Fabrication of anti-freezing and self-healing nanocomposite hydrogels based on phytic acid and cellulose nanocrystals for high strain sensing applications.

For hydrogel-based flexible sensors, it is a challenge to enhance the stability at sub-zero temperatures while maintaining good self-healing properties. Herein, an anti-freezing nanocomposite hydrogel with self-healing properties and conductivity was designed by introducing cellulose nanocrystals (CNCs) and phytic acid (PA). The CNCs were grafted with polypyrrole (PPy) by chemical oxidation, which were used as the nanoparticle reinforcement phase to reinforce the mechanical strength of hydrogels (851.8%). PA as a biomass material could form strong hydrogen bond interactions with H2O molecules, endowing hydrogels with prominent anti-freezing properties. Based on the non-covalent interactions, the self-healing rate of the hydrogels reached 92.9% at -15 °C as the content of PA was 40.0 wt%. Hydrogel-based strain sensors displayed high sensitivity (GF = 0.75), rapid response time (350 ms), good conductivity (3.1 S m-1) and stability at -15 °C. Various human movements could be detected by using them, including small (smile and frown) and large changes (elbow and knee bending). This work provides a promising method for the development of flexible wearable sensors that work stably in frigid environments.

Ethyl caffeate inhibits macrophage polarization via SIRT1/NF-κB to attenuate traumatic heterotopic ossification in mice.

Heterotopic ossification (HO) denotes the presence of mature bone tissue in soft tissues or around joints. Inflammation is a key driver of traumatic HO, and macrophages play an important role in this process. Ethyl caffeate (ECF), a critical active compound found in Petunia, exerts significant anti-inflammatory effects. Herein, we established a mouse model of HO by transection of the Achilles tendon and back burn and found abundant macrophage infiltration in the early stage of HO, which decreased with time. In vitro and in vivo experiments indicated that ECF inhibited macrophage polarization, and mechanistic studies showed that it inhibited the SIRT1/NF-κB signalling pathway, thereby suppressing the release of downstream inflammatory cytokines. ECF reduced HO in mice, and its effect was comparable to indomethacin (INDO). In vitro studies revealed that ECF did not directly affect the mineralization of mesenchymal stem cells (MSCs) or osteogenic differentiation but inhibited these processes by reducing the level of inflammatory cytokines in the conditioned medium (CM). Thus, M1 macrophages may play a crucial role in the pathogenesis of HO, and ECF is a prospective candidate for the prevention of trauma-induced HO. DATA AVAILABILITY: Data will be made available on request.

Fabrication of Janus-type nanocomposites from cellulose nanocrystals for self-healing hydrogels' flexible sensors.

Janus bio-nanomaterials have great application potential in functional solid surfactants, probes and flexible sensors. In this manuscript, the sustainable Janus cellulose nanocrystals-type (CNCs-type) nanomaterials were prepared by Pickering emulsion template method. The asymmetric functionalism of Janus nanorods was realized by asymmetrically grafting polypyrrole (PPy) and polydopamine (PDA) onto different sides of CNCs (Janus CNCs-PPy /PDA (JCNs)). JCNs was successfully applied to self-healing nanocomposite hydrogels and further applied to the development of flexible sensors. The self-healing efficiency of nanocomposite hydrogels was 87.2%, and the stress and strain reached 3.50 MPa and 453.45%, respectively. It is worth noting that flexible sensors have been widely used in the field of wearable electronic sensing for real-time monitoring of human movement due to their high sensitivity (gauge factor (GF) = 9.9) and fast response time (260 ms).

Stretchable, rapid self-healing guar gum-poly(acrylic acid) hydrogels as wearable strain sensors for human motion detection based on Janus graphene oxide.

Wearable strain sensors have received widespread attention in research fields due to their applications in human motion detection. In this manuscript, the fabrication of functionalized Janus graphene oxide (GO) nanosheets were used by Pickering emulsion template. Polypyrrole (PPy) and poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) were asymmetrically grafted on the two sides of GO (GO@PPy/PDMAEMA Janus NS), which successfully applied to synthesize Janus NS/guar gum-poly(acrylic acid) (GG-PAA) self-healing nanocomposite hydrogels. The outstandingly improved self-healing efficiency (92.8% for 2 h) and mechanical properties (strength of 4.12 MPa and toughness of 873.8%) of nanocomposite hydrogels were mainly supported by the collaborative effect of reversible electrostatic interactions, multiple hydrogen bonds and metal-ligand coordination. Moreover, the hydrogels exhibited strain sensitivity and could be able to monitor a variety of human motions, which have outstanding application prospects in wearable flexible sensors.

