Antibacterial Vancomycin@ZIF-8 Loaded PVA Nanofiber Membrane for Infected Bone Repair.

Bone substitutes with strong antibacterial properties and bone regeneration effects have an inherent potential in the treatment of severe bone tissue infections, such as osteomyelitis. In this study, vancomycin (Van) was loaded into zeolitic imidazolate framework-8 (ZIF-8) to prepare composite particles, which is abbreviated as V@Z. As a pH-responsive particle, ZIF-8 can be cleaved in the weak acid environment caused by bacterial infection to realize the effective release of drugs. Then, V@Z was loaded into polyvinyl alcohol (PVA) fiber by electrospinning to prepare PVA/V@Z composite bone filler. The drug-loading rate of V@Z was about 6.735%. The membranes exhibited super hydrophilicity, water absorption and pH-controlled Van release behavior. The properties of anti E. coli and S. aureus were studied under the pH conditions of normal physiological tissues and infected tissues (pH 7.4 and pH 6.5, respectively). It was found that the material had good surface antibacterial adhesion and antibacterial property. The PVA/V@Z membrane had the more prominent bacteria-killing effect compared with the same amount of single antibacterial agent containing membrane such as ZIF-8 or Van loaded PVA, and the antibacterial rate was up to 99%. The electrospun membrane had good biocompatibility and can promote MC3T3-E1 cell spreading on it.

Paclitaxel-loaded lignin particle encapsulated into electrospun PVA/PVP composite nanofiber for effective cervical cancer cell inhibition.

Electrospun composite nanofibrous scaffolds have been regarded as a potential carrier for local drug delivery to prevent tumor recurrence. Herein, a model drug (paclitaxel) was creatively loaded into lignin nanoparticles (PLNPs) and then encapsulated into the polymer of poly (vinyl alcohol)/polyvinyl pyrrolidone which has been fabricated into a composite nanofibrous membrane (PVA/PVP-PLNPs) for use as a drug carrier using the electrospinning technique. The fabricated PVA/PVP-PLNPs membranes exhibited good particle distribution, mechanical properties, thermal stability and biocompatibility. In vitro experiments showed that combining lignin nanoparticles by electrospinning not only improved the drug release profile, but also enhanced the hydrophilicity of nanofibrous membranes which was beneficial to cell adhesion and proliferation. Cellular experiments demonstrated that PVA/PVP-2%PLNPs membrane showed good cell inhibition ability, and the cell survival rate was only 21% at day 7. It indicates that the as-prepared PVA/PVP-PLNPs composite nanofibers are promising candidates for local anticancer therapy.

3D MXene microspheres with honeycomb architecture for tumor photothermal/photodynamic/chemo combination therapy.

The MXene combining high surface area, prominent biocompatibility, and wide near infrared (NIR) absorption has been recognized as one of the most promising materials for tumor therapy. The application of MXene in tumor therapy is negatively affected by the current design methods lack the control of size distribution and the great tendency to agglomerate as well as poor photodynamic therapy. To solve the above problems, we report a facile strategy to process Ti3C2 nanosheets into three-dimensional (3D) structure with honeycomb structure and anti-aggregation properties for synergistic therapy of chemotherapy, photothermal and photodynamic therapy. The 3D MXene is synthesized by spray drying, in which the MXene surface is oxidized to TiO2. The microspheres present prominent NIR light trigger photothermal effect and excellent NIR light photostability, which respond in an on-off manner. Moreover, the microspheres exhibit outstanding drug-loading capability of doxorubicin (DOX) as high as 87.3%, and substantial singlet oxygen generation (1O2) was shown under 808 nm laser and UV light irradiation. Our studies indicate that 3D MXene-DOX could effectively achieve Hela cells killing in vitro, which provides a multifunctional drug delivery platform as a prospective candidate for future combined cancer therapy.

Carbon nanotube-collagen@hydroxyapatite composites with improved mechanical and biological properties fabricated by a multi in situ synthesis process.

