Temperature- and strain-dependent transient microstructure and rheological responses of endblock-associated triblock gels of different block lengths in a midblock selective solvent.

Endblock associative ABA gels in midblock selective solvents are attractive due to their easily tunable mechanical properties. Here, we present the effects of A- and B-block lengths on the rheological properties and microstructure of ABA gels by considering three low and one high polymer concentrations. The triblock polymer considered is poly(methyl methacrylate)-poly(n-butyl acrylate)-poly(methyl methacrylate) [PMMA-PnBA-PMMA] and the midblock solvent is 2-ethyl-1-hexanol. The gelation temperature has been found to be strongly dependent on the B-block (PnBA) length, as longer B-blocks facilitate network formation resulting in higher gelation temperature even with lower polymer chain density. Longer A-blocks (PMMA chains) make the endblock association stronger and significantly increase the relaxation time of gels. Temperature-dependent microstructure evolution for the gels with high polymer concentration reveals that the gel microstructure does not change significantly after the gel formation takes place. The dynamic change of microstructure in an applied strain cycle was captured using RheoSAXS experiments. The microstructure orients with the applied strain and the process is reversible in nature, indicating no significant A-block pullout. Our results provide new understandings regarding the temperature and strain-dependent microstructural change of ABA gels in midblock selective solvents.

Correction: Temperature- and strain-dependent transient microstructure and rheological responses of endblock-associated triblock gels of different block lengths in a midblock selective solvent.

Correction for 'Temperature- and strain-dependent transient microstructure and rheological responses of endblock-associated triblock gels of different block lengths in a midblock selective solvent' by Rosa Maria Badani Prado et al., Soft Matter, 2022, 18, 7020-7034, https://doi.org/10.1039/D2SM00567K.

Structure and rheology of dual-associative protein hydrogels under nonlinear shear flow.

Dual-associative protein di- and triblock copolymers composed of sticker-decorated midblocks and micelle-forming elastin-like polypeptide (ELP) endblocks form shear-thinning, thermoresponsively reinforceable hydrogels that are potentially useful as injectable materials for a variety of applications. Here, the combination of rheological and in situ scattering measurements under shear on these dual-associative gels is employed in order to better understand how block architecture plays a role in controlling microscopic structural rearrangement and the resulting macroscopic mechanical responses. These gels, which form a disordered sphere phase due to endblock aggregation under quiescent conditions with the midblock domains physically crosslinked by protein associations, exhibit both viscoelastic and thixotropic signatures with relative magnitudes dependent upon gel concentration and block architecture. In situ SAXS measurements during flow indicate that these thixotropic responses correspond to the development of ordered domains following start-up of shear. For both architectures, the rate of alignment increases with increasing concentration. However, the rate of domain formation when increasing the temperature from 35 to 50 °C depends on the interplay between thermoresponsive toughening of the endblocks and softening of the coiled-coil domains such that rate of rearrangement decreases in the triblock while it increases in the diblock. Following a step-down in shear flow, structural rearrangement within the samples results in a thixotropic stress response. Upon cessation of flow, gel recovery is characterized by a concentration-dependent restoration of the micellar network over time, with two timescales observed that correspond to two different length scales of network relaxation.

Structural response of an ordered block copolymer melt to uniaxial extensional flow.

We report in situ small-angle X-ray scattering (SAXS) studies of a cylindrically ordered styrene-ethylene butylene-styrene (SEBS) triblock copolymer melt subjected to uniaxial extensional flow. The flow is applied by stretching strips of polymer melt using a counter-rotating drum extensional flow fixture housed in a custom oven designed to provide X-ray access. SAXS patterns show two distinct modes of structural response during extensional flow: deformation of the microscopic structure, and re-orientation of PS microdomains towards the flow direction. The d-spacings of the hexagonally ordered domains measured parallel and perpendicular to the flow direction deform affinely until Hencky strains of ∼0.2. Departures in extensional viscosity from linear viscoelastic predictions are observed at similar strain. The azimuthal dependence of the primary diffraction peak reveals a complex re-orientation process whereby PS microdomains rotate toward the stretching direction. At intermediate strains, a '4-point' diffraction pattern indicates the presence of two discrete populations of microdomain orientation, attributed to a buckling instability of microdomains initially oriented perpendicular to the stretching direction. Flow-induced deformation and orientation both relax upon cessation of flow, albeit at very different rates, suggesting that these two modes of structural response are largely decoupled.

