Peptides that comprise the functional subunits of proteins have been conjugated to versatile materials (biomolecules, polymers, surfaces and nanoparticles) in an effort to modulate cell responses, ...specific binding affinity and/or self-assembly behavior. However, the efficient and convenient synthesis of peptide-conjugates, especially the constructs with multiple types of peptide functionality remains challenging. In this critical review, we focus on "click" reactions that have been used to synthesis peptide-functionalized conjugates, introducing their reaction conditions, specifically elucidating parameters that influence reaction kinetics and total conversion, and highlighting examples that have been completed recently. Moreover, orthogonal "click" reactions that synthesize multi-functional biomaterials in a one-pot or sequential manner are noted. Through this review, a comprehensive understanding of "click" reactions aims to provide insight on how one might choose suitable "click" reactions to constitute peptide-functionalized molecules/surfaces/matrices for the development of advanced biomaterials.
Hospital-acquired infections arising from implanted polymeric medical devices continue to pose a significant challenge for medical professionals and patients. Often times, these infections arise from ...biofilm accumulation on the device, which is difficult to eradicate and usually requires antibiotic treatment and device removal. In response, significant efforts have been made to design functional polymeric devices or coatings that possess antimicrobial or antifouling properties that limit biofilm formation and subsequent infection by inhibiting or eliminating bacteria near the device surface or by limiting the initial attachment of proteins and bacteria. In this Viewpoint, we highlight the magnitude of device-associated infections, the role of biofilm formation in human pathogenesis, and recent advances in antimicrobial and antifouling polymers, as well as current strategies employed in commercial devices for preventing infection.
Complex three-dimensional (3D) pore geometries, useful for tissue engineering scaffolds, can be fabricated via photo-crosslinking of resorbable poly(propylene fumarate) (PPF) resins using ...stereolithography (SLA) and/or continuous digital light processing (cDLP) methods. Physico-chemical parameters inherent to 3D printable resin design, include viscosity, polymer concentration, degree of polymerization, and resin printing temperature. We report here on our study of these parameters and their influence the cDLP 3D printing process and the resulting mechanical properties. A series of PPF oligomers were synthesized by the ring-opening copolymerization (ROCOP) of maleic anhydride and propylene oxide followed by a base-catalyzed isomerization. The resin viscosities were measured as a function of number-average molecular mass ( M n ̅ ) of the PPF oligomers (1.1, 1.7 and 2.0 kDa), concentrations of PPF in the reactive diluent diethyl fumarate (DEF) (50 and 75 wt %) and resin temperature (25 to 55 °C). The zero-shear viscosity (η0) of the resins was found to be temperature-dependent and follow a linear Arrhenius relationship. Tensile tests demonstrated mechanical properties within the range of trabecular bone, with the ultimate strength at break above 15 MPa and elastic moduli between 178 and 199 MPa.
Degradable polymers are used widely in tissue engineering and regenerative medicine. Maturing capabilities in additive manufacturing coupled with advances in orthogonal chemical functionalization ...methodologies have enabled a rapid evolution of defect-specific form factors and strategies for designing and creating bioactive scaffolds. However, these defect-specific scaffolds, especially when utilizing degradable polymers as the base material, present processing challenges that are distinct and unique from other classes of materials. The goal of this review is to provide a guide for the fabrication of biodegradable polymer-based scaffolds that includes the complete pathway starting from selecting materials, choosing the correct fabrication method, and considering the requirements for tissue specific applications of the scaffold.
3D/4D printing is enabling transformative advances in device manufacturing and medicine but remains limited by the lack of printable resorbable materials with advanced properties and functions. ...Herein, we report the rapid and precise 4D printing of shape-memory scaffolds based on poly(propylene fumarate) (PPF) star polymers. Scaffolds with tunable and distinguishable properties can be produced with identical polymer formulation and stoichiometry. The resulting scaffold glass transition temperatures and Young’s moduli increase with the postcuring time. Significantly, both the extent and rate of shape recovery following compression can be tuned by varying the strut design, the postcuring step duration, and/or the temperature applied for the recovery step. Finally, accelerated degradation studies confirmed the resorbability of the PPF star polymer gyroid scaffolds.
Room‐temperature solution‐processed flexible photodetectors with spectral response from 300 to 2600 nm are reported. Solution‐processed polymeric thin film with transparency ranging from 300 to 7000 ...nm and superior electrical conductivity as the transparent electrode is reported. Solution‐processed flexible broadband photodetectors with a “vertical” device structure incorporating a perovskite/PbSe quantum dot bilayer thin film based on the above solution‐processed transparent polymeric electrode are demonstrated. The utilization of perovskite/PbSe quantum dot bilayer thin film as the photoactive layer extends spectral response to infrared region and boosts photocurrent densities in both visible and infrared regions through the trap‐assisted photomultiplication effect. Operated at room temperature and under an external bias of ‐1 V, the solution‐processed flexible photodetectors exhibit over 230 mA W‐1 responsivity, over 1011 cm Hz1/2/W photodetectivity from 300 to 2600 nm and ≈70 dB linear dynamic ranges. It is also found that the solution‐processed flexible broadband photodetectors exhibit fast response time and excellent flexibility. All these results demonstrate that this work develop a facile approach to realize room‐temperature operated ultrasensitive solution‐processed flexible broadband photodetectors with “vertical” device structure through solution‐processed transparent polymeric electrode.
