peri-Dimethylamino substituent effects on proton transfer at carbon in α-naphthylacetate esters: a model for mandelate racemase

The rate constants for exchange of hydrogen for deuterium at the α-CH(2) positions of 8-(N,N-dimethylaminonaphthalen-1-yl)acetic acid tert-butyl ester 1 and naphthalen-1-ylacetic acid tert-butyl ester 2 have been determined in potassium deuteroxide solutions in 1 : 1 D(2)O : CD(3)CN, in order to quantify the effect of the neighbouring peri-dimethylamino substituent on α-deprotonation. Intramolecular general base catalysis by the (weakly basic) neighbouring group was not detected. Second-order rate constants, k(DO), for the deuterium exchange reactions of esters 1 and 2 have been determined as 1.35 × 10(-4) M(-1) s(-1) and 3.95 × 10(-3) M(-1) s(-1), respectively. The unexpected 29-fold decrease in the k(DO) value upon the introduction of a peri-dimethylamino group is attributed to an unfavourable steric and/or electronic substituent effect on intermolecular deprotonation by deuteroxide ion. From the experimental k(DO) values, carbon acid pK(a) values of 26.8 and 23.1 have been calculated for esters 1 and 2.     

A damage accumulation model for complex strain paths: Prediction of ductile failure in metals

The characterisation of strain path with respect to the directionality of defect formation is discussed. The criterion of non-monotonic strain path is used in the scalar and tensor models for damage accumulation and recovery. Comparable analysis of models and their verification has been obtained by simulation of crack initiation in a two-stage metal forming operation consisting of wire drawing followed by constrained upsetting.     

S K-edge X-ray absorption studies of tetranuclear iron-sulfur clusters: mu-sulfide bonding and its contribution to electron delocalization.

X-ray absorption spectroscopy (XAS) at the sulfur ( approximately 2470 eV) and chlorine ( approximately 2822 eV) K-edges has been applied to a series of 4Fe-4S model complexes. These are compared to 2Fe-2S model complexes to obtain insight into the localized ground state in the mixed-valence dimer versus the delocalized ground state in the mixed-valence tetramer. The preedges of hypothetical delocalized mixed-valence dimers [Fe(2)S(2)](+) are estimated using trends from experimental data and density functional calculations, for comparison to the delocalized mixed-valence tetramer [Fe(4)S(4)](2+). The differences between these two mixed-valence sites are due to the change of the sulfide-bridging mode from micro(2) to micro(3). The terminal chloride and thiolate ligands are used as spectator ligands for the electron density of the iron center. From the intensity of the preedge, the covalency of the terminal ligands is found to increase in the tetramer as compared to the dimer. This is associated with a higher effective nuclear charge on the iron in the tetramer (derived from the energies of the preedge). The micro(3)-bridging sulfide in the tetramer has a reduced covalency per bond (39%) as compared to the micro(2)-bridging sulfide in the dimer (51%). A simple perturbation model is used to derive a quadratic dependence of the superexchange coupling constant J on the covalency of the metal ions with the bridging ligands. This relationship is used to estimate the superexchange contribution in the tetramer (J = -156 cm(-)(1)) as compared to the mixed-valence dimer (J = -360 cm(-)(1)). These results, combined with estimates for the double exchange and the vibronic coupling contributions of the dimer sub-site of the tetramer, lead to a delocalized S(t) = (9)/(2) spin ground state for the mixed-valence dimer in the tetramer. Thus, the decrease in the covalency, hence the superexchange pathway associated with changing the bridging mode of the sulfides from micro(2) to micro(3) on going from the dimer to the tetramer, significantly contributes to the delocalization of the excess electron over the dimer sub-site in the tetramer.     

Acoustic radiation from the elastic impact of a sphere with a slab

The transient sound radiation from the impact of a spherical object with a slab is analysed theoretically and compared with experimental results. It is shown that the major source of sound radiation when a sphere impinges on a massive plate is due to the sudden change of velocity of the sphere. By using the method of images, an analytical expression predicting the sound pressure waveform is obtained. Experimental results confirm the theoretical analysis and provide further explanation of this rigid body type of acoustic radiation.     

High-power solid-state lasers with unstable resonators

The thermal lensing properties of stable and unstable resonators are compared and rules are given for the design of optimized unstable resonators containing a focusing rod. Experimental verification with a high-power Nd: YAG system proved that for unstable resonators the restricting relationship between beam quality and output power no longer holds. Careful resonator design enables high output power to be extracted with unstable resonators without destroying the output couplers.     

Ray-tracing evaluation of empirical models for predicting noise in industrial workshops

To evaluate the accuracy of empirical models for predicting steady-state noise levels and reverberation times in typical industrial workshops, predictions by these models were compared with predictions by a ray-tracing model, nominally using the same input data. Comparisons were made for three workshops—‘long’, ‘flat’ and ‘quasi-cubic’ in shape—with reflective and absorbent ceilings, when empty and with four densities of fittings. In the case of the ‘long’ room, noise levels were predicted along both the long and short major horizontal axes. In ‘long’ and ‘flat’ workshops, steady-state prediction by the empirical models often agreed with ray-tracing prediction within 2 dB. This result suggests that the empirical models are fundamentally valid. However, agreement was worse at large source/receiver distances, and at 500 Hz. Empirical reverberation-time prediction generally agreed less well with ray tracing, possibly indicating that the empirical reverberation-time prediction models are less valid. Strong disagreement occurred between the models in the case of steady-state prediction in the ‘quasi-cubic’ workshop, indicating that the empirical steady-state models are invalid in this case. Agreement for reverberation time was good with a non-absorbent ceiling, but poor with an absorbent ceiling.