In situ densification and heparin immobilization of bacterial cellulose vascular patch for potential vascular applications.

Nowadays, developing vascular grafts (e.g., vascular patches and tubular grafts) is challenging. Bacterial cellulose (BC) with 3D fibrous network has been widely investigated for vascular applications. In this work, different from BC vascular patch cultured with the routine culture medium, dopamine (DA)-containing culture medium is employed to in situ synthesize dense BC fibrous structure with significantly increased fiber diameter and density. Simultaneously, BC fibers are modified by DA during in situ synthesis process. Then DA on BC fibers can self-polymerize into polydopamine (PDA) accompanied with the removal of bacteria in NaOH solution, obtaining PDA-modified dense BC (PDBC) vascular patch. Heparin (Hep) is subsequently covalently immobilized on PDBC fibers to form Hep-immobilized PDBC (Hep@PDBC) vascular patch. The obtained results indicate that Hep@PDBC vascular patch exhibits remarkable tensile and burst strength due to its dense fibrous structure. More importantly, compared with BC and PDBC vascular patches, Hep@PDBC vascular patch not only displays reduced platelet adhesion and improved anticoagulation activity, but also promotes the proliferation, adhesion, spreading, and protein expression of human umbilical vein endothelial cells, contributing to the endothelialization process. The combined strategy of in situ densification and Hep immobilization provides a feasible guidance for the construction of BC-based vascular patches.

Strong, tough, and elastic poly(vinyl alcohol)/polyacrylamide DN hydrogels based on the Hofmeister effect for articular cartilage replacement.

Traditional hydrogels are usually weak and brittle, which limit their application in articular cartilage replacement because cartilage is generally strong, tough, and elastic in nature. Therefore, it is highly desirable to construct hydrogels to mimic the mechanical properties of the native articular cartilage. Herein, in this work, poly(vinyl alcohol)/polyacrylamide (PVA/PAM) DN hydrogels were prepared by in situ polymerization, which were then treated with Hofmeister series ions (Cit3-, SO42-, and Cl-) to achieve H-PVA/PAM DN hydrogels. Among the three Hofmeister ions, the DN hydrogel treated with Cit3- (named PVA/PAM-Cit) showed the densest microstructure and the highest crystallinity degree. In this context, PVA/PAM-Cit exhibited a tensile strength of 18.9 ± 1.6 MPa, a compressive strength of 102.3 ± 7.9 MPa, a tensile modulus of 10.6 ± 2.1 MPa, a compressive modulus of 8.9 ± 0.8 MPa, and a roughness of 66.2 ± 4.2 MJ m-3, respectively, which were the highest strength and modulus, and the second highest toughness when compared with those of the reported PVA and PVA based DN hydrogels so far. It also showed an extreme high elasticity, which could maintain a stress of 99.2% after 500 cycles of fatigue testing. Additionally, PVA/PAM-Cit can promote the adhesion, spreading and proliferation of chondrocytes. These results verify that such a strong, tough, and elastic hydrogel could be a novel candidate material for articular cartilage replacement.

Water-Induced Expanded Bilayer Vascular Graft with Good Hemocompatibility and Biocompatibility.

Shape memory polymer (SMP) vascular grafts are promising interventional vascular grafts for cardiovascular disease (CAD) treatment; However, hemocompatibility and biocompatibility, which are the critical issues for the SMP vascular grafts, are not systematically concerned. Furthermore, the water-induced SMP grafts are more convenient and safer than the thermally induced ones in case of the bioapplication. Herein, in this work, the new water-induced expanded bilayer vascular graft with the inner layer of crosslinked poly(ε-caprolactone) (cPCL) and the outer layer of water-induced SMP of regenerated chitosan/polyvinyl alcohol (RCS/PVA) are prepared by hot pressing and programming approaches. The results show that the inner and outer layer surfaces of the prepared grafts are smooth, and they exhibit good interfacial interaction properties. The bilayer grafts show good mechanical properties and can be expanded in water with a diameter expansion of ≈30%. When compared with commercial expanded polytetrafluoroethylene (ePTFE), the bilayer graft shows better hemocompatibility (platelet adhesion, hemolysis rate, various clotting times, and plasma recalcification time (PRT)) and in vitro and in vivo biocompatibility, which thus is a promising material for the vascular graft.

