Rheological Properties of Ionically Crosslinked Viscoelastic 2D Films vs. Corresponding 3D Bulk Hydrogels

Ionically crosslinked hydrogels containing metal coordination motifs have piqued the interest of researchers in recent decades due to their self-healing and adhesive properties. In particular, catechol-functionalized bulk hydrogels have received a lot of attention because of their bioinspired nature. By contrast, very little is known about thin viscoelastic membranes made using similar chelator–ion pair motifs. This shortcoming is surprising because the unique interfacial properties of these membranes, namely, their self-healing and adhesion, would be ideal for capsule shells, adhesives, or for drug delivery purposes. We recently demonstrated the feasibility to fabricate 10 nm thick viscoelastic membranes from catechol-functionalized surfactants that are ionically crosslinked at the liquid/liquid interface. However, it is unclear if the vast know-how existing on the influence of the chelator–ion pair on the mechanical properties of ionically crosslinked three-dimensional (3D) hydrogels can be translated to two-dimensional (2D) systems. To address this question, we compare the dynamic mechanical properties of ionically crosslinked pyrogallol functionalized hydrogels with those of viscoelastic membranes that are crosslinked using the same chelator–ion pairs. We demonstrate that the storage and loss moduli of viscoelastic membranes follow a trend similar to that of the hydrogels, with the membrane becoming stronger as the ion–chelator affinity increases. Yet, membranes relax significantly faster than bulk equivalents. These insights enable the targeted design of viscoelastic, adhesive, self-healing membranes possessing tunable mechanical properties. Such capsules can potentially be used, for example, in cosmetics, as granular inks, or with additional work that includes replacing the fluorinated block by a hydrocarbon-based one in drug delivery and food applications

Intermicellar Interactions and the Viscoelasticity of Surfactant Solutions: Complementary Use of SANS and SAXS

In ionic surfactant micelles, basic interactions among distinct parts of surfactant monomers, their counterion, and additives are fundamental to tuning molecular self-assembly and enhancing viscoelasticity. Here, we investigate the addition of sodium salicylate (NaSal) to hexa­decyl­tri­methyl­am­monium chloride and bromide (CTAC and CTAB) and 1-hexa­decyl­py­ri­di­nium chloride and bromide (CPyCl and CPyBr), which have distinct counterions and headgroup structures but the same hydrophobic tail. Different contrasts are obtained from small-angle neutron scattering (SANS), which probes differences between the nucleus of atoms, and X-rays SAXS, which probes differences in electron density. If combined, this contrast allows us to define specific intramicellar length scales and intermicellar interactions. SANS signals are sensitive to the contrast between the solvent (D₂O) and the hydrocarbonic tails in the micellar core (hydrogen), and SAXS can access the inner structure of the polar shell because the headgroups, counterions, and penetrated salt have higher electron densities compared to the solvent and to the micellar core. The number density, intermicellar distances, aggregation number, and inter/intramicellar repulsions are discussed on the basis of the dependence of the structure factor and form factor on the micellar aggregate morphology. Therefore, we confirm that micellar growth can be tuned by variations in the flexibility and size of the the headgroup as well as the ionic dissociation rate of its counterion. Additionally, we show that the counterion binding is even more significant to the development of viscoelasticity than the headgroup structure of a surfactant molecule. This is a surprising finding, showing the importance of electrostatic charges in the self-assembly process of ionic surfactant molecules

Hierarchical Structure of Cellulose Nanofibril-Based Foams Explored by Multimodal X‑ray Scattering

Structural characterization techniques are fundamental to correlate the material macro-, nano-, and molecular-scale structures to their macroscopic properties and to engineer hierarchical materials. Here, we combine X-ray transmission with scanning small- and wide-angle X-ray scattering (sSWAXS) to investigate ultraporous and lightweight biopolymer-based foams using cellulose nanofibrils (CNFs) as building blocks. The power of multimodal sSWAXS for multiscale structural characterization of self-assembled CNFs is demonstrated by spatially resolved maps at the macroscale (foam density and porosity), at the nanoscale (foam structural compactness, CNF orientation in the foam walls, and CNF packing state), and at the molecular scale (cellulose crystallite dimensions). Specifically, we compare the impact of freeze–thawing–drying (FTD) fabrication steps, such as static/stirred freezing and thawing in ethanol/water, on foam structural hierarchy spanning from the molecular to the millimeter scale. As such, we demonstrate the potential of X-ray scattering imaging for hierarchical characterization of biopolymers

Pluronic F68 Micelles as Carriers for an Anti-Inflammatory Drug: A Rheological and Scattering Investigation

Age-long ambition of medical scientists has always been advancement in healthcare and therapeutic medicine. Biomedical research indeed claims paramount importance in nanomedicine and drug delivery, and the development of biocompatible storage structures for delivering drugs stands at the heart of emerging scientific works. The delivery of drugs into the human body is nevertheless a nontrivial and challenging task, and it is often addressed by using amphiphilic compounds as nanosized delivery vehicles. Pluronics belong to a peculiar class of biocompatible and thermosensitive nonionic amphiphilic copolymers, and their self-assemblies are employed as drug delivery excipients because of their unique properties. We herein report on the encapsulation of diclofenac sodium within Pluronic F68 self-assemblies in water, underpinning the impact of the drug on the rheological and microstructural evolution of pluronic-based systems. The self-assembly and thermoresponsive micellization were studied through isothermal steady rheological experiments at different temperatures on samples containing 45 wt % Pluronic F68 and different amounts of diclofenac sodium. The adoption of scattering techniques, small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS), allowed for the description of the system features at the nanometer length scale, providing information about the characteristic size of each part of the micellar structures as a function of temperature and drug concentration. Diclofenac sodium is not a good fellow for Pluronic F68. The triblock copolymer aids the encapsulation of the drug, highly improving its water solubility, whereas diclofenac sodium somehow hinders Pluronic self-assembly. By using a simple empirical model and no fitting parameters, the steady viscosity can be predicted, although qualitatively, through the volume fraction of the micelles extracted through scattering techniques and compared to the rheological one. A tunable control of the viscous behavior of such biomedical systems may be achieved through the suitable choice of their composition

