Molecular modeling and structural characterization of a high glycine-tyrosine hair keratin associated protein.

High glycine-tyrosine (HGT) proteins are an important constituent of the keratin associated proteins (KAPs) present in human hair. The glassy state physics of hair fibres are thought to be largely regulated by KAPs, which exist in an amorphous state and are readily affected by environmental conditions. However, there are no studies characterizing the individual KAPs. In this paper, we present the first step to fill this gap by computational modeling and experimental studies on a HGT protein, KAP8.1. In particular, we have modeled the three-dimensional structure of this 63-residue protein using homology information from an anti-freeze protein in snow flea. The model for KAP8.1 is characterized by four strands of poly-proline II (or PPII) type helical secondary structures, held together by two cysteine disulphide bridges. Computer simulations confirm the stability of the modelled structure and show that the protein largely samples the PPII and ß-sheet conformations during the molecular dynamics simulations. Spectroscopic studies including Raman, IR and vibrational circular dichroism have also been performed on synthesized KAP8.1. The experimental studies suggest that KAP8.1 is characterised by ß-sheet and PPII structures, largely consistent with the simulation studies. The model built in this work is a good starting point for further simulations to study in greater depth the glassy state physics of hair, including its water sorption isotherms, glass transition, and the effect of HGT proteins on KAP matrix plasticization. These results are a significant step towards our goal of understanding how the properties of hair can be affected and manipulated under different environmental conditions of temperature, humidity, ageing and small molecule additives.

Trehalose in hair care: heat styling benefits at high humidity.

Human hair switches that have been treated with trehalose solution and straightened using hot irons show longevity of the straight style even in high-humidity conditions. This anti-humidity benefit is especially noticeable if the straight style has been created at low relative humidity. It is proposed that hot-iron straightening of trehalose-treated switches produces in situ glassy forms of the sugar that act as water sinks at high humidity to provide anti-humidity benefits. Adsorption isotherms and powder x-ray studies of different forms of trehalose and moisture uptake of hair treated with the sugar suggest that the ability of a glassy form of trehalose to regulate moisture in the fiber and consequently affect its viscoelastic properties is a major factor in providing long-lasting straight style in humid conditions.

Effects of disulfide bridges and backbone connectivity on water sorption by protein matrices.

Understanding the water sorption behavior of protein powders is important in applications such as the preservation of protein-based pharmaceuticals. Most globular proteins exhibit a characteristic sigmoidal water adsorption isotherm at ambient conditions. However, it is not well understood how water sorption behavior is influenced by intrinsic factors that are related to structural properties of proteins. We investigate computationally how structural constraints on proteins influence the water sorption isotherms of amorphous protein powders. Specifically, we study the effects of non-local disulfide linkages and backbone connectivity using pheromone ER-23 and lysozyme as model proteins. We find that non-local disulfide linkages can significantly restrict structural changes during hydration and dehydration, and this in turn greatly reduces the extent of hysteresis between the adsorption and desorption branches. Upon removing the backbone connectivity by breaking all peptide bonds in lysozyme, we find that the hysteresis shifts towards the lower humidity regime, and the water uptake capacity is significantly enhanced. We attribute these changes to the higher aggregation propensity of the constraint-free amino acids in dehydrated condition, and the formation of a spanning water network at high hydration levels.

Prediction of vapour pressure using descriptors derived from molecular dynamics.

Vapour pressures of organic materials can be predicted to high levels of accuracy using cohesive energies and solubility parameters derived from molecular dynamics simulations that use good forcefields. It is found that over 90% of the correlation with vapour pressure is accounted for by a single cross term involving the product of either the molecular weight or molar volume of a molecule and its cohesive energy density.

Structures of carbohydrate-boronic acid complexes determined by NMR and molecular modelling in aqueous alkaline media.

The structures of thermodynamically stable aromatic boronic acid : cyclic carbohydrate chelates in aqueous alkaline media have been studied using 1H NMR spectroscopy and molecular modelling. It is found that interacting saccharides must necessarily possess a synperiplanar diol functionality for complexation to occur. While this is possible for furanose structures which tend to have a puckered planar geometry, for pyranose forms it is postulated that bis-complexation occurs with twist conformers of the pyranose ring, providing the ring has the requisite 1,2 : 3,4 polyol stereochemistry; specifically axial,equatorial : equatorial,axial or equatorial,axial : axial,equatorial orientations. In this respect it is possible to be predictive with regard to individual carbohydrate boronic acid interactions and to give reasonably comprehensive structural assignments to complexed components. In this paper twenty four polyhydroxy compounds have been screened using 1H NMR to monitor complexation along with computational techniques on a model system to substantiate proposed structures. It has been found that all of these materials interact with aromatic mono boronic acids as expected and structures for the resulting chelates are proposed.

Linking atomistic and mesoscale simulations of water-soluble polymers.

A link between molecular and mesoscopic simulations for water-soluble polymers is made using the potential of mean force (PMF) method. Mesoscale parameters are adjusted to match selected thermodynamic quantities such as the monomer second virial coefficient or the limiting slope of the monomer adsorption isotherm, which are computed directly from atomistic PMFs. The method is illustrated by computing the bulk and surface interaction parameters (chi parameters in self-consistent field theory) for the adsorption of ethylene oxide (EO) and propylene oxide (PO) polymers from aqueous solution onto silica.