Recent advances in biological molecule detection based on a three-dimensional graphene structure.

Graphene has become an attractive material in the field of electrochemical detection owing to its unique electrical properties. Although the simple stacking structures of two-dimensional (2D) graphene sheets can provide excellent detection properties, a macroscopic three-dimensional (3D) structure needs to be constructed to enhance its functional properties. Graphene with a 3D structure has elegant functions, unlike graphene with a 2D structure. These properties include a large specific surface area, easy loading of nanomaterials with electrocatalytic and redox functions, and so on. Herein, we outline the preparation methods (self-assembly, chemical vapor deposition, templates, and 3D printing) for 3D graphene structures for obtaining excellent detection performