From molecular complexes to zwitterions and final products. Reactions between C3O2 and amines

The formation of molecular complexes (prereactive intermediates) between C3O2 and amines (ammonia, dimethylamine, trimethylamine, and 4-(dimethylamino)pyridine) as well as the subsequent transformation of the complexes into C3O2-amine zwitterions in cryogenic matrixes (ca. 40 K) has been observed. In the case of dimethylamine, the formation of tetramethylmalonamide has also been documented. Calculations using density functional theory (B3LYP/6-31G(2d, p)) are used to assign all above species and are in excellent agreement with the IR spectra.

Child welfare workers' use of theory in working with physical child abuse: Implications for professional supervision

This article examines child welfare workers' understanding of physical child abuse and the Implications for those supervising these workers. The article Is based on the results of a study that involved In-depth Interviews and focus groups with statutory child welfare workers. Analysis revealed that workers' understanding of physical child abuse embodied a wide range of ideas that were generally consistent with existing literature. The study highlights the value and utility of a reflective approach In stimulating and making explicit the theoretical underpinnings of child welfare workers practice. Specific Implications for professional supervision are addressed.

Exact theory of sedimentation equilibrium made useful

The exact description of the thermodynamics of solutions has been used to describe, without approximation, the distribution of all the components of an incompressible solution in a centrifuge cell at sedimentation equilibrium. Thermodynamic parameters describing the interactions between solute components of known molar mass can be obtained by direct analysis of the experimental data. Interpretation of the measured thermodynamic parameters in terms of molecular interactions requires that an arbitrary distinction be made between nonassociative forces, like hard-sphere volume-exclusion and mean-field electrostatic repulsion or attraction, and specific short-range forces of association that give rise to the formation of molecular aggregates. Provided the former can be accounted for adequately, the effects of the latter can be elucidated in the form of good estimates of the equilibrium constants for the reactions of aggregation.

Theory of mind and peer acceptance in preschool children

Two studies tested the hypothesis that preschool children's theory of mind ability is related to their levels of peer acceptance. In Study 1, 78 children between the ages of 4 and 6 provided peer nominations that allowed determination of social preference and social impact scores, and classification in one of five peer status groups (following Coie & Dodge, 1983). Children were also tested on five different theory of mind tasks. The results showed that theory of mind scores were significantly related to social preference scores in a subsample of children who were over 5 years old. Further, popular children were found to score higher on theory of mind tasks than children classified as rejected. Study 2 replicated and extended the first study with a new sample of 87 4- to 6-year-old children. Study 2 included measures of peer acceptance, theory of mind ability and verbal intelligence, as well as teacher ratings of prosocial and aggressive behaviours. The results of Study 2 showed that for the total group of children, prosocial behaviour was the best predictor of social preference scores. When the Study 2 sample was split into older and younger children, theory of mind ability was found to be the best predictor of social preference scores for the older children (over age 5), while aggressive and prosocial behaviours were the best predictors of peer acceptance in the younger children. Overall, the pattern of results suggests that the impact of theory of mind ability on peer acceptance is modest but increases with children's age.

Calculation of resonances and product state distributions for the unimolecular dissociation of H2S

Resonance phenomena associated with the unimolecular dissociation of H2S --> SH + H have been investigated quantum mechanically by the Lanczos homogeneous filter diagonalization method using a newly developed potential energy surface (J. Chem. Phys. 2001, 114, 320). Resonance energies, widths (rates), and product state distributions have been obtained. Both dissociation rates and product state distributions of SH show, strong fluctuations, indicating that the dissociation of H2S is essentially irregular. Statistical analysis of neighboring level spacing and width distributions also confirms this behavior. The dissociation rates and product state distributions are compared to the predictions of quantum phase space theory.

Prediction of absolute rate coefficients and product branching ratios for the C(P-3) plus allene reaction system

Complex chemical reactions in the gas phase can be decomposed into a network of elementary (e.g., unimolecular and bimolecular) steps which may involve multiple reactant channels, multiple intermediates, and multiple products. The modeling of such reactions involves describing the molecular species and their transformation by reaction at a detailed level. Here we focus on a detailed modeling of the C(P-3)+allene (C3H4) reaction, for which molecular beam experiments and theoretical calculations have previously been performed. In our previous calculations, product branching ratios for a nonrotating isomerizing unimolecular system were predicted. We extend the previous calculations to predict absolute unimolecular rate coefficients and branching ratios using microcanonical variational transition state theory (mu-VTST) with full energy and angular momentum resolution. Our calculation of the initial capture rate is facilitated by systematic ab initio potential energy surface calculations that describe the interaction potential between carbon and allene as a function of the angle of attack. Furthermore, the chemical kinetic scheme is enhanced to explicitly treat the entrance channels in terms of a predicted overall input flux and also to allow for the possibility of redissociation via the entrance channels. Thus, the computation of total bimolecular reaction rates and partial capture rates is now possible. (C) 2002 American Institute of Physics.