Interface Engineering of Zinc Electrode for Rechargeable Alkaline Zinc-Based Batteries.

Rechargeable aqueous zinc-based batteries have gained considerable interest because of their advantages of high theoretical capacity, being eco-friendly, and cost effectiveness. In particular, zinc-based batteries with alkaline electrolyte show great promise due to their high working voltage. However, there remain great challenges for the commercialization of the rechargeable alkaline zinc-based batteries, which are mainly impeded by the limited reversibility of the zinc electrode. The critical problems refer to the dendrites growth, electrode passivation, shape change, and side reactions, affecting discharge capacity, columbic efficiency, and cycling stability of the battery. All the issues are highly associated with the interfacial properties, including both electrons and ions transport behavior at the electrode interface. Herein, this work concentrates on the fundamental electrochemistry of the challenges in the zinc electrode and the design strategies for developing high-performance zinc electrodes with regard to optimizing the interfaces between host and active materials as well as electrode and electrolyte. In addition, potential directions for the investigation of electrodes and electrolytes for high-performance zinc-based batteries are presented, aiming at promoting the development of rechargeable alkaline zinc-based batteries.

Zwitterionic Polysaccharide-Based Hydrogel Dressing as a Stem Cell Carrier to Accelerate Burn Wound Healing.

Stem cell therapy integrated with hydrogels has shown promising potential in wound healing. However, the existing hydrogels usually cannot reach the desired therapeutic efficacy for burn wounds due to the inadaptability to wound shape and weak anti-infection ability. Moreover, it is difficult to improve the environment for the survival and function of stem cells under complicated wound microenvironments. In this study, an injectable and self-healing hydrogel (DSC), comprising sulfobetaine-derived dextran and carboxymethyl chitosan, is fabricated through a Schiff-base reaction. Meanwhile, the DSC hydrogel shows high nonfouling properties, including resistance to bacteria and nonspecific proteins; moreover, the prepared hydrogel can provide a biomimetic microenvironment for cell proliferation whilst maintaining the stemness of adipose-derived stem cells (ADSCs) regardless of complex microenvironments. In burnt murine animal models, the ADSCs-laden hydrogel can significantly accelerate wound healing rate and scarless skin tissue regeneration through multiple pathways. Specifically, the ADSCs-laden DSC hydrogel can avoid immune system recognition and activation and thus reduce the inflammatory response. Moreover, the ADSCs-laden DSC hydrogel can promote collagen deposition, angiogenesis, and enhance macrophage M2 polarization in the wound area. In summary, sulfobetaine-derived polysaccharide hydrogel can serve as a versatile platform for stem cell delivery to promote burn wound healing.

Smart-Temporary-Film-Based Local-Delivery System with Controllable Drug-Release Behavior.

The development of a simple local drug-delivery system that exhibits the advantages of macro- and microscale carriers with controllable drug-release behavior is still highly desired. Herein, in this work, a smart temporary film was prepared from doxorubicin (DOX)-loaded shape-memory microgels via a simple hot-compression programming method. The temporary film showed a very smooth surface and easy handing, as well as macroscopy mechanical properties, which could disintegrate into the microgels with heating at 45 °C. In this case, the temporary film showed a controllable DOX release behavior when compared with the microgels, which could release the DOX on demand. Consequently, the temporary film exhibited weaker cytotoxicity to normal cells and a much longer antitumor capability, as well as a higher drug-utilization efficiency when compared with microgels. Therefore, the smart temporary film has high potential as a candidate for use as a local drug-delivery system.

Designment of polydopamine/bacterial cellulose incorporating copper (II) sulfate as an antibacterial wound dressing.

