A dimensional analysis of the benzylic hydroxylase active site in mortierella isabellina

The spatial limits of the active site in the benzylic hydroxylase enzyme of the fungus Mortierella isabellina were investigated. Several molecular probes were used in incubation experiments to determine the acceptability of each compound by this enzyme. The yields of benzylic alcohols provided information on the acceptability of the particular compound into the active site, and the enantiomeric excess values provided information on the "fit" of acceptable substrates. Measurements of the molecular models were made using Cambridge Scientific Computing Inc. CSC Chem 3D Plus modeling program. i The dimensional limits of the aromatic binding pocket of the benzylic hydroxylase were tested using suitably substituted ethyl benzenes. Both the depth (para substituted substrates) and width (ortho and meta substituted substrates) of this region were investigated, with results demonstrating absolute spatial limits in both directions in the plane of the aromatic ring of 7.3 Angstroms for the depth and 7.1 Angstroms for the width. A minimum requirement for the height of this region has also been established at 6.2 Angstroms. The region containing the active oxygen species was also investigated, using a series of alkylphenylmethanes and fused ring systems in indan, 1,2,3,4-tetrahydronaphthalene and benzocycloheptene substrates. A maximum distance of 6.9 Angstroms (including the 1.5 Angstroms from the phenyl substituent to the active center of the heme prosthetic group of the enzyme) has been established extending directly in ii front of the aromatic binding pocket. The other dimensions in this region of the benzylic hydroxylase active site will require further investigation to establish maximum allowable values. An explanation of the stereochemical distributions in the obtained products has also been put forth that correlates well with the experimental observations.

An analysis of the methyl rotation dynamics in the So (x' A) and T (a A) states of thioacetaldehyde from Pyrolysis jet spectra /

Jet-cooled, laser-induced phosphorescence excitation spectra (LIP) of thioacetaldehyde CH3CHS, CH3CDS, CD3CHS and CD3CDS have been observed over the region 15800 - 17300 cm"^ in a continuous pyrolysis jet. The vibronic band structure of the singlet-triplet n -* n* transition were attributed to the strong coupling of the methyl torsion and aldehydic hydrogen wagging modes . The vibronic peaks have been assigned in terms of two upper electronic state (T^) vibrations; the methyl torsion mode v^g, and the aldehydic hydrogen wagging mode v^^. The electronic origin O^a^ is unequivocally assigned as follows: CH3CHS (16294.9 cm"'' ), CH3CDS (16360.9 cm"'' ), CD3CHS (16299.7 cm"^ ), and CD3CDS (16367.2 cm"'' ). To obtain structural and dynamical information about the two electronic states, potential surfaces V(e,a) for the 6 (methyl torsion) and a (hydrogen wagging) motions were generated by ab initio quantum mechanical calculations with a 6-3 IG* basis in which the structural parameters were fully relaxed. The kinetic energy coefficients BQ(a,e) , B^(a,G) , and the cross coupling term B^(a,e) , were accurately represented as functions of the two active coordinates, a and 9. The calculations reveal that the molecule adopts an eclipsed conformation for the lower Sq electronic state (a=0°,e=0"') with a barrier height to internal rotation of 541.5 cm"^ which is to be compared to 549.8 cm"^ obtained from the microwave experiment. The conformation of the upper T^ electronic state was found to be staggered (a=24 . 68° ,e=-45. 66° ) . The saddle point in the path traced out by the aldehyde wagging motion was calculated to be 175 cm"^ above the equilibrium configuration. The corresponding maxima in the path taken by methyl torsion was found to be 322 cm'\ The small amplitude normal vibrational modes were also calculated to aid in the assignment of the spectra. Torsional-wagging energy manifolds for the two states were derived from the Hamiltonian H(a,e) which was solved variationally using an extended two dimensional Fourier expansion as a basis set. A torsionalinversion band spectrum was derived from the calculated energy levels and Franck-Condon factors, and was compared with the experimental supersonic-jet spectra. Most of the anomalies which were associated with the interpretation of the observed spectrum could be accounted for by the band profiles derived from ab initio SCF calculations. A model describing the jet spectra was derived by scaling the ab initio potential functions. The global least squares fitting generates a triplet state potential which has a minimum at (a=22.38° ,e=-41.08°) . The flatter potential in the scaled model yielded excellent agreement between the observed and calculated frequency intervals.

