Using the Quartz Crystal Microbalance to Monitor the Curing of Drying Oils.

Drying oils such as linseed oil form a polymer network through a complex free-radical polymerization process. We have studied polymerization in this challenging class of polymers using a quartz crystal microbalance (QCM). The QCM is able to measure the evolution of polymer mass and mechanical properties as the oil transitions from a liquid-like to a solid-like state. Measurements using bulk materials and thin films provide information about the initial polymerization phase as well as the evolution of the mass and mechanical properties over the first two years of cure. The temperature-dependent response of the cured linseed oil films was also measured. These results were combined with previously published results obtained from traditional dynamic mechanical analysis to give a unified picture of the properties of these materials across a very broad temperature range.

Tailoring Interactions of Random Copolymer Polyelectrolyte Complexes to Remove Nanoplastic Contaminants from Water.

We investigate the usage of polyelectrolyte complex materials for water remediation purposes, specifically their ability to remove nanoplastics from water, on which there is currently little to no prior research. We demonstrate that oppositely charged random copolymers are effective at quantitatively removing nanoplastic contamination from aqueous solution. The mechanisms underlying this remediation ability are explored through computational simulations, with corroborating quartz crystal microbalance adsorption experiments. We find that hydrophobic nanostructures and interactions likely play an important role.

Crack Surface Analysis of Elastomers Using Transfer Learning.

Cracks that form during fatigue offer critical information regarding the fracture process of the associated material, such as the crack speed, energy dissipation, and material stiffness. Characterization of the surfaces formed after these cracks have propagated through the material can provide important information complementary to other in-depth analyses. However, because of the complex nature of these cracks, their characterization is difficult, and most of the established characterization techniques are inadequate. Recently, Machine Learning techniques are being applied to image-based material science problems in predicting structure-property relations. Convolutional neural networks (CNNs) have proven their capacity on modeling complex and diverse images. The downside of CNNs for supervised learning is that that they require large amounts of training data. One work-around is using a pre-trained model, i.e., transfer learning (TL). However, TL models cannot be used directly without modification. In this paper, to use TL for crack surface feature-property mapping, we propose to prune the pre-trained model to retain the weights of the first several convolutional layers. Those layers are then used to extract relevant underlying features from the microstructural images. Next, principal component analysis (PCA) is used to further reduce the feature dimension. Finally, the extracted crack features together with the temperature effect are correlated with the properties of interest using regression models. The proposed approach is first tested on artificial microstructures created by spectral density function reconstruction. It is then applied to experimental data of silicone rubbers. With the experimental data, two analyses are performed: (i) analysis of the correlation of the crack surface feature and material property and (ii) predictive model for property estimation, whereby the experiments can be potentially replaced altogether.

Quantitative high-throughput measurement of bulk mechanical properties using commonly available equipment.

Machine learning approaches have introduced an urgent need for large datasets of materials properties. However, for mechanical properties, current high-throughput measurement methods typically require complex robotic instrumentation, with enormous capital costs that are inaccessible to most experimentalists. A quantitative high-throughput method using only common lab equipment and consumables with simple fabrication steps is long desired. Here, we present such a technique that can measure bulk mechanical properties in soft materials with a common laboratory centrifuge, multiwell plates, and microparticles. By applying a homogeneous force on the particles embedded inside samples in the multiwell plate using centrifugation, we show that our technique measures the fracture stress of gels with similar accuracy to a rheometer. However, our method has a throughput on the order of 103 samples per run and is generalizable to virtually all soft material systems. We hope that our method can expedite materials discovery and potentially inspire the future development of additional high-throughput characterization methods.

In vitro assessment of varying peptide surface density on the suppression of angiogenesis by micelles displaying αvß3 blocking peptides.

Ligand targeted therapy (LTT) is a precision medicine strategy that can selectively target diseased cells while minimizing off-target effects on healthy cells. Integrin-targeted LTT has been developed recently for angiogenesis-related diseases. However, the clinical success is based on the optimal design of the nanoparticles for inducing receptor clustering within the cell membrane. The current study focused on determining the surface density of Ser-Asp-Val containing anti-integrin heptapeptide on poly (ethylene glycol)-b-poly(propylene sulfide) micelles (MC) required for anti-angiogenic effects on HUVECs. Varying peptide density on PEG-b-PPS/Pep-PA MCs (Pep-PA-Peptide-palmitoleic acid) was used in comparison to a random peptide (SGV) and cRGD (cyclic-Arginine-Glycine-Aspartic acid) construct at 5%-density on MCs. Immunocytochemistry using CD51/CD31 antibody was performed to study the integrin blocking by MCs. In addition, the expression of VWF and PECAM-1, cell migration and tube formation was evaluated in the presence of PEG-b-PPS/Pep-PA MCs. The results show PEG-b-PPS/SDV-PA MCs with 5%-peptide density to achieve significantly higher αvß3 blocking compared to random peptide as well as cRGD. In addition, αvß3 blocking via MCs further reduced the expression of vWF and PECAM-1 angiogenesis protein expression in HUVECs. Although a significant level of integrin blocking was observed for 1%-peptide density on MCs, the cell migration and tube formation were not significantly affected. In conclusion, the results of this study demonstrate that the peptide surface density on PEG-b-PPS/Pep-PA MCs has a significant impact in integrin blocking as well as inhibiting angiogenesis during LTT. The outcomes of this study provides insight into the design of ligand targeted nanocarriers for various disease conditions.

Sterilizable and Reusable UV-Resistant Graphene-Polyurethane Elastomer Composites.

Shortages of personal protective equipment (PPE) at the start of the COVID-19 pandemic caused medical workers to reuse medical supplies such as N95 masks. While ultraviolet germicidal irradiation (UVGI) is commonly used for sterilization, UVGI can also damage the elastomeric components of N95 masks, preventing effective fit and thus weakening filtration efficacy. Although PPE shortage is no longer an acute issue, the development of sterilizable and reusable UV-resistant elastomers remains of high interest from a long-term sustainability and health perspective. Here, graphene nanosheets, produced by scalable and sustainable exfoliation of graphite in ethanol using the polymer ethyl cellulose (EC), are utilized as UV-resistant additives in polyurethane (PU) elastomer composites. By increasing the graphene/EC loading up to 1 wt %, substantial UV protection is imparted by the graphene nanosheets, which strongly absorb UV light and hence suppress photoinduced degradation of the PU matrix. Additionally, graphene/EC provides mechanical reinforcement, such as increasing Young's modulus, elongation at break, and toughness, with negligible changes following UV exposure. These graphene/EC-PU composites remain mechanically robust over at least 150 sterilization cycles, enabling safe reuse following UVGI. Beyond N95 masks, these UVGI-compatible graphene/EC-PU composites have potential utility in other PPE applications to address the broader issue of single-use waste.

High-Throughput Screening Test for Adhesion in Soft Materials Using Centrifugation.

High-throughput screening of mechanical properties can transform materials science research by both aiding in materials discovery and developing predictive models. However, only a few such assays have been reported, requiring custom or expensive equipment, while the mounting demand for enormous data sets of materials properties for predictive models is unfulfilled by the current characterization throughput. We address this problem by developing a high-throughput colorimetric adhesion screening method using a common laboratory centrifuge, multiwell plates, and microparticles. The technique uses centrifugation to apply a homogeneous mechanical detachment force across individual formulations in a multiwell plate. We also develop a high-throughput sample deposition method to prepare films with uniform thickness in each well, minimizing well-to-well variability. After establishing excellent agreement with the well-known probe tack adhesion test, we demonstrate the consistency of our method by performing the test on a multiwell plate with two different formulations in an easily discernible pattern. The throughput is limited only by the number of wells in the plates, easily reaching 103 samples/run. With its simplicity, low cost, and large dynamic range, this high-throughput method has the potential to change the landscape of adhesive material characterization.

Exploring the effect of humidity on thermoplastic starch films using the quartz crystal microbalance.

The quartz crystal microbalance (QCM) is used as a non-destructive and efficient characterization tool for thin thermoplastic starch (TPS) films. Thin TPS films (1-2 µm) were prepared with 30% (w/w starch) plasticizers using either glycerol or an ionic liquid, 1-ethyl-3-methylimidiazolium acetate ([emim+][Ac-]), as the plasticizer. The differences in the mechanical properties and environmental effects on the plasticized TPS films were explored. The modulus of starch-glycerol films was higher than starch-[emim+][Ac-], consistent with literature data and bulk AFM measurements, likely due to superior plasticization by the ionic liquid. The starch-[emim+][Ac-] films were shown to have relative stable properties at low humidity that may be due to some antiplasticization effects at low water content despite absorbing more water than starch-glycerol films at higher humidity.

Processing Polyelectrolyte Complexes with Deep Eutectic Solvents.

Polyelectrolyte complexes (PECs) formed from mixtures of polycations and polyanions are useful in a variety of applications and can be processed by the addition of salt. Salt mediates the ionic interactions within the polyelectrolyte complexes, with appropriately chosen salts enabling complete dissolution of solid PEC in aqueous media. Substantial complications arise from the crystallization of the salt during subsequent processing steps. Here we show that appropriately chosen noncrystallizing deep eutectic solvents can be used to process solid PECs. Mixtures of ethylene glycol and guanidine thiocyanate are used for a particularly effective deep eutectic solvent. The phase behaviors of this deep eutectic system and of its mixtures with a model polyelectrolyte complex were quantified.

Functionalizing a Polyelectrolyte Complex with Chitosan Derivatives to Tailor Membrane Surface Properties.

Polyelectrolyte complex (PEC) materials show promise in the development of tunable membranes for aqueous and organic solvent separations, as well as in the creation of surface layers for fouling control. In this study, we developed a polyelectrolyte complex (PEC) functionalized by negatively charged carboxymethyl chitosan (CMC-) and positively charged quaternized chitosan (QC+) to tailor its surface properties and antibacterial efficacy. CMC- and QC+ were prepared and characterized using FT-IR and 1H NMR, which confirmed the presence of the carboxymethyl group and trimethylammonium group in CMC- and QC+ with 65.6% and 83.9% substitution, respectively. The CMC- functionalized PEC (CMC-/PEC) and QC+ functionalized PEC materials (QC+/PEC) were evaluated for their stability in water, resistance to organic and inorganic adsorption, and antibacterial action against a model microorganism, Pseudomonas putida. The results showed no release of chitosan derivatives after adsorption, and CMC-/PEC and QC+/PEC exhibited charge-based, selective repulsion of model organic and inorganic substances. Moreover, the functionalized PEC surfaces displayed lower bacterial attachment due to their smoother surfaces as compared to the bare ceramic membrane and their antimicrobial properties. Among the PEC samples, CMC-/PEC had the lowest cell attachment, while QC+/PEC showed the highest attachment due to electrostatic attraction. The ceramic and bare PEC surfaces were negligibly bactericidal, while cell viability decreased to 34.4 ± 10.2% and 30.6 ± 8.2% with the CMC-/PEC and QC+/PEC surfaces, respectively. In the filtration experiments, the unmodified PEC and CMC-/PEC showed lower rates of flux decline due to organic fouling than did the bare ceramic or QC+/PEC due to electrostatic repulsion. Furthermore, PECs as protective layers promoted much higher flux recoveries than simply backwashing the uncoated membranes. This surface tunability, then, enhances the potential of PECs either as fouling resistant materials or as a method to create a sacrificial, protective layer on surfaces that once fouled can be dissolved and re-established.

High-Fidelity Hydrogel Thin Films Processed from Deep Eutectic Solvents.

Polyampholyte (PA) hydrogels are a fascinating class of soft materials that can exhibit high toughness while retaining self-healing characteristics. This behavior results from the random distribution of oppositely charged monomers along the polymer chains that form transient bonds with a range of bond strengths. PAs can be dissolved in aqueous salt solutions and then recast via immersion precipitation, making them particularly useful as surface coatings in biomedical applications. Moreover, this immersion precipitation technique allows these PA hydrogels to be fabricated into films less than 100 nm. One critical challenge to this aqueous processing method is the recrystallization of the salt upon water evaporation. Such recrystallization can disrupt the hydrogel morphology especially in thin films. In this study, a deep eutectic solvent (DES) formed from urea and choline chloride was used to dissolve PAs made from p-styrenesulfonic acid sodium salt and 3-(methacryloylamino)propyl trimethylammonium chloride. This DES has a freezing point of 12 °C, allowing it to remain stable and liquid-like at room temperatures. Thus, these PAs can be processed in DES solutions, without this issue of recrystallization and with simple methods such as spin coating and dip coating. These methods allow these hydrogels to be used in thin (<100 nm)-film coating applications. Finally, the complete miscibility of DES in water allows a wider range of one-phase compositions and expands the processing window of these polyampholyte materials.

Tough, Transparent, Photocurable Hybrid Elastomers.

We investigated polydimethylsiloxane/poly(methyl methacrylate) (PDMS/PMMA) interpenetrating polymer networks (IPNs) by both sequential and simultaneous syntheses. In the sequential IPN, the PDMS network was first thermally cured after which methyl methacrylate was swelled in and UV photopolymerized in situ. The simultaneous IPN consists of a one-pot, single-step UV cure of both components. Pure shear fracture and tensile tests were used to extract the Young's modulus, critical fracture strain, and fracture energy of the materials at varying PMMA fractions (up to 50 wt %). At high PMMA fractions, a maximum increase in Young's modulus (42×) and fracture energy (21×) was observed with little sacrifice in the optical properties and the extensibility of notched samples. The Krieger-Dougherty model for particle reinforcement was fit to the modulus data as a function of the PMMA fraction and showed good agreement. The optical properties and microstructure of the IPNs were investigated by UV-visible light transmission, small-angle X-ray scattering (SAXS), and atomic force microscopy (AFM). As the weight fraction of PMMA increased, the simultaneous IPN became less transparent, while the sequential material showed the opposite trend. In the sequential IPN, the minority phase size decreased with increasing PMMA fraction, while it was constant for the simultaneous IPN. Therefore, it was concluded that the sequential IPN transparency is controlled by the size of the PMMA domains, but the simultaneous IPN transparency is controlled by the PMMA fraction. SAXS and AFM also showed evidence of bicontinuous network formation in the simultaneous IPN, which may affect the optical and mechanical properties.

Control over electroless plating of silver on silica nanoparticles with sodium citrate.

We describe the use of citrate to control the electroless plating of silver metal on silica nanoparticles. We find that the incorporation of relatively small amounts of citrate during the reduction of the Tollens' reagent in the presence of sensitized silica nanoparticles induces a continuous transition from conformal to raspberry particle coatings. This transition is dependent on both the citrate concentration and the silver precursor concentration. We characterize this transition using electron microscopy and spectroscopy and use these results to confirm citrate's ability to cap and restrict silver growth. We compliment these structural measurements with in-situ quartz crystal microbalance experiments to quantify citrate's role as a complexing agent to slow silver reduction kinetics. These results confirm citrate's dual role in controlling the morphology of silver deposits produced in this work.

Investigations of the high-frequency dynamic properties of polymeric systems with quartz crystal resonators.

Opportunities arising from the use of the rheometric quartz crystal microbalance (RheoQCM) as a fixed frequency rheometer operating at 15 MHz are discussed. The technique requires the use of films in a specified thickness range that depends on the mechanical properties of the material of interest. A regime map quantifying the appropriate thicknesses is developed, based on the properties of a highly crosslinked epoxy sample that is representative of a broad class of polymeric materials. Relative errors in the measured film properties are typically in the range of several percent or less and are minimized by using a power law model to relate the rheological properties at two different resonant harmonics of the quartz crystal. Application of the RheoQCM technique is illustrated by measuring the temperature- and molecular weight-dependent properties of polystyrene and poly(methyl methacrylate) in the vicinity of the glass transition.

High Density Display of an Anti-Angiogenic Peptide on Micelle Surfaces Enhances Their Inhibition of αvß3 Integrin-Mediated Neovascularization In Vitro.

Diabetic retinopathy (DR), Retinopathy of Pre-maturity (ROP), and Age-related Macular Degeneration (AMD) are multifactorial manifestations associated with abnormal growth of blood vessels in the retina. These three diseases account for 5% of the total blindness and vision impairment in the US alone. The current treatment options involve heavily invasive techniques such as frequent intravitreal administration of anti-VEGF (vascular endothelial growth factor) antibodies, which pose serious risks of endophthalmitis, retinal detachment and a multitude of adverse effects stemming from the diverse physiological processes that involve VEGF. To overcome these limitations, this current study utilizes a micellar delivery vehicle (MC) decorated with an anti-angiogenic peptide (aANGP) that inhibits αvß3 mediated neovascularization using primary endothelial cells (HUVEC). Stable incorporation of the peptide into the micelles (aANGP-MCs) for high valency surface display was achieved with a lipidated peptide construct. After 24 h of treatment, aANGP-MCs showed significantly higher inhibition of proliferation and migration compared to free from aANGP peptide. A tube formation assay clearly demonstrated a dose-dependent angiogenic inhibitory effect of aANGP-MCs with a maximum inhibition at 4 µg/mL, a 1000-fold lower concentration than that required for free from aANGP to display a biological effect. These results demonstrate valency-dependent enhancement in the therapeutic efficacy of a bioactive peptide following conjugation to nanoparticle surfaces and present a possible treatment alternative to anti-VEGF antibody therapy with decreased side effects and more versatile options for controlled delivery.

Sample Preparation in Quartz Crystal Microbalance Measurements of Protein Adsorption and Polymer Mechanics.

In this study, we present various examples of how thin film preparation for quartz crystal microbalance experiments informs the appropriate modeling of the data and determines which properties of the film can be quantified. The quartz crystal microbalance offers a uniquely sensitive platform for measuring fine changes in mass and/or mechanical properties of an applied film by observing the changes in mechanical resonance of a quartz crystal oscillating at high frequency. The advantages of this approach include its experimental versatility, ability to study changes in properties over a wide range of experimental time lengths, and the use of small sample sizes. We demonstrate that, based on the thickness and shear modulus of the layer deposited on the sensor, we can acquire different information from the material. Here, this concept is specifically exploited to display experimental parameters resulting in mass and viscoelastic calculations of adsorbed collagen on gold and polyelectrolyte complexes during swelling as a function of salt concentration.

Self-Assembly of Charge-Containing Copolymers at the Liquid-Liquid Interface.

Quantitatively understanding the self-assembly of amphiphilic macromolecules at liquid-liquid interfaces is a fundamental scientific concern due to its relevance to a broad range of applications including bottom-up nanopatterning, protein encapsulation, oil recovery, drug delivery, and other technologies. Elucidating the mechanisms that drive assembly of amphiphilic macromolecules at liquid-liquid interfaces is challenging due to the combination of hydrophobic, hydrophilic, and Coulomb interactions, which require consideration of the dielectric mismatch, solvation effects, ionic correlations, and entropic factors. Here we investigate the self-assembly of a model block copolymer with various charge fractions at the chloroform-water interface. We analyze the adsorption and conformation of poly(styrene)-block-poly(2-vinylpyridine) (PS-b-P2VP) and of the homopolymer poly(2-vinylpyridine) (P2VP) with varying charge fraction, which is controlled via a quaternization reaction and distributed randomly along the backbone. Interfacial tension measurements show that the polymer adsorption increases only marginally at low charge fractions (<5%) but increases more significantly at higher charge fractions for the copolymer, while the corresponding randomly charged P2VP homopolymer analogues display much more sensitivity to the presence of charged groups. Molecular dynamics (MD) simulations of the experimental systems reveal that the diblock copolymer (PS-b-P2VP) interfacial activity could be mediated by the formation of a rich set of complex interfacial copolymer aggregates. Circular domains to elongated stripes are observed in the simulations at the water-chloroform interface as the charge fraction increases. These structures are shown to resemble the spherical and cylindrical helicoid structures observed in bulk chloroform as the charge fraction increases. The self-assembly of charge-containing copolymers is found to be driven by the association of the charged component in the hydrophilic block, with the hydrophobic segments extending away from the hydrophilic cores into the chloroform phase.