A novel carbon nanotube-collagen@hydroxyapatite (CNT-Col@HA) composite with good mechanical and biological properties was fabricated successfully by a multi in situ synthesis process, which can be used to repair or replace the damaged bone tissues. The carbon nanotube (CNT)/hydroxyapatite (HA) composite powders were firstly synthesized by the in situ chemical vapor deposition method. After the acidification of CNTs, the collagen (Col) molecules were covalently grafted onto the surface of CNTs in situ by the formation of amide linkages, obtaining Col-encapsulated CNTs powders. And then, a HA layer was deposited in situ onto the Col-encapsulated CNTs to form HA- and Col-encapsulated CNTs, consequently the ideal CNT-Col@HA composite was fabricated by the powder metallurgy method, and its mechanical and biological properties were investigated. The results showed that, the multi in situ synthesis process ensured the homogeneous dispersion of CNTs in HA matrix, and via the intermediate layer of Col, the close chemical bonding between CNT reinforcements and HA matrix was obtained, thereby the flexural strength and fracture toughness of the in situ synthesized 3 wt.% CNT-Col@HA composite were increased by approximately 74.2% and 274.6% compared with those of pure HA bulk, and better cell adhesion, spreading and proliferation were also observed on the in situ synthesized CNT-Col@HA composites. Therefore, the obtained composites in this work have great potential to be applied as implant material in clinic.

Biological and antibacterial properties of TiO2 coatings containing Ca/P/Ag by one-step and two-step methods.

The porous TiO2 coatings containing Ca/P/Ag were separately prepared on titanium (Ti) surface by one-step (micro-arc oxidation) and two-step methods (micro-arc oxidation and cathodic deposition), and then their surface morphology, composition, biological and antibacterial properties were compared. The results showed that the porous coatings containing Ca/P/Ag achieved by different methods showed similar surface morphology and elemental composition, however, by one-step method, silver existed in the coating as silver phosphate, while in the coatings prepared by two-step method, silver existed as metallic silver. Although both coatings showed excellent antibacterial property (the antimicrobial rate is over 99.9%), the surface coating prepared by one-step method had a more suitable release curve of Ag. In addition, the surface coating prepared by one-step method also presented better biological property, which was due to its enhanced surface roughness and hydrophilicity. Combining with its easy operation and long-term antibacterial property, its prospect for clinical application is more promising.

Spindle-like porous N-doped TiO2 encapsulated (Ca,Y)F2:Yb3+,Tm3+ as the efficient photocatalyst near-infrared range.

In this study, a novel photocatalyst composed of N-doped TiO2 (N-TiO2) and (Ca, Y)F2:Yb3+, Tm3+ was prepared by simple dealloying followed by a hydrothermal method. The composite exhibits a homogeneous nanoporous structure consisting of large quantities of the spindle-like N-doped TiO2 nanorods, on which the (Ca, Y)F2:Yb3+, Tm3+ particles with a diameter of around 5 nm are uniformly dispersed. In addition, morphology and property of the N-TiO2 can be controlled by adjusting the dealloying period. Results show that a short immersion time leads to a small size, large surface area and low band gap. As a result, the N-TiO2/(Ca, Y)F2:Yb3+, Tm3+ composite after dealloying for 48 h (TiO2-48-C) exhibits higher degradation rates (65.6% for 10 h irradiation by 980 nm NIR) than others after dealloying for 60 h (TiO2-60-C) and 72 h (TiO2-72-C), indicating its excellent potential for practical applications.

Influence of nanostructures on the biological properties of Ti implants after anodic oxidation.

Anodic oxidation was applied to produce nanostructures on the surface of titanium (Ti) implants. The bioactivity of the Ti implants was evaluated by simulated body fluid soaking test. The biocompatibility was investigated by in vitro cell culture test. The results showed that bone-like apatite was formed on the anodized Ti surface, but not on the as-polished Ti surface after immersion in simulated body fluid for 2 weeks. Cells cultured on the anodized Ti surface showed enhanced cell adhesion and proliferation, compared to those cultured on the as-polished Ti surface. Based on these results, it can be concluded that anodic oxidation improved the bioactivity and biocompatibility of Ti surface, which was attributed to the formation of nanostructures as well as the nanostructure induced high surface roughness and hydrophilicity.

Bone ingrowth induced by gelatin/chitosan internal matrix of 3DP Ti6Al4V scaffold.

