Metal—Metal Triple Bonds Possessing the Electron-Rich σ2π4δ2δ*2 Electronic Configuration

The structural and reaction chemistry of dimetal complexes containing metal—metal triple bonds of the electron-rich type (σ²π⁴δ²δ^*2 configuration) is reviewed. Metal cores possessing this unit are Mo²⁺₂, Re⁴⁺₂, Ru⁶⁺₂, and Os⁶⁺₂, of which only Re⁴⁺₂ has yet been subject to a detailed study. Emphasis is placed upon the more recent developments in this field.     

Ionization of Acetylacetone in Me2SO—Water Mixtures. Reactivity—Selectivity Principle or Principle of Imperfect Synchronization?

Rate constants for the reversible deprotonation of acetylacetone were measured in carboxylate and amine buffers in water and in 50%, 90% and 95% Me₂SO at 20°C. The Brønsted plot for the carboxylate ions is curved in the Me₂SO—water mixtures, but straight in water. The curvature is in the direction predicted by the Reactivity—Selectivity Principle (RSP). However, the Brønsted plot for the reaction with primary amines is straight in all solvents. This suggests that the curvature observerd with the carboxylate ions is caused by loss of solvation of the base; this loss of solvation is ahead of bond formation in the transition state rather than being a manifestation of the RSP. (Note that all Brønsted plots are based on pK_a values measured in the respective solvents.) The intrinsic rate constant (k₀) for proton transfer increases with the addition of Me₂SO, and more so with the carboxylate buffers than with the amines. This increase in k₀ is attributed to delayed solvation of the developing enolate ion in the transition state; with the carboxylate buffers, an additional factor is the early loss of solvation of the base. The various solvation effects observed in this study can all be understood in the context of the Principle of Imperfect Synchronization (PIS).     

Mixed anaclitic-introjective psychopathology in treatment-resistant inpatients undergoing psychoanalytic psychotherapy.

Utilizing data from the Riggs-Yale Project, 45 male and 45 female 18-29-year-old treatment-resistant inpatients undergoing intensive psychoanalytically oriented treatment were studied. Twenty-seven mixed-type anaclitic-introjective inpatients were compared with 29 "pure" anaclitic and 34 "pure" introjective inpatients. At intake, mixed-type inpatients were more clinically impaired (i.e., were more symptomatic, cognitively impaired, and thought disordered) and more vulnerable (i.e., less accurate object representations and more frequently used maladaptive defense mechanisms) in comparison with clearly defined anaclitic and introjective patients. Mixed-type patients, however, improved significantly more in the course of psychoanalytically oriented treatment, in terms of clinical functioning (i.e., symptoms, cognitive functioning) and psychological vulnerability (i.e., utilization of more adaptive defense mechanisms). (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Midplane-symmetry breaking in the flow between two counter-rotating disks

This paper considers the axisymmetric steady flow driven by exact counter rotation of two co-axial disks of finite radius. At the edges of the rotating disks one of three conditions is (typically) imposed: (i) zero velocity, corresponding to a stationary, impermeable, cylindrical shroud (ii) zero normal velocity and zero tangential fluid traction, corresponding to a (confined) free surface and (iii) an edge constraint that is consistent with a similarity solution of von Kármán form. The similarity solution is valid in an infinite geometry and possesses a pitchfork bifurcation that breaks the midplane symmetry at a critical Reynolds number. In this paper, similar bifurcations of the global (finite-domain) flow are sought and comparisons are made between the resulting bifurcation structure and that found for the similarity solution. The aim is to assess the validity of the nonlinear similarity solutions in finite domains and to explore the sensitivity of the solution structure to edge conditions that are implicitly neglected when assuming a self-similar flow. It is found that, whilst the symmetric similarity solution can be quantitatively useful for a range of boundary conditions, the bifurcated structure of the finite-domain flow is rather different for each boundary condition and bears little resemblance to the self-similar flow.     

The role of experience in liking "read-to-drink" alcoholic beverages.

Ready-to-drinks (RTDs) are composed of an alcoholic component and a soft-drink base and are primarily consumed by a youth market. The authors explored whether liking and experience with an RTD soft-drink base predicts liking for the RTD. Participants (N=350) from ages 12 to 30 years sampled 3 RTDs and their respective soft-drink and alcoholic components. For milk- and fruit-based RTDs, liking for and familiarity with their soft-drink base was the best predictor of liking for and familiarity with the RTD itself. For the Coke-based RTD, familiarity with and liking for bourbon best predicted familiarity with and liking for the RTD. All of these effects were consistent across blind and nonblind testing. The authors' results suggest that where there is perceptual similarity between the RTD and its soft-drink base, these beverages may provide an easy transition into alcohol consumption for novice drinkers. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Defining Yield from Bender Element Measurements in Triaxial Stress Probe Experiments

This paper describes the elastic response of a block sample of compressible Chicago glacial clay under a variety of stresses and its relationship with the deformation characteristics at relatively large strains. The elastic shear stiffness was obtained from bender element tests during consolidation and shearing in drained triaxial stress probe tests. An empirical correlation was established based on the elastic shear stiffness in a preyield condition. By comparing the empirical correlation with the measured elastic shear stiffness in the stress region during probing, the changes of elastic shear stiffness were investigated. The departure of elastic shear stiffness from values computed by the empirical relation based on K0 loading directly relates to the yielding characteristics of the clay. The large-scale change of soil structure at yielding alters the well-established relationship between the elastic shear stiffness and stresses in the preyield condition. The mechanical yielding response of clays can be detected based on the systematic analysis of the elastic shear wave velocities.     

Two-Dimensional Physical and Numerical Modeling of a Pile-Supported Earth Platform over Soft Soil

This paper focuses on the mechanisms occurring in a granular earth platform over soft ground improved by rigid piles. Two-dimensional physical model experiments were performed using the Schneebeli’s analogical soil to investigate the load transfer mechanisms by arching and the settlement reduction and homogenization. Experimental outputs are compared to results obtained on a numerical model using a plane strain continuum approach. The impact of the constitutive model complexity to simulate the platform material behavior was first assessed, but no large difference was recorded. As far as the proposed model, which takes the main features of the observed behavior satisfactorily into account, the numerical procedure could be validated and the parametric studies extended numerically. Both approaches of this study underlined the main geometrical and geotechnical parameters which should inevitably be taken into account in a simplified design method, namely the capping ratio, the platform height, and the platform material shear strength.     

A novel method for determination of polyester end-groups by NMR spectroscopy

An efficient, convenient and quantitative method for characterising polyester end-groups is described. We have found that trichloroacetyl isocyanate (TAI) reacts rapidly and quantitatively with both carboxyl [C(O)OH] and hydroxyl (OH) chain ends to form derivatives that can be readily determined by ¹H NMR spectroscopy. The TAI capped end-groups give rise to characteristic imidic NH resonances in a normally clear region of the ¹H NMR spectrum [δ∼10-11.5 for C(O)-O-C(O)-NH-C(O)CCl₃ from C(O)OH, δ∼8-9 for O-C(O)-NH-C(O)CCl₃ from OH]. The method has been successfully applied to quantitative determination of the end-groups of a wide variety of oligomeric polyesters. It has also been applied to higher molecular weight polyesters including commercial, bottle grade, poly(ethylene terephthalate) (PET) and PET based copolyesters (e.g. PETG).