Insight into Calcium-Binding Motifs of Intrinsically Disordered Proteins

Motifs within proteins help us categorize their functions. Intrinsically disordered proteins (IDPs) are rich in short linear motifs, conferring them many different roles. IDPs are also frequently highly charged and, therefore, likely to interact with ions. Canonical calcium-binding motifs, such as the EF-hand, often rely on the formation of stabilizing flanking helices, which are a key characteristic of folded proteins, but are absent in IDPs. In this study, we probe the existence of a calcium-binding motif relevant to IDPs. Upon screening several carefully selected IDPs using NMR spectroscopy supplemented with affinity quantification by colorimetric assays, we found calcium-binding motifs in IDPs which could be categorized into at least two groups—an Excalibur-like motif, sequentially similar to the EF-hand loop, and a condensed-charge motif carrying repetitive negative charges. The motifs show an affinity for calcium typically in the ~100 μM range relevant to regulatory functions and, while calcium binding to the condensed-charge motif had little effect on the overall compaction of the IDP chain, calcium binding to Excalibur-like motifs resulted in changes in compaction. Thus, calcium binding to IDPs may serve various structural and functional roles that have previously been underreported.

Partition-Coefficient Relations for Improved Equation-of-State Description of Microemulsion-Phase Behavior

Summary Surfactant-mediated enhanced-oil-recovery (EOR) techniques, such as surfactant/polymer (SP) flooding, have received increased attention because of their ability to reduce capillary forces at the pore-scale to ultralow values and mobilize trapped oil. Recently, there have been increased efforts in microemulsion-phase-behavior modeling capabilities by relying on the hydrophilic/lipophilic-difference (HLD) measure for surfactant-affinity quantification. One common assumption of most microemulsion-phase-behavior models is the assumption of pure excess phases, which states that the surfactant component is only present in the microemulsion phase. This assumption can lead to significant errors for some surfactant systems, especially when applied to chemical simulations in which discontinuities may arise. The main novelty of this paper is to allow for surfactant partitioning into both the water and oil excess phases by use of a simple approach, and then relate relevant surfactant-partitioning coefficients (i.e., K-values) to HLD. Surfactant screening that is based on surfactant-structure parameters is also considered based on estimated K-values. Key dimensionless groups are identified as a function of activity coefficients, which allow for a simplified description of the surfactant-partition coefficients. These surfactant-partition coefficients are combined with the chemical-potentials (CP) equation-of-state (EoS) model to describe and predict the phase behavior when the excess phases are not pure. Further, the developed surfactant-partitioning model can be used in other microemulsion-phase-behavior models to allow for impure excess phases.