Regarding its structural and mechanical adaptability to bone defects, 3D printed (3DP) Ti6Al4V scaffolds are widely used in orthopedics now, purposed to restore the function and mechanical stability of impaired bone. In scaffold fabrication, surface modification is acknowledged as a reliable strategy to enhance the interface interaction between 3DP Ti6Al4V scaffold and bone. Despite its advantage in bone-Ti6Al4V bonding improvement, surface modification lacks the ability to induce bone in-growth efficiently as expected. As an attempt to overcome this challenge, in the current work the inner voids of 3DP Ti6Al4V scaffold were occupied by a gelatin/chitosan porous matrix, purposed to act as a platform for guiding bone ingrowth. Firstly, the gelatin/chitosan matrix was prepared via freeze-drying using genipin as a crosslinker, resulting in a trabecular bone-like interconnected porous network characterized with a gelatin/chitosan ratio dependent swelling capability, degradation and model anti-bacterial drug release behavior. Besides of that, gelatin in the matrix was witnessed to accelerate biomineralization in simulated body fluid. Secondly, a formulated gelatin/chitosan matrix was embedded into 3DP Ti6Al4V scaffold to generate a composite scaffold capable of inducing bone in-growth. The followed studies showed gelatin/chitosan matrix can endow the scaffold with good biological and sustained drug release properties, along with minimal change to the compressive strength of the scaffold. The in vivo experiment results revealed that after 4 weeks of implantation, more new bone formation was witnessed in the inner structure of the composite scaffold than the 3DP Ti6Al4V scaffold, with the average bone volume fraction (BV/TV) value increased from 24.09 % to 46.08 %, the average trabecular bone thickness (Tb. Th) value increased from 0.118 mm to 0.278 mm. Therefore, it was confirmed an inner matrix in 3DP Ti6Al4V scaffold played an essential role in guiding bone in-growth.

Fe3O4@TiO2 Microspheres: Harnessing O2 Release and ROS Generation for Combination CDT/PDT/PTT/Chemotherapy in Tumours.

In the treatment of various cancers, photodynamic therapy (PDT) has been extensively studied as an effective therapeutic modality. As a potential alternative to conventional chemotherapy, PDT has been limited due to the low Reactive Oxygen Species (ROS) yield of photosensitisers. Herein, a nanoplatform containing mesoporous Fe3O4@TiO2 microspheres was developed for near-infrared (NIR)-light-enhanced chemodynamical therapy (CDT) and PDT. Titanium dioxide (TiO2) has been shown to be a very effective PDT agent; however, the hypoxic tumour microenvironment partly affects its in vivo PDT efficacy. A peroxidase-like enzyme, Fe3O4, catalyses the decomposition of H2O2 in the cytoplasm to produce O2, helping overcome tumour hypoxia and increase ROS production in response to PDT. Moreover, Fe2+ in Fe3O4 could catalyse H2O2 decomposition to produce cytotoxic hydroxyl radicals within tumour cells, which would result in tumour CDT. The photonic hyperthermia of Fe3O4@TiO2 could not only directly damage the tumour but also improve the efficiency of CDT from Fe3O4. Cancer-killing effectiveness has been maximised by successfully loading the chemotherapeutic drug DOX, which can be released efficiently using NIR excitation and slight acidification. Moreover, the nanoplatform has high saturation magnetisation (20 emu/g), making it suitable for magnetic targeting. The in vitro results show that the Fe3O4@TiO2/DOX nanoplatforms exhibited good biocompatibility as well as synergetic effects against tumours in combination with CDT/PDT/PTT/chemotherapy.

Porous Nb2O5 Formed by Anodic Oxidation as the Sulfur Host for Enhanced Performance Lithium-Sulfur Batteries.

Lithium-sulfur batteries (LSBs), with their high theoretical specific capacity and energy density, have great potential to be a candidate for secondary batteries in the future. However, Li-S batteries suffer from multiple issues and challenges, for example, uneven growth of lithium dendrites, low utilization of the active material (sulfur), and low specific capacity. This paper reports a low-cost and anodic oxidation method to produce niobium pentoxide with a porous structure (P-Nb2O5). A simple one-step process was used to synthesize P-Nb2O5 with porous structures by anodizing niobium at 40 V in fluorinated glycerol. The porous Nb2O5 showed excellent rate capability and good capacity retention by maintaining its structural integrity, allowing us to determine the advantages of its porous structure. As a result of the highly porous structure, the sulfur was not only provided with adequate storage space and abundant adsorption points, but it was also utilized more effectively. The initial discharge capacity with the P-Nb2O5 cathode rose to 1106.8 mAh·g-1 and dropped to 810.7 mAh·g-1 after 100 cycles, which demonstrated the good cycling performance of the battery. This work demonstrated that the P-Nb2O5 prepared by the oxidation method has strong adsorption properties and good chemical affinity.

