Dynamic monitoring soft tissue healing via visualized Gd-crosslinked double network MRI microspheres.

By integrating magnetic resonance-visible components with scaffold materials, hydrogel microspheres (HMs) become visible under magnetic resonance imaging(MRI), allowing for non-invasive, continuous, and dynamic monitoring of the distribution, degradation, and relationship of the HMs with local tissues. However, when these visualization components are physically blended into the HMs, it reduces their relaxation rate and specificity under MRI, weakening the efficacy of real-time dynamic monitoring. To achieve MRI-guided in vivo monitoring of HMs with tissue repair functionality, we utilized airflow control and photo-crosslinking methods to prepare alginate-gelatin-based dual-network hydrogel microspheres (G-AlgMA HMs) using gadolinium ions (Gd (III)), a paramagnetic MRI contrast agent, as the crosslinker. When the network of G-AlgMA HMs degrades, the cleavage of covalent bonds causes the release of Gd (III), continuously altering the arrangement and movement characteristics of surrounding water molecules. This change in local transverse and longitudinal relaxation times results in variations in MRI signal values, thus enabling MRI-guided in vivo monitoring of the HMs. Additionally, in vivo data show that the degradation and release of polypeptide (K2 (SL)6 K2 (KK)) from G-AlgMA HMs promote local vascular regeneration and soft tissue repair. Overall, G-AlgMA HMs enable non-invasive, dynamic in vivo monitoring of biomaterial degradation and tissue regeneration through MRI, which is significant for understanding material degradation mechanisms, evaluating biocompatibility, and optimizing material design.

Prevented Cell Clusters' Migration Via Microdot Biomaterials for Inhibiting Scar Adhesion.

Cluster-like collective cell migration of fibroblasts is one of the main factors of adhesion in injured tissues. In this research, a microdot biomaterial system is constructed using α-helical polypeptide nanoparticles and anti-inflammatory micelles, which are prepared by ring-opening polymerization of α-amino acids-N-carboxylic anhydrides (NCAs) and lactide, respectively. The microdot biomaterial system slowly releases functionalized polypeptides targeting mitochondria and promoting the influx of extracellular calcium ions under the inflammatory environment, thus inhibiting the expression of N-cadherin mediating cell-cell interaction, and promoting apoptosis of cluster fibroblasts, synergistically inhibiting the migration of fibroblast clusters at the site of tendon injury. Meanwhile, the anti-inflammatory micelles are celecoxib (Cex) solubilized by PEG/polyester, which can improve the inflammatory microenvironment at the injury site for a long time. In vitro, the microdot biomaterial system can effectively inhibit the migration of the cluster fibroblasts by inhibiting the expression of N-cadherin between cell-cell and promoting apoptosis. In vivo, the microdot biomaterial system can promote apoptosis while achieving long-acting anti-inflammation effects, and reduce the expression of vimentin and α-smooth muscle actin (α-SMA) in fibroblasts. Thus, this microdot biomaterial system provides new ideas for the prevention and treatment of tendon adhesion by inhibiting the cluster migration of fibroblasts.

Three-dimensional RuCo alloy nanosheets arrays integrated pinewood-derived porous carbon for high-efficiency electrocatalytic nitrate reduction to ammonia.

Electricity-driven nitrate (NO3-) to ammonia (NH3) conversion presents a unique opportunity to simultaneously eliminate nitrate from sewage while capturing ammonia. However, the Faradaic efficiency and ammonia yield in this eight-electron process remain unsatisfactory, underscoring the critical need for more effective electrocatalysts. In this study, a RuCo alloy nanosheets electrodeposited on pinewood-derived three-dimensional porous carbon (RuCo@TDC) is introduced as a highly-efficient electrocatalyst for the nitrate reduction reaction. The RuCo@TDC catalyst exhibits superior electrocatalytic performance, achieving the highest NH3 yield of 2.02 ± 0.11 mmol h-1 cm-2 at -0.6 V versus the reversible hydrogen electrode (vs. RHE) and the highest Faradaic efficiency of 95.7 ± 0.8 % at -0.2 V vs. RHE in an electrolyte mixture of 0.1 M KOH and 0.1 M KNO3. Furthermore, the Zn-NO3- battery using RuCo@TDC as the cathode provides a maximum power density of 2.46 mW cm-2 and a satisfactory NH3 yield of 1110 µg h-1 cm-2.

Efficient bubble/precipitate traffic enables stable seawater reduction electrocatalysis at industrial-level current densities.

Seawater electroreduction is attractive for future H2 production and intermittent energy storage, which has been hindered by aggressive Mg2+/Ca2+ precipitation at cathodes and consequent poor stability. Here we present a vital microscopic bubble/precipitate traffic system (MBPTS) by constructing honeycomb-type 3D cathodes for robust anti-precipitation seawater reduction (SR), which massively/uniformly release small-sized H2 bubbles to almost every corner of the cathode to repel Mg2+/Ca2+ precipitates without a break. Noticeably, the optimal cathode with built-in MBPTS not only enables state-of-the-art alkaline SR performance (1000-h stable operation at -1 A cm-2) but also is highly specialized in catalytically splitting natural seawater into H2 with the greatest anti-precipitation ability. Low precipitation amounts after prolonged tests under large current densities reflect genuine efficacy by our MBPTS. Additionally, a flow-type electrolyzer based on our optimal cathode stably functions at industrially-relevant 500 mA cm-2 for 150 h in natural seawater while unwaveringly sustaining near-100% H2 Faradic efficiency. Note that the estimated price (~1.8 US$/kgH2) is even cheaper than the US Department of Energy's goal price (2 US$/kgH2).

