Functional Zwitterionic Polyurethanes: State-of-the-Art Review.

Recent advancements in bioengineering and medical devices have been greatly influenced and dominated by synthetic polymers, particularly polyurethanes (PUs). PUs offer customizable mechanical properties and long-term stability, but their inherent hydrophobic nature poses challenges in practically biological application processes, such as interface high friction, strong protein adsorption, and thrombosis. To address these issues, surface modifications of PUs for generating functionally hydrophilic layers have received widespread attention, but the durability of generated surface functionality is poor due to irreversible mechanical wear or biodegradation. As a result, numerous researchers have investigated bulk modification techniques to incorporate zwitterionic polymers or groups onto the main or side chains of PUs, thereby improving their hydrophilicity and biocompatibility. This comprehensive review presents an extensive overview of notable zwitterionic PUs (ZPUs), including those based on phosphorylcholine, sulfobetaine, and carboxybetaine. The review explores their wide range of biomedical applications, from blood-contacting devices to antibacterial coatings, fouling-resistant marine coatings, separation membranes, lubricated surfaces, and shape memory and self-healing materials. Lastly, the review summarizes the challenges and future prospects of ZPUs in biological applications.

Shear-Stable Polymer Brush Surfaces.

Research on polymer brushes (PBs) has aroused great interest due to their wide range of applications in lubrication, antifogging, antifouling, self-cleaning, antiadhesion, antibacterial effects, and so forth. However, the weak mechanical strength, especially the low bond strength between the PBs and the substrate surface, is a long-standing challenge for its practical applications, which is directly related to the service life of the PB surface. Fortunately, the imperfection of the PB surface was gradually solved by researchers by combining the action of the chemical and physical anchoring strength, and many shear-stable PB surfaces were developed. In this Perspective, we present recent developments in the studies of shear-stable PBs. Conventional strategies that altered the structure of PB chain methods, including increasing grafted density, cross-linking of PBs, cyclic PBs, and so forth, are introduced briefly. The systematic subsurface grafting of the polymer brush (SSPB) strategy was introduced emphatically. The SSPB method grafted PB into the subsurface with considerable depth and gave a robust and reusable PB layer, which provided an approach for tackling the shear-resistance issue. Besides, the robust hydrophobic poly(dimethylsiloxane) (PDMS) brush surface that lubricated itself in air was also introduced. Finally, we provide a synopsis and discuss the outlook of the shear-stable PB surface.

A Strong and Double-sided Self-Adhesive Hydrogel Sensor.

Flexible self-adhesive hydrogel sensors are attracting considerable concerns in recent years. However, creating a self-adhesive hydrogel sensor with excellent mechanical properties remains to be challenging. Herein, a double-sided self-adhesive hydrogel capable of strain sensor with high strength is demonstrated by penetration strategy. The middle poly(acrylic acid)-polyacrylamide/Fe3+ (PAA-PAM/Fe3+ ) tough layer endows the double-sided self-adhesive hydrogel with high mechanical properties, while the bilateral poly[2-(methacryloyloxy) ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide-polyacrylamide (PSBMA-PAM) adhesive layers are used to ensure excellent adhesiveness on diverse substrates. The tough layer of the double-sided self-adhesive hydrogel sensor shows a strong interface bonding force against the adhesive layer. The double-sided self-adhesive hydrogel sensor enables excellent adhesiveness on diverse substrates. More importantly, it can accurately detect different strains and human motions as a self-adhesive hydrogel strain sensor. This work manifests a new route of structural design to develop a self-adhesive hydrogel sensor with excellent mechanical properties that is suitable for a wide range of applications.

In Situ Surface-Initiated ATRP Mediated by Gallium-Based Liquid Metal Nanodroplets.

Surface-initiated atom transfer radical polymerization (SI-ATRP) is one of the most popular methods for surface modifications with functional polymer films, which has attracted significant attention in recent years. Herein, a facile method of gallium-based liquid metal (GLM) nanodroplets mediated SI-ATRP to prepare polymer brushes on GLM surfaces is reported. The ATRP initiator modified GLM (GLM-Br) nanodroplets act as a substrate for the in situ SI-ATRP and participate as a reducing agent to reduce Cu(II) deactivators to Cu(I) activators. UV-vis spectra confirm the feasibility of the in situ SI-ATRP and indicate that the thickness and density of polymer brushes play an important role in performing a successful ATRP on GLM nanodroplets surfaces. Homo- and block copolymers, poly(3-sulfopropyl methacrylate potassium salt) (PSPMA) and poly((2-dimethylamino)ethyl methacrylate-b-(3-sulfopropyl methacrylate potassium salt)) P(DMAEMA-b-SPMA) are successfully grafted to the GLM nanodroplets. Polymer brushes modified GLM nanodroplets show potential applications such as friction reduction and oil-water emulsion separation. GLM nanodroplets mediated SI-ATRP provides a novel and robust approach to preparing multifunctional GLM nanodroplets for different applications.

