The experimental calorimetric two-state criterion requires the van't Hoff enthalpy DeltaH(vH) around the folding/unfolding transition midpoint to be equal or very close to the calorimetric enthalpy DeltaH(cal) of the entire transition. We use an analytical model with experimental parameters from chymotrypsin inhibitor 2 to elucidate the relationship among several different van't Hoff enthalpies used in calorimetric analyses. Under reasonable assumptions, the implications of these DeltaH(vH)'s being approximately equal to DeltaH(cal) are equivalent: Enthalpic variations among denatured conformations in real proteins are much narrower than some previous lattice-model estimates, suggesting that the energy landscape theory "folding to glass transition temperature ratio" T(f) /T(g) may exceed 6.0 for real calorimetrically two-state proteins. Several popular three-dimensional lattice protein models, with different numbers of residue types in their alphabets, are found to fall short of the high experimental standard for being calorimetrically two-state. Some models postulate a multiple-conformation native state with substantial pre-denaturational energetic fluctuations well below the unfolding transition temperature, or predict a significant post-denaturational continuous conformational expansion of the denatured ensemble at temperatures well above the transition point, or both. These scenarios either disagree with experiments on protein size and dynamics, or are inconsistent with conventional interpretation of calorimetric data. However, when empirical linear baseline subtractions are employed, the resulting DeltaH(vH)/DeltaH(cal)'s for some models can be increased to values closer to unity, and baseline subtractions are found to correspond roughly to an operational definition of native-state conformational diversity. These results necessitate a re-assessment of theoretical models and experimental interpretations.

Hydrogen bonding interactions play an important role in many chemical and physical processes occurring in bulk liquids and at interfaces. In this study, hydrous species (H 2 O and Si-OH) on nano-porous alteration layers (gels) formed on a boroaluminosilicate glass called International Simple Glass corroded in aqueous solutions at pH 7 and pH 9, and initially saturated with soluble siliconcontaining species were analyzed using linear and non-linear vibrational spectroscopy in combination with molecular dynamics simulations. The simulation results revealed various possible types of hydrogen bonds among these hydrous species in nanoconfinement environments with their populations depending on pore-size distribution. The nano-porous gels formed on corroded glass surfaces enhance hydrogen bond strength between hydrous species as revealed by attenuated total reflectance infrared spectroscopy. Sum frequency generation spectroscopy showed some significant differences in hydrogen bonding interactions on alteration layers formed at pH 7 and pH 9. The glass dissolution under the leaching conditions used in this study has been known to be ten times faster at pH 7 in comparison to that at pH 9 due to unknown reasons. The simulation and experimental results obtained in this study indicate that the water mobility in the gel formed at pH 9 could be slower than that in the gel formed at pH 7, and as a result, the leaching rate at pH 9 is slower than that at pH 7.npj Materials Degradation (2020) 4:1 ; https://doi.

Vibrational spectroscopy has been widely used to investigate various structural aspects of the glass network, and there are a plethora of papers reporting subtle but consistent changes in infrared and Raman spectral features of glass upon alterations of glass compositions, thermal histories, mechanical stresses, or surface treatments. However, interpretations of such spectral features are still obscured due to the lack of well-established physical principles accurately describing vibrational modes of the non-crystalline glass network. Due to the non-equilibrium nature of the glass network, three-dimensionally connected without any long-range orders, vibrational spectral features of glass cannot be interpreted using the analogy with those of isolated molecular moieties or crystalline counterparts. This feature article explains why such comparisons are outdated and describes the recent advances made from theoretical calculations of vibrational spectral features of amorphous networks or comparisons of computational results with experimental data. For the interpretation of vibrational spectral features of silica and silicate glasses, the following empirical relationships are suggested: (i) the intensity-weighted peak position of the Si-O-Si stretch mode negatively correlates with the weighted average of the Si-O bond length distribution, and (ii) the broad band of the Si-O-Si bending mode negatively correlates with the Si-O-Si bond angle distribution. Selected examples of vibrational spectroscopic imaging of surface defects are discussed to deliberate the implication of these findings in the structure-property relationship of silica and silicate glass materials. Unanswered questions and continuing research challenges are identified.

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