Surface Force Measurements of Mussel-Inspired Pressure-Sensitive Adhesives.

Translating fundamental studies of marine mussel adhesion into practical mussel-inspired wet adhesives remains an important technological challenge. To adhere, mussels secrete adhesive proteins rich in the catecholic amino acid 3,4-dihydroxyphenylalanine (Dopa) and positively charged lysine. Consequently, numerous synthetic adhesives incorporating catecholic and cationic functionalities have been designed. However, despite widespread research, uncertainties remain about the optimal design of synthetic mussel-inspired adhesives. Here, we present a study of the adhesion of mussel-inspired pressure-sensitive adhesives. We explore the effects of catechol content, molecular architecture, and solvent quality on pressure-sensitive adhesive (PSA) adhesion and cohesion measured in a surface forces apparatus. Our findings demonstrate that the influence of catechol content depends on the choice of solvent and that adhesive performance is dictated by film composition rather than molecular architecture. Our results also highlight the importance of electrostatic and hydrophobic interactions for adhesion and cohesion in aqueous environments. Together, our findings contribute to an improved understanding of the interplay between materials chemistry, environmental conditions, and adhesive performance to facilitate the design of bioinspired wet adhesives.

Electropolymerized-molecularly imprinted polymers (E-MIPS) as sensing elements for the detection of dengue infection.

A straightforward in situ detection method for dengue infection was demonstrated through the molecular imprinting of a dengue nonstructural protein 1 (NS1) epitope into an electropolymerized molecularly imprinted polyterthiophene (E-MIP) film sensor. The key enabling step in the sensor fabrication is based on an epitope imprinting strategy, in which short peptide sequences derived from the original target molecules were employed as the main template for detection and analysis. The formation of the E-MIP sensor films was facilitated using cyclic voltammetry (CV) and monitored in situ by electrochemical quartz crystal microbalance (EC-QCM). Surface properties were analyzed using different techniques including atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and polarization modulation-infrared reflection-adsorption (PM-IRRAS). The standard calibration curve (R = 0.9830) was generated for the detection of the epitope, Ac-VHTWTEQYKFQ-NH2, with a linear range of 0.2 to 30 µg/mL and detection limit of 0.073 µg/mL. A separate calibration curve (R = 0.9786) was obtained using spiked buffered solutions of dengue NS1 protein, which resulted in a linear range of 0.2 to 10 µg/mL and a detection limit of 0.056 µg/mL. The fabricated E-MIP sensor exhibited long-term stability, high sensitivity, and good selectivity towards the targeted molecules. These results indicated that the formation of the exact and stable cavity imprints in terms of size, shape, and functionalities was successful. In our future work, we aim to use our E-MIP sensors for NS1 detection in real-life samples such as serum and blood.

A Modular Strategy for Functional Pressure Sensitive Adhesives.

A modular approach to synthesizing functional pressure sensitive adhesives (PSAs) was introduced, wherein a modifiable acrylic PSA copolymer was synthesized by copolymerizing common PSA monomers with 6 mol % glycidyl methacrylate, allowing for subsequent functional group modification via the pendant epoxide functionality. This postmodification technique has the advantage of allowing the installation of a variety of functional groups relevant to adhesion, without variation of molecular weight. Because comparisons of cohesive and adhesive performance of candidate PSAs can be complicated by molecular weight differences, this strategy simplifies direct comparisons of the effects of functional groups on performance. As a proof of concept, a mussel-inspired catecholic PSA was synthesized by postreaction of the epoxide scaffold polymer with a thiol-modified catechol, allowing the effect of catechol on underlying structure-property relationships to be determined without variation in molecular weight. The mechanical performance of catecholic PSA was compared to relevant control PSAs by using industry-standard 180° peel and static shear tests, revealing an increase in peel strength achieved through catechol modification. Moreover, we observed an unexpected enhancement in PSA cohesive strength attributed to oxidation of catechol, which cannot be attributed to differences in molecular weight, a common source of changes in PSA cohesive strength.

Cooperativity of Catechols and Amines in High-Performance Dry/Wet Adhesives.

