Tunable backbone-degradable robust tissue adhesives via in situ radical ring-opening polymerization

Abstract Adhesives with both robust adhesion and tunable degradability are clinically and ecologically vital, but their fabrication remains a formidable challenge. Here we propose an in situ radical ring-opening polymerization (rROP) strategy to design a backbone-degradable robust adhesive (BDRA) in physiological environment. The hydrophobic cyclic ketene acetal and hydrophilic acrylate monomer mixture of the BDRA precursor allows it to effectively wet and penetrate substrates, subsequently forming a deep covalently interpenetrating network with a degradable backbone via redox-initiated in situ rROP. The resulting BDRAs show good adhesion strength on diverse materials and tissues (e.g., wet bone >16 MPa, and porcine skin >150 kPa), higher than that of commercial cyanoacrylate superglue (~4 MPa and 56 kPa). Moreover, the BDRAs have enhanced tunable degradability, mechanical modulus (100 kPa-10 GPa) and setting time (seconds-hours), and have good biocompatibility in vitro and in vivo. This family of BDRAs expands the scope of medical adhesive applications and offers an easy and environmentally friendly approach for engineering

Optimization of Alkyl Side Chain Length in Polyimide for Gate Dielectrics to Achieve High Mobility and Outstanding Operational Stability in Organic Transistors

Alkyl chain modification strategies in both organic semiconductors and inorganic dielectrics play a crucial role in improving the performance of organic thin-film transistors (OTFTs). Polyimide (PI) and its derivatives have received extensive attention as dielectrics for application in OTFTs because of flexibility, high-temperature resistance, and low cost. However, low-temperature solution processing PI-based gate dielectric for flexible OTFTs with high mobility, low operating voltage, and high operational stability remains an enormous challenge. Furthermore, even though di-n-decyldinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (C10-DNTT) is known to have very high mobility as an air-stable and high-performance organic semiconductor, the C10-DNTT-based TFTs on the PI gate dielectrics still showed relatively low mobility. Here, inspired by alkyl side chain engineering, we design and synthesize a series of PI materials with different alkyl side chain lengths and systematically investigate the PI surface properties and the evolution of organic semiconductor morphology deposited on PI surfaces during the variation of alkyl side chain lengths. It is found that the alkyl side chain length has a critical influence on the PI surface properties, as well as the grain size and molecular orientation of semiconductors. Good field-effect characteristics are obtained with high mobilities (up to 1.05 and 5.22 cm2/Vs, which are some of the best values reported to date), relatively low operating voltage, hysteresis-free behavior, and high operational stability in OTFTs. These results suggest that the strategy of optimizing alkyl side-chain lengths opens up a new research avenue for tuning semiconductor growth to enable high mobility and outstanding operational stability of PI-based OTFTs

Degradable Nanohydroxyapatite-Reinforced Superglue for Rapid Bone Fixation and Promoted Osteogenesis

Bone glue with robust adhesion is crucial for treating complicated bone fractures, but it remains a formidable challenge to develop a “true” bone glue with high adhesion strength, degradability, bioactivity, and satisfactory operation time in clinical scenarios. Herein, inspired by the hydroxyapatite and collagen matrix composition of natural bone, we constructed a nanohydroxyapatite (nHAP) reinforced osteogenic backbone-degradable superglue (O-BDSG) by in situ radical ring-opening polymerization. nHAP significantly enhances adhesive cohesion by synergistically acting as noncovalent connectors between polymer chains and increasing the molecular weight of the polymer matrix. Moreover, nHAP endows the glue with bioactivity to promote osteogenesis. The as-prepared glue presented a 9.79 MPa flexural adhesion strength for bone, 4.7 times that without nHAP, and significantly surpassed commercial cyanoacrylate (0.64 MPa). O-BDSG exhibited degradability with 51% mass loss after 6 months of implantation. In vivo critical defect and tibia fracture models demonstrated the promoted osteogenesis of the O-BDSG, with a regenerated bone volume of 75% and mechanical function restoration to 94% of the native tibia after 8 weeks. The glue can be flexibly adapted to clinical scenarios with a curing time window of about 3 min. This work shows promising prospects for clinical application in orthopedic surgery and may inspire the design and development of bone adhesives

Facile Fabrication of Lubricant-Infused Wrinkling Surface for Preventing Thrombus Formation and Infection

Despite the advanced modern biotechniques, thrombosis and bacterial infection of biomedical devices remain common complications that are associated with morbidity and mortality. Most antifouling surfaces are in solid form and cannot simultaneously fulfill the requirements for antithrombosis and antibacterial efficacy. In this work, we present a facile strategy to fabricate a slippery surface. This surface is created by combining photografting polymerization with osmotically driven wrinkling that can generate a coarse morphology, and followed by infusing with fluorocarbon liquid. The lubricant-infused wrinkling slippery surface can greatly prevent protein attachment, reduce platelet adhesion, and suppress thrombus formation in vitro. Furthermore, <i>E. coli</i> and <i>S. aureus</i> attachment on the slippery surfaces is reduced by ∼98.8% and ∼96.9% after 24 h incubation, relative to poly­(styrene-<i>b</i>-isobutylene-<i>b</i>-styrene) (SIBS) references. This slippery surface is biocompatible and has no toxicity to L929 cells. This surface-coating strategy that effectively reduces thrombosis and the incidence of infection will greatly decrease healthcare costs

Antibacterial and Hemocompatibility Switchable Polypropylene Nonwoven Fabric Membrane Surface

In this article, a facile approach to fabricate a biofunctional polypropylene nonwoven fabric membrane (PP NWF) with a switchable surface from antibacterial property to hemocompatibility is presented. In the first step, a cationic carboxybetaine ester monomer, [(2-(methacryboxy) ethyl)]-<i>N</i>,<i>N</i>-dimethylamino-ethylammonium bromide, methyl ester (CABA-1-ester) was synthesized. Subsequently, this monomer was introduced on the PP NWF surface via plasma pretreatment and a UV-induced graft polymerization technique. Finally, a switchable surface from antibacterial property to hemocompatibility was easily realized by hydrolysis of poly­(CABA-1-ester) moieties on the PP NWF surface under mild conditions. Surface hydrolysis behaviors under different pH conditions were investigated. These PP NWFs grafted with poly­(CABA-1-ester) segments can cause significant suppression of S. aureus proliferation; after hydrolysis, these surfaces covered by poly­[(2-(methacryloxy) ethyl)] carboxybetaine (poly­(CABA)) chains exhibited obvious reduction in protein adsorption and platelet adhesion, and remarkably enhanced antithrombotic properties. This strategy demonstrated that a switchable PP NWF surface from antibacterial property to hemocompatibility was easily developed by plasma pretreatment and UV-induced surface graft polymerization and that this surface may become an attractive platform for a range of biomedical applications

Degradable Nanohydroxyapatite-Reinforced Superglue for Rapid Bone Fixation and Promoted Osteogenesis

Bone glue with robust adhesion is crucial for treating complicated bone fractures, but it remains a formidable challenge to develop a “true” bone glue with high adhesion strength, degradability, bioactivity, and satisfactory operation time in clinical scenarios. Herein, inspired by the hydroxyapatite and collagen matrix composition of natural bone, we constructed a nanohydroxyapatite (nHAP) reinforced osteogenic backbone-degradable superglue (O-BDSG) by in situ radical ring-opening polymerization. nHAP significantly enhances adhesive cohesion by synergistically acting as noncovalent connectors between polymer chains and increasing the molecular weight of the polymer matrix. Moreover, nHAP endows the glue with bioactivity to promote osteogenesis. The as-prepared glue presented a 9.79 MPa flexural adhesion strength for bone, 4.7 times that without nHAP, and significantly surpassed commercial cyanoacrylate (0.64 MPa). O-BDSG exhibited degradability with 51% mass loss after 6 months of implantation. In vivo critical defect and tibia fracture models demonstrated the promoted osteogenesis of the O-BDSG, with a regenerated bone volume of 75% and mechanical function restoration to 94% of the native tibia after 8 weeks. The glue can be flexibly adapted to clinical scenarios with a curing time window of about 3 min. This work shows promising prospects for clinical application in orthopedic surgery and may inspire the design and development of bone adhesives

Liquid-Infused Poly(styrene‑<i>b</i>‑isobutylene‑<i>b</i>‑styrene) Microfiber Coating Prevents Bacterial Attachment and Thrombosis

Infection and thrombosis associated with medical implants cause significant morbidity and mortality worldwide. As we know, current technologies to prevent infection and thrombosis may cause severe side effects. To overcome these complications without using antimicrobial and anticoagulant drugs, we attempt to prepare a liquid-infused poly­(styrene-<i>b</i>-isobutylene-<i>b</i>-styrene) (SIBS) microfiber coating, which can be directly coated onto medical devices. Notably, the SIBS microfiber was fabricated through solution blow spinning. Compared to electrospinning, the solution blow spinning method is faster and less expensive, and it is easy to spray fibers onto different targets. The lubricating liquids then wick into and strongly adhere the microfiber coating. These slippery coatings can effectively suppress blood cell adhesion, reduce hemolysis, and inhibit blood coagulation in vitro. In addition, <i>Pseudomonas aeruginosa</i> (<i>P. aeruginosa</i>) on the lubricant infused coatings slides readily, and no visible residue is left after tilting. We furthermore confirm that the lubricants have no effects on bacterial growth. The slippery coatings are also not cytotoxic to L929 cells. This liquid-infused SIBS microfiber coating could reduce the infection and thrombosis of medical devices, thus benefiting human health

Functionalization of Polypropylene with Chiral Monomer for Improving Hemocompatibility

Polypropylene (PP) is one of the most commonly used plastics because of its low density, outstanding mechanical properties, and low cost. However, its drawbacks such as low surface energy, poor dyeability, lack of chemical functionalities, and poor compatibility with polar polymers and inorganic materials, have restricted the application of PP. To expand its application in biomedical materials, functionalization is considered to be the most effective way. In this study, PP was functionalized with a chiral monomer, (S)-1-acryloylpyrrolidine-2-carboxylic acid ((S)-APCA), by free-radical grafting in the solid phase. The grafting degree of PP-g-APCA was determined by chemical titration method, and the chemical structure of functionalized PP was characterized by FTIR spectroscopy, which confirmed that the chiral monomer (S)-APCA was successfully grafted onto PP. Static water contact angle results suggested that the surface hydrophilicity of PP was significantly improved by solid phase grafting and assistance of surface water treatment. Protein adsorption and platelet adhesion results showed that hemocompatibility of PP was greatly improved by grafting the chiral monomer