Use of the Supermolecule Approach To Model the Syn and Anti Conformations of Solvated Cyclic 3‘,5‘-Adenosine Monophosphate

The supermolecule approach has been used to model the hydration of cyclic 3‘,5‘-adenosine monophosphate, cAMP. Model building combined with PM3 optimizations predict that the anti conformer of cAMP is capable of hydrogen bonding to an additional solvent water molecule compared to the syn conformer. The addition of one water to the syn superstructure with concurrent rotation of the base about the glycosyl bond to form the anti superstructure leads to an additional enthalpy of stabilization of approximately −6 kcal/mol at the PM3 level. This specific solute−solvent interaction is an example of a large solvent effect, as the method predicts that cAMP has a conformational preference for the anti isomer in solution. This conformational preference results from a change in the number of specific solute−solvent interactions in this system. This prediction could be tested by NMR techniques. The number of waters predicted to be in the first hydration sphere around cAMP is in agreement with the results of hydration studies of nucleotides in DNA. In addition, the detailed picture of solvation about this cyclic nucleotide is in agreement with infrared experimental results.

Hydraulic Conductivity of Model Soil-Bentonite Backfills Subjected to Wet-Dry Cycling

The potential for changes in hydraulic conductivity, k, of two model soil-bentonite (SB) backfills subjected to wet-dry cycling was investigated. The backfills were prepared with the same base soil (clean, fine sand) but different bentonite contents (2.7 and 5.6 dry wt %). Saturation (S), volume change, and k of consolidated backfill specimens (effective stress = 24 kPa) were evaluated over three to seven cycles in which the matric suction, Ym, in the drying stage ranged from 50 to 700 kPa. Both backfills exhibited susceptibility to degradation in k caused by wet-dry cycling. Mean values of k for specimens dried at Ym = 50 kPa (S = 30-60 % after drying) remained low after two cycles, but increased by 5- to 300-fold after three or more cycles. Specimens dried at Ym ≥ 150 kPa (S < 30 % after drying) were less resilient and exhibited 500- to 10 000-fold increases in k after three or more cycles. The greater increases in k for these specimens correlated with greater vertical shrinkage upon drying. The findings suggest that increases in hydraulic conductivity due to wet-dry cycling may be a concern for SB vertical barriers located within the zone of a fluctuating groundwater table.