Synthesis of Porous Hollow Spheres Co@TiO2-x-Carbon Composites for Highly Efficient Lithium-Ion Batteries.

The hollow TiO2 anode material has received great attention for next-generation LIBs because of its excellent stability, environmental friendly, and low volume change during lithiation/delithiation. However, there are some problems associated with the current anatase TiO2 anode materials in practical application owing to low lithium-ion diffusivity and poor reversible theoretical capacities. The introduction of defects has been turned out to be a significant and effective method to improve electronic conductivity, especially oxygen vacancies. In this paper, a facile hydrothermal reaction and subsequent chemical vapor deposition method were successfully used to fabricate Co@TiO2-x-carbon hollow nanospheres. These results suggest that the synthesized product exhibits good rate performance and superior cycling stability.

Progress of laser surface treatment on magnesium alloy.

Magnesium (Mg) metals have been widely used in various fields as one of the most promising lightweight structural materials. However, the low corrosion resistance and poor mechanical properties restrict its applications. Surface treatments are common approach to enhance the mechanical strength and corrosion resistance of Mg metals. Among them, laser surface treatment generates novel tissues and structures in situ on the sample surface, thereby improving properties of mechanical strength and corrosion resistance. We briefly describe the changes in surface organization that arise after laser treatment of Mg surfaces, as well as the creation of structures such as streaks, particles, holes, craters, etc., and provide an overview of the reasons for the alterations. The effect of laser processing on wettability, hardness, friction wear, degradation, biocompatibility and mechanical properties were reviewed. At last, the limitations and development trend of laser treatment on Mg metals research were further pointed out.

Improve endothelialization of metallic cardiovascular stent via femtosecond laser induced micro/nanostructure dependent cells proliferation and drug delivery control.

Regarding restenosis occurrence risk after metallic stent deployment in artery, stents with vascular smooth muscle cells antiproliferative agents sustained released from poly(lactic-co-glycolic acid) (PLGA) coating and endothelial cells proliferation favored surface textures were both attempted for endothelialization enhancement. In order to explore the interaction between the surface texture and performance of drug loaded PLGA coating, femtosecond laser surface treatment was used to change the surface characteristics of 316L stainless steel. Two different surface patterns in form of stripe (FSL100) and isolated island-like structure (FSL800) were firstly generated by femtosecond laser processing with 100 and 800 mW energy, then Rapamycin loaded PLGA coating was further deposited to polished and femtosecond laser processed 316L surfaces via a dip-coating method. The subsequent drug loading capacity and release profile studies confirmed the roles of surface texture. Morphological transition characteristics of the PLGA coating on the FLS100 sample indicate that the coating has integrity during degradation compared to the polished one. Finally, rapamycin eluting FLS100 stent was deployed to iliac arteries of New Zealand White rabbits with vascular plaques to demonstrate its endothelialization potential and resistance to restenosis.

MXene Quantum Dot/Zeolitic Imidazolate Framework Nanocarriers for Dual Stimulus Triggered Tumor Chemo-Phototherapy.

It is critical to construct stimuli-responsive multifunctional nanoparticles for the drug delivery system for cancer treatment. Zeolitic imidazolate framework-8 (ZIF-8) has a large specific surface area and decomposes quickly under acidic conditions, which presents an excellent potential in pH-sensitive drug carriers. However, the mere chemotherapeutic drug loaded into ZIF-8 is a monotherapy and may restrict the therapeutic efficacy of malignancies. In this work, an effective nanoparticle-based delivery platform is established to simultaneously encapsulate doxorubicin (DOX) and MXene quantum dot (MQD) in ZIF-8 nanoparticles (MQD@ZIF-8/DOX). Under near-infrared (NIR) laser (808 nm) and UV light (365 nm) irradiation, MQD@ZIF-8 demonstrates a high photothermal conversion efficiency and reactive oxygen species (ROS) production, which shows excellent photothermal therapy and photodynamic therapy effects. Furthermore, the release of DOX-loaded into MQD@ZIF-8 nanoparticles is significantly increased under NIR laser irradiation and at pH 5.6, indicating that acidic conditions and NIR laser irradiation can be effectively combined to stimulate the drug release. The cellular experiments show that MQD@ZIF-8/DOX has an obvious killing effect on HeLa cells and achieves the combined anti-tumor effect of chemotherapy and phototherapy.

