Highly plastic Zn-0.3Ca alloy for guided bone regeneration membrane:Breaking the trade-off between antibacterial ability and biocompatibility

A common problem for Zn alloys is the trade-off between antibacterial ability and biocompatibility.This paper proposes a strategy to solve this problem by increasing release ratio of Ca^(2+)ions,which is realized by significant refinement of CaZn13 particles through bottom circulating water-cooled casting(BCWC)and rolling.Compared with conventionally fabricated Zn-0.3Ca alloy,the BCWC-rolled alloy shows higher antibacterial abilities against E.coli and S.aureus,meanwhile much less toxicity to MC3T3-E1 cells.Additionally,plasticity,degradation uniformity,and ability to induce osteogenic differentiation in vitro of the alloy are improved.The elongation up to 49%,which is the highest among Zn alloys with Ca,and is achieved since the sizes of CaZn_(13) particles and Zn grains are small and close.As a result,the long-standing problem of low formability of Zn alloys containing Ca has also been solved due to the elimination of large CaZn_(13) particles.The BCWC-rolled alloy is a promising candidate of making GBR membrane.

Mussel-inspired Methacrylic Gelatin-dopamine/Ag Nanoparticles/Graphene Oxide Hydrogels with Improved Adhesive and Antibacterial Properties for Applications as Wound Dressings

A novel strategy was developed to prepare the methacrylic gelatin-dopamine(GelMA-DA)/Ag nanoparticles(NPs)/graphene oxide(GO) composite hydrogels with good biocompatibility,mechanical properties,and antibacterial activity.Mussel-inspired DA was utilized to modify the GelMA molecules,which imparts good adhesive performance to the hydrogels.GO,interfacial enhancer,not only improves mechanical properties of the hydrogels,but also provides anchor sites for loading Ag NPs through numerous oxygencontaining functional groups on the surface.The experimental results show that the GelMA/Ag NPs/GO hydrogels have good biocompatibility,and exhibit a swelling rate of 202±16%,the lap shear strength of 147±17 kPa,and compressive modulus of 136±53 kPa,in the case of the Ag NPs/GO content of 2 mg/mL.Antibacterial activity of the hydrogels against both gram-negative and gram-positive bacteria is dependent on the Ag NPs/GO content derived from the release of Ag^(+).Furthermore,the GelMA/Ag NPs/GO hydrogels possess good adhesive ability,which is resistant to highly twisted state when stuck on the surface of pigskin.These results demonstrate promising potential of the GelMA-DA/Ag NPs/GO hydrogels as wound dressings for biomedical applications in clinical and emergent treatment.

The effect of applied voltages on the structure,apatite-inducing ability and antibacterial ability of micro arc oxidation coating formed on titanium surface

The micro arc oxidation(MAO)coatings with different concentrations of Ca,P and Zn elements are successfully formed on the titanium substrate at the different applied voltages.After MAO treatment,the MAO coating exhibits the porous surface structure and composed of anatase and rutile TiO2 phases.Meanwhile,the average size and density of micro-pores on the MAO coatings have been modified via the adjusting the applied voltages.In addition,the contents of the incorporated elements such as Zn,Ca and P elements in the MAO coatings have been optimized.The bonding strength test results reveal that the MAO coating shows higher bonding strength,which is up to 45±5 MPa.Compared to the pure Ti plate,the MAO coating formed at 350 and 400 V show good apatite-inducing ability.Meanwhile,the MAO coating containing Zn,Ca and P elements have better antibacterial ability for E.coli and S.aureus.Thus,the incorporation of Zn,Ca and P elements was an effective method to improve the antibacterial ability.Moreover,the concentrations of Zn,Ca and P elements could be adjusted with the changing of the applied voltages.As a result,the enhancement of the antibacterial ability on the MAO coating surfaces was depended on the comprehensive effect of the incorporated elements and the surface property of MAO coatings.

Corrosion behavior,antibacterial ability,and osteogenic activity of Zn-incorporated Ni-Ti-O nanopore layers on NiTi alloy

Development of bone fixation devices with excellent corrosion resistance,antibacterial ability,and osteogenic activity is critical for promoting fracture healing.In this study,Zn-incorporated nanopore(NP)layers were prepared on the NiTi alloy through anodization and hydrothermal treatment.Results show that Zn can be evenly incorporated into the NP layers in the form of ZnTiO_(2).The Zn-incorporated samples exhibit good corrosion resistance and significantly reduce Ni^(2+)release.Meanwhile,the samples can continuously release Zn^(2+),which is responsible for excellent long-term antibacterial ability.Furthermore,the synergetic effect of Zn^(2+) release and nanoporous structure of the NP layers endues the NiTi alloy excellent osteogenic activity,as verified by upregulated alkaline phosphatase activity,secretion of type I collagen,and extracellular matrix mineralization.Therefore,Zn-incorporated Ni-Ti-O NP layers have great potential as biomedical coatings of NiTi-based implant materials.

Effect of N_(2) partial pressure on comprehensive properties of antibacterial TiN/Cu nanocomposite coating

Foreign body reactions to the wear debris and corrosion products from the implants,and bacterial infections are the main factors leading to the implant failures.In order to resolve these problems,the antibacterial TiN/Cu nanocomposite coatings with various N_(2) partial pressures were deposited on 304 stainless steels(SS)using an arc ion plating(AIP)system,named TiN/Cu-x(x=0.5,1.0,1.5 Pa).The results of X-ray diffraction analysis,energy-dispersive X-ray spectroscopy,and scanning electron microscopy showed that the N_(2) partial pressures determined the Cu contents,surface defects,and crystallite sizes of TiN/Cu nanocomposite coatings,which further influenced the comprehensive abilities.And the hardness and wear resistances of TiN/Cu coatings were enhanced with increase of the crystallite sizes.Under the co-actions of surface defects,crystallite sizes,and Cu content,TiN/Cu-1.0 and TiN/Cu-1.5 coatings possessed excellent corrosion resistance.Besides,the biological tests proved that all the TiN/Cu coatings showed no cytotoxicity with strong antibacterial ability.Among them,TiN/Cu-1.5 coating significantly promoted the cell proliferation,which is expected to be a novel antibacterial,corrosion-resistant,and wear-resistant coating on the surfaces of medical implants.

Preparation of biomedical Ag incorporated hydroxyapatite/titania coatings on Ti6Al4V alloy by plasma electrolytic oxidation

Nano-Ag incorporated hydroxyapatite/titania （HA/TiO2） coatings were deposited on Ti6A14V substrates by the plasma electrolytic oxidation process. Compared with the substrate, the deposited coatings display attractive mechani- cal and biomedical properties. First, the coatings have stronger wear resistance and corrosion resistance. Second, they show a strong antibacterial ability. The mean vitality of the P. gingivalis on the coating surfaces is reduced to about 21%. Third, the coatings have good biocompatibility. The mean viability of the fibroblast cells on the coating surface is increased to about 130%. With these attractive properties, Ag incorporated HA/TiO2 coatings may be useful in the biomedical field.

One-step co-doping of ZnO and Zn^(2+)in osteoinductive calcium phosphate ceramics with synergistic antibacterial activity for regenerative repair of infected bone defect

How to endow bone grafts with long-term antibacterial activity and good bone regenerative ability to achieve the regenerative repair of infected bone defects has been the focus of the clinical treatment of osteomyelitis.The present study introduced a novel one-step route to realizing the co-doping of zinc oxide(ZnO)and zinc ion(Zn^(2+))in biphasic calcium phosphate(BCP)ceramics to utilize their synergistic antibacterial.Compared with the conventional BCP ceramics(BCP-Ca),the ZnO/Zn^(2+)co-doping ones(BCP-Zn)possessed strong antibacterial ability on E.coli and S.aureus as well as stimulated the osteogenic differentiation of bone marrow mesenchymal stem cells(BMSCs)effectively.The synergistic antibacterial mechanism of ZnO and Zn^(2+)was also investigated.BCP-Zn showed excellent osteoinductivity and angiogenesis at three months postoperatively in the canine intramuscular implantation model.Moreover,BCP-Zn exhibited excellent anti-infective ability and bone regenerative repair compared to BCP-Ca and control groups in the infected bone defect model of rat femur.Collectively,these findings suggest that the simultaneous introduction of ZnO/Zn^(2+)could have immense potential to expand the application of osteoinductive BCP ceramics in the regenerative repair of infected bone defects.

Jellyfish bio-inspired Fe@CNT@CuNC derived from ZIF-8 for cathodic oxygen reduction

Biomimetics provides guidance to design and synthesize advanced catalysts for oxygen reduction reaction in microbial fuel cells(MFCs).Herein,jellyfish-inspired Fe clusters on carbon nanotubes connected with CuNC(Fe@CNT@CuNC)were designed and prepared by using zeolitic imidazolate framework(ZIF)-8 precursors to imitate the organic texture and function of jellyfish.The antibacterial effect of Cu^(+)ions depressed the growth of cathode biofilm to ensure rapid mass transport.Fe clusters and CuNC connected by CNTs accelerated the electron transfer from Fe to CuNC.The optimization of oxygen adsorption was caused by electron redistribution between sites of Fe and Cu.Jellyfish-like catalysts achieved a half-wave potential of 0.86 V and onset potential of 0.95 V vs.reversible hydrogen electrode(RHE).MFCs gained the maximum power density of 1600 mW·m^(-2) after 500 h measurement.This work provides insights into the special design of advanced catalysts based on bio-inspiration and biomimetics.

Microstructure, biodegradation, antibacterial and mechanical properties of ZK60-Cu alloys prepared by selective laser melting technique

Magnesium （Mg） alloys are receiving increasing attention for body implants owing to their good bio- compatibility and biodegradability. However, they often suffer from bacterial infections on account of their insufficient antibacterial ability. In this study, ZK60-xCu （x = O, 0.2, 0.4, 0.6 and 0.8 wt%） alloys were prepared by selective laser melting （SLM） with alloying copper （Cu） to enhance their antibacterial ability. Results showed that ZK60-Cu alloys exhibited strong antibacterial ability due to combination of release of Cu ions and alkaline environment which could kill bacteria by destroying cellular membrane structure, denaturing enzymes and inhibiting deoxyribonucleic acid （DNA） replication. In addition, their compres- sive strength increased due to grain refinement and uniformly dispersing of short-bar shaped MgZnCu phases. Moreover, ZK60-Cu alloys also exhibited good cytocompatibility. In summary, ZK60-Cu alloys with antibacterial ability may be Dromising implants for biomedical anDlications.

Fabricating antibacterial CoCrCuFeNi high-entropy alloy via selective laser melting and in-situ alloying

A quasi-equiatomic CoCrFeCuNi high-entropy alloy(HEA) with a broad-spectrum antibacterial ability and good mechanical properties has been fabricated by selective laser melting(SLM) and in-situ alloying of a blend of pre-alloyed CoCrFeNi powder and Cu elemental powder.The as-built HEA alloy has a homogeneous distribution of Cu and presents a single FCC phase.Compared with the same HEA fabricated using the traditional ingot metallurgy(IM) process,the HEA alloy fabricated by SLM releases more Cu ions to prevent growth and biofilm formation by gram-negative Escherichia coli and gram-positive Staphylococcus aureus,which enhances the applicability of the HEA alloy in potential applications that requires antibacterial ability.The results of this study confirm the feasibility of combining the antibacterial CoCrFeCuNi HEA alloy and SLM technology in fabricating complex shaped parts or structures with a strong antibacterial ability to be used in medical application or other environments desired for antibacterial ability.

Antibacterial and pH-responsive Quaternized Hydroxypropyl Cellulose-g-Poly(THF-co-epichlorohydrin)Graft Copolymer:Synthesis,Characterization and Properties

The novel quaternized hydroxypropyl cellulose-g-poly(THF-co-epichlorohydrin)graft copolymers,HPC-g-QCP(THF-co-ECH),have been successfully synthesized to combine the properties from hydrophilic hard HPC biomacromolecular backbone and hydrophobic flexible polyether branches.Firstly,the P(THF-co-ECH)living chains were synthesized by cationic ring-opening copolymerization of THF with ECH.Secondly,P(THF-co-ECH)living chains were grafted onto HPC backbone by reaction with-OH groups along HPC to produce HPC-g-P(THF-co-ECH)graft copolymers.Thirdly,the mentioned graft copolymers were quaternized by reaction with ternanyamine to generate functionalized HPC-g-QCP(THF-co-ECH).The HPC-g-QCP(THF-co-ECH)graft copolymers exhibited good antibacterial ability against S.aureus or E.coli bacteria.The ibuprofen(IBU)-loaded microparticles of HPC-g-(QC)P(THF-co-ECH)graft copolymers were prepared by electrospraying.The in vitro pH-responsive drug-release behavior of IBU reached up to 75%of drug-loaded at pH=7A.This quaternized graft copolymer was beneficial to solving the problems of a burst effect and fast release of HPC as drug carriers.

