Macromolecular Engineering and Additive Manufacturing of Polyisobutylene-Based Thermoplastic Elastomers. II. The Poly(styrene-b-isobutylene-b-styrene)/Poly(phenylene oxide) System.

This series of publications describes research rendering soft polyisobutylene (PIB)-based thermoplastic elastomers 3D printable by blending with rigid chemically compatible thermoplastics. The molecular structure, morphology, physical properties, and 3D printability of such blends have been systematically investigated. The authors' first report was concerned with the rendering of soft poly(styrene-b-isobutylene-b-styrene) (SIBS) 3D printable by blending with rigid polystyrene (PS). Here they report the macromolecular engineering of SIBS/polyphenylene oxide (PPO) blends for 3D printing. PPO, a rigid high-performance thermoplastic, is compatible with the hard PS block in SIBS; however, neither PPO nor SIBS can be directly 3D printed. The microphase-separated structures and physical properties of SIBS/PPO blends are systematically tuned by controlling blending ratios and molecular weights. Suitable composition ranges and desirable properties of SIBS/PPO blends for 3D printing are optimized. The morphology and properties of SIBS/PPO blends are characterized by an ensemble of techniques, including atomic force microscopy, small-angle X-ray scattering, and thermal and mechanical properties testing. The elucidation of processing-structure-property relationship of SIBS/PPO blends is essential for 3D printing and advanced manufacturing of high-performance polymer systems.

Multicomponent DNA Polymerization Motor Gels.

Hydrogels with the ability to change shape in response to biochemical stimuli are important for biosensing, smart medicine, drug delivery, and soft robotics. Here, a family of multicomponent DNA polymerization motor gels with different polymer backbones is created, including acrylamide-co-bis-acrylamide (Am-BIS), poly(ethylene glycol) diacrylate (PEGDA), and gelatin-methacryloyl (GelMA) that swell extensively in response to specific DNA sequences. A common mechanism, a polymerization motor that induces swelling is driven by a cascade of DNA hairpin insertions into hydrogel crosslinks. These multicomponent hydrogels can be photopatterned into distinct shapes, have a broad range of mechanical properties, including tunable shear moduli between 297 and 3888 Pa and enhanced biocompatibility. Human cells adhere to the GelMA-DNA gels and remain viable during ≈70% volumetric swelling of the gel scaffold induced by DNA sequences. The results demonstrate the generality of sequential DNA hairpin insertion as a mechanism for inducing shape change in multicomponent hydrogels, suggesting widespread applicability of polymerization motor gels in biomaterials science and engineering.

Self-Folding Hybrid Graphene Skin for 3D Biosensing.

Biological samples such as cells have complex three-dimensional (3D) spatio-molecular profiles and often feature soft and irregular surfaces. Conventional biosensors are based largely on 2D and rigid substrates, which have limited contact area with the entirety of the surface of biological samples making it challenging to obtain 3D spatially resolved spectroscopic information, especially in a label-free manner. Here, we report an ultrathin, flexible skinlike biosensing platform that is capable of conformally wrapping a soft or irregularly shaped 3D biological sample such as a cancer cell or a pollen grain, and therefore enables 3D label-free spatially resolved molecular spectroscopy via surface-enhanced Raman spectroscopy (SERS). Our platform features an ultrathin thermally responsive poly( N-isopropylacrylamide)-graphene-nanoparticle hybrid skin that can be triggered to self-fold and wrap around 3D micro-objects in a conformal manner due to its superior flexibility. We highlight the utility of this 3D biosensing platform by spatially mapping the 3D molecular signatures of a variety of microparticles including silica microspheres, spiky pollen grains, and human breast cancer cells.

Branched Polyhedral Oligomeric Silsesquioxane Nanoparticles Prepared via Strain-Promoted 1,3-Dipolar Cycloadditions.

Conjugation of small organic molecules and polymers to polyhedral oligosilsesquioxane (POSS) cores results in novel hybrid materials with unique physical characteristics. We report here an approach in which star-shaped organic-inorganic scaffolds bearing eight cyclooctyne moieties can be rapidly functionalized via strain-promoted azide-alkyne cycloaddition (SPAAC) to synthesize a series of nearly monodisperse branched core-shell nanoparticles with hydrophobic POSS cores and hydrophilic arms. We established that SPAAC is a robust method for POSS core octafunctionalization with the reaction rate constant of 1.9 × 10(-2) M(-1) s(-1). Functionalization with poly(ethylene glycol) (PEG) azide, fluorescein azide, and unprotected lactose azide gave conjugates which represent different classes of compounds: polymer conjugates, fluorescent dots, and bioconjugates. These resulting hybrid compounds were preliminarily tested for their ability to self-assemble in solution and at the air-water interface. We observed the formation of robust smooth Langmuir monolayers with diverse morphologies. We found that polar lactose moieties are completely submerged into the subphase whereas the relatively hydrophobic fluorescein arms had extended conformation at the interface, and PEG arms were partially submerged. Finally, we observed the formation of stable micelles with sizes between 70 and 160 nm in aqueous solutions with size and morphology of the structures dependent on the molecular weight and the type of the peripheral hydrophilic moieties.

Engineered Living Structures with Shape-Morphing Capability Enabled by 4D Printing with Functional Bacteria.

Engineered living structures with the incorporation of functional bacteria have been explored extensively in recent years and have shown promising potential applications in biosensing, environmental remediation, and biomedicine. However, it is still rare and challenging to achieve multifunctional capabilities such as material production, shape transformation, and sensing in a single-engineered living structure. In this study, we demonstrate bifunctional living structures by synergistically integrating cellulose-generating bacteria with pH-responsive hydrogels, and the entire structures can be precisely fabricated by three-dimensional (3D) printing. Such 3D-printed bifunctional living structures produce cellulose nanofibers in ambient conditions and have reversible and controlled shape-morphing properties (usually referred to as four-dimensional printing). Those functionalities make them biomimetic versions of silkworms in the sense that both can generate nanofibers and have body motion. We systematically investigate the processing-structure-property relationship of the bifunctional living structures. The on-demand separation of 3D cellulose structures from the hydrogel template and the living nature of the bacteria after processing and shape transformation are also demonstrated.

Star polymer unimicelles on graphene oxide flakes.

We report the interfacial assembly of amphiphilic heteroarm star copolymers (PSnP2VPn and PSn(P2VP-b-PtBA)n (n = 28 arms)) on graphene oxide flakes at the air-water interface. Adsorption, spreading, and ordering of star polymer micelles on the surface of the basal plane and edge of monolayer graphene oxide sheets were investigated on a Langmuir trough. This interface-mediated assembly resulted in micelle-decorated graphene oxide sheets with uniform spacing and organized morphology. We found that the surface activity of solvated graphene oxide sheets enables star polymer surfactants to subsequently adsorb on the presuspended graphene oxide sheets, thereby producing a bilayer complex. The positively charged heterocyclic pyridine-containing star polymers exhibited strong affinity onto the basal plane and edge of graphene oxide, leading to a well-organized and long-range ordered discrete micelle assembly. The preferred binding can be related to the increased conformational entropy due to the reduction of interarm repulsion. The extent of coverage was tuned by controlling assembly parameters such as concentration and solvent polarity. The polymer micelles on the basal plane remained incompressible under lateral compression in contrast to ones on the water surface due to strongly repulsive confined arms on the polar surface of graphene oxide and a preventive barrier in the form of the sheet edges. The densely packed biphasic tile-like morphology was evident, suggesting the high interfacial stability and mechanically stiff nature of graphene oxide sheets decorated with star polymer micelles. This noncovalent assembly represents a facile route for the control and fabrication of graphene oxide-inclusive ultrathin hybrid films applicable for layered nanocomposites.

Ultrathin Polydopamine-Graphene Oxide Hybrid Coatings on Polymer Filters with Improved Filtration Performance and Functionalities.

Thin polymer fiber mats, in particular those made of nonwoven polypropylene (PP) fibers, are extensively used for medical and industrial filtration. The recent pandemic has increased the demand for the fabrication of protective masks. The nonwoven PP filter has limitations in filtration efficiency and lacks advanced functionalities. Here, we propose a simple, effective, and low-cost method to functionalize PP filters and endow antimicrobial and photothermal properties. Our approach is based on the deposition of an ultrathin hybrid coating composed of graphene oxide (GO) and polydopamine on the surface of PP filters by spray-coating. The complementary properties and synergic effects of GO and polydopamine in the ultrathin coating improved the filtration efficiency of the PP filter by 20% with little change in pressure drop. Single component coatings did not result in similar improvements in performance. The ultrathin coating also makes the surface of the filter more hydrophilic with negative charges. The photothermal property of GO enables a rapid temperature increase of the surface-coated filter upon light irradiation for easy sterilization. Furthermore, cationic polymer brushes can be grafted to the ultrathin hybrid coating, which adds the highly desired antimicrobial property to the PP filters for their more effective protection against microorganisms.

Architecture, Assembly, and Emerging Applications of Branched Functional Polyelectrolytes and Poly(ionic liquid)s.

Branched polyelectrolytes with cylindrical brush, dendritic, hyperbranched, grafted, and star architectures bearing ionizable functional groups possess complex and unique assembly behavior in solution at surfaces and interfaces as compared to their linear counterparts. This review summarizes the recent developments in the introduction of various architectures and understanding of the assembly behavior of branched polyelectrolytes with a focus on functional polyelectrolytes and poly(ionic liquid)s with responsive properties. The branched polyelectrolytes and poly(ionic liquid)s interact electrostatically with small molecules, linear polyelectrolytes, or other branched polyelectrolytes to form assemblies of hybrid nanoparticles, multilayer thin films, responsive microcapsules, and ion-conductive membranes. The branched structures lead to unconventional assemblies and complex hierarchical structures with responsive properties as summarized in this review. Finally, we discuss prospectives for emerging applications of branched polyelectrolytes and poly(ionic liquid)s for energy harvesting and storage, controlled delivery, chemical microreactors, adaptive surfaces, and ion-exchange membranes.