Designable Nanoadaptor for Enhanced Recognition of Natural Killer Cell to Tumor via Bio-orthogonal Click Reaction.

Highly efficient recognition of cancer cells by immune cells is important for successful therapeutic-cell-based cancer immunotherapy. Herein, we present a facile NIR-II nanoadaptor [hyaluronic acid (HA)/dibenzocyclooctyne (DBCO)-Au:Ag2Te quantum dots (QDs)] for enhancing the tumor recognition and binding ability of natural killer (NK) cells via a bio-orthogonal click reaction in vivo. The Nanoadaptor possesses superior tumor-targeting capacity, facilitating the accumulation of the chemical receptor DBCO at the tumor sites. Subsequently, the enrichment of DBCO on tumor cell surfaces provides multivalent recognition sites for capturing pretreated azide engineered NK92 cells (NK92-N3) through an efficient click reaction, thereby significantly enhancing the therapeutical efficiency. The dynamic process of nanoadaptor-mediated recognition of NK cells to tumor cells could be vividly observed using multiplexed NIR-II fluorescence imaging in a mouse model of lung cancer. Such a nanoadaptor strategy can be extended to other therapeutic cellular systems and holds promise for future clinical applications.

Polydopamine-Coated Copper-Doped Co3O4 Nanosheets Rich in Oxygen Vacancy on Titanium and Multimodal Synergistic Antibacterial Study.

Medical titanium-based (Ti-based) implants in the human body are prone to infection by pathogenic bacteria, leading to implantation failure. Constructing antibacterial nanocoatings on Ti-based implants is one of the most effective strategies to solve bacterial contamination. However, single antibacterial function was not sufficient to efficiently kill bacteria, and it is necessary to develop multifunctional antibacterial methods. This study modifies medical Ti foils with Cu-doped Co3O4 rich in oxygen vacancies, and improves their biocompatibility by polydopamine (PDA/Cu-Ov-Co3O4). Under near-infrared (NIR) irradiation, nanocoatings can generate •OH and 1O2 due to Cu+ Fenton-like activity and a photodynamic effect of Cu-Ov-Co3O4, and the total reactive oxygen species (ROS) content inside bacteria significantly increases, causing oxidative stress of bacteria. Further experiments prove that the photothermal process enhances the bacterial membrane permeability, allowing the invasion of ROS and metal ions, as well as the protein leakage. Moreover, PDA/Cu-Ov-Co3O4 can downregulate ATP levels and further reduce bacterial metabolic activity after irradiation. This coating exhibits sterilization ability against both Escherichia coli and Staphylococcus aureus with an antibacterial rate of ca. 100%, significantly higher than that of bare medical Ti foils (ca. 0%). Therefore, multifunctional synergistic antibacterial nanocoating will be a promising strategy for preventing bacterial contamination on medical Ti-based implants.

Bismuth-Doped Carbon Dots Decorated Escherichia coli for Enhanced Hydrogen Production.

Photosynthetic inorganic biohybrid systems (PBSs) combining an inorganic photosensitizer with intact living cells provide an innovative view for solar hydrogen production. However, typical whole-cell biohybrid systems often suffer from sluggish electron transfer kinetics during transmembrane diffusion, which severely limits the efficiency of solar hydrogen production. Here, a unique biohybrid system with a quantum yield of 8.42% was constructed by feeding bismuth-doped carbon dots (Bi@CDS) to Escherichia coli (E. coli). In this biohybrid system, Bi@CDS can enter the cells and transfer the electrons upon light irradiation, greatly reducing the energy loss and shortening the distance of electron transfer. More importantly, the photocatalytic hydrogen production of the E. coli-Bi@CDs biohybrid system reached up to 0.95 mmol within 3 h under light irradiation (420-780 nm, 2000 W m-2), which is 1.36 and 2.38 times higher than that in the E. coli-CDs biohybrid system and the E. coli system, respectively. In addition, the mechanism of enhanced hydrogen production was further explored. It was found that the accelerated decomposition of glucose, the accelerated production of pyruvate, the inhibition of lactic acid, and the increase of formic acid were the reasons for the increase of hydrogen production. This work provides a novel strategy for improving the hydrogen production in photosynthetic inorganic biohybrid systems.