Versatile and High-Throughput Polyelectrolyte Complex Membranes via Phase Inversion.

High-flux filtration membranes constructed through scalable and sustainable methods are desirable for energy-efficient separations. Often, these criteria are difficult to be reconciled with one another. Polymeric membranes can provide high flux but frequently involve organic solvents in processing steps. Solubility of many polymeric membranes in organic media also restricts their implementation in solvent filtration. In the present work, we report a simple and high-throughput aqueous processing approach for polyelectrolyte complex (PEC) membranes with controllable porosity and stability in various aqueous and organic environments. PECs are materials composed of oppositely charged polymer chains that can form solids in aqueous environments, yet which can be dissolved in very specific salt solutions capable of breaking the interpolymer ion pairs. By exploiting the salt-induced dissolution and subsequent reformation of the complex, nano- to microporous films are rapidly synthesized which resemble membranes obtained through conventional solvent-phase inversion techniques. PECs remain stable in organic solvents because of the low dielectric constant of the environment, which enhances electrostatic interactions, making them suitable for a wide range of water and solvent filtration applications. Here, we elucidate how the polymer-phase behavior can be manipulated to exercise morphological control, test membrane performance for water and solvent filtration, and quantify the mechanical stability of PECs in relevant conditions.

Guanidinium Can Break and Form Strongly Associating Ion Complexes.

Guanidinium is one of nature's strongest denaturants and is also a motif that appears in several interfacial contexts such as the RGD sequence involved in cell adhesion, cell penetrating peptides, and antimicrobial molecules. It is important to quantify the origin of guanidinium's ion-specific interactions so that its unique behavior may be exploited in synthetic applications. The present work demonstrates that guanidinium ions can both break and form strongly associating ion complexes in a context-dependent way. These insights into guanidinium's behavior are elucidated using polyelectrolyte complexes (PECs), where interpolymer ion pairs between oppositely charged polymers play an important role in determining material stability. Different polycation-polyanion combinations can span a large range of association affinities, where more strongly associating complexes can remain insoluble in concentrated salt solutions and in extreme pH conditions. This high stability is desirable in several application contexts for PECs, but also renders them challenging to process and, therefore, to study since they cannot be dissolved into polymer solutions. Here we demonstrate that guanidinium salts are very effective in dissolving the poly(styrenesulfonate)/poly(allylamine) (PSS:PAH) complex, which has one of the highest reported polycation-polyanion association affinities. We also demonstrate the importance of charge identity in complexation phenomena by functionalizing guanidinium directly into poly(allylamine), resulting in a complex that remains stable under highly denaturing conditions. The model system of PSS:PAH is used to glean insights into guanidinium's denaturing activity, as well as to broadly comment on the nature of ion-specific interactions in charged macromolecules.

Sustained micellar delivery via inducible transitions in nanostructure morphology.

Nanocarrier administration has primarily been restricted to intermittent bolus injections with limited available options for sustained delivery in vivo. Here, we demonstrate that cylinder-to-sphere transitions of self-assembled filomicelle (FM) scaffolds can be employed for sustained delivery of monodisperse micellar nanocarriers with improved bioresorptive capacity and modularity for customization. Modular assembly of FMs from diverse block copolymer (BCP) chemistries allows in situ gelation into hydrogel scaffolds following subcutaneous injection into mice. Upon photo-oxidation or physiological oxidation, molecular payloads within FMs transfer to micellar vehicles during the morphological transition, as verified in vitro by electron microscopy and in vivo by flow cytometry. FMs composed of multiple distinct BCP fluorescent conjugates permit multimodal analysis of the scaffold's non-inflammatory bioresorption and micellar delivery to immune cell populations for one month. These scaffolds exhibit highly efficient bioresorption wherein all components participate in retention and transport of therapeutics, presenting previously unexplored mechanisms for controlled nanocarrier delivery.