Local and Global Stretching of Polymer Chains during Startup of Extensional Flow.

The nonlinear rheological response to extensional flows in entangled polymers is related to the segmental chain stretching and to the chemical identity of the monomeric units. The latter has a strong effect on the drag coefficients, and therefore, quantification of molecular conformation changes in the subnanometer scale (at the monomer level) are crucial to fully understand nonlinear viscoelastic behavior in polymer melts. We report in situ time-resolved extensional rheo-small-angle neutron scattering (tEr-SANS) and wide-angle X-ray scattering (tEr-WAXS) during startup of uniaxial flow on a monodisperse polystyrene melt. Flow-induced segmental alignment was quantified with tEr-SANS, whereas local alignment of the backbone-backbone and phenyl-phenyl interactions were measured with tEr-WAXS. Linear relations between the three alignment factors and stress were observed at low stresses, which confirmed the validity of simple stress-SANS and stress-WAXS rules (SSR and SWR, respectively). Significant differences in SSR and SWR coefficients, as well as the stress values for failure of the two rules suggest very different correlations between global (at the segmental level) and local (at the monomer level) conformations with stress.

Orientation dynamics in multiwalled carbon nanotube dispersions under shear flow.

We report studies of the orientation state of multiwalled carbon nanotubes (MWNTs) dispersions in steady and transient shear flows. Uncured epoxy was used as a viscous Newtonian suspending medium and samples were prepared from "aligned" MWNTs using methods previously reported [S. S. Rahatekar et al., J. Rheol. 50, 599 (2006)]. Orientation measurements were performed in both the flow-gradient (1-2) and flow-vorticity (1-3) plane of simple shear flow using in situ x-ray scattering techniques. Steady state measurements in the 1-2 plane indicate that the MWNT orientation is shear rate dependent, with the MWNTs orienting closer to the flow direction at higher shear rates. During steady shear, anisotropy was measured to be higher in the 1-2 plane than in the 1-3 plane, demonstrating that the nanotube orientation state is not unaxially symmetric in shear. It is hypothesized that the steady state MWNT orientation is governed primarily by a rate-dependent state of nanotube aggregation/disaggregation, which was separately characterized by optical microscopy of the same samples under shear. High flux synchrotron radiation allowed for time-resolved structural studies in transient flows. A partial relaxation of flow-induced anisotropy was observed following flow cessation, despite the very small rotational diffusivity estimated for these nanotubes. Long transients are observed in step-down experiments, as the orientation state changes in response to the slow tube aggregation process.

Employing PEG crosslinkers to optimize cell viability in gel phase bioinks and tailor post printing mechanical properties.

The field of 3D bioprinting has rapidly grown, yet the fundamental ability to manipulate material properties has been challenging with current bioink methods. Here, we change bioink properties using our PEG cross-linking (PEGX) bioink method with the objective of optimizing cell viability while retaining control of mechanical properties of the final bioprinted construct. First, we investigate cytocompatible, covalent cross-linking chemistries for bioink synthesis (e.g. Thiol Michael type addition and bioorthogonal inverse electron demand Diels-Alder reaction). We demonstrate these reactions are compatible with the bioink method, which results in high cell viability. The PEGX method is then exploited to optimize extruded cell viability by manipulating bioink gel robustness, characterized by mass flow rate. Below a critical point, cell viability linearly decreases with decreasing flow rates, but above this point, high viability is achieved. This work underscores the importance of building a foundational understanding of the relationships between extrudable bioink properties and cell health post-printing to more efficiently tune material properties for a variety of tissue and organ engineering applications. Finally, we also develop a post-printing, cell-friendly cross-linking strategy utilizing the same reactions used for synthesis. This secondary cross-linking leads to a range of mechanical properties relevant to soft tissue engineering as well as highly viable cell-laden gels stable for over one month in culture. STATEMENT OF SIGNIFICANCE: We demonstrate that a PEG crosslinking bioink method can be used with various cytocompatible, covalent cross-linking reactions: Thiol Michael type addition and tetrazine-norbornene click. The ability to vary bioink chemistry expands candidate polymers, and therefore can expedite development of new bioinks from unique polymers. We confirm post-printed cell viability and are the first to probe, in covalently cross-linked inks, how cell viability is impacted by different flow properties (mass flow rate). Finally, we also present PEG cross-linking as a new method of post-printing cross-linking that improves mechanical properties and stability while maintaining cell viability. By varying the cross-linking reaction, this method can be applicable to many types of polymers/inks for easy adoption by others investigating bioinks and hydrogels.