Improving antibacterial performance is one of the prerequisites for the clinical application of bacterial cellulose (BC)-based dressings. In this study, a novel copper (Cu) ion loaded BC-based antibacterial wound dressing was prepared via codeposition of polydopamine (PDA) and copper ion. The scanning electron microscope (SEM) results showed that the copper ion/PDA coating was more uniform than the PDA coating, and the 3D nanopore structure of BC was retained in Cu2+@PBC. Cu ions were immobilized by forming a chelate with PDA. The thermal stability and mechanical properties of the Cu2+@PBC dressing decreased with the addition of copper ions. Cu2+@PBC-2 film with a certain amount of copper sulfate used (10 nM) exhibited favorable antibacterial properties against both S. aureus and E. coli without obvious cytotoxicity. The results of the in vivo study also demonstrated that the Cu2+@PBC-2 film can eliminate S. aureus infections and inflammatory response, promote collagen deposition, capillary angiogenesis, hair follicle growth and wound healing. These results suggest that the Cu2+@PBC-2 film has prospective application as a wound dressing.

De novo strategy with engineering a multifunctional bacterial cellulose-based dressing for rapid healing of infected wounds.

The treatment and healing of infected skin lesions is one of the major challenges in surgery. To solve this problem, collagen I (Col-I) and the antibacterial agent hydroxypropyltrimethyl ammonium chloride chitosan (HACC) were composited into the bacterial cellulose (BC) three-dimensional network structure by a novel membrane-liquid interface (MLI) culture, and a Col-I/HACC/BC (CHBC) multifunctional dressing was designed. The water absorption rate and water vapor transmission rate of the obtained CHBC dressing were 35.78 ± 2.45 g/g and 3084 ± 56 g m-2·day-1, respectively. The water retention of the CHBC dressing was significantly improved compared with the BC caused by the introduced Col-I and HACC. In vitro results indicated that the combined advantages of HACC and Col-I confer on CHBC dressings not only have outstanding antibacterial properties against Staphylococcus aureus (S. aureus) compared with BC and CBC, but also exhibit better cytocompatibility than BC and HBC to promote the proliferation and spread of NIH3T3 cells and HUVECs. Most importantly, the results of in vivo animal tests demonstrated that the CHBC dressings fully promoted wound healing for 8 days and exhibited shorter healing times, especially in the case of wound infection. Excellent skin regeneration effects and higher expression levels of collagen during infection were also shown in the CHBC group. We believe that CHBC composites with favorable multifunctionality have potential applications as wound dressings to treat infected wounds.

Lithiophilic Carbon Nanofiber/Graphene Nanosheet Composite Scaffold Prepared by a Scalable and Controllable Biofabrication Method for Ultrastable Dendrite-Free Lithium-Metal Anodes.

Li metal is regarded as a promising anode for high-energy-density Li batteries, while the limited cycle life and fast capacity decay caused by notorious Li dendrite growth seriously impedes its application. Herein, a robust and highly lithiophilic bacterial cellulose-derived carbon nanofiber@reduced graphene oxide nanosheet (BC-CNF@rGO) composite scaffold is fabricated as a host for dendrite-free Li metal anode through an in situ biofabrication method. The abundant lithiophilic functional groups, conductive 3D network, and excellent mechanical property can effectively regulate uniform Li nucleation and deposition, enable fast reaction kinetics, and alleviate volume change. As a result, the BC-CNF@rGO skeleton achieves exceptional Li plating/stripping performance with a high average Coulombic efficiency of 98.3% over 800 cycles, and a long cycle life span of 5000 h at 2 mA cm-2 @1 mAh cm-2 with a low overpotential of ≈15 mV for lithium plating. Furthermore, full cells coupling BC-CNF@rGO-Li anode with LiFePO4 cathode achieves an unprecedented cycling stability with a long cycle life of 3000 cycles at 1 C. This work sheds light on a promising material design and fabrication strategy for realizing high performance Li metal batteries.

Fabrication of Robust, Shape Recoverable, Macroporous Bacterial Cellulose Scaffolds for Cartilage Tissue Engineering.

Recently, the fabricating of three-dimensional (3D) macroporous bacterial cellulose (MP-BC) scaffolds with mechanically disintegrated BC fragments has attracted considerable attention. However, the successful implementation of these materials depends mainly on their mechanical stability and robustness. Here, a non-toxic crosslinker, 1-ethyl-3-(-3-dimethylaminopropyl) carbodiimide hydrochloride/N-hydroxysuccinimide (EDC/NHS), is employed to induce crosslinking reactions between BC fragments. In addition to their large pore sizes, the EDC/NHS-crosslinked MP-BC scaffolds exhibit excellent compression properties and shape recovery ability, owing to the EDC/NHS-induced crosslinking on the BC nanofibers. The results of in vitro studies reveal that the biocompatibility of MP-BC scaffolds is better than that of pristine BC scaffolds because the former provided more space for cell proliferation. The results of in vivo studies show that the neocartilage tissue with native cartilage appearance and abundant cartilage-specific extracellular matrix deposition is successfully regenerated in nude mice. The findings reveal the immense application potential of mechanically robust BC scaffolds with controllable pore sizes and shape-recoverable properties in tissue engineering.