Ni─Co─O─S Derived Catalysts on Hierarchical N-doped Carbon Supports with Strong Interfacial Interactions for Improved Hybrid Water Splitting Performance.

Simultaneously improving electrochemical activity and stability is a long-term goal for water splitting. Herein, hierarchical N-doped carbon nanotubes on carbon nanowires derived from PPy are grown on carbon cloth, serving as a support for NiCo oxides/sulfides. The hierarchical electrodes annealed in N2 or H2/N2 display improved intrinsic activity and stability for hydrogen evolution reaction (HER) and glucose oxidation reaction. Compared with Pt/C||Ir/C in alkaline media, the glucose electrolysis assembled with electrodes exhibits a cell voltage of 1.38 V at 10 mA cm-2, durability for >12 h at 50 mA cm-2, and resistance to glucose/gluconic acid poisoning. In addition, electrocatalysts can also be applied in ethanol oxidation reactions. Systematic characterizations reveal the strong interactions between NiCo and N-doped carbon support-induced partial charge transfer at the interface and regulate the local electronic structure of active sites. Density functional theory calculations demonstrate that the synergistic effect between N-doped carbon supports, metallic NiCo, and NiCo oxides/sulfides optimize the adsorption energy of H2O and the H* free energy for HER. The energy barrier of the dehydrogenation of glucose effectively decreased. This work will attract attention to the role of metal-support interactions in enhancing the intrinsic activity and stability of electrocatalysts.

Conductive and capacitive network for enriching the exoelectrogens and enhancing the extracellular electron transfer in microbial fuel cells.

Although lots of nanomaterials modified anodes have been reported to improve the bacterial attachment and extracellular electron transfer (EET) in microbial fuel cells (MFCs), the lack of a three dimensional (3D) conductive and capacitive network severely limited MFCs performance. In this work, 3D conductive networks derived from mucor mycelia were grown on carbon cloth (CC), and capacitive FeMn phosphides/oxides were further anchored on these 3D networks by electrochemical deposition (denoted as FeMn/CMM@CC) to simultaneously address the above challenges. As a result, the multivalent metal active sites were evenly distributed on 3D conductive network, which favored the enrichment of exoelectrogens, mass transport and EET. Consequently, the as-prepared FeMn/CMM@CC anode displayed accumulated charge of 131.4C/m2, higher than bare CC. Meanwhile, FeMn/CMM@CC anode substantially promoted flavin excretion and the amounts of nano conduits. The abundance of Geobacter was 63 % on bare CC, and greatly increased to 83 % on FeMn/CMM@CC. MFCs equipped by FeMn/CMM@CC anode presented the power density of 3.06 W/m2 and coulombic efficiency (29.9 %), evidently higher than bare CC (1.29 W/m2, 7.3 %), and the daily chemical oxygen demand (COD) removal amount also increased to 92.6 mg/L/d. This work developed a facile method to optimize the abiotic-biotic interface by introducing 3D conductive and capacitive network, which was proved to be a promising strategy to modify macro-porous electrodes.

An electrochemical biosensor for Staphylococcus aureus detection based on a multilevel surface 3D micro/nanostructure.

Detection of pathogens is one of the key concerns for hospitals, the food industry, water suppliers, or other environmental engineering practices because pathogens can cause a wide range of infectious risks. Staphylococcus aureus (S. aureus) is one of the most common pathogens that are hazardous to human health and its existence is an important index to the safety of food, environmental sanitation, or medical products. In this study, we prepared an electrode with designed surface multilevel 3D micro/nano protrusions for facile and efficient S. aureus detection. The existence of these multilevel protrusions enhanced the adsorption of S. aureus. Hence, the detection limit could be as low as 10 CFU mL-1. Furthermore, the electrode was also successfully used to detect S. aureus in actual samples, such as milk and artificial human tissue fluid. It was found that the recovery of the reported approach showed no significant difference from that of the traditional plate count method. However, compared with the plate count method, the detection process of our approach is much more time-saving and easy-operating. These advantages of the approach we report, such as high sensitivity, reliability, quickness, and user-friendliness, make it a potential platform for detecting S. aureus in relation to the food industry and clinical diagnosis.