Construction of Core-Shell NanoMOFs@microgel for Aqueous Lubrication and Thermal-Responsive Drug Release.

The construction of porous nanocarriers with good lubricating performance and stimuli-responsive drug release is significant for the synergetic therapy of osteoarthritis (OA). Although metal-organic framework nanoparticles (nanoMOFs) as carriers can support drug delivery, achieving the synergy of aqueous lubrication and stimuli-responsive drug release is challenging. In this work, a core-shell nanoMOFs@poly(N-isopropylacrylamide) (PNIPAm) microgel hybrid via one-pot soap-free emulsion polymerization is developed. Programmable growth of the PNIPAm microgel layer on the surface of nanoMOFs is achieved by tuning the concentration of the monomer and the crosslinker in the reaction. Reversible swelling-collapsing behaviors of the hybrid are realized by tuning the temperature below and above the lower critical solution temperature. When used as water lubrication additives, the hybrid enables reductions in both the coefficient of friction and wear volume. In vitro thermal-responsive drug release is demonstrated on the diclofenac sodium-loaded hybrid by controlling the swelling and collapsing states of the PNIPAm nanolayer. Moreover, the good biocompatibility of the hybrid is verified by culturing toward HeLa and BEAS-2B cells. These results establish a nanoMOFs@microgel hybrid that can achieve friction and wear reduction and thermal-responsive drug release.

Bioinspired Polysaccharide Derivative with Efficient and Stable Lubrication for Silicon-Based Devices.

It is becoming increasingly important to synthesize efficient biomacromolecule lubricants suitable for medical devices. Even though the development of biomimetic lubricants has made great progress, the current system suitable for hydrophobic silicone-based medical devices is highly limited. In this work, we synthesize one kind of novel polysaccharide-derived macromolecule lubricant of chitosan (CS) grafted polyethylene glycol (PEG) chains and catechol groups (CT) (CS-g-PEG-g-CT). CS-g-PEG-g-CT shows good adsorption ability by applying quantitative analysis of quartz crystal microbalance (QCM), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), and confocal fluorescence imaging technique, as well as the typical shear-thinning feature. CS-g-PEG-g-CT exhibits low and stable coefficients of friction (COFs) (0.01-0.02) on polydimethylsiloxane (PDMS) surfaces at a wide range of mass concentrations in diverse media including pure water, physiological saline, and PBS buffer solution and is even tolerant to various normal loads and sliding frequencies for complex pressurizing or shearing environments. Subsequently, systematic surface characterizations are used to verify the dynamic attachment ability of the CS-g-PEG-g-CT lubricant on the loading/shearing process. The lubrication mechanism of CS-g-PEG-g-CT can be attributed to the synergy of strong adsorption from catechol groups to form a uniform assembly layer, excellent hydration effect from PEG chains, and typical shear-thinning feature to dissipate viscous resistance. Surprisingly, CS-g-PEG-g-CT exhibits efficient lubricity on silicone-based commercial contact lenses and catheters. The current macromolecule lubricant demonstrates great real application potential in the fields of medical devices and disease treatments.

Mussel-inspired hydrogels: from design principles to promising applications.

Mussel-inspired chemistry, owing to its unique and versatile functions to manipulate dynamic molecular-scale interactions, has emerged as a powerful tool for the rational design and synthesis of new hydrogels. In particular, possessing a myriad of unique advantages that are otherwise impossible by conventional counterparts, mussel-inspired hydrogels have been widely explored in numerous fields such as biomedical engineering, soft electronics and actuators, and wearable sensors. Despite great excitement and vigor, a comprehensive and timely review on this emerging topic is missing. In this review, we discuss (1) the fundamental interaction mechanisms underpinning the spectacular wet adhesion in natural mussels and mussel-inspired materials; (2) the key routes to engineering hydrogels by leveraging on the interactions of mussel-inspired building blocks; (3) the emerging applications of mussel-inspired hydrogels, especially in the areas of flexible electronics and biomedical engineering; (4) the future perspectives and unsolved challenges of this multidisciplinary field. We envision that this review will provide an insightful perspective to stimulate new thinking and innovation in the development of next-generation hydrogels and beyond.

PDLSCs Regulate Angiogenesis of Periodontal Ligaments via VEGF Transferred by Exosomes in Periodontitis.