Optimized Mechanical Properties,Corrosion Resistance and Bactericidal Ability of Ti-15Zr-xCu Biomedical Alloys During Aging Treatment

The effects of different aging conditions on the microstructure,strength,corrosion resistance,cytotoxicity and antibacterial ability of Ti-15Zr-xCu(3≤x≤7,wt%)(TZC)alloys were systematically investigated.Microstructural evolution and behavior were analyzed by X-ray diffraction(XRD)patterns and scanning electron microscopy with energy-dispersive spectroscopy(SEM-EDS),while potentiodynamic polarization technique was employed to characterize the corrosion response of the alloys after solution-treatment and aging(STA).High-temperature aging at 660℃ for 4 h(660-4)gave the best combination of properties by enabling significant precipitation of the Cu-rich Ti_(2)Cu and Zr_(2)Cu compounds,and mild formation of the Zr_(7)Cu_(10) secondary phase.The high kinetics at this condition was beneficial to the complete precipitation and more homogeneous distribution of the intermetallic particles.These led to the inhibition of dislocation movements and allowed for significantly improved mechanical strengths with added ductility,availability of more Cu ions for the desired oligodynamic activity without evoking cytotoxicity,better corrosion resistance and very high antibacterial ability(over 99.5%),thus improving the overall properties of the TZC alloys for biomedical applications.

Ultrasound-triggered piezocatalytic composite hydrogels for promoting bacterial-infected wound healing

Wound healing has become one of the basic issues faced by the medical community because of the susceptibility of skin wounds to bacterial infection.As such,it is highly desired to design a nanocomposite hydrogel with excellent antibacterial activity to achieve high wound closure effectiveness.Here,based on ultrasound-triggered piezocatalytic therapy,a multifunctional hydrogel is designed to promote bacteria-infected wound healing.Under ultrasonic vibration,the surface of barium titanate(BaTiO_(3),BT)nanoparticles embedded in the hydrogel rapidly generate reactive oxygen species(ROS)owing to the established strong built-in electric field,endowing the hydrogel with superior antibacterial efficacy.This modality shows intriguing advantages over conventional photodynamic therapy,such as prominent soft tissue penetration ability and the avoidance of serious skin phototoxicity after systemic administration of photosensitizers.Moreover,the hydrogel based on N-[tris(hydroxymethyl)methyl]acrylamide(THM),N-(3-aminopropyl)methacrylamide hydrochloride(APMH)and oxidized hyaluronic acid(OHA)exhibits outstanding self-healing and bioadhesive properties able to accelerate full-thickness skin wound healing.Notably,compared with the widely reported mussel-inspired adhesive hydrogels,OHA/THM-APMH hydrogel due to the multiple hydrogen bonds from unique tri-hydroxyl structure overcomes the shortage that catechol groups are easily oxidized,giving it long-term and repeatable adhesion performance.Importantly,this hybrid hydrogel confines BT nanoparticles to wound area and locally induced piezoelectric catalysis under ultrasound to eradicate bacteria,markedly improving the therapeutic biosafety and exhibits great potential for harmless treatment of bacteria-infected tissues.

Biodegradable Zn-0.5Li alloy rib plate:Processing procedure development and in vitro performance evaluation

Trauma kills more than four million people worldwide each year,with chest trauma accounting for 25%of these deaths.Rib fractures are the main manifestation of chest trauma.Biodegradable Zn alloys offer a new option to overcome clinical problems caused by permanent rib fracture internal fixation mate-rials,e.g.,long-term stress masking and secondary surgery.In this study,the fabrication procedure of biodegradable Zn-0.5Li alloy rib plates is successfully developed,which consists of casting,hot-warm rolling,cutting,and pressing sequentially.Biomechanical three-point bending performance of the Zn al-loy rib plates is comparable to that of commercial pure Ti rib plates,much higher than that of pure Zn rib plates.In addition,the Zn alloy exhibits the best antibacterial ability against E.coli and S.aureus among the three materials.Although the Zn alloy exhibits a weaker MC3T3 cytocompatibility than pure Ti,it is better than pure Zn.This study provides a foundation for the future development of various biodegrad-able Zn alloy rib plates.

Advances in layer-by-layer self-assembled coatings upon biodegradable magnesium alloys

Magnesium(Mg)and its alloys are considered as ideal biodegradable materials due to their excellent mechanical properties and biocompatibility.In order to improve the surface properties to allow better adaptation to the surrounding tissue of the body,surface modification has played a significant role in satisfying multiple clinical requirements such as corrosion resistance,biocompatibility,and antibacterial ability.Here,layer-by-layer(LbL)self-assembly,which can be applied for biodegradable Mg alloys due to its extensive choice of usable units,holds great promise among all the surface techniques.In this review,the mechanisms of the driving force(i.e.,electrostatic interaction,hydrogen bonding,charge transfer interaction and covalent bonding),cuttingedge advances in preparation methods(e.g.,dipping,spraying,and spinning)and the functional properties(corrosion resistance,antibacterial activity,and biocompatibility)that could be achieved by the LbL coatings are summarized.A reasonable trend of the potential development of LbL for bioMg alloys is also proposed at the end of this article.