Fabrication of a gradient hydrophobic surface with parallel ridges on pyrolytic carbon for artificial heart valves.

Effective surface modification to endow pyrolytic carbon (PYC) with long-term anti-thrombotic performance is highly demanded. In this work, a gradient hydrophobic surface on PYC was prepared by creating parallel ridges via the combination of laser etching technology and surface fluorosilanization. Scanning electron microscopy (SEM) observation confirms that the gradient hydrophobic surface is composed of a bare PYC region and four regions of parallel ridges with varying distances. The gradient hydrophobic surface is stable in air, phosphate buffer solution (PBS), and flowing PBS. Additionally, the gradient hydrophobic surface on PYC shows spontaneous droplet motion and much lower flow resistance than bare PYC. Compared to bare PYC, the gradient hydrophobic surface on PYC exhibits better blood compatibility and anti-adhesion performance. The results presented in this paper confirm that creating a gradient hydrophobic surface is an effective way of achieving long-lasting anti-thrombosis property.

Ultrathin, Strong, and Highly Flexible Ti3C2Tx MXene/Bacterial Cellulose Composite Films for High-Performance Electromagnetic Interference Shielding.

The fabrication of ultrathin films that are electrically conductive and mechanically strong for electromagnetic interference (EMI) shielding applications is challenging. Herein, ultrathin, strong, and highly flexible Ti3C2Tx MXene/bacterial cellulose (BC) composite films are fabricated by a scalable in situ biosynthesis method. The Ti3C2Tx MXene nanosheets are uniformly dispersed in the three-dimensional BC network to form a mechanically entangled structure that endows the MXene/BC composite films with excellent mechanical properties (tensile strength of 297.5 MPa at 25.7 wt % Ti3C2Tx) and flexibility. Importantly, a 4 µm thick Ti3C2Tx/BC composite film with 76.9 wt % Ti3C2Tx content demonstrates a specific EMI shielding efficiency of 29141 dB cm2 g-1, which surpasses those of most previously reported MXene-based polymer composites with similar MXene contents and carbon-based polymer composites. Our findings show that the facile, environmentally friendly, and scalable fabrication method is a promising strategy for producing ultrathin, strong, and highly flexible EMI shielding materials such as the freestanding Ti3C2Tx/BC composite films for efficient EMI shielding to address EMI problems of a fast-developing modern society.

Simultaneous engineering of nanofillers and patterned surface macropores of graphene/hydroxyapatite/polyetheretherketone ternary composites for potential bone implants.

Incorporating bioactive nanofillers and creating porous surfaces are two common strategies used to improve the tissue integration of polyetheretherketone (PEEK) material. However, few studies have reported the combined use of both strategies to modify PEEK. Herein, for the first time, dual nanoparticles of graphene oxide (GO) and hydroxyapatite (HAp) were incorporated into PEEK matrix to obtain ternary composites that were laser machined to create macropores with diameters ranging from 200 µm to 600 µm on the surfaces. The surface morphology and chemistry, mechanical properties, and cellular responses of the composites were investigated. The results show that micropatterned pores with a depth of 50 µm were created on the surfaces of the composites, which do not significantly affect the mechanical properties of the resultant composites. More importantly, the incorporation of GO and HAp significantly improves the cell adhesion and proliferation on the surface of PEEK. Compared to the smooth surface composite, the composites with macroporous surface exhibit markedly enhanced cell viability. The combined use of nanofillers and surface macropores may be a promising way of improving tissue integration of PEEK for bone implants.

Heparinization and hybridization of electrospun tubular graft for improved endothelialization and anticoagulation.