Abnormal angiogenesis is one of the significant features in periodontitis leading to progressive inflammation, but angiogenic changes of periodontal ligaments under inflammatory condition were rarely reported. Periodontal ligament stem cells (PDLSCs) were a kind of dental stem cells associated with vascularization. Here we investigated the alteration of angiogenesis of periodontal ligament in periodontitis, and revealed an exosome-mediated pathway to support the effect of PDLSCs on angiogenic improvement. Vascular specific marker CD31 and VEGFA were found to be highly expressed in periodontal ligaments of periodontitis. The VEGFA expression was up-regulated in inflamed PDLSCs compared to control, meanwhile the tube formation of HUVECs was improved when co-cultured with inflamed PDLSCs. Exosomes secretion of PDSLCs was augmented by inflammation, and promoted angiogenesis of HUVECs, whereas blocking secretion of exosomes led to degenerated angiogenesis of HUVECs. Exosome-trasferred VEGFA was proven to be the crucial communicator between PDLSCs and HUVECs. Inflammation inhibited miR-17-5p expression of PDLSCs and relieved its target VEGFA. However, overexpression of miR-17-5p blocked the pro-angiogenic ability of inflamed PDLSCs. In conclusion, the findings indicated that vascularization of periodontal ligaments was enhanced, and inflammatory micro-environment of periodontitis facilitated pro-angiogenesis of PDLSCs through regulating exosome-mediated transfer of VEGFA, which was targeted by miR-17-5p.

3D Printing of Photocuring Elastomers with Excellent Mechanical Strength and Resilience.

Three-dimensional (3D) printing elastomers, as a combination of transformative technology and widely used materials, have received great demand in many fields. However, commercial photocuring elastomer inks for 3D printing usually exhibit poor mechanical strength, inferior resilience, and lower elongation at break. In this study, photocuring inks that can be employed for digital light processing 3D printing are developed with acryloyl-modified polyethylene glycol (Acryl@PEG). The resultant photocuring inks exhibit not only high tensile strength of 14.1 MPa and elongation of 245.0%, but also excellent resilience (recover to 90.85% after 30 min under the 200% strain). With the photocuring elastomer inks, a variety of architectures including hollow vases, eggs, finger rings, and porous lattices are built with excellent precision, which all could experience large shape deformations repeatedly without any damage, indicating the excellent elasticity, outstanding shape-recovery property, and mechanical stability. The present photocuring elastomer inks for 3D printing are therefore believed to be promising for soft robots, wearable devices, flexible electronics, and many other applications.

Topological Glycopolymers as Agglutinator and Inhibitor: Cyclic versus Linear.

Carbohydrates play an important role in biological processes for their specific interactions with proteins. Cyclic glycopolymers are promising to mimic the topology of natural macrocycle-biomacromolecules due to their unique architecture of lacking chain ends. To systematically study the effect of glycopolymer architecture on the interactions with protein, the cyclic glycopolymers bearing galactose side-chain (cyclic PMAGn ) with three degrees of polymerization (n = 14, 24, 47) are prepared for the first time. The cyclic PMAGn exhibits unique properties in agglutinating and inhibiting proteins in subsequent studies by comparison with the linear precursor with the same molecular weights. More impressively, the cyclic PMAGn highlight the improved performance of cyclic architecture. For example, the cyclic PMAGn shows superior inhibition abilities to suppress amyloid formation from amyloid ß protein fragment 1-42 aggregation and block the specific interaction between bacteria and galactose-modified surface compared to that of respective linear counterpart. This interesting finding suggests that the architecture of cyclic glycopolymers may be capable of optimizing the ability to bind or inhibit proteins in biological processes.

A biomimetic tumor tissue phantom for validating diffusion-weighted MRI measurements.

PURPOSE: To develop a biomimetic tumor tissue phantom which more closely reflects water diffusion in biological tissue than previously used phantoms, and to evaluate the stability of the phantom and its potential as a tool for validating diffusion-weighted (DW) MRI measurements. METHODS: Coaxial-electrospraying was used to generate micron-sized hollow polymer spheres, which mimic cells. The bulk structure was immersed in water, providing a DW-MRI phantom whose apparent diffusion coefficient (ADC) and microstructural properties were evaluated over a period of 10 months. Independent characterization of the phantom's microstructure was performed using scanning electron microscopy (SEM). The repeatability of the construction process was investigated by generating a second phantom, which underwent high resolution synchrotron-CT as well as SEM and MR scans. RESULTS: ADC values were stable (coefficients of variation (CoVs) < 5%), and varied with diffusion time, with average values of 1.44 ± 0.03 µm2 /ms (Δ = 12 ms) and 1.20 ± 0.05 µm2 /ms (Δ = 45 ms). Microstructural parameters showed greater variability (CoVs up to 13%), with evidence of bias in sphere size estimates. Similar trends were observed in the second phantom. CONCLUSION: A novel biomimetic phantom has been developed and shown to be stable over 10 months. It is envisaged that such phantoms will be used for further investigation of microstructural models relevant to characterizing tumor tissue, and may also find application in evaluating acquisition protocols and comparing DW-MRI-derived biomarkers obtained from different scanners at different sites. Magn Reson Med 80:147-158, 2018. © 2017 The Authors Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