DataSheet1_Solvent modulation in peptide sub-microfibers obtained by solution blow spinning.docx

Peptides possess high chemical diversity at the amino acid sequence level, which further translates into versatile functions. Peptides with self-assembling properties can be processed into diverse formats giving rise to bio-based materials. Peptide-based spun fibers are an interesting format due to high surface-area and versatility, though the field is still in its infancy due to the challenges in applying the synthetic polymer spinning processes to protein fibers to peptides. In this work we show the use of solution blow-spinning to produce peptide fibers. Peptide fiber formation was assisted by the polymer poly (vinyl pyrrolidone) (PVP) in two solvent conditions. Peptide miscibility and further self-assembling propensity in the solvents played a major role in fiber formation. When employing acetic acid as solvent, peptide fibers (0.5 μm) are formed around PVP fibers (0.75 μm), whereas in isopropanol only one type of fibers are formed, consisting of mixed peptide and PVP (1 μm). This report highlights solvent modulation as a mean to obtain different peptide sub-microfibers via a single injection nozzle in solution blow spinning. We anticipate this strategy to be applied to other small peptides with self-assembly propensity to obtain multi-functional proteinaceous fibers.</p

Scanning Small-Angle X‑ray Scattering of Injection-Molded Polymers: Anisotropic Structure and Mechanical Properties of Low-Density Polyethylene

Injection molding is known to create a layered anisotropic morphology across the sample thickness due to varying shear and cooling rates during the manufacturing process. In this study, scanning small-angle X-ray scattering was used to visualize and quantify the distribution of hierarchical structures present in injection-molded parts of low-density polyethylene (LDPE) with varying viscosities. By combining scattering data with results from injection molding simulations and tensile testing, we find that oriented shish-kebab structures, as well as elongated spherulite structures consisting of semicrystalline ellipsoids, contribute to high ultimate tensile strength along the flow direction. Furthermore, we show that a higher degree of orientation is found close to the injection gate and in LDPE with higher viscosity, consequently from elevated shear and cooling rates present during the injection molding process

DataSheet1_Hierarchical self-assembly of a reflectin-derived peptide.docx

Reflectins are a family of intrinsically disordered proteins involved in cephalopod camouflage, making them an interesting source for bioinspired optical materials. Understanding reflectin assembly into higher-order structures by standard biophysical methods enables the rational design of new materials, but it is difficult due to their low solubility. To address this challenge, we aim to understand the molecular self-assembly mechanism of reflectin’s basic unit—the protopeptide sequence YMDMSGYQ—as a means to understand reflectin’s assembly phenomena. Protopeptide self-assembly was triggered by different environmental cues, yielding supramolecular hydrogels, and characterized by experimental and theoretical methods. Protopeptide films were also prepared to assess optical properties. Our results support the hypothesis for the protopeptide aggregation model at an atomistic level, led by hydrophilic and hydrophobic interactions mediated by tyrosine residues. Protopeptide-derived films were optically active, presenting diffuse reflectance in the visible region of the light spectrum. Hence, these results contribute to a better understanding of the protopeptide structural assembly, crucial for the design of peptide- and reflectin-based functional materials.</p

Surface Cross-Linking by Macromolecular Tethers Enhances Virus-like Particles’ Resilience to Mucosal Stress Factors

Virus-like particles (VLPs) are emerging as nanoscaffolds in a variety of biomedical applications including delivery of vaccine antigens and cargo such as mRNA to mucosal surfaces. These soft, colloidal, and proteinaceous structures (capsids) are nevertheless susceptible to mucosal environmental stress factors. We cross-linked multiple capsid surface amino acid residues using homobifunctional polyethylene glycol tethers to improve the persistence and survival of the capsid to model mucosal stressors. Surface cross-linking enhanced the stability of VLPs assembled from Acinetobacter phage AP205 coat proteins in low pH (down to pH 4.0) and high protease concentration conditions (namely, in pig and mouse gastric fluids). Additionally, it increased the stiffness of VLPs under local mechanical indentation applied using an atomic force microscopy cantilever tip. Small angle X-ray scattering revealed an increase in capsid diameter after cross-linking and an increase in capsid shell thickness with the length of the PEG cross-linkers. Moreover, surface cross-linking had no effect on the VLPs’ mucus translocation and accumulation on the epithelium of in vitro 3D human nasal epithelial tissues with mucociliary clearance. Finally, it did not compromise VLPs’ function as vaccines in mouse subcutaneous vaccination models. Compared to PEGylation without cross-linking, the stiffness of surface cross-linked VLPs were higher for the same length of the PEG molecule, and also the lifetimes of surface cross-linked VLPs were longer in the gastric fluids. Surface cross-linking using macromolecular tethers, but not simple conjugation of these molecules, thus offers a viable means to enhance the resilience and survival of VLPs for mucosal applications