Constructing biomimetic structure and immobilizing antithrombus factors are two effective methods to ensure rapid endothelialization and long-term anticoagulation for small-diameter vascular grafts. However, few literatures are available regarding simultaneous implementation of these two strategies. Herein, a nano-micro-fibrous biomimetic graft with a heparin coating was prepared via a step-by-step in situ biosynthesis method to improve potential endothelialization and anticoagulation. The 4-mm-diameter tubular graft consists of electrospun cellulose acetate (CA) microfibers and entangled bacterial nanocellulose (BNC) nanofibers with heparin coating on dual fibers. The hybridized and heparinized graft possesses suitable pore structure that facilitates endothelia cells adhesion and proliferation but prevents infiltration of fibrous tissue and blood leakage. In addition, it shows higher mechanical properties than those of bare CA and hybridized CA/BNC grafts, which match well with native blood vessels. Moreover, this dually modified graft exhibits improved blood compatibility and endothelialization over the counterparts without hybridization or heparinization according to the testing results of platelet adhesion, cell morphology, and protein expression of von Willebrand Factor. This novel graft with dual modifications shows promising as a new small-diameter vascular graft. This study provides a guidance for promoting endothelialization and blood compatibility by dual modifications of biomimetic structure and immobilized bioactive molecules.

Engineering a novel antibacterial agent with multifunction: Protocatechuic acid-grafted-quaternized chitosan.

As a mild cationic antibacterial agent, hydroxypropyltrimethyl ammonium chloride chitosan (HACC) could kill gram-positive bacteria and gram-positive drug-resistant bacteria without cytotoxicity. Nevertheless, it was not effective against gram-negative bacteria. Herein, protocatechuic acid (PA) with broad-spectrum antibacterial properties and pharmacological activities was grafted on HACC. PA-g-HACC showed favourable antioxidant capacity and anti-inflammatory properties. Most importantly, the results of antibacterial assay indicated that the antibacterial rates of all PA-g-HACC groups against Staphylococcus aureus (S. aureus) and methicillin-resistant Staphylococcus aureus (MRSA) were above 92 %, and the antibacterial rate of PA-g-HACC against E. coli was increased with the amount of grafted PA. Furthermore, the cytocompatibility of PA-g-HACC was improved by appropriate grafting ratio of PA, while excessive grafted PA can lead to toxicity. We believe that PA-g-HACC in optimum grafting ratio of PA with favorable antibacterial properties, pharmacological activities and cytocompatibility will be potential antibacterial agent for treating infections.

Enhanced Physicochemical and Biological Properties of a Low-Temperature Copperized Layer on Gradient Nanograined Pure Titanium.

The application of titanium as medical implants is limited to a certain extent due to its insufficient corrosion resistance, biological activity, and antibacterial ability. In this work, a gradient nanograined (GNG) layer was fabricated on the titanium surface by surface ultrasonic rolling treatment (SURT). The subsequent copperizing kinetics was greatly enhanced so that a thick copperized layer could be obtained on the surface of GNG Ti at a relatively low diffusion temperature (450 °C). Meanwhile, the GNG structure accelerated the release rate of Cu2+, which endows GNG Cu/Ti with strong antibacterial activity. Moreover, the corrosion resistance and cytocompatibility of GNG Cu/Ti were also evidently improved compared with coarse-grained Ti, indicating a good biomedical application prospect.

Enwrapping Polydopamine on Doxorubicin-Loaded Lamellar Hydroxyapatite/Poly(lactic-co-glycolic acid) Composite Fibers for Inhibiting Bone Tumor Recurrence and Enhancing Bone Regeneration.

