Comparison of Experimental and Theoretical Structures of a Transition State Analogue Used for the Induction of Anti-Cocaine Catalytic Antibodies

Comparison of the crystal structure of a transition state analogue that was used to raise catalytic antibodies for the benzoyl ester hydrolysis of cocaine with structures calculated by ab initio, semiempirical, and solvation semiempirical methods reveals that modeling of solvation is crucial for replicating the crystal structure geometry. Both SM3 and SM2 calculations, starting from the crystal structure TSA I, converged on structures similar to the crystal structure. The 3-21G(*)/HF, 6-31G*/HF, PM3, and AM1 calculations converged on structures similar to each other, but these gas-phase structures were significantly extended relative to the condensed phase structures. Two transition states for the hydrolysis of the benzoyl ester of cocaine were located with the SM3 method. The gas phase calculations failed to locate reasonable transition state structures for this reaction. These results imply that accurate modeling of the potential energy surfaces for the hydrolysis of cocaine requires solvation methods.

Scales of Impact: Settlement History and Landscape Change in the Gordion Region, Central Anatolia

The expansion of agriculture in the Near East during the middle Holocene significantly altered the physical landscape. However, the relationship between the scale of agriculture and the magnitude and timing of the environmental impacts is not well known. The Gordion Regional Survey provides a novel dataset to compare settlement density during archaeological periods to rates of environmental disruption. Sediment samples from alluvial cores directly date the environmental disruption, which can be matched to period-specific settlement intensities in the watershed as constructed from archaeological survey ceramics. Degradation rates rose sharply within a millennium of the earliest Chalcolithic occupation. Early Bronze Age (EBA) land use induced the greatest rates of environmental degradation, although settlement density was relatively low on the landscape. The degradation rate subsequently decreased to one-third its early peak by the Iron Age, even as settlement intensity climbed. This trajectory reveals how complex interaction effects can amplify or subdue the responses of the landscape-land use system. Prior to settlement, landscape soil reservoirs were highly vulnerable, easily tipped by early agricultural expansion. Subsequent reduced rates of erosion are tied both to changes in sociopolitical organization and to depletion of the vulnerable soil supply.