Hydration free energies are dictated by a subtle balance of hydrophobic and hydrophilic interactions. We present here a spectroscopic approach, which gives direct access to the two main contributions: Using THz-spectroscopy to probe the frequency range of the intermolecular stretch (150-200 cm À 1 ) and the hindered rotations (450-600 cm À 1 ), the local contributions due to cavity formation and hydrophilic interactions can be traced back. We show that via THz calorimetry these fingerprints can be correlated 1 : 1 with the group specific solvation entropy and enthalpy. This allows to deduce separately the hydrophobic (i.e. cavity formation) and hydrophilic contributions to thermodynamics, as shown for hydrated alcohols as a case study. Accompanying molecular dynamics simulations quantitatively support our experimental results. In the future our approach will allow to dissect hydration contributions in inhomogeneous mixtures and under non-equilibrium conditions.

Hydration free energies are dictated by a subtle balance of hydrophobic and hydrophilic interactions. We present here a spectroscopic approach, which gives direct access to the two main contributions: Using THz‐spectroscopy to probe the frequency range of the intermolecular stretch (150–200 cm−1) and the hindered rotations (450–600 cm−1), the local contributions due to cavity formation and hydrophilic interactions can be traced back. We show that via THz calorimetry these fingerprints can be correlated 1 : 1 with the group specific solvation entropy and enthalpy. This allows to deduce separately the hydrophobic (i.e. cavity formation) and hydrophilic contributions to thermodynamics, as shown for hydrated alcohols as a case study. Accompanying molecular dynamics simulations quantitatively support our experimental results. In the future our approach will allow to dissect hydration contributions in inhomogeneous mixtures and under non‐equilibrium conditions.

Enhancing the thermal stability of proteins is an important task for protein engineering. There are several ways to increase the thermal stability of proteins in biology, such as greater hydrophobic interactions, increased helical content, decreased occurrence of thermolabile residues, or stable hydrogen bonds. Here, we describe a well-defined polymer based on β-helical polyisocyanotripeptides (TriPIC) that uses biological approaches, including hydrogen bonding and hydrophobic interactions for its exceptional thermal stability in aqueous solutions. The multiple hydrogen bonding arrays along the polymer backbone shield the hydrophobic core from water. Variable temperature CD and FTIR studies indicate that, on heating, a better packed polymer conformation further stiffens the backbone. Driven by hydrophobic interactions, TriPIC solutions give fully reversible hydrogels that can withstand high temperatures (80 °C) for extended times. Cryo-scanning electron microscopy (cryo-SEM), small-angle X-ray scattering (SAXS), and thorough rheological analysis show that the hydrogel has a bundled architecture, which gives rise to strain stiffening effects on deformation of the gel, analogous to many biological hydrogels.

An LC-ESI-MS method is presented as a novel approach for the study of aged drying oils and oil paints in various stages of oxidation and hydrolysis. The method involves separation and detection of glycerides and fatty acids on a reversed phase column using a polar gradient ranging from methanol/water to methanol/isopropanol with post-column addition of NH 4 Ac to facilitate electrospray ionisation. This setup allows for a reasonable separation of non-polar triglycerides in drying oil as well as very polar oxidised and hydrolysed tri, di and monoglycerides as well as free fatty acids. Detection is performed by using both positive and negative ionisation mode: positive ions for glycerides, negative ions for carboxylic acid containing degradation products and free fatty acids.In this way, distinction can be made between components in oil and metal stearate mixtures by independently probing the palmitic acid/stearic acid (P/S) ratios of the free fatty acids which mostly derive from the metal stearates, and the glycerides which derive only from the drying oil components.Analyses of 10 year-old titanium white oil paints with medium exudations and 62 year-old paints from Winsor&Newton are presented as examples to show the applicability of the method.

Shape-preserving conversion offers a promising strategy to transform self-assembled structures into advanced functional components with customizable composition and shape. Specifically, the assembly of barium carbonate nanocrystals and amorphous silica nanocomposites (BaCO 3 /SiO 2 ) offers a plethora of programmable three-dimensional (3D) microscopic geometries, and the nanocrystals can subsequently be converted into functional chemical compositions, while preserving the original 3D geometry. Despite this progress, the scope of these conversion reactions has been limited by the requirement to form carbonate salts. Here, we overcome this limitation using a single-step cation/anion exchange that is driven by the temporal pH change at the converting nanocomposite. We demonstrate the proof of principle by converting BaCO 3 /SiO 2 nanocomposites into tin-containing nanocomposites, a metal without a stable carbonate. We find that BaCO 3 /SiO 2 nanocomposites convert in a single step into hydroromarchite nanocomposites (Sn 3 (OH) 2 O 2 /SiO 2 ) with excellent preservation of the 3D geometry and fine features. We explore the versatility and tunability of these Sn 3 (OH) 2 O 2 /SiO 2 nanocomposites as a precursor for functional compositions by developing shape-preserving conversion routes to two desirable compositions: tin perovskites (CH 3 NH 3 SnX 3 , with X = I or Br) with tunable photoluminescence (PL) and cassiterite (SnO 2 )—a widely used transparent conductor. Ultimately, these findings may enable integration of functional chemical compositions into advanced morphologies for next-generation optoelectronic devices.