Development of hydrofluoric acid-cleaned silicon nitride implants for periprosthetic infection eradication and bone regeneration enhancement.

Orthopedic implant is commonly associated with occurrence or relapse of osteomyelitis. This study developed a hydrofluoric acid (HF) cleaned silicon nitride (Si3N4) implant Si3N4_AC for osteomyelitis control and established a rat tibial osteomyelitis model to evaluate its efficacy on eradicating periprosthetic infection and enhancing bone regeneration. In vitro studies revealed Si3N4_AC had improved biocompatibility and inhibited Staphylococcus aureus adhesion. A custom-made Si3N4_AC implant was prepared and inserted into the rat tibia longitudinal cavity inoculated with Staphylococcus aureus. The in vivo bacteriostatic and osteogenic efficacies of Si3N4_AC implant were evaluated by histological, microbiological and Micro-CT analyses and compared with implants of pure Ti and Si3N4 . Si3N4_AC implant group revealed 99.5% inhibition of periprosthetic Staphylococcus aureus compared to the osteomyelitis group after 14 days post-operation. Implant-adhering bacteria density of Si3N4_AC was also much lower than pure Ti and Si3N4. In addition, micro-CT evaluation of peri-implant bone formation under the condition of periprosthetic osteomyelitis after 30 days post-surgery confirmed the osteogenic ability of Si3N4_AC. Taken together, Si3N4_AC can be an effective orthopedic biomaterial to eradicate periprosthetic infection and enhance bone regeneration.

Self-healing and toughness cellulose nanocrystals nanocomposite hydrogels for strain-sensitive wearable flexible sensor.

Recently, self-healing and high mechanical strength hydrogels have aroused much research due to their potential future in strain-sensitive flexible sensors. In this manuscript, we successfully designed self-healing and toughness cellulose nanocrystals (CNCs) nanocomposite hydrogels by grafted polypyrrole (PPy) on the surface of CNCs to enhance electrical conductivity. The obtained nanocomposite hydrogels exhibit outstanding self-healing and mechanical behaviors, and the optimal mechanical strength, toughness and self-healing efficiency can be up to 5.7 MPa, 810% and 89.6%, respectively. Using these functional nanocomposite hydrogels, strain-sensitive wearable flexible sensors were designed to monitor finger joint motions, bending of knee, and even the slight pulse beating. Surprisingly, the flexible sensors could evidently perceive body motions from large movements (knee bending) to tiny signals (pulse beating). In addition, it exhibited excellent durability after repeated cycles. This method of prepared self-healing nanocomposite hydrogels will have a potential prospect in the design of biomedical, biosensors, and flexible electronic devices.

Highly sensitive electrochemical immunosensor for the simultaneous detection of multiple tumor markers for signal amplification.

A novel sandwich-type electrochemical immunosensor has been fabricated for simultaneous determination of three kinds of tumor markers (TMs). The signal-amplified platform for sensor was assisted by graphene oxide (GO) loaded with Poly(styrene-alt-maleic anhydride) (PSMA). Three TMs of prostate specific antigen (PSA), human a-fetoprotein (AFP) and carbohydrate antigen 125 (CA 125) were employed as model test molecules. This sandwich-type immunoassay could detect the three antigens in differential pulse voltammetry (DPV) scan well at the same time. Under the optimized conditions, the multiplexed immunosensor displayed a splendid linear response in the range of 1.13 pg mL-1 - 113 ng mL-1 for PSA, 0.35 pg mL-1 - 35 ng mL-1 for AFP and 0.025 U mL-1 - 250 U mL-1 for CA 125. The detection limit was 86 fg mL-1, 14 fg mL-1 and 0.0019 U mL-1 for PSA, AFP and CA 125, respectively. This strategy provides a simple and sensitive method for immunoassay for the identification and validation of specific early cancers.

Facile fabrication of a controlled polymer brush-type functional nanoprobe for highly sensitive determination of alpha fetoprotein.