Femtosecond laser-induced nanoporous layer for enhanced osteogenesis of titanium implants.

The osteogenic activity of medical metal can be improved by lowering its surface stiffness and elastic modulus. However, it is very difficult to directly reduce the elastic modulus of medical metal surfaces. In this paper, with selected parameters, the titanium surface was treated via femtosecond laser irradiation. Micro indentation revealed that the femtosecond laser ablation can effectively reduce the surface Young's modulus and Vickers hardness of titanium. Besides, In order to explain the mechanical properties of degradation of titanium surface, Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) was used to simulate the process of laser ablation process of titanium surface, and it was found that after the ablation of titanium surface, voids were produced in the subsurface layer. The simulation showed that the voids are formed by the cavitation of metastable liquid induced by high tensile stress and high temperature during femtosecond laser irradiation. Subsurface voids with a thickness of about 40 nm were observed under the oxide layer in the experiment. Cell experiments showed that the surface with low Young's modulus was more conducive to cell proliferation and osteogenic differentiation.

Thermosensitive -hydrogel-coated titania nanotubes with controlled drug release and immunoregulatory characteristics for orthopedic applications.

Although Ti is widely used in orthopedic implants, its bio-inert characteristics and poor antibacterial activity may result in implant failure. To counter this problem, in this study, we loaded simvastatin, a bioactive compound that promotes osteogenesis, in TiO2 nanotubes and a thermosensitive chitosan-glycerin-hydroxypropyl methyl cellulose hydrogel (CGHH) was then layered on top of these nanotubes. At normal human-body temperature (37 °C), CGHH was present in a sol state, thus facilitating the controlled release of simvastatin to enhance differentiation in MC3T3-E1 osteoblasts. In vitro cell-culture studies suggested that CGHH in a gel state would induce macrophage polarization to the pro-inflammatory M1 phenotype. In vitro testing against Escherichia coli and Staphylococcus aureus indicated no antibacterial activity in CGHH in both sol and gel states. However, the results of subcutaneous infection animal models suggested that CGHH showed excellent in vivo antibacterial activity, which can be explained by the fact at high temperatures induced by an infection, CGHH transitioned into a gel state and released large amounts of glycerin. Such a high glycerin dosage induced an acute inflammatory reaction and antibacterial activity. Thus, due to their enhanced osteogenesis capacity at normal body temperature and antibacterial characteristics in the presence of infection, the newly designed simvastatin-loaded CGHH-encapsulated TiO2 nanotubes are promising materials for application in orthopedic implants.

Surface microstructuring of Ti plates by femtosecond lasers in liquid ambiences: a new approach to improving biocompatibility.

Microstructuring of Ti plates with femtosecond laser pulses is investigated in three different liquids. In these ambiences, complex microstructures with voids and islands are produced on the sample surfaces, whose feature sizes are controlled by the laser parameters. Through adopting supersaturated Hydroxyapatite suspension with higher incident laser fluences, it is for the first time to observe the firm deposition of biocompatible elements Ca-P on the microstructures. At lower laser fluence, only porous structure is present but without additional elements deposition. Both plasma-related ablation under the confinement of liquids and micro-bubbles striking are employed to discuss such structures formation. Tight combining elements Ca-P onto the structured surfaces provide a new way to improve the biocompatibility of body-embedded devices.

Synthesis and Characterization of Flower-like Carbon-encapsulated Fe-C Nanoparticles for Application as Adsorbing Material.

