Calculation of Partial Specific Volumes and Other Volumetric Properties of Small Molecules and Polymers

Volumetric properties of macromolecules and low‐molecular compounds are necessary auxiliary means for the determination of molar masses from solution‐scattering and hydrodynamic techniques. In many cases experimental determinations of partial volumes can or have to be replaced by calculative procedures. A universal approach for the calculation of both low‐molecular organic compounds and polymers of different chemical composition and structure in aqueous solution is described. It is based on volume increments for the constituent atoms, ions and/or groups and allows corrections for covolume, ring formation, micellization, ionization etc . Application of this approach is of particular interest in connection with: (i) nonionic and ionic organic solutes; (ii) inorganic electrolytes; (iii) monomeric and micellar detergents and lipids; (iv) carbohydrates and polysaccharides; (v) nucleobases, nucleosides, nucleotides, polynucleotides, nucleic acids; (vi) amino acids, amino‐acid residues, peptides, polyaminoacids, nonconjugated and conjugated proteins; (vii) synthetic polymers. The results of the volume predictions show a high degree of reliability, if compared to experimental data. Special approaches dealing with simple and conjugated proteins and protein‐ligand complexes in two‐ and multicomponent solutions allow the prediction of both isomolal and isopotential volumes under a variety of native and denaturing conditions, including the presence of high amounts of additives.