Flexible‐solution processed photodetectors with a vertical device structure incorporating a CH3NH3PbI3/PbSe quantum dot bilayer on polymeric thin film are demonstrated. They exhibit a spectral response ranging from 300 nm to 2600 nm, photodetectivity of over 1011 cm Hz1/2 W−1, and linear dynamic range of 70 dB.
Ocular applications of polymeric materials have been widely investigated for medical diagnostics, treatment, and vision improvement. The human eye is a vital organ that connects us to the outside ...world so when the eye is injured, infected, or impaired, it needs immediate medical treatment to maintain clear vision and quality of life. Moreover, several essential parts of the eye lose their functions upon aging, causing diminished vision. Modern polymer science and polymeric materials offer various alternatives, such as corneal and scleral implants, artificial ocular lenses, and vitreous substitutes, to replace the damaged parts of the eye. In addition to the use of polymers for medical treatment, polymeric contact lenses can provide not only vision correction, but they can also be used as wearable electronics. In this Review, we highlight the evolution of polymeric materials for specific ocular applications such as intraocular lenses and current state-of-the-art polymeric systems with unique properties for contact lens, corneal, scleral, and vitreous body applications. We organize this Review paper by following the path of light as it travels through the eye. Starting from the outside of the eye (contact lenses), we move onto the eye’s surface (cornea and sclera) and conclude with intraocular applications (intraocular lens and vitreous body) of mostly synthetic polymers and several biopolymers. Initially, we briefly describe the anatomy and physiology of the eye as a reminder of the eye parts and their functions. The rest of the Review provides an overview of recent advancements in next-generation contact lenses and contact lens sensors, corneal and scleral implants, solid and injectable intraocular lenses, and artificial vitreous body. Current limitations for future improvements are also briefly discussed.
Stereocomplexation has been shown to enhance the thermal and mechanical properties of polymers. The scope and utility of stereocomplexation have focused primarily on toughening of poly(l-lactic ...acid) (PLLA). Recently, additional polyester and polycarbonate systems with more diverse properties and functionality have also exhibited the ability to form stereocomplexes which is coupled to enhanced thermal properties similar to those exhibited by stereocomplexed-PLA (SC-PLA). This Perspective will highlight recent and future efforts that aim to discover new stereocomplexable scaffolds and expand their use in the formation of molecular and supramolecular assemblies and in biomaterial applications.
Shape memory materials have emerged as an important class of materials in medicine due to their ability to change shape in response to a specific stimulus, enabling the simplification of medical ...procedures, use of minimally invasive techniques, and access to new treatment modalities. Shape memory polymers, in particular, are well suited for such applications given their excellent shape memory performance, tunable materials properties, minimal toxicity, and potential for biodegradation and resorption. This review provides an overview of biodegradable shape memory polymers that have been used in medical applications. The majority of biodegradable shape memory polymers are based on thermally responsive polyesters or polymers that contain hydrolyzable ester linkages. These materials have been targeted for use in applications pertaining to embolization, drug delivery, stents, tissue engineering, and wound closure. The development of biodegradable shape memory polymers with unique properties or responsiveness to novel stimuli has the potential to facilitate the optimization and development of new medical applications.
Stents have evolved significantly since their introduction to the medical field in the early 1980s, becoming widely used in percutaneous coronary interventions and following nephrological procedures. ...However, the current commercially available stents do not degrade and remain in the body forever, leading to problems like restenosis in cardiovascular applications or requiring removal procedures in ureteral applications. Efforts to replace metal with resorbable materials have largely been halted after the commercial failure of and safety concerns elicited by Abbott’s Absorb stent in 2017. Industry continues to use common polymers such as poly(l-lactide) (PLLA) and polycaprolactone (PCL) for biomedical products, but due to the weak mechanical properties of these bioresorbable materials in comparison to metals, these devices have struggled to accomplish the goals set, increasing risk of thrombosis. 3D printing stents using bioresorbable and shape memory materials could provide a method of patient-personalized production, remove the need for balloon expansion, and limit stent migration, thus bringing a new age of stent technology. The investigation of a range of 3D-printable and bioresorbable shape-memory polymers can provide solutions to the shortcomings of previously explored bioresorbable stents and revitalize the medical device industry efforts into advancing stent technology.