In Situ Endothelialization Promoted by SEMA4D and CXCL12 for Titanium-Based Biomaterials.

In situ endothelialization, aiming to create implantation surfaces capable of self-endothelialization, seems to be an extremely promising solution, particularly on those blood-contacting surfaces. In this research study, we immobilized the soluble semaphorin 4D (SEMA4D) and C-X-C motif chemokine ligand 12 (CXCL12) biomolecules together with heparin onto the metal-based biomaterial surfaces to achieve in situ endothelialization of modified samples both by stimulating the neighboring endothelial cells (ECs) migration and by capturing the circulating endothelial progenitor cells (EPCs) directly from the blood circulation. X-ray photoelectron spectroscopy data demonstrate the successful immobilization of SEMA4D and CXCL12. Due to the presence of heparin, hemocompatibility was also improved after modification. Although EC migration was mainly mediated by SEMA4D with the coordination of CXCL12, EC proliferation and haptotaxis property were also enhanced, while EC chemotaxis was slightly suppressed because the further immobilization of CXCL12 influences the release of SEMA4D. The results of the ex vivo EPC capturing assay indicated the mobilization of CXCL12 promotes EPC adhesion. In vivo implantation further demonstrated that CXCL12 cooperates with SEMA4D to promote a process of in situ endothelialization.

Cooperation of Amphiphilicity and Smectic Order in Regulating the Self-Assembly of Cholesterol-Functionalized Brush-Like Block Copolymers.

Nanoparticle morphology significantly affects the application of nanometer-scale materials. Understanding nanoparticle formation mechanisms and directing morphological control in nanoparticle self-assembly processes have received wide attention. Herein, a series of brush-like amphiphilic liquid crystalline block copolymers, PChEMA m- b-POEGMA n, containing cholesteryl mesogens with different hydrophobic/hydrophilic block ratios were designed and synthesized. The self-assembly behaviors of the resulting PChEMA m- b-POEGMA n block copolymers in different solvents (tetrahydrofuran/H2O, 1,4-dioxane/H2O, and N, N-dimethylformamide) were investigated in detail. Desirable micellar aggregates with well-organized architectures, including short cylindrical micelles, nanofibers, fringed platelets, and ellipsoidal vesicles with smectic micellar cores, were observed in 1,4-dioxane/H2O with an increasing hydrophobic block ratio. Although both amphiphilicity and smectic order governed the self-assembly, these two factors were differently balanced in the different solvents. This unique supramolecular system provides a new strategy for the design of advanced functional nanomaterials with tunable morphologies.

Bio-Inspired Design and Fabrication of Micro/Nano-Brush Dual Structural Surfaces for Switchable Oil Adhesion and Antifouling.

The underwater superoleophobic surfaces play a significant role in anti-oil contamination, marine antifouling, etc. Inspired by the Gecko's feet and its self-cleaning property, a hierarchical structure composed of poly (acrylic acid) gel micro-brushes is designed by the liquid-infused method. This surface exhibits underwater superoleophobicity with very low oil adhesion. It is then modified with stimuli-responsive polymer nano-brushes via surface-initiated atom transfer radical polymerization from the embedded initiator. The micro/nano-brush dual structural surfaces can switch the underwater oil adhesion between low and high while keeping the superoleophobicity. The antifouling properties against algae attachment under different mediums are also investigated to show a strong link between oleophobicity and antibiofouling property. The model surface will be very useful in directing the design of marine self-cleaning coatings to both living and non-living species.

Squid Suckerin Biomimetic Peptides Form Amyloid-like Crystals with Robust Mechanical Properties.