Kneadable dough-type hydrogel transforming from dynamic to rigid network to repair irregular bone defects.

Irregular bone defects, characterized by unpredictable size, shape, and depth, pose a major challenge to clinical treatment. Although various bone grafts are available, none can fully meet the repair needs of the defective area. Here, this study fabricates a dough-type hydrogel (DR-Net), in which the first dynamic network is generated by coordination between thiol groups and silver ions, thereby possessing kneadability to adapt to various irregular bone defects. The second rigid covalent network is formed through photocrosslinking, maintaining the osteogenic space under external forces and achieving a better match with the bone regeneration process. In vitro, an irregular alveolar bone defect is established in the fresh porcine mandible, and the dough-type hydrogel exhibits outstanding shape adaptability, perfectly matching the morphology of the bone defect. After photocuring, the storage modulus of the hydrogel increases 8.6 times, from 3.7 kPa (before irradiation) to 32 kPa (after irradiation). Furthermore, this hydrogel enables effective loading of P24 peptide, which potently accelerates bone repair in Sprague-Dawley (SD) rats with critical calvarial defects. Overall, the dough-type hydrogel with kneadability, space-maintaining capability, and osteogenic activity exhibits exceptional potential for clinical translation in treating irregular bone defects.

Mitochondrial-Oriented Injectable Hydrogel Microspheres Maintain Homeostasis of Chondrocyte Metabolism to Promote Subcellular Therapy in Osteoarthritis.

Subcellular mitochondria serve as sensors for energy metabolism and redox balance, and the dynamic regulation of functional and dysfunctional mitochondria plays a crucial role in determining cells' fate. Selective removal of dysfunctional mitochondria at the subcellular level can provide chondrocytes with energy to prevent degeneration, thereby treating osteoarthritis. Herein, to achieve an ideal subcellular therapy, cartilage affinity peptide (WYRGRL)-decorated liposomes loaded with mitophagy activator (urolithin A) were integrated into hyaluronic acid methacrylate hydrogel microspheres through microfluidic technology, named HM@WY-Lip/UA, that could efficiently target chondrocytes and selectively remove subcellular dysfunctional mitochondria. As a result, this system demonstrated an advantage in mitochondria function restoration, reactive oxygen species scavenging, cell survival rescue, and chondrocyte homeostasis maintenance through increasing mitophagy. In a rat post-traumatic osteoarthritis model, the intra-articular injection of HM@WY-Lip/UA ameliorated cartilage matrix degradation, osteophyte formation, and subchondral bone sclerosis at 8 weeks. Overall, this study indicated that HM@WY-Lip/UA provided a protective effect on cartilage degeneration in an efficacious and clinically relevant manner, and a mitochondrial-oriented strategy has great potential in the subcellular therapy of osteoarthritis.

Oxalate anions-intercalated NiFe layered double hydroxide as a highly active and stable electrocatalyst for alkaline seawater oxidation.

Seawater electrolysis is gaining recognition as a promising method for hydrogen production. However, severe anode corrosion caused by the high concentration of chloride ions (Cl-) poses a challenge for the long-term oxygen evolution reaction. Herein, an anti-corrosion strategy of oxalate anions intercalation in NiFe layered double hydroxide on nickel foam (NiFe-C2O42- LDH/NF) is proposed. The intercalation of these highly negatively charged C2O42- serves to establish electrostatic repulsion and impede Cl- adsorption. In alkaline seawater, NiFe-C2O42- LDH/NF requires an overpotential of 337 mV to gain the large current density of 1000 mA cm-2 and operates continuously for 500 h. The intercalation of C2O42- is demonstrated to significantly boost the activity and stability of NiFe LDH-based materials during alkaline seawater oxidation.

Fabrication of a hierarchical NiTe@NiFe-LDH core-shell array for high-efficiency alkaline seawater oxidation.

Herein, a hierarchical NiTe@NiFe-LDH core-shell array on Ni foam (NiTe@NiFe-LDH/NF) demonstrates its effectiveness for oxygen evolution reaction (OER) in alkaline seawater electrolyte. This NiTe@NiFe-LDH/NF array showcases remarkably low overpotentials of 277 mV and 359 mV for achieving current densities of 100 and 500 mA cm-2, respectively. Also, it shows a low Tafel slope of 68.66 mV dec-1. Notably, the electrocatalyst maintains robust stability over continuous electrolysis for at least 50 h at 100 mA cm-2. The remarkable performance and hierarchical structure advantages of NiTe@NiFe-LDH/NF offer innovative insights for designing efficient seawater oxidation electrocatalysts.

Stabilizing NiFe sites by high-dispersity of nanosized and anionic Cr species toward durable seawater oxidation.

Electrocatalytic H2 production from seawater, recognized as a promising technology utilizing offshore renewables, faces challenges from chloride-induced reactions and corrosion. Here, We introduce a catalytic surface where OH- dominates over Cl- in adsorption and activation, which is crucial for O2 production. Our NiFe-based anode, enhanced by nearby Cr sites, achieves low overpotentials and selective alkaline seawater oxidation. It outperforms the RuO2 counterpart in terms of lifespan in scaled-up stacks, maintaining stability for over 2500 h in three-electrode tests. Ex situ/in situ analyses reveal that Cr(III) sites enrich OH-, while Cl- is repelled by Cr(VI) sites, both of which are well-dispersed and close to NiFe, enhancing charge transfer and overall electrode performance. Such multiple effects fundamentally boost the activity, selectively, and chemical stability of the NiFe-based electrode. This development marks a significant advance in creating durable, noble-metal-free electrodes for alkaline seawater electrolysis, highlighting the importance of well-distributed catalytic sites.