Di-Tyrosine Cross-Linking of Elastin-Like Polypeptides through Ruthenium Photoreaction To Form Scaffolds: Fine Tuning Mechanical Properties and Improving Cytocompatibility.

Ensuring that the mechanical properties of tissue engineering scaffolds align with those of the target tissues is crucial for their successful integration and functional performance. Tyrosine-tyrosine cross-links are found in nature in numerous proteins including resilin that exhibit enhanced toughness and energy storage capacity. Herein, we investigated the potential of tuning the mechanical properties of scaffolds made from elastin-like polypeptides (ELPs) containing tyrosine residues.

Challenging the Kauzmann paradox using an ultra-stable perfluoropolymer glass with a fictive temperature below the dynamic VFT temperature.

Ultra-stable fluoropolymer glasses were created using vacuum pyrolysis deposition that show large fictive temperature T reductions relative to the glass transition temperature T of the rejuvenated material. T was also found to be 11.4 K below the dynamic VFT temperature T.

Prediction of the Synergistic Glass Transition Temperature of Coamorphous Molecular Glasses Using Activity Coefficient Models.

The glass transition temperature () of a binary miscible mixture of molecular glasses, termed a coamorphous glass, is often synergistically increased over that expected for an athermal mixture due to the strong interactions between the two components. This synergistic interaction is particularly important for the formulation of coamorphous pharmaceuticals since the molecular interactions and resulting strongly impact stability against crystallization, dissolution kinetics, and bioavailability. Current models that describe the composition dependence of for binary systems, including the Gordon-Taylor, Fox, Kwei, and Braun-Kovacs equations, fail to describe the behavior of coamorphous pharmaceuticals using parameters consistent with experimental Δ and Δα.

Isothermal Crystallization and Time-Temperature Transformation of Amorphous Nifedipine: A Case of Polymorphism Formation and Conversion.

Crystallization of active pharmaceutical ingredients (APIs) from the supercooled liquid state is an important issue in determining the stability of amorphous pharmaceutical dispersions. In the present study, the isothermal crystallization from the supercooled liquid state of the pharmaceutical compound nifedipine was investigated by both rheological and differential scanning calorimetry (DSC) measurements, and the crystallization kinetics was fitted to the Johnson-Mehl-Avrami (JMA) equation. Both the crystallization induction time and completion time from the two methods were used to construct the time-temperature-transformation (TTT) diagram for nifedipine.

Mechanical spectral hole burning in glassy polymers-Investigation of polycarbonate, a material with weak β-relaxation.

Mechanical spectral hole burning (MSHB) has been used to investigate the nonlinear dynamics in polymers, ranging from melts, solutions, block co-polymers, and glasses. MSHB was developed as an analog to the dielectric spectral hole burning method, which is not readily applicable in polymers due to weak dielectric response. While similar holes were observed in both mechanical and dielectric hole burning, the interpretations were different.

Isothermal Crystallization Monitoring and Time-Temperature-Transformation of Amorphous GDC-0276: Differential Scanning Calorimetric and Rheological Measurements.

Cold crystallization of amorphous pharmaceuticals is an important aspect in the search to stabilize amorphous or glassy compounds used as amorphous pharmaceutical ingredients (APIs). In the present work, we report results for the isothermal crystallization of the compound GDC-0276 based on differential scanning calorimetric and rheometric measurements. The kinetics of isothermal crystallization from the induction time to the completion of crystallization can be described by the classic Johnson-Mehl-Avrami (JMA) equation.

"Dense diffusion" in colloidal glasses: short-ranged long-time self-diffusion as a mechanistic model for relaxation dynamics.

Despite decades of exploration of the colloidal glass transition, mechanistic explanation of glassy relaxation processes has remained murky. State-of-the-art theoretical models of the colloidal glass transition such as random first order transition theory, active barrier hopping theory, and non-equilibrium self-consistent generalized Langevin theory assert that relaxation reported at volume fractions above the ideal mode coupling theory prediction φg,MCT requires some sort of activated process, and that cooperative motion plays a central role. However, discrepancies between predicted and measured values of φg and ambiguity in the role of cooperative dynamics persist.

Mechanical hole-burning spectroscopy of PMMA deep in the glassy state.

Nonlinear mechanics of soft materials such as polymer melts or polymer solutions are frequently investigated by Large Amplitude Oscillatory Shear (LAOS) spectroscopy tests. Less work has been reported on the characterization of the nonlinear viscoelastic properties of glassy polymers within a similar framework. In the present work, we use an extension of LAOS, i.

Effect of molecular architecture on ring polymer dynamics in semidilute linear polymer solutions.

Understanding the dynamics of ring polymers is a particularly challenging yet interesting problem in soft materials. Despite recent progress, a complete understanding of the nonequilibrium behavior of ring polymers has not yet been achieved. In this work, we directly observe the flow dynamics of DNA-based rings in semidilute linear polymer solutions using single molecule techniques.

Physical aging and compressed exponential behaviors in a model soft colloidal system.

Diffusing wave spectroscopy (DWS)-based micro-rheology has been used in different optical geometries (backscattering and transmission) as well as different sample thicknesses in order to probe system dynamics at different length scales [D. J. Pine, D.

Nanoconfinement Effects on the Glass Transition and Crystallization Behaviors of Nifedipine.