Participation and older people: Meaning, theory and practice

Increasing older people's participation in society is important in ageing policies worldwide. There is a need to understand the challenges for health professionals of transforming policy on participation into liberating social change practices on the ground. This paper explores the meaning, theory and practice of participation. It uses the example of a work in progress project that has attempted to address structural barriers to older people's participation within an Australian aged care facility, to illustrate theoretical and practice principles surrounding participation.

Taxonomic theory and the ICF: Foundations for a unified disability athletics classification

Development of a unified classification system to replace four of the systems currently used in disability athletics (i.e., track and field) has been widely advocated. The definition and purpose of classification, underpinned by taxonomic principles and collectively endorsed by relevant disability sport organizations, have not been developed but are required for successful implementation of a unified system. It is posited that the International classification of functioning. disability, and health (ICF), published by the World Health Organization (2001), and current disability athletics systems are, fundamentally, classifications of the functioning and disability associated with health conditions and are highly interrelated. A rationale for basing a unified disability athletics system on ICF is established. Following taxonomic analysis of the current systems, the definition and purpose of a unified disability athletics classification are proposed and discussed. The proposed taxonomic framework and definitions have implications for other disability sport classification systems.

Evaluating two morningness scales with item response theory

Using a student sample (n = 692) and an organization sample (n = 180), we scrutinized two morning-evening orientation scales using item response theory (IRT) methods. We used IRT to compare the measurement precision of the Composite Scale (CS) and the Early/Late Preferences Scale (PS). The CS had slightly higher measurement precision at all ranges of orientations, except for extreme morning and evening orientations for which the PS had slightly higher precision. IRT item-level statistics were also computed to try to understand how morning-orientation items functioned. Items that asked questions about morning activities tended to be more discriminating indicators of morning-orientation than items that asked about evening or peak performance activities. Items that involved unpleasant activities were less frequently endorsed than items that involved neutral or enjoyable activities. Implications for measurement of morning-evening orientation are discussed. (C) 2002 Elsevier Science Ltd. All rights reserved.

The politics of suffering: Progress, modernity and the adolescent crisis

A concern for progress is central to the public agendas of modern societies. Political actors compete with one another mainly with regard to their respective claims to bring about a better future, particularly in the economic and technological spheres. The focus on progress has, however, deeper roots which date back to the aspirations of the Enlightenment. Around that time, the belief arose that systematic improvements are made possible by the structural features of modern society and culture, improvements that will gradually release humanity from much of the suffering characterising its historical past. This article argues the persistence of a culture of progress, rather than easing suffering, in fact enhances and mobilises it for the pursuit of superficial forms of gain. It is also claimed the attempt by Habermas' critical theory to develop a broader and more satisfactory conception of progress fails to address this problem. The article suggests an alternative and more fundamental critique of progressive ideas is required. It reflects upon these abstract theoretical questions in connection with the concrete example of the 'adolescent crisis' and the role ideas of progress play within it.

Laparoscopic appendectomy in modern gynecology

Gynecologists frequently manage women with acute or chronic pain in the right iliac fossa. Appendicitis is one of the common conditions encountered in this setting. From the gynecologic perspective, issues regarding the role of laparoscopic appendectomy include radioimaging and laparoscopic diagnosis, operative technique, advantages and disadvantages, and laparoscopic appendectomy in pregnancy and in complicated appendicitis. Most studies are in favor of the procedure, and it seems reasonable to include it in training programs in gynecology.

An atomistic simulation of solid state sintering using Monte Carlo methods

This paper presents results on the simulation of the solid state sintering of copper wires using Monte Carlo techniques based on elements of lattice theory and cellular automata. The initial structure is superimposed onto a triangular, two-dimensional lattice, where each lattice site corresponds to either an atom or vacancy. The number of vacancies varies with the simulation temperature, while a cluster of vacancies is a pore. To simulate sintering, lattice sites are picked at random and reoriented in terms of an atomistic model governing mass transport. The probability that an atom has sufficient energy to jump to a vacant lattice site is related to the jump frequency, and hence the diffusion coefficient, while the probability that an atomic jump will be accepted is related to the change in energy of the system as a result of the jump, as determined by the change in the number of nearest neighbours. The jump frequency is also used to relate model time, measured in Monte Carlo Steps, to the actual sintering time. The model incorporates bulk, grain boundary and surface diffusion terms and includes vacancy annihilation on the grain boundaries. The predictions of the model were found to be consistent with experimental data, both in terms of the microstructural evolution and in terms of the sintering time. (C) 2002 Elsevier Science B.V. All rights reserved.