As robust functional polymers, polymer brush-based hybrid nanomaterials have potential application in the highly sensitive determination of tumor markers (TMs). Currently, there are plentiful reports on the polymerization methods of functional polymer brushes. Low ppm ATRP (activators (re)generated by electron transfer for atom transfer radical polymerization (A(R)GET ATRP), initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP) and electrochemically mediated atom transfer radical polymerization (eATRP)) is a facile and robust methodology with the advantages of simplicity, eco-friendliness and wide applicability to prepare well-defined polymeric materials. In this work, a controlled polymer brush-type functional nanoprobe is successfully fabricated by functional AGET ATRP and used as a sandwich-type electrochemical immunosensor for precise detection of TMs (alpha-fetoprotein, AFP). Using graphene oxide (GO) as an excellent conductive matrix, a GO-based poly-heterozygosis pyridine nanomaterial (GO@PHPY) is obtained by surface-initiated AGET ATRP and photocatalytic modification. The nanoprobe is assembled using GO@PHPY and a detection antibody (Ab2) to detect AFP, in which Cu(ii) serves as a signal label to coordinate with the pyridyl group. Under optimized conditions, the electrochemical sensor exhibits a good detection effect on AFP, with a detection range of 0.1 pg mL-1 to 100 ng mL-1 and a low detection limit of 0.08 pg mL-1. It is worth noting that the detection platform can be applied to the detection of real human serum samples. Thus, it is a desirable platform for AFP detection in clinical diagnosis and practical applications. Meanwhile, this work proves that designing and constructing functional polymer brushes is one of the most effective methods for developing new materials for analytical scientific applications.

Surface degradation-enabled osseointegrative, angiogenic and antiinfective properties of magnesium-modified acrylic bone cement.

OBJECTIVE: This work focuses on tackling the inadequate bone/implant interface strength of acrylic bone cements, which is a formidable problem diminishing their clinical performance, especially in percutaneous kyphoplasty surgery. METHODS: A new strategy of incorporating magnesium particles into clinically used poly(methylmethacrylate) (PMMA) bone cement to prepare a surface-degradable bone cement (SdBC) is proposed and validated both in vitro and in vivo. RESULTS: This surface degradation characteristic enables osseointegrative, angiogenic and antiinfective properties. SdBC showed fast surface degradation and formed porous surfaces as designed, while the desirable high compressive strengths (≥70 MPa) of the cement were preserved. Besides, the SdBC with proper Mg content promoted osteoblast adhesion, spreading, proliferation and endothelial cell angiogenesis capacity compared with PMMA. Also, SdBC demonstrated clear inhibitory effect on Staphylococcus aureus and Escherichia coli. In vivo evaluation on SdBC by the rat femur defect model showed that the bone/implant interface strength was significantly enhanced in SdBC (push-out force of 11.8 ± 1.5 N for SdBC vs 7.0 ± 2.3N for PMMA), suggesting significantly improved osseointegration and bone growth induced by the surface degradation of the cement. The injectability, setting times and compressive strengths of SdBC with proper content of Mg particles (2.8 wt% and 5.4 wt%) were comparable with those of the clinical acrylic bone cement, while the heat release during polymerization was reduced (maximum temperature 78 ± 1 °C for PMMA vs 73.3 ± 1.5 °C for SdBC). CONCLUSIONS: This work validates a new concept of designing bioactive bone/implant interface in PMMA bone cement. And this surface-degradable bone cement possesses great potential for minimally invasive orthopaedic surgeries such as percutaneous kyphoplasty. THE TRANSLATIONAL POTENTIAL OF THIS ARTICLE: This work reports PMMA/Mg surface-degradable acrylic bone cements that possess enhanced osseointegrative, angiogenic and antiinfective properties that are lacking in the clinically used acrylic bone cements. This new kind of bone cements could improve the treatment outcome of many orthopaedic surgeries such as percutaneous kyphoplasty and arthroplasty.

Sodium dodecyl benzene sulfonate functionalized graphene for confined electrochemical growth of metal/oxide nanocomposites for sensing application.

The electrochemical fructose sensor attracts considerable attention in the food industry and for clinical applications. Here, a novel fructose biosensor was developed based on immobilization of highly dispersed CuO-Cu nanocomposites on Graphene that was non-covalently functionalized by sodium dodecyl benzene sulfonate (SDBS) (denoted briefly as SDBS/GR/CuO-Cu). The structure and morphology of SDBS/GR/CuO-Cu were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemistry and electrocatalysis were evaluated by cyclic voltammetry (CV). The fructose sensing performances were evaluated by chronoamperometry (i-t). Those properties were also compared with that of CuO-Cu. Results revealed the distinctly enhanced sensing properties of SDBS/GR/CuOCu towards fructose, showing significantly lowered overpotential of +0.40V, ultrafast (<1s) and ultra-sensitive current response (932 µAm M(-1)cm(-2)) in a wide linear range of 3-1000 µM, with satisfactory reproducibility and stability. Those could be ascribed to the good electrical conductivity, large specific surface area, high dispersing ability and chemical stability of GR upon being functionalized non-covalently by SDBS, as well as the outstanding cation anchoring ability of SDBS on GR to resist aggregation among Cu-based nanoparticles during electro-reduction. More importantly, an improved selectivity in fructose detection was achieved. SDBS/GR/CuO-Cu is one of the promising electrode materials for electrochemical detection of fructose.