Programmed Remodeling of the Tumor Milieu to Enhance NK Cell Immunotherapy Combined with Chemotherapy for Pancreatic Cancer.

Natural killer (NK) cell-based adoptive immunotherapy has demonstrated encouraging therapeutic effects in clinical trials for hematological cancers. However, the effectiveness of treatment for solid tumors remains a challenge due to insufficient recruitment and infiltration of NK cells into tumor tissues. Herein, a programmed nanoremodeler (DAS@P/H/pp) is designed to remodel dense physical stromal barriers and for dysregulation of the chemokine of the tumor environment to enhance the recruitment and infiltration of NK cells in tumors. The DAS@P/H/pp is triggered by the acidic tumor environment, resulting in charge reversal and subsequent hyaluronidase (HAase) release. HAase effectively degrades the extracellular matrix, promoting the delivery of immunoregulatory molecules and chemotherapy drugs into deep tumor tissues. In mouse models of pancreatic cancer, this nanomediated strategy for the programmed remodeling of the tumor microenvironment significantly boosts the recruitment of NK92 cells and their tumor cell-killing capabilities under the supervision of multiplexed near-infrared-II fluorescence.

Novel Acid-Driven Bioinspired Self-Resettable Bilayer Hydrogel Actuator Mimicking Natural Muscles.

Soft robots have great potential applications in manufacturing, disaster rescue, medical treatment, etc. Artificial muscle is one of the most important components of a soft robot. In previous years, hydrogel actuators that can be controllably deformed by the stimuli of external signals have been developed as good candidates for muscle-like materials. In this article, we successfully prepared a chemical fuel-driven self-resettable bilayer hydrogel actuator mimicking natural muscles with the aid of a new negative feedback reaction network. The actuator can temporarily deform upon the addition of H+ (chemical fuel). Subsequently, H+ accelerated the reaction between BrO3- and Fe(CN)64-, which consume H+. It resulted in the spontaneous recovery of the pH as well as the shape of the actuator. Such an actuator exhibits a great similarity with natural muscles in actuation mechanisms and automaticity in the manipulation compared to the widely reported stimuli-responsive hydrogel actuators. This illustrates that fuel-driven self-resettable hydrogel is a promising dynamic material for mimicking the functions of living creatures.

Amperometry for real-time and on-site monitoring of phenol and H2O2 during the treatments.

In conventional wastewater treatment processes, a predetermined quantity of chemicals is introduced at the onset, without ongoing monitoring of the treatment progress. Thus, it is difficult to perform timely intervention in the treatment process. Herein, we develop an amperometry-guided wastewater treatment strategy based on a green oxidation process with H2O2 and an iron-tetraamidomacrocyclic ligand (Fe-TAML) catalyst. During the process, users can monitor both phenol and H2O2 concentrations in real time and then intervene by adding more H2O2 to accelerate the reaction. As a proof of concept, a wastewater sample containing 9.3 ppm of phenol is treated by using the amperometry-guided strategy with 1 dosage of Fe-TAML (0.45 ppm) and 3 dosages of H2O2 (1.86 ppm). After the treatment, phenol concentration in the wastewater decreases to 0 ppm after 21 min. In contrast, with only 1 dosage of Fe-TAML (0.45 ppm) and 1 dosage of H2O2 (1.86 ppm), the reaction slows down after 5 min and stops prematurely. After that, the reaction kinetics of ppb-level phenol are investigated, in which the phenol rate and the rate constant are estimated. Compared to conventional detections, the designed amperometry shows faster response, lower limit of detection (LOD, phenol: 11 ppb, H2O2: 80 ppb) and consumable cost, easier operation, and no pollution generated. This example demonstrates the importance of early intervention during wastewater treatment with the help of real-time information.

Nanomaterials-Induced Redox Imbalance: Challenged and Opportunities for Nanomaterials in Cancer Therapy.