The outstanding adhesive performance of mussel byssal threads has inspired materials scientists over the past few decades. Exploiting the amino-catechol synergy, polymeric pressure-sensitive adhesives (PSAs) have now been synthesized by copolymerizing traditional PSA monomers, butyl acrylate and acrylic acid, with mussel-inspired lysine- and aromatic-rich monomers. The consequences of decoupling amino and catechol moieties from each other were compared (that is, incorporated as separate monomers) against a monomer architecture in which the catechol and amine were coupled together in a fixed orientation in the monomer side chain. Adhesion assays were used to probe performance at the molecular, microscopic, and macroscopic levels by a combination of AFM-assisted force spectroscopy, peel and static shear adhesion. Coupling of catechols and amines in the same monomer side chain produced optimal cooperative effects in improving the macroscopic adhesion performance.

Enhanced Adhesion and Cohesion of Bioinspired Dry/Wet Pressure-Sensitive Adhesives.

The byssus-mediated adhesion of marine mussels is a widely mimicked system for robust adhesion in both dry and wet conditions. Mussel holdfasts are fabricated from proteins that contain a significant amount of the unique catecholic amino acid dihydroxyphenylalanine, which plays a key role in enhancing interfacial adhesion to organic and inorganic marine surfaces and contributes to cohesive strength of the holdfast. In this work, pressure-sensitive adhesives (PSAs) were synthesized by copolymerization of dopamine methacrylamide (DMA) with common PSA monomers, butyl acrylate and acrylic acid, with careful attention paid to the effects of catechol on adhesive and cohesive properties. A combination of microscopic and macroscopic adhesion assays was used to study the effect of catechol on adhesion performance of acrylic PSAs. Addition of only 5% DMA to a conventional PSA copolymer containing butyl acrylate and acrylic acid resulted in 6-fold and 2.5-fold increases in work required to separate the PSA from silica and polystyrene, respectively, and a large increase in 180° peel adhesion against stainless steel after 24 h storage in both ambient and underwater conditions. Moreover, the holding power of the catechol PSAs on both steel and high-density polyethylene under shear load continuously increased as a function of catechol concentration, up to a maximum of 10% DMA. We also observed stark increases in shear and peel adhesion for the catecholic adhesives over PSAs with noncatecholic aromatic motifs, further underlining the benefits of catechols in PSAs. Overall, catechol PSAs perform extremely well on polar and metallic surfaces. The advantage of incorporating catechols in PSA formulations, however, is less straightforward for peel adhesion in nonpolar, organic substrates and tackiness of the PSAs.

Plasmonic Retrofitting of Membrane Materials: Shifting from Self-Regulation to On-Command Control of Fluid Flow.

This work calls for a paradigm shift in order to change the operational patterns of self-regulated membranes in response to chemical signals. To this end, the fabrication of a retrofitting material is introduced aimed at developing an innovative generation of porous substrates endowed with symbiotic but fully independent sensing and actuating capabilities. This is accomplished by transferring carefully engineered plasmonic architectures onto commercial microfiltration membranes lacking of such features. The integration of these materials leads to the formation of a coating surface proficient for ultrasensitive detection and "on-command" gating. Both functionalities can be synergistically modulated by the spatial and temporal distribution of an impinging light beam offering an unprecedented control over the membrane performance in terms of permeability. The implementation of these hybrid nanocomposites in conventional polymeric porous materials holds great potential in applications ranging from intelligent fluid management to advanced filtration technologies and controlled release.

Nanomanufacture of Free-Standing, Porous, Janus-Type Films of Polymer-Plant Virus Nanoparticle Arrays.

We present a facile method for preparing hierarchical assemblies of cowpea mosaic virus (CPMV) nanoparticles adsorbed onto patterned polypyrrole copolymer arrays, which can be released as a freely standing and microporous polymer-protein membrane with a Janus-type structure. The patterning protocol is based on colloidal sphere lithography wherein a sacrificial honeycomb pattern composed of colloidal polystyrene (PS) microspheres is assembled on an electrode. A thin layer of polypyrrole film is electropolymerized within the interstices of the template and monitored using an electrochemical quartz crystal microbalance with dissipation (EC-QCM-D) and microscopy. Dissolving the PS template reveals an inverse opaline pattern capable of electrostatically capturing the CPMV particles. Through an electrochemical trigger, the polypyrrole-CPMV delaminates from the surface producing a self-sustaining polymer-protein membrane that can potentially be used for sensing and nanocargo applications.

Slow-Release Formulation of Cowpea Mosaic Virus for In Situ Vaccine Delivery to Treat Ovarian Cancer.

The plant viral nanoparticle cowpea mosaic virus (CPMV) is shown to be an effective immunotherapy for ovarian cancer when administered as in situ vaccine weekly, directly into the intraperitoneal (IP) space in mice with disseminated tumors. While the antitumor efficacy is promising, the required frequency of administration may pose challenges for clinical implementation. To overcome this, a slow release formulation is developed. CPMV and polyamidoamine generation 4 dendrimer form aggregates (CPMV-G4) based on electrostatic interactions and as a function of salt concentration, allowing for tailoring of aggregate size and release of CPMV. The antitumor efficacy of a single administration of CPMV-G4 is compared to weekly administration of soluble CPMV in a mouse model of peritoneal ovarian cancer and found to be as effective at reducing disease burden as more frequent administrations of soluble CPMV; a single injection of soluble CPMV, does not significantly slow cancer development. The ability of CPMV-G4 to control tumor growth following a single injection is likely due to the continued presence of CPMV in the IP space leading to prolonged immune stimulation. This enhanced retention of CPMV and its antitumor efficacy demonstrates the potential for viral-dendrimer hybrids to be used for delayed release applications.

Polymer Nanosheet Containing Star-Like Copolymers: A Novel Scalable Controlled Release System.

Poly(ε-caprolactone) (PCL)-based nanomaterials, such as nanoparticles and liposomes, have exhibited great potential as controlled release systems, but the difficulties in large-scale fabrication limit their practical applications. Among the various methods being developed to fabricate polymer nanosheets (PNSs) for different applications, such as Langmuir-Blodgett technique and layer-by-layer assembly, are very effort consuming, and only a few PNSs can be obtained. In this paper, poly(ε-caprolactone)-based PNSs with adjustable thickness are obtained in large quantity by simple water exposure of multilayer polymer films, which are fabricated via a layer multiplying coextrusion method. The PNS is also demonstrated as a novel controlled guest release system, in which release kinetics are adjustable by the nanosheet thickness, pH values of the media, and the presence of protecting layers. Theoretical simulations, including Korsmeyer-Peppas model and Finite-element analysis, are also employed to discern the observed guest-release mechanisms.

Electrostatic layer-by-layer construction of fibrous TMV biofilms.

As nature's choice in designing complex architectures, the bottom-up assembly of nanoscale building blocks offers unique solutions in achieving more complex and smaller morphologies with wide-ranging applications in medicine, energy, and materials science as compared to top-down manufacturing. In this work, we employ charged tobacco mosaic virus (TMV-wt and TMV-lys) nanoparticles in constructing multilayered fibrous networks via electrostatic layer-by-layer (LbL) deposition. In neutral aqueous media, TMV-wt assumes an anionic surface charge. TMV-wt was paired with a genetically engineered TMV-lys variant that displays a corona of lysine side chains on its solvent-exposed surface. The electrostatic interaction between TMV-wt and TMV-lys nanoparticles became the driving force in the highly controlled buildup of the multilayer TMV constructs. Since the resulting morphology closely resembles the 3-dimensional fibrous network of an extracellular matrix (ECM), the capability of the TMV assemblies to support the adhesion of NIH-3T3 fibroblast cells was investigated, demonstrating potential utility in regenerative medicine. Lastly, the layer-by-layer deposition was extended to release the TMV scaffolds as free-standing biomembranes. To demonstrate potential application in drug delivery or vaccine technology, cargo-functionalized TMV biofilms were programmed.

Photon Management through Virus-Programmed Supramolecular Arrays.

Photon extraction and capture efficiency is a complex function of the material's composition, its molecular structure at the nanoscale, and the overall organization spanning multiple length scales. The architecture of the material defines the performance; nanostructured features within the materials enhance the energy efficiency. Photon capturing materials are largely produced through lithographic, top-down, manufacturing schemes; however, there are limits to the smallest dimension achievable using this technology. To overcome these technological barriers, a bottom-up nanomanufacturing is pursued. Inspired by the self-programmed assembly of virus arrays in host cells resulting in iridescence of infected organisms, virus-programmed, nanostructured arrays are studied to pave the way for new design principles in photon management and biology-inspired materials science. Using the nanoparticles formed by plant viruses in combination with charged polymers (dendrimers), a bottom-up approach is illustrated to prepare a family of broadband, low-angular dependent antireflection mesoscale layered materials for potential application as photon management coatings. Measurement and theory demonstrate antireflectance and phototrapping properties of the virus-programmed assembly. This opens up new bioengineering principles for the nanomanufacture of coatings and films for use in LED lighting and photovoltaics.

Free-Standing, Nanopatterned Janus Membranes of Conducting Polymer-Virus Nanoparticle Arrays.

Nanostructured mesoscale materials find wide-ranging applications in medicine and energy. Top-down manufacturing schemes are limited by the smallest dimension accessible; therefore, we set out to study a bottom-up approach mimicking biological systems, which self-assemble into systems that orchestrate complex energy conversion functionalities. Inspired by nature, we turned toward protein-based nanoparticle structures formed by plant viruses, specifically the cowpea mosaic virus (CPMV). We report the formation of hierarchical CPMV nanoparticle assemblies on colloidal-patterned, conducting polymer arrays using a protocol combining colloidal lithography, electrochemical polymerization, and electrostatic adsorption. In this approach, a hexagonally close-packed array of polystyrene microspheres was assembled on a conductive electrode to function as the sacrificial colloidal template. A thin layer of conducting polypyrrole material was electrodeposited within the interstices of the colloidal microspheres and monitored in situ using electrochemical quartz crystal microbalance with dissipation (EC-QCM-D). Etching the template revealed an inverse opaline conducting polymer pattern capable of forming strong electrostatic interactions with CPMV and therefore enabling immobilization of CPMV on the surface. The CPMV-polymer films were characterized by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). Furthermore, molecular probe diffusion experiments revealed selective ion transport properties as a function of the presence of the CPMV nanoparticles on the surface. Lastly, by utilizing its electromechanical behavior, the polymer/protein membrane was electrochemically released as a free-standing film, which can potentially be used for developing high surface area cargo delivery systems, stimuli-responsive plasmonic devices, and chemical and biological sensors.

Production of Immunoabsorbent Nanoparticles by Displaying Single-Domain Protein A on Potato Virus X.

The combination of antibodies with nanoparticles provides wide-ranging applications in biosensing. While several covalent presentation strategies have been established, there is need for alternative, non-covalent methods to provide a routine for scalable nanomanufacturing. We report the multivalent presentation of the B domain of Staphylococcus aureus protein A (SpAB) on potato virus X (PVX) nanoparticles. Three different synthetic strategies were used to obtain chimeric PVX(SpAB) filaments. The protein A fragments displayed on the surface of all three PVX chimeras remained fully functional as an immunoabsorbent for antibody capture enabling biosensing. The new biomaterials presented could find applications as diagnostic tools for biomedical or environmental monitoring.

Conducting polymer-gold co-patterned surfaces via nanosphere lithography.

HYPOTHESIS: Co-patterned arrays comprised of conjugated polymers and nanostructured gold is an important matrix for sensing and stimuli-responsive plasmonic applications. Nanosphere lithography (NSL) is an easy-to-use patterning technique and viable method to fabricate inverse honeycomb structures with electrochemically deposited conjugated polymers. The cross-sectional height of the conducting polymer pattern can be tuned such that the macropores of the honeycomb structure expose electrochemically accessible areas for further gold deposition. Using time-dependent electrochemical reduction, Au(3+) is reduced to Au(0) and selectively deposit on the macropores thus forming a co-patterned surface. EXPERIMENTS: The Langmuir-Blodgett-like deposition was used to assemble polystyrene spheres on a conductive substrate. Then the carbazole-based monomer was electropolymerized within the interstices of the colloidal template, which was subsequently dissolved. A potentiostatic technique was used to deposit Au in the macropores. FINDINGS: Fabrication of the polycarbazole-Au co-patterned surface was characterized by atomic force microscopy (AFM), electrochemical quartz crystal microbalance (EC-QCM), and X-ray photoelectron spectroscopy (XPS). Surface plasmon resonance spectroscopy (SPS) data supported backfilling behavior and quantified the complex refractive index of the array. UV-Vis absorption spectroscopy shows overlapping polycarbazole and gold LSPR peaks useful for plasmonic sensing applications. The colloidal templating approach reported in this study was further used in the fabrication of highly ordered Au nanodisks.

Nanostructured, molecularly imprinted, and template-patterned polythiophenes for chiral sensing and differentiation.

An innovation to thin-film molecular imprinting is presented for the sensitive detection and effective discrimination of chiral compounds using a portable quartz crystal microbalance transduction technique. The facile approach involves i) colloidal sphere layering of latex particles onto the surface via a Langmuir-Blodgett-like technique followed by ii) template molecular imprinting using electrodeposition of a single functional and cross-linking monomer.