A multimaterial bioink method for 3D printing tunable, cell-compatible hydrogels.

A multimaterial bio-ink method using polyethylene glycol crosslinking is presented for expanding the biomaterial palette required for 3D bioprinting of more mimetic and customizable tissue and organ constructs. Lightly crosslinked, soft hydrogels are produced from precursor solutions of various materials and 3D printed. Rheological and biological characterizations are presented, and the promise of this new bio-ink synthesis strategy is discussed.

Time-resolved small-angle x-ray scattering measurements of a polymer bicontinuous microemulsion structure factor under shear.

In situ synchrotron x-ray scattering is used in conjunction with a novel annular cone and plate shear cell to study the nonequilibrium structure factor of a polymer bicontinuous microemulsion within the flow-gradient plane. At equilibrium the scattering is well described by the Teubner-Strey structure factor. In steady shear, the structure factor becomes highly anisotropic, owing to loss of scattering intensity along the flow direction and growth of intensity in peaks that progressively rotate towards the velocity-gradient direction. These results contrast with the predictions of a time-dependent Landau-Ginzburg model of Pätzold and Dawson, which generally predicts suppression of scattered intensity. The model assumption of a uniform velocity profile at the microemulsion length scale may be inappropriate owing to high viscosity contrast between the constituents of this sample. While the model anticipates a "stress-x-ray" rule, the data do not support its existence in this system. Nevertheless, strong connections do exist between x-ray anisotropy and stress during transient flow inception experiments. These connections break down upon flow cessation, where stress decays much more rapidly than anisotropy in the structure factor. The mechanical response of this sample exhibits a Rouse-like spectrum of relaxation times, whereas the second moment tensor used to characterize anisotropy in the structure factor exhibits nearly single-exponential relaxation. A phenomenological upper-convected-Maxwell/Lodge model for the second moment tensor provides essentially quantitative predictions of the structural response in step strain and oscillatory shear flow at moderate strains, although additional nonlinearity is found at higher strains.

Mussel-inspired histidine-based transient network metal coordination hydrogels.

Transient network hydrogels cross-linked through histidine-divalent cation coordination bonds were studied by conventional rheologic methods using histidine-modified star poly(ethylene glycol) (PEG) polymers. These materials were inspired by the mussel, which is thought to use histidine-metal coordination bonds to impart self-healing properties in the mussel byssal thread. Hydrogel viscoelastic mechanical properties were studied as a function of metal, pH, concentration, and ionic strength. The equilibrium metal-binding constants were determined by dilute solution potentiometric titration of monofunctional histidine-modified methoxy-PEG and were found to be consistent with binding constants of small molecule analogs previously studied. pH-dependent speciation curves were then calculated using the equilibrium constants determined by potentiometric titration, providing insight into the pH dependence of histidine-metal ion coordination and guiding the design of metal coordination hydrogels. Gel relaxation dynamics were found to be uncorrelated with the equilibrium constants measured, but were correlated to the expected coordination bond dissociation rate constants.

X-ray photon correlation spectroscopy during homogenous shear flow.

We report x-ray photon correlation spectroscopy measurements of advective and diffusive dynamics in a dispersion of colloidal particles subjected to homogeneous shear flow in a rotating-disk shear cell. Intensity autocorrelation functions from scattering data collected using homodyne detection respond to the variation in velocity across the scattering volume when the scattering vector has a component parallel to the flow direction. Theoretical expressions for the impact of homogenous shear flow on the correlation function provide a quantitative prediction of the dependence of correlation functions on the scattering vector and shear rate. Under most circumstances, the applied shear deformation dominates the decay of the intensity correlation function. When scattering data are collected perpendicular to the flow direction, it is possible to measure the diffusive dynamics of the particles free from effects of the superimposed shear flow; however, this approach only works below some upper shear rate limit, beyond which data are affected either by shear effects (caused by the finite width of the detector) or by particle transit through the scattering volume.