Cancer cells typically display redox imbalance compared with normal cells due to increased metabolic rate, accumulated mitochondrial dysfunction, elevated cell signaling, and accelerated peroxisomal activities. This redox imbalance may regulate gene expression, alter protein stability, and modulate existing cellular programs, resulting in inefficient treatment modalities. Therapeutic strategies targeting intra- or extracellular redox states of cancer cells at varying state of progression may trigger programmed cell death if exceeded a certain threshold, enabling therapeutic selectivity and overcoming cancer resistance to radiotherapy and chemotherapy. Nanotechnology provides new opportunities for modulating redox state in cancer cells due to their excellent designability and high reactivity. Various nanomaterials are widely researched to enhance highly reactive substances (free radicals) production, disrupt the endogenous antioxidant defense systems, or both. Here, the physiological features of redox imbalance in cancer cells are described and the challenges in modulating redox state in cancer cells are illustrated. Then, nanomaterials that regulate redox imbalance are classified and elaborated upon based on their ability to target redox regulations. Finally, the future perspectives in this field are proposed. It is hoped this review provides guidance for the design of nanomaterials-based approaches involving modulating intra- or extracellular redox states for cancer therapy, especially for cancers resistant to radiotherapy or chemotherapy, etc.

Spatiotemporally Controlled Photolabeling of Genetically Unmodified Proteins in Live Cells.

Selective labeling of the protein of interest (POI) in genetically unmodified live cells is crucial for understanding protein functions and kinetics in their natural habitat. In particular, spatiotemporally controlled installation of the labels on a POI under light control without affecting their original activity is in high demand but is a tremendous challenge. Here, we describe a novel ligand-directed photoclick strategy for spatiotemporally controlled labeling of endogenous proteins in live cells. It was realized with a designer labeling reagent skillfully integrating the photochemistries of 2-nitrophenylpropyloxycarbonyl and 3-hydroxymethyl-2-naphthol with an affinity ligand. Highly electrophilic ortho-naphthoquinone methide was photochemically released and underwent a proximity coupling reaction with nucleophilic amino acid residues on the POI in live cells. With fluorescein as a marker, this photoclick strategy enables time-resolved labeling of carbonic anhydrase subtypes localized either on the cell membrane or in the cytoplasm and a discriminable visualization of their metabolic kinetics. Given the versatility underlined by facilely tethering other functional entities (e.g., biotin, a peptide short chain) via acylation or (in cell) Huisgen cycloaddition, this affinity-driven photoclick chemistry opens up enormous opportunities for discovering dynamic functions and mechanistic interrogation of endogenous proteins in live cells.

A Synergistic Antibacterial Study of Copper-Doped Polydopamine on Ti3C2Tx Nanosheets with Enhanced Photothermal and Fenton-like Activities.

In response to the trend of drug-resistant and super bacteria, the existing single antibacterial methods are not sufficient to kill bacteria, and the development of multifunctional antibacterial nanomaterials is urgent. Our study aims to construct copper-doped polydopamine-coated Ti3C2Tx (CuPDA@Ti3C2Tx) with an enhanced photothermal property and Fenton-like activity. The nanocomposite hydrogel consisting of CuPDA@Ti3C2Tx and alginate can improve the antioxidant activity of two-dimensional MXene nanosheets by coating them with a thin layer of PDA nanofilm. Meanwhile, Cu ions are adsorbed through the coordination of PDA-rich oxygen-containing functional groups and amino groups. Calcium ions were further used to crosslink sodium alginate to obtain antibacterial hydrogel materials with combined chemotherapy and photothermal therapy properties. The photothermal conversion efficiency of CuPDA@Ti3C2Tx is as high as 57.7% and the antibacterial rate of Escherichia coli reaches 96.12%. The photothermal effect leads to oxidative stress in bacteria, increases cell membrane permeability, and a high amount of ROS and copper ions enter the interior of the bacteria, causing protein denaturation and DNA damage, synergistically leading to bacterial death. Our study involves a multifunctional synergistic antibacterial nanodrug platform, which is conducive to the development of high-performance antibacterial agents and provides important research ideas for solving the problem of drug-resistant bacteria.

Polymer-Based Self-Assembled Drug Delivery Systems for Glaucoma Treatment: Design Strategies and Recent Advances.

Glaucoma has become the world's leading cause of irreversible blindness, and one of its main characteristics is high intraocular pressure. Currently, the non-surgical drug treatment scheme to reduce intraocular pressure is a priority method for glaucoma treatment. However, the complex and special structure of the eye poses significant challenges to the treatment effect and safety adherence of this drug treatment approach. To address these challenges, the application of polymer-based self-assembled drug delivery systems in glaucoma treatment has emerged. This review focuses on the utilization of polymer-based self-assembled structures or materials as important functional and intelligent carriers for drug delivery in glaucoma treatment. Various drug delivery systems, such as eye drops, hydrogels, and contact lenses, are discussed. Additionally, the review primarily summarizes the design strategies and methods used to enhance the treatment effect and safety compliance of these polymer-based drug delivery systems. Finally, the discussion delves into the new challenges and prospects of employing polymer-based self-assembled drug delivery systems for the treatment of glaucoma.

Regulating reconstruction of oxide-derived Cu for electrochemical CO2 reduction toward n-propanol.

Oxide-derived copper (OD-Cu) is the most efficient and likely practical electrocatalyst for CO2 reduction toward multicarbon products. However, the inevitable but poorly understood reconstruction from the pristine state to the working state of OD-Cu under strong reduction conditions largely hinders the rational construction of catalysts toward multicarbon products, especially C3 products like n-propanol. Here, we simulate the reconstruction of CuO and Cu2O into their derived Cu by molecular dynamics, revealing that CuO-derived Cu (CuOD-Cu) intrinsically has a richer population of undercoordinated Cu sites and higher surficial Cu atom density than the counterpart Cu2O-derived Cu (Cu2OD-Cu) because of the vigorous oxygen removal. In situ spectroscopes disclose that the coordination number of CuOD-Cu is considerably lower than that of Cu2OD-Cu, enabling the fast kinetics of CO2 reaction and strengthened binding of *C2 intermediate(s). Benefiting from the rich undercoordinated Cu sites, CuOD-Cu achieves remarkable n-propanol faradaic efficiency up to ~17.9%, whereas the Cu2OD-Cu dominantly generates formate.

Reactive wetting enabled anchoring of non-wettable iron oxide in liquid metal for miniature soft robot.

Magnetic liquid metal (LM) soft robots attract considerable attentions because of distinctive immiscibility, deformability and maneuverability. However, conventional LM composites relying on alloying between LM and metallic magnetic powders suffer from diminished magnetism over time and potential safety risk upon leakage of metallic components. Herein, we report a strategy to composite inert and biocompatible iron oxide (Fe3O4) magnetic nanoparticles into eutectic gallium indium LM via reactive wetting mechanism. To address the intrinsic interfacial non-wettability between Fe3O4 and LM, a silver intermediate layer was introduced to fuse with indium component into AgxIny intermetallic compounds, facilitating the anchoring of Fe3O4 nanoparticles inside LM with improved magnetic stability. Subsequently, a miniature soft robot was constructed to perform various controllable deformation and locomotion behaviors under actuation of external magnetic field. Finally, practical feasibility of applying LM soft robot in an ex vivo porcine stomach was validated under in-situ monitoring by endoscope and X-ray imaging.

Gaucher disease in a patient with membranoproliferative glomerulonephritis: case report.

BACKGROUND: Gaucher disease (GD) is a rare autosomal recessive inherited, lysosomal storage disoder that involves liver, spleen, lung, bone, bone marrow even central nervous. However, GD associated membranoproliferative glomerulonephritis (MPGN) is seldom reported. CASE PRESENTATION: Here we described a case of 35-year-old man suffering from GD with hepatosplenomegaly, ascites, bone destruction, myelofibrosis and MPGN. Renal biopsy revealed MPGN and Gaucher cells presented in the glomeruli capillaries. ß-glucosidase activity was 1.95nmol/1 h/mg and gene detection demonstrated that one homozygous pathogenic variant Leu483Pro in GBA. He received the treatment of oral prednisone and mycophenolate mofetil and his ascites and renal outcomes had been significantly improved. CONCLUSIONS: Therapy of prednisone and mycophenolate mofetil may be an optional choice for patients with Gaucher disease who have no opportunity to use enzyme treatment.

Bifunctional defect mediated direct Z-scheme g-C3N4-x/Bi2O3-y heterostructures with enhanced piezo-photocatalytic properties for efficient tooth whitening and biofilm eradication.

Biofilm-associated dental diseases and tooth discoloration have recently become the major barriers to achieve healthy teeth. However, there are few effective strategies to address these issues. Herein, the piezo-photocatalytic process is first proposed to be applied for biofilm eradication and tooth whitening with well-designed direct Z scheme g-C3N4-x/Bi2O3-y heterostructures. DFT calculation and XPS results verify the formation of direct Z scheme g-C3N4/Bi2O3 heterostructures theoretically and experimentally. Using the direct Z scheme g-C3N4-x/Bi2O3-y heterostructure, excellent piezo-photocatalytic effects for tooth whitening and biofilm removal are achieved. For piezo-photocatalytic degradation of the typical food colorant of indigo carmine the degradation rate constant is about quadruple that of piezocatalytic and 2.6 times of photocatalytic treatment. Tooth whitening experiments indicate that g-C3N4-x/Bi2O3-y could whiten the stained teeth through the synergistic piezo-photocatalysis. In addition, excellent antibacterial performances can be obtained on the g-C3N4-x/Bi2O3-y heterostructure through piezo-photocatalytic treatment. Not only the planktonic S. mutans but also those bacteria embedded in biofilms can be effectively killed. The analyses of the piezo-photocatalytic mechanism indicates that the enhanced piezo-photocatalytic performance of the g-C3N4-x/Bi2O3-y heterostructure could be attributed to the much higher separation efficiency of photoexcited charge carriers, increased production amounts of ROS and superior adsorption ability for bacteria than those with bare semiconductors of g-C3N4-x and Bi2O3-y and those treated only with ultrasonic vibration or irradiation. Biosafety results show that the g-C3N4-x/Bi2O3-y heterostructure is biologically safe and piezo-photocatalytic treatment has no harm the tooth structure, demonstrating the great potential of piezo-photocatalytic effect based new tooth whitening and antibacterial technology in future dental care fields.

Unexcited Light Source Imaging for Biomedical Applications.

Optical imaging has a wide range of applications in the biomedical field, allowing the visualization of physiological processes and helping in the diagnosis and treatment of diseases. Unexcited light source imaging technologies, such as chemiluminescence imaging, bioluminescence imaging and afterglow imaging have attracted great attention in recent years because of the absence of excitation light interference in their application and the advantages of high sensitivity and high signal-to-noise ratio. In this review, the latest advances in unexcited light source imaging technology for biomedical applications are highlighted. The design strategies of unexcited light source luminescent probes in improving luminescence brightness, penetration depth, quantum yield and targeting, and their applications in inflammation imaging, tumor imaging, liver and kidney injury imaging and bacterial infection imaging are introduced in detail. The research progress and future prospects of unexcited light source imaging for medical applications are further discussed.

Biodegradation of di(2-ethylhexyl) phthalate by a new bacterial consortium.

Di(2-ethylhexyl) phthalate (DEHP) with continuous high concentration was used as the sole carbon and energy source to isolate a new bacterial consortium (K1) from agricultural soil covered with plastic film for a long time. Unclassified Comamonadaceae, Achromobacter, and Pseudomonas in K1 were identified as major genera of the consortium by high-throughput sequencing, and unclassified Commanadaceae was first reported to be related to DEHP degradation. Response surface method (RSM) showed that the optimum conditions for K1 to degrade DEHP were 31.4 °C, pH 7.3, and a concentration of 420 mg L-1. K1 maintains normal cell viability and stable DEHP degradation efficiency in the range of 10-3000 mg L-1 DEHP concentration, which is superior to existing research. The biodegradation of DEHP followed first-order kinetics when the initial concentration of DEHP was between 100 and 3,000 mg L-1. GC-MS analysis of different treatment groups showed that DEHP was degraded by the consortium group through the de-esterification pathway, and treatment effect was significantly better than that of the single bacteria treatment group. The subsequent substrate utilization experiment further confirmed that K1 could quickly mineralize DEHP. In addition, K1 has high degradation capacity for the most common phthalate acid esters in the environment.