We measured the local glass transition temperature T g(z) of polystyrene (PS) as a function of distance z from a silica substrate with end-grafted chains using fluorescence, where competing effects from the free surface have been avoided to focus only on the influence of the tethered interface. The local T g(z) increase next to the chain-grafted substrate is found to exhibit a maximum increase of 49 ± 2 K relative to bulk at an optimum grafting density that corresponds to the mushroom-to-brush transition regime. This perturbation to the local T g(z) dynamics of the matrix is observed to persist out to a distance z ≈ 100–125 nm for this optimum grafting density before bulk T g is recovered, a distance comparable to that previously observed by Baglay and Roth [J. Chem. Phys. 2017, 146, 203307] for PS next to the higher-T g polymer polysulfone.

Density changes in thin polymer films have long been considered as a possible explanation for shifts in the thickness-dependent glass transition temperature Tg(h) in such nanoconfined systems, given that the glass transition is fundamentally associated with packing frustration during material densification on cooling. We use ellipsometry to compare the temperature-dependent refractive index with decreasing thickness n(h) for supported films of poly(2-vinyl pyridine) (P2VP), poly(methyl methacrylate) (PMMA), and polystyrene (PS), as these polymers have different silica substrate interactions. We observe similar n(h) trends for all three polymers, with near equivalence of P2VP and PS, characterized by a large apparent increase in refractive index for h ≤ 40 nm–65 nm depending on the polymer. Possible sources of molecular dipole orientation within the film are tested by varying molecular weight, polydispersity, chain conformation, and substrate chemistry. Such film inhomogeneities associated with non-uniform polarizability would invalidate the use of homogeneous layer approximations inherent in most thin film analysis methods, which we believe likely explains recent reports of large unphysical increases in film density with decreasing thickness by a variety of different experimental techniques.

Recent studies have measured or predicted thickness-dependent shifts in density or specific volume of polymer films as a possible means of understanding changes in the glass transition temperature Tg(h) with decreasing film thickness with some experimental works claiming unrealistically large (25%-30%) increases in film density with decreasing thickness. Here we use ellipsometry to measure the temperature-dependent index of refraction of polystyrene (PS) films supported on silicon and investigate the validity of the commonly used Lorentz-Lorenz equation for inferring changes in density or specific volume from very thin films. We find that the density (specific volume) of these supported PS films does not vary by more than ±0.4% of the bulk value for film thicknesses above 30 nm, and that the small variations we do observe are uncorrelated with any free volume explanation for the Tg(h) decrease exhibited by these films. We conclude that the derivation of the Lorentz-Lorenz equation becomes invalid for very thin films as the film thickness approaches ∼20 nm, and that reports of large density changes greater than ±1% of bulk for films thinner than this likely suffer from breakdown in the validity of this equation or in the difficulties associated with accurately measuring the index of refraction of such thin films. For larger film thicknesses, we do observed small variations in the effective specific volume of the films of 0.4 ± 0.2%, outside of our experimental error. These shifts occur simultaneously in both the liquid and glassy regimes uniformly together starting at film thicknesses less than ∼120 nm but appear to be uncorrelated with Tg(h) decreases; possible causes for these variations are discussed.

Lysozymes in human urine have crucial clinical significance as an indicator of renal tubular and glomerular diseases. Most lysozyme detection methods rely on the enzyme-linked immunosorbent assay (ELISA), which is usually a tedious procedure. Meanwhile, aptamer sensors and fluorescence-based techniques for lysozyme detection have emerged in recent studies. However, these methods are time-consuming and highly complex in operation, and some even require exorbitant reagents and instruments, which restricts real-time clinical monitoring as diagnostic approaches. Therefore, a rapid and low-cost lysozyme detection method with facile preparation is still in demand for modern precision medicine. Herein, we propose a magnetoelastic (ME) immunosensor for lysozyme detection by detecting changes in resonance frequency under a magnetostrictive effect. The detection system is composed of a magnetoelastic chip with an immobilized lysozyme antibody, a solenoid coil, and a vector network analyzer. Since the ME sensor is ultrasensitive to mass change, the frequency offset caused by mass change can be utilized to detect the content of lysozyme. The immunosensor is evaluated to possess superior sensitivity of 138 Hz/μg mL–1 in terms of the resonance frequency shift (RFS). In addition, our sensor displays an outstanding performance in specificity experiments and shows a relatively lower detection limit (1.26 ng/mL) than other conventional lysozyme detection methods (such as ELISA, chemiluminescence assay, fluorescence, and aptamer biosensors).

Numerous computer simulations have shown that local dynamics associated with the glass transition can be slower next to rough interfaces compared with smooth interfaces. Even though the impact of surface roughness has been frequently considered computationally and theoretically, almost no experimental studies exist investigating these effects. Using a hydrogen fluoride vapor treatment, we created silica substrates with an increase in roughness that left the surface chemistry unchanged. The local glass transition temperature Tg near silica substrates with an increase in roughness was measured using fluorescence, finding an increase in local Tg of 10 K with an increase in the root-mean-square roughness Rrms from 0.5 nm to 11 nm. Characterization of the substrate roughness needed to create an experimental change in local Tg was found to be quite large, leaving the mechanism for this observed behavior uncertain. We discuss possible causes associated with polymer chains being more readily able to make surface contacts and adsorb to roughened interfaces.