A Foucaultian analysis of power relations in child protection case work with youth and families

This thesis takes some steps in examining the child protection system from a position that is rarely discussed. Specifically, I explore how Foucault's concept of disciplinary power can be used to demonstrate how power operates within the client/worker relationship. This relationship is shown to be quite complex with power flowing bidirectionally, rather than hierarchically. Instead of viewing power imbalances as a function of state control, I show how the client/worker relationship is constituted by the worker, the client, the organization and the social body. A postmodern auto ethnography is used to document my journey as I expose the disciplinary practices and instruments that I was subject to and used with my clients. 2 Given that the child protection system is constantly shifting and changing in order to improve its ability to safeguard children a greater emphasis is required to examine how workers operate within this complex, overwhelming and multi-dimensional world. This thesis has shown that by engaging in a reflexive examination of my position of power different approaches to making intervention beneficial to all involved become available. This is important if child protection work aims to work with clients rather than on clients.

The Effects of Body Posture on Emotion Perception: A Developmental and Theoretical Analysis

Previously, studies investigating emotional face perception - regardless of whether they involved adults or children - presented participants with static photos of faces in isolation. In the natural world, faces are rarely encountered in isolation. In the few studies that have presented faces in context, the perception of emotional facial expressions is altered when paired with an incongruent context. For both adults and 8- year-old children, reaction times increase and accuracy decreases when facial expressions are presented in an incongruent context depicting a similar emotion (e.g., sad face on a fear body) compared to when presented in a congruent context (e.g., sad face on a sad body; Meeren, van Heijnsbergen, & de Gelder, 2005; Mondloch, 2012). This effect is called a congruency effect and does not exist for dissimilar emotions (e.g., happy and sad; Mondloch, 2012). Two models characterize similarity between emotional expressions differently; the emotional seed model bases similarity on physical features, whereas the dimensional model bases similarity on underlying dimensions of valence an . arousal. Study 1 investigated the emergence of an adult-like pattern of congruency effects in pre-school aged children. Using a child-friendly sorting task, we identified the youngest age at which children could accurately sort isolated facial expressions and body postures and then measured whether an incongruent context disrupted the perception of emotional facial expressions. Six-year-old children showed congruency effects for sad/fear but 4-year-old children did not for sad/happy. This pattern of congruency effects is consistent with both models and indicates that an adult-like pattern exists at the youngest age children can reliably sort emotional expressions in isolation. In Study 2, we compared the two models to determine their predictive abilities. The two models make different predictions about the size of congruency effects for three emotions: sad, anger, and fear. The emotional seed model predicts larger congruency effects when sad is paired with either anger or fear compared to when anger and fear are paired with each other. The dimensional model predicts larger congruency effects when anger and fear are paired together compared to when either is paired with sad. In both a speeded and unspeeded task the results failed to support either model, but the pattern of results indicated fearful bodies have a special effect. Fearful bodies reduced accuracy, increased reaction times more than any other posture, and shifted the pattern of errors. To determine whether the results were specific to bodies, we ran the reverse task to determine if faces could disrupt the perception of body postures. This experiment did not produce congruency effects, meaning faces do not influence the perception of body postures. In the final experiment, participants performed a flanker task to determine whether the effect of fearful bodies was specific to faces or whether fearful bodies would also produce a larger effect in an unrelated task in which faces were absent. Reaction times did not differ across trials, meaning fearful bodies' large effect is specific to situations with faces. Collectively, these studies provide novel insights, both developmentally and theoretically, into how emotional faces are perceived in context.