The impact of nanoconfinement on the crystallization and glass transition behaviors of nifedipine (NIF) has been investigated using differential scanning calorimetry. Nanoconfinement was provided by imbibing the NIF into a porous medium (controlled pore glass, CPG), and results were compared with the unconfined bulk material. Consistent with previous results from the literature, both glass transition temperature T and melting temperature T decrease with decreasing pore size.

Testing the paradigm of an ideal glass transition: Dynamics of an ultrastable polymeric glass.

A major challenge to understanding glass-forming materials is obtaining equilibrium data far below the laboratory glass transition temperature . The challenge arises because it takes geologic aging times to achieve the equilibrium glassy state when temperatures are well below . Here, we finesse this problem through measurements on an ultrastable amorphous Teflon with fictive temperature near to its Kauzmann temperature .

Mechanical spectral hole burning of an entangled polymer solution in the stress-controlled domain.

Nonresonant spectral hole burning has proven to be a versatile method to characterize the dynamics of complex fluids, including polymers. Early work focused on dielectric susceptibility measurements in glass forming liquids, while recent work from our lab used mechanical viscoelastic measurements to investigate polymer melts and solutions. While the observed results were similar, the interpretations were different, with the former being interpreted by attributing the "holes" in the response as being due to dynamic heterogeneity in the system that is related to the glass or other transition, while the latter was interpreted in a way that suggested that the observed holes depend on the type of dynamics (Rouse, terminal, etc.

Isochoric structural recovery in molecular glasses and its analog in colloidal glasses.

Concentrated colloidal dispersions have been regarded as models for molecular glasses. One of the many ways to compare the behavior in these two different systems is by comparing the structural recovery or the physical aging behavior. However, recent investigations from our group to examine structural recovery in thermosensitive colloidal dispersions have shown contrasting results between the colloidal and the molecular glasses.

Soft matter: rubber and networks.

Rubber networks are important and form the basis for materials with properties ranging from rubber tires to super absorbents and contact lenses. The development of the entropy ideas of rubber deformation thermodynamics provides a powerful framework from which to understand and to use these materials. In addition, swelling of the rubber in the presence of small molecule liquids or solvents leads to materials that are very soft and 'gel' like in nature.

Long-term aging behaviors in a model soft colloidal system.

Colloidal and molecular systems share similar behaviors near to the glass transition volume fraction or temperature. Here, aging behaviors after volume fraction up-jump (induced by performing temperature down-jumps) conditions for a PS-PNIPAM/AA soft colloidal system were investigated using light scattering (diffusing wave spectroscopy, DWS). Both aging responses and equilibrium dynamics were investigated.

Molecular mobility in glassy dispersions.

Dielectric spectroscopy was used to characterize the structural relaxation in pharmaceutical dispersions containing nifedipine (NIF) and either poly(vinyl) pyrrolidone (PVP) or hydroxypropyl methylcellulose acetate succinate (HPMCAS). The shape of the dielectric response (permittivity versus log time) curve was observed to be independent of temperature. Thus, for the pure NIF as well as the dispersions, the validity of the time-temperature superposition principle was established.

Dynamic and temperature dependent response of physical vapor deposited Se in freely standing nanometric thin films.

Here, we report results from an investigation of nano-scale size or confinement effects on the glass transition and viscoelastic properties of physical vapor deposited selenium films. The viscoelastic response of freely standing Se films was determined using a biaxial membrane inflation or bubble inflation method [P. A.

Physical aging and structural recovery in a colloidal glass subjected to volume-fraction jump conditions.

Three important kinetic phenomena have been cataloged by Kovacs in the investigation of molecular glasses during structural recovery or physical aging. These are responses to temperature-jump histories referred to as intrinsic isotherms, asymmetry of approach, and memory effect. Here we use a thermosensitive polystyrene-poly (N-isopropylacrylamide)-poly (acrylic acid) core-shell particle-based dispersion as a colloidal model and by working at a constant number concentration of particles we use temperature changes to create volume-fraction changes.

Correlation between Molecular Mobility and Physical Stability in Pharmaceutical Glasses.

We investigated a possible correlation between molecular mobility and physical stability in glassy celecoxib and indomethacin and identified the specific mobility mode responsible for physical instability (crystallization). In the glassy state, because the structural relaxation times are very long, the measurement was enabled by time domain dielectric spectroscopy. However, the local motions in the glassy state were characterized by frequency domain dielectric spectroscopy.

Comparison of the physical aging behavior of a colloidal glass after shear melting and concentration jumps.

Colloidal systems are considered good models of molecular glasses and we further explore the range of validity of this paradigm using a thermosensitive core-shell particle dispersion to study the aging response of a colloidal glass subsequent to both shear-melting and temperature (concentration)-jump perturbations in the vicinity of the glass transition concentration or temperature. Sequential creep experiments were used to probe the different aging responses of the system. The colloidal glass displays aging behavior after both types of perturbation and our results indicate that this colloidal glass is similar to a molecular glass, in that shift rates are found to be below unity and to decrease towards zero as the glass temperature (or concentration) is approached as temperature increases.

Dynamics of a thermo-responsive microgel colloid near to the glass transition.

In a previous study, we used diffusing wave spectroscopy (DWS) to investigate the aging signatures of a thermo-sensitive colloidal glass and compared them with those of molecular glasses from the perspective of the Kovacs temperature-jump, volume recovery experiments [X. Di, K. Z.