Carbon-encapsulated Fe-C (Fe-C@C) nanoparticles with a divergently flower-like morphology were successfully synthesized for application as an adsorbing material by using freeze-drying and chemical vapor deposition (CVD) methods. The Fe metallic source was first loaded onto a sodium chloride (NaCl) supporter via freeze-drying to obtain the Fe/NaCl composite powder. Then, Fe-C@C nanoparticles were synthesized in the temperature range of 300⁻450 °C via CVD of acetylene in the Fe/NaCl composite powder using Fe nanoparticles as catalysts and NaCl as supporters. Because the NaCl supporter is water-soluble, the synthesized Fe-C@C nanoparticles were easy to purify, and a high purity was obtained by simple washing and centrifugation. The optimal Fe-C@C nanoparticles, synthesized at 400 °C, possessed a unique divergently flower-like structure and a high specific surface area of 169.4 m²/g that can provide more adsorption sites for contaminants. Adsorption experiments showed that the flower-like Fe-C@C adsorbent exhibited high adsorption capacity (90.14 mg/g) and fast removal of methylene blue (MB). Moreover, the magnetic properties of the nanoparticles, with saturation magnetization of 36.544 emu/g, facilitated their magnetic separation from wastewater. Therefore, the novel flower-like Fe-C@C nanoparticles with integrated adsorptive and magnetic properties have the potential to be an effective adsorbent in dye wastewater treatment.

Preparation and properties of carbon nanotube (Fe)/hydroxyapatite composite as magnetic targeted drug delivery carrier.

A novel magnetic targeted drug delivery carrier based on a carbon nanotube (Fe)/hydroxyapatite (CNT(Fe)/HA) composite was successfully fabricated by an in situ synthesis of CNTs in HA nanopowder using Fe catalysts and subsequent chemical modification of the as-fabricated CNT(Fe)/HA by chitosan (CS) and folic acid (FA) for a controllable release of an anticancer drug doxorubicin (DOX). The synthesized CNTs, Fe, and HA self-assembled into a composite structure in situ during the synthesis. After the acid treatment, the CNTs were shorter and homogeneously dispersed, the tips of the CNTs were opened, and oxygen-containing functional groups were introduced onto the CNTs. Upon the functional modification through the surface coating with CS and FA, the functionalized CNT(Fe)/HA became capable of loading DOX through both π-π stacking and electrostatic adsorption of FA. The results showed that the average drug-loading rate of DOX was 130 wt%. Furthermore, the pH response of FA-CS-CNT(Fe)/HA enabled the release of a large amount of DOX in phosphate-buffered saline (PBS) at pH = 5.5 with an average drug release rate of 52 wt% after 72 h. In contrast, the drug release in PBS at pH = 7.4 was only 8 wt%. In addition, the saturation magnetization, coercive force, and remanence to saturation magnetization ratio of DOX-FA-CS-CNT(Fe)/HA were 0.88 emu g-1, 668.96 Oe, and 0.44, respectively, indicating its potential for drug transport under strong external magnetic fields, which could enable magnetic targeted delivery.

Self-adjusting antibacterial properties of Ag-incorporated nanotubes on micro-nanostructured Ti surfaces.

Titanium (Ti) is a widely used implant material in clinics; however, failures still frequently occur due to its bioinertness and poor antibacterial capability. Post-implant infections most likely occur within the first two weeks. Thereafter, the host immune system lowers the infection risk, and biosafety becomes the first consideration. Therefore, endowing biomedical Ti with a time-dependent bactericidal effect is of considerable interest. In this study, Ag nanoparticles (NPs) as the antibacterial agent were incorporated deeply into TiO2 nanotubes prepared on the sandblasted and etched (SLA) Ti surface. The incorporated Ag NPs were verified to automatically transform from a free state to an immobilized state, rendering the constructed platform exhibit a self-adjusting antibacterial effect. It showed strong "release bactericidal" activity in the early phase that gradually changed to the "contact bactericidal" ability. Such a smart alteration could satisfy the varied antibacterial requirements in different periods after biomaterial implantation. Moreover, the nanotubular structure could accelerate apatite formation and improve cell adhesion and proliferation when compared with those of commercially used SLA implants. Based on these results, it can be concluded that Ag-NP-incorporated micro-nanostructured Ti has worthwhile biological and time-dependent antibacterial properties, and it can have promising applications in orthopedics, dentistry, and fabrication of other biomedical devices.