Correlation between the mobility of spin-labeled peptide chains and resin solvation: An approach to optimize the synthesis of aggregating sequences

Resin solvation properties affect the efficiency of the coupling reactions in solid-phase peptide synthesis. Here we report a novel approach to evaluate resin solvation properties, making use of spin label electron paramagnetic resonance (EPR) spectroscopy. The aggregating VVLGAAIV and ING sequences were assembled in benzhydrylamine-resin with different amino group contents (up to 2.6 mmol/g) to examine the extent of chain association within the beads. These model peptidyl-resins were first labeled at their N-terminus with the amino acid spin label 2,2,6,6-tetramethylpiperidine-N-oxyl-4-amino-4-carboxylic acid (Toac). Their solvation properties in different solvents were estimated, either by bead swelling measurement or by assessing the dynamics of their polymeric matrixes through the analysis of Toac EPR spectra, and were correlated with the yield of the acylation reaction. In most cases the coupling rate was found to depend on bead swelling. Comparatively, the EPR approach was more effective. Line shape analysis allowed the detection of more than one peptide chain population, which influenced the reaction. The results demonstrated the unique potential of EPR spectroscopy not only for improving the yield of peptide synthesis, even in challenging conditions, but also for other relevant polymer-supported methodologies in chemistry and biology.

C-H center dot center dot center dot O and N-H center dot center dot center dot O hydrogen bonds in liquid amides investigated by Monte Carlo simulation

Monte Carlo simulations of liquid formamide, N-methylformamide (MF), and N,N-dimethylformamide (DMF) have been performed in the isothermal and isobaric ensemble at 298 K and 1 atm, aiming to investigate the C-H ... O and N-H ... O hydrogen bonds. The interaction energy was calculated using the classical 6-12 Lennard-Jones pairwise potential plus a Coulomb term on a rigid six-site molecular model with the potential parameters being optimized in this work. Theoretical values obtained for heat of vaporization and liquid densities are in good agreement with the experimental data. The radial distribution function [RDF, g(r)] obtained compare well with R-X diffraction data available. The RDF and molecular mechanics (MM2) minimization show that the C-H ... O interaction has a significant role in the structure of the three liquids. These results are supported by ab initio calculations. This Interaction is particularly important in the structure of MF. The intensity of the N-H ... O hydrogen bond is greater in the MF than formamide. This could explain some anomalous properties verified in MF. (C) 1997 John Wiley & Sons, Inc.

The effect of polymerization cycles on porosity of microwave-processed denture base resin

Statement of problem. Although most of the physical properties of denture base resin polymerized by microwave energy have been shown to be similar to resins polymerized by the conventional heat polymerization method, the presence of porosity is a problem.Purpose. This study evaluated the effect of different microwave polymerization cycles on the porosity of a denture base resin designed for microwave polymerization.Material and methods. Thirty-two rectangular resin specimens (65 X 40 X 5 mm) were divided into 3 experimental groups (A, B, and C; Onda-Cryl, microwave-polymerized resin) and I control group (T; Classico, heat-polymerized resin), according to the following polymerization cycles: (A) 500 W for 3 minutes, (B) 90 W for 13 minutes + 500 W for 90 seconds, (C) 320 W for 3 minutes + 0 W for 4 minutes + 720 W for 3 minutes, and (T) 74degreesC for 9 hours. Porosity was calculated by measurement of the specimen volume before and after its immersion in water. Data were analyzed using 1-way analysis of variance (alpha = .05).Results. The mean values and SDs of the percent mean porosity were: A = 1.05% +/- 0.28%, B = 0.91% +/- 0.15%, C = 0.88% +/- 0.23%, T = 0.93% +/- 0.23%. No significant differences were found in mean porosity among the groups evaluated.Conclusion. Within the limitations of this study, a denture base resin specifically designed for microwave Polymerization tested was not affected by different polymerization cycles. Porosity was similar to the conventional heat-polymerized denture base resin tested.