other shape properties of an object.

Energy Conversion in Shape Memory Alloy Heat Engine Part I: Theory

Shape Memory Alloy (SMA) can be easily deformed to a new shape by applying a small external load at low temperature, and then recovers its original configuration upon heating. This unique shape memory phenomenon has inspired many novel designs. SMA based heat engine is one among them. SMA heat engine is an environment-friendly alternative to extract mechanical energy from low-grade energies, for instance, warm wastewater, geothermal energy, solar thermal energy, etc. The aim of this paper is to present an applicable theoretical model for simulation of SMA-based heat engines. First, a micro-mechanical constitutive model is derived for SMAs. The volume fractions of austenite and martensite variants are chosen as internal variables to describe the evolution of microstructure in SMA upon phase transition. Subsequently, the energy equation is derived based on the first thermodynamic law and the previous SMA model. From Fourier’s law of heat conduction and Newton’s law of cooling, both differential and integral forms of energy conversion equation are obtained.