An apparatus for in situ x-ray scattering measurements during polymer injection molding.

We report a novel instrument for synchrotron-based in situ x-ray scattering measurements during injection molding processing. It allows direct, real-time monitoring of molecular-scale structural evolution in polymer materials undergoing a complex processing operation. The instrument is based on a laboratory-scale injection molding machine, and employs customized mold tools designed to allow x-ray access during mold filling and subsequent solidification, while providing sufficient robustness to withstand high injection pressures. The use of high energy, high flux synchrotron radiation, and a fast detector allows sufficiently rapid data acquisition to resolve time-dependent orientation dynamics in this transient process. Simultaneous monitoring of temperature and pressure signals allows transient scattering data to be referenced to various stages of the injection molding cycle. Representative data on a commercial liquid crystalline polymer, Vectra(R) B950, are presented to demonstrate the features of this apparatus; however, it may find application in a wide range of polymeric materials such as nanocomposites, semicrystalline polymers and fiber-reinforced thermoplastics.

Oral and oropharyngeal perceptions of fluid viscosity across the age span.

Research demonstrates that varying sensory input, including the characteristics of a bolus, changes swallow physiology. Altering the consistency of fluids is a common compensatory technique used in dysphagia management to facilitate change. However, it is not known what variations in viscosity can be perceived in the oral cavity or oropharynx or if age affects oral and oropharyngeal perceptions of fluid viscosity. This study aims to establish the ability of normal adults to perceive fluid viscosity in the oral cavity and oropharynx and to determine if, within this population, there are age-related changes in oral and oropharyngeal perceptions. Sensitivity was established by deriving the exponent for the psychophysical law for fluid viscosity in both the oral cavity and the oropharynx, using modulus-free magnitude estimation with Newtonian fluids of corn syrup and water. Sixty normal volunteers, aged 21-84 years, participated. Results indicate that the exponent for oral perception of fluid viscosity was 0.3298, while for oropharyngeal perception it was 0.3148. Viscosity perception deteriorates with increasing age. Men exhibited a more marked deterioration in sensitivity than women. This study contributes to the literature on oral and oropharyngeal perceptions and on aging. The results provide a basis for work with individuals with dysphagia.

Poly(N-isopropylacrylamide)-based semi-interpenetrating polymer networks for tissue engineering applications. Effects of linear poly(acrylic acid) chains on rheology.

Semi-interpenetrating polymer networks (semi-IPNs), comprised of poly(N-isopropylacrylamide-co-acrylic acid) (p(NIPAAm-co-AAc)) hydrogels and linear p(AAc) chains, were synthesized, and the effects of the p(AAc) chains on semi-IPN rheology were examined. Oscillatory shear rheometry studies were performed and the rheological data were analyzed as a function of temperature, frequency, and p(AAc) chain amount (weight average molecular weight (Mw) 4.5 x 10(5) g/mol). At 22 degrees C, the semi-IPNs, as well as control p(NIPAAm-co-AAc) hydrogels, demonstrated rheological data that were representative of soft, loosely cross-linked solids. Furthermore, only the highest p(AAc) chain amount tested affected the rigidity of the p(NIPAAm-co-AAc)-based semi-IPNs, as compared to the p(NIPAAm-co-AAc) hydrogels. At 37 degrees C, the complex shear moduli (G*) demonstrated by the p(NIPAAm-co-AAc)-based semi-IPNs were significantly greater than G* exhibited by the p(NIPAAm-co-AAc) hydrogels, and the semi-IPN G* values significantly increased with increasing p(AAc) chain amount. These results can be used to develop p(NIPAAm)-based semi-IPNs with tailored mechanical properties that may function as scaffolds in tissue engineering initiatives.

Thermoreversible, epitaxial fcc<-->bcc transitions in block copolymer solutions.

Uncharged block copolymer micelles display thermoreversible transitions between close-packed and bcc lattices for a range of concentration, solvent selectivity, and copolymer composition. Using small-angle x-ray scattering on shear-oriented solutions, highly aligned fcc crystals are seen to transform epitaxially to bcc crystals, with fcc/bcc orientational relationships that are well established in martensitic transformations in metals. The transition is driven by decreasing solvent selectivity with increasing temperature, inducing solvent penetration of the micellar core.