Simultaneous prevention of bone tumor recurrence and promotion of repairing bone defects resulting from tumorectomy remain a challenge. Herein, we report a polydopamine (PDA)-coated composite scaffold consisting of doxorubicin (DOX)-loaded lamellar hydroxyapatite (LHAp) and poly(lactic-co-glycolic acid) (PLGA) in an attempt to reach dual functions of tumor inhibition and bone repair. The DOX was intercalated into LHAp, and the DOX-loaded LHAp was incorporated into PLGA solution to prepare a DOX-intercalated LHAp/PLGA (labeled as DH/PLGA) scaffold that was coated with PDA to obtain a PDA@DH/PLGA scaffold. The morphology, structure, wettability, mechanical properties, drug release, biocompatibility, and in vitro and in vivo bioactivities of the PDA@DH/PLGA scaffold were evaluated. It is found that PDA coating not only improves hydrophilicity and mechanical properties, but also leads to more sustainable drug release. More importantly, the PDA@DH/PLGA scaffold shows significantly inhibited growth of tumor cells initially and subsequent improved adhesion and proliferation of osteoblasts. In addition, the PDA coating improves the bioactivity of the DH/PLGA scaffold as suggested by the in vitro biomineralization. Further in vivo study demonstrates the improved bone growth around PDA@DH/PLGA over DH/PLGA after 20 days of drug release. The dual functional PDA@DH/PLGA scaffold shows great promise in the treatment of bone tumor.

Gaseous sulfur trioxide induced controllable sulfonation promoting biomineralization and osseointegration of polyetheretherketone implants.

Fabricating a desired porous structure on the surface of biomedical polyetheretherketone (PEEK) implants for enhancing biological functions is crucial and difficult due to its inherent chemical inertness. In this study, a porous surface of PEEK implants was fabricated by controllable sulfonation using gaseous sulfur trioxide (SO3) for different time (5, 15, 30, 60 and 90 min). Micro-topological structure was generated on the surface of sulfonated PEEK implants preserving original mechanical properties. The protein absorption capacity and apatite forming ability was thus improved by the morphological and elemental change with higher degree of sulfonation. In combination of the appropriate micromorphology and bioactive sulfonate components, the cell adhesion, migration, proliferation and extracellular matrix secretion were obviously enhanced by the SPEEK-15 samples which were sulfonated for 15 min. Finding from this study revealed that controllable sulfonation by gaseous SO3 would be an extraordinarily strategy for improving osseointegration of PEEK implants by adjusting the microstructure and chemical composition while maintaining excellent mechanical properties.

Controllable synthesis of biomimetic nano/submicro-fibrous tubes for potential small-diameter vascular grafts.

Mimicking the morphological structure of native blood vessels is critical for the development of vascular grafts. Herein, small-diameter composite vascular grafts that integrate the nanofibrous bacterial cellulose (BC) and submicrofibrous cellulose acetate (CA) were fabricated via a combined electrospinning and step-by-step in situ biosynthesis. Scanning electron microscopy (SEM) observation shows the nano/submicro-fibrous morphology and well-interconnected porous structure of the BC/CA grafts. It is found that the BC/CA graft with a suitable BC content demonstrates lower potential of thrombus formation and enhanced endothelialization as compared to the BC and CA counterparts. Western blotting and RT-qPCR results suggest that the BC/CA-2 graft promotes endothelialization by improving expressions of genes vWF-1 and CD31 and protein CD31. The in vivo tests demonstrate much lower inflammatory response to the BC/CA graft. These results suggest that the BC/CA graft shows a great potential as an artificial graft for rapid formation of an endothelial cell monolayer.

From Molecular Reconstruction of Mesoscopic Functional Conductive Silk Fibrous Materials to Remote Respiration Monitoring.

Turning insulating silk fibroin materials into conductive ones turns out to be the essential step toward achieving active silk flexible electronics. This work aims to acquire electrically conductive biocompatible fibers of regenerated Bombyx mori silk fibroin (SF) materials based on carbon nanotubes (CNTs) templated nucleation reconstruction of silk fibroin networks. The electronical conductivity of the reconstructed mesoscopic functional fibers can be tuned by the density of the incorporated CNTs. It follows that the hybrid fibers experience an abrupt increase in conductivity when exceeding the percolation threshold of CNTs >35 wt%, which leads to the highest conductivity of 638.9 S m-1 among organic-carbon-based hybrid fibers, and 8 times higher than the best available materials of the similar types. In addition, the silk-CNT mesoscopic hybrid materials achieve some new functionalities, i.e., humidity-responsive conductivity, which is attributed to the coupling of the humidity inducing cyclic contraction of SFs and the conductivity of CNTs. The silk-CNT materials, as a type of biocompatible electronic functional fibrous material for pressure and electric response humidity sensing, are further fabricated into a smart facial mask to implement respiration condition monitoring for remote diagnosis and medication.