Selective inhibition effects on cancer cells and bacteria of Ni–Ti–O nanoporous layers grown on biomedical NiTi alloy by anodization

Stents made of nearly equiatomic NiTi alloy are used to treat malignant obstruction caused by cancer,but prevention of re-obstruction after surgery is still a challenge because the bare stents possess poor anticancer and antibacterial properties to inhibit cancer/bacteria invasion.The present work aims at endowing the NiTi alloy with anticancer and antibacterial abilities by surface modification.Ni–Ti–O nanoporous layers with different thicknesses were prepared on NiTi by anodization,and biological experiments were conducted to evaluate the effects on gram-positive Staphylococcus aureus,human lung epithelial cancer cells(A549),as well as human endothelial cells(EA.hy926).The nanoporous layer with a thickness of 10.1 lm inhibits growth of cancer cells and kill bacteria but shows little adverse effects on normal cells.Such selectivity is related to the larger amount of Ni ions leached from the sample in the acidic microenvironment of cancer cells in comparison with normal cells.The Ni–Ti–O nanoporous layers are promising as coatings on NiTi stents to prevent re-obstruction after surgery.

Construction of a magnesium hydroxide/graphene oxide/hydroxyapatite composite coating on Mg-Ca-Zn-Ag alloy to inhibit bacterial infection and promote bone regeneration

The improved corrosion resistance, osteogenic activity, and antibacterial ability are the key factors for promoting the large-scale clinical application of magnesium (Mg)-based implants. In the present study, a novel nanocomposite coating composed of inner magnesium hydroxide, middle graphene oxide, and outer hydroxyapatite (Mg(OH)_(2)/GO/HA) is constructed on the surface of Mg-0.8Ca-5Zn-1.5Ag by a combined strategy of hydrothermal treatment, electrophoretic deposition, and electrochemical deposition. The results of material characterization and electrochemical corrosion test showed that all the three coatings have high bonding strength, hydrophilicity and corrosion resistance. In vitro studies show that Mg(OH)2 indeed improves the antibacterial activity of the substrate. The next GO and GO/HA coating procedures both promote the osteogenic differentiation of MC3T3-E1 cells and show no harm to the antibacterial activity of Mg(OH)2 coating, but the latter exhibits the best promoting effect. In vivo studies demonstrate that the Mg alloy with the composite coating not only ameliorates osteolysis induced by bacterial invasion but also promotes bone regeneration under both normal and infected conditions. The current study provides a promising surface modification strategy for developing multifunctional Mg-based implants with good corrosion resistance, antibacterial ability and osteogenic activity to enlarge their biomedical applications.

Enhanced physicochemical and biological properties of C/Cu dual ions implanted medical titanium

It is increasingly popular for titanium and its alloys to be utilized as the medical implants.However,their bioinert nature and lack of antibacterial ability limit their applications.In this work,by utilizing plasma immersion ion implantation and deposition(PIII&D)technology,the titanium surface was modified by C/Cu co-implantation.The mechanical property,corrosion resistance,antibacterial ability and cytocompatibility of modified samples were studied.Results indicate that after C/Cu co-implantation,copper nanoparticles were observed on the surface of titanium,and titanium carbide existed on the near surface region of titanium.The modified surface displayed good mechanical property and corrosion resistance.The Cu/C galvanic corrosion existed on the titanium surface implanted by C/Cu dual ions,and release of copper ions can be effectively controlled by the galvanic corrosion effect.Moreover,improved antibacterial performance of titanium surface can be achieved without cytotoxicity.

Improving exposure of anodically ordered Ni-Ti-O and corrosion resistance and biological properties of NiTi alloys by substrate electropolishing

Although Ni-Ti-O nanopores(NPs) can be fabricated by anodization of mechanically polished NiTi alloys, the top disordered layer is difficult to remove thus hindering the functionality of the Ni-Ti-O NPs. In this work, an electropolishing(EP) pretreatment was performed on the NiTi substrate prior to anodization to thoroughly expose the NPs. Our results show that the EP pretreatment for 5 min perfectly removes the top disordered layer on the Ni-Ti-O NPs to expose the underlying NPs and consequently, the corrosion resistance and antibacterial ability are enhanced. The exposed NPs can elongate bone marrow mesenchymal stem cells, which may be responsible for the upregulated alkaline phosphatase activity, secretion of Type I collagen, and extracellular matrix mineralization. These results suggest that EP is a desirable pretreatment before anodization of the NiTi alloys because the irregular surface layer on the Ni-Ti-O NPs can be removed to enhance the corrosion resistance and biological functions.