Molecular Origin of the Elastic State of Aqueous Hyaluronic Acid.

The macroscopic mechanical properties of biological hydrogels are broadly studied and successfully mimicked in synthetic materials, but little is known about the molecular interactions that mediate these properties. Here, we use two-dimensional infrared spectroscopy to study the pH-induced gelation of hyaluronic acid, a ubiquitous biopolymer, which undergoes a transition from a viscous to an elastic state in a narrow pH range around 2.5.

Rotational Cation Dynamics in Metal Halide Perovskites: Effect on Phonons and Material Properties.

The dynamics of organic cations in metal halide hybrid perovskites (MHPs) have been investigated using numerous experimental and computational techniques because of their suspected effects on the properties of MHPs. In this Perspective, we summarize and reconcile key findings and present new data to synthesize a unified understanding of the dynamics of the cations. We conclude that theory and experiment collectively paint a relatively complete picture of rotational dynamics within MHPs.

Temperature-Induced Collapse of Elastin-like Peptides Studied by 2DIR Spectroscopy.

Elastin-like peptides are hydrophobic biopolymers that exhibit a reversible coacervation transition when the temperature is raised above a critical point. Here, we use a combination of linear infrared spectroscopy, two-dimensional infrared spectroscopy, and molecular dynamics simulations to study the structural dynamics of two elastin-like peptides. Specifically, we investigate the effect of the solvent environment and temperature on the structural dynamics of a short (5-residue) elastin-like peptide and of a long (450-residue) elastin-like peptide.

Observation of Ultrafast Vibrational Energy Transfer in Fibrinogen and Fibrin Fibers.

We study the secondary structure of the blood protein fibrinogen using two-dimensional infrared spectroscopy. With this technique, we identify the amide I' vibrational modes of the antiparallel β-sheets and turns of fibrinogen. We observe ultrafast energy flow among these amide I' vibrational modes with a time constant of ∼7 ps.

Strategies To Increase the Thermal Stability of Truly Biomimetic Hydrogels: Combining Hydrophobicity and Directed Hydrogen Bonding.

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.

Organic Cation Rotation and Immobilization in Pure and Mixed Methylammonium Lead-Halide Perovskites.

Three-dimensional lead-halide perovskites have attracted a lot of attention due to their ability to combine solution processing with outstanding optoelectronic properties. Despite their soft ionic nature these materials demonstrate a surprisingly low level of electronic disorder resulting in sharp band edges and narrow distributions of the electronic energies. Understanding how structural and dynamic disorder impacts the optoelectronic properties of these perovskites is important for many applications.

Real-Time Observation of Organic Cation Reorientation in Methylammonium Lead Iodide Perovskites.

The introduction of a mobile and polarized organic moiety as a cation in 3D lead-iodide perovskites brings fascinating optoelectronic properties to these materials. The extent and the time scales of the orientational mobility of the organic cation and the molecular mechanism behind its motion remain unclear, with different experimental and computational approaches providing very different qualitative and quantitative description of the molecular dynamics. Here we use ultrafast 2D vibrational spectroscopy of methylammonium (MA) lead iodide to directly resolve the rotation of the organic cations within the MAPbI3 lattice.

Mode-selective vibrational modulation of charge transport in organic electronic devices.

The soft character of organic materials leads to strong coupling between molecular, nuclear and electronic dynamics. This coupling opens the way to influence charge transport in organic electronic devices by exciting molecular vibrational motions. However, despite encouraging theoretical predictions, experimental realization of such approach has remained elusive.