We present the self-assembly of fibers formed from a peptide sequence (A1H1) derived from suckerin proteins of squid sucker ring teeth (SRT). SRT are protein-only biopolymers with an unconventional set of physicochemical and mechanical properties including high elastic modulus coupled with thermoplastic behavior. We have identified a conserved peptide building block from suckerins that possess the ability to assemble into materials with similar mechanical properties as the native SRT. A1H1 displays amphiphilic characteristics and self-assembles from the bottom-up into mm-scale fibers initiated by the addition of a polar aprotic solvent. A1H1 fibers are thermally resistant up to 239 °C, coupled with an elastic modulus of ∼7.7 GPa, which can be explained by the tight packing of ß-sheet-enriched crystalline building blocks as identified by wide-angle X-ray scattering (WAXS), with intersheet and interstrand distances of 5.37 and 4.38 Å, respectively. A compact packing of the peptides at their Ala-rich terminals within the fibers was confirmed from molecular dynamics simulations, and we propose a hierarchical model of fiber assembly of the mature peptide fiber.

Ultrafast Killing and Self-Gelling Antimicrobial Imidazolium Oligomers.

Infectious diseases and the increasing threat of worldwide pandemics have underscored the importance of antibiotics and hygiene. Intensive efforts have been devoted to developing new antibiotics to meet the rapidly growing demand. In particular, advancing the knowledge of the structure-property-activity relationship is critical to expedite the design and development of novel antimicrobial with the needed potential and efficacy. Herein, a series of new antimicrobial imidazolium oligomers are developed with the rational manipulation of terminal group's hydrophobicity. These materials exhibit superior activity, excellent selectivity, ultrafast killing (>99.7% killing within 30 s), and desirable self-gelling properties. Molecular dynamic simulations reveal the delicate effect of structural changes on the translocation motion across the microbial cell membrane. The energy barrier of the translocation process analyzed by free energy calculations provides clear kinetic information to suggest that the spontaneous penetration requires a very short timescale of seconds to minutes for the new imidazolium oligomers.

Gecko-inspired but chemically switched friction and adhesion on nanofibrillar surfaces.

Chemically switched friction nano-fibrillar surfaces (SiNWAs-PSPMA & SiNWAs-PMAA arrays) can be constructed by finely decorating ordered Si nanowire arrays with responsive polymer brushes. As expected, these surfaces sense humidity or pH smartly and show reversible friction switching, based on swelling and shrinking of the polymer brushes, which is successfully monitored by AFM in liquid media.

One-step modification of fabrics with bioinspired polydopamine@octadecylamine nanocapsules for robust and healable self-cleaning performance.

An in-situ polymerization to coat fabrics with polydopamine-encapsulated octadecylamine endows the fabrics with self-cleaning and self-healing abilities. The treated fabric exhibits self-healing after losing its hydrophobicity. It is durable against washing and mechanical abrasion without changing the hydrophobicity. Thanks to the versatile adhesive property of polydopamine, the approach is compatibile with a variety of substrates, such as fabrics, glass, sponge, paper, and polymeric materials.

Mussel-Inspired Photografting on Colloidal Spheres: A Generalized Self-Template Route to Stimuli-Responsive Hollow Spheres for Controlled Pesticide Release.

A thermo-controlled pesticide release system composed of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) thin film grafted polydopamine (PDA) (PDMAEMA-g-PDA) microcapsules is reported. SiO2 microparticles are used as a template to prepare PDA-coated SiO2 microparticles. The thermally-responsive PDMAEMA thin films are grafted on PDA surfaces using a metal-free surface-initiated photopolymerization approach without adding any photo-initiator or photosensitizer under UV light irradiation. The subsequent acid etching yields PDMAEMA-g-PDA hollow microcapsules. PDMAEMA-g-PDA microcapsules exhibit well-controlled release of avermectin (Av). The results show that the loading ability of PDMAEMA-g-PDA microcapsules of Av is up to 52.7% (w/w). The release kinetics of Av demonstrate that Av@PDMAEMA-g-PDA microcapsules exhibit temperature-controlled release performance. This work is significant for controlled release systems. This simple design is expected to be used in various applications, such as in controlled drug release and agriculture-related fields.

[Chemical Constituents from Macaranga denticulata Root].

OBJECTIVE: To study the chemical constituents from Macaranga denticulata Root. METHODS: The chemical constituents were isolated and purified by silica-gel column chromatography and recrystallization, and their structures were identified by physicochemical properties and spectral data. RESULTS: Nine compounds were isolated and identified as: gheddic acid (1), aleuritolic acid-3-acetate (2), ß-sitosterol (3), stigmast-4-en-6ß-ol-3 -one (4), 2α-hydroxyaleuritolic acid 3-p-hydroxybenzoate (5), scopoletin (6), daucosterol (7), 2, 6-dimethoxy-1,4-benzoquinone (8) and maslinic acid(9). CONCLUSION: Compounds 1-9 are obtained from this plant for the first time.