Disordered materials make up a large proportion of condensed phase systems, but the difficulties in describing their structures and molecular dynamics limit their potential applications. Disordered crystalline systems, also known as plastic crystals, offer a unique perspective into these factors because the systems retain a degree of crystallinity, reducing the degrees of freedom that must be explored when interpreting the results. However, while disordered crystals do diffract X-rays, it is difficult to fully resolve meaningful crystalline structures, with the best scenario resulting in lattice parameters. In this study, we use a combination of experimental terahertz time-domain spectroscopy, and theoretical solid-state ab initio density functional theory and molecular dynamics simulations to fully elucidate the structures and associated dynamics of organic molecular solids. The results highlight that this combination provides a complete description of the energetic and mechanistic pathways involved in the formation of disordered crystals, and highlights the importance of low-frequency dynamics in their properties. Finally, with structures fully determined and validated by the experimental results, recent progress into anharmonic calculations, namely the quasi-harmonic approximation method, enables full temperature and pressuredependent properties to be understood within the framework of the potential energy hyper-surface structure.
The solvation shell is essential for the folding and function of proteins, but how it contributes to protein misfolding and aggregation has still to be elucidated. We show that the mobility of solvation shell H 2 O molecules influences the aggregation rate of the amyloid protein α-synuclein (αSyn), a protein associated with Parkinson's disease. When the mobility of H 2 O within the solvation shell is reduced by the presence of NaCl, αSyn aggregation rate increases. Conversely, in the presence CsI the mobility of the solvation shell is increased and αSyn aggregation is reduced. Changing the solvent from H 2 O to D 2 O leads to increased aggregation rates, indicating a solvent driven effect. We show the increased aggregation rate is not directly due to a change in the structural conformations of αSyn, it is also influenced by a reduction in both the H 2 O mobility and αSyn mobility. We propose that reduced mobility of αSyn contributes to increased aggregation by promoting intermolecular interactions.
A versatile setup based on terahertz time-domain spectroscopy was developed to monitor the process of crystallisation and characterise the structure of the crystals as well as the dynamics of the solvent in situ. The setup can be used to investigate crystallisation processes over a wide range of temperature, either under static conditions or during continuous flow. An attached optical imaging probe can be used to monitor the process in parallel to the terahertz spectroscopy investigation. The implementation of terahertz spectroscopy offers a great opportunity to investigate the dielectric relaxation dynamics of the solvent and the vibrational modes characteristic for the crystalline phases simultaneously. The details of the crystallisation setup are demonstrated at the example of the crystallisation process of magnesium sulphate heptahydrate from its aqueous phase.
A versatile setup based on terahertz time-domain spectroscopy was developed to monitor the process of crystallisation and characterise the structure of the crystals as well as the dynamics of the solvent in situ. The setup can be used to investigate crystallisation processes over a wide range of temperature, either under static conditions or during continuous flow. An attached optical imaging probe can be used to monitor the process in parallel to the terahertz spectroscopy investigation. The implementation of terahertz spectroscopy offers a great opportunity to investigate the dielectric relaxation dynamics of the solvent and the vibrational modes characteristic for the crystalline phases simultaneously. The details of the crystallisation setup are demonstrated at the example of the crystallisation process of magnesium sulphate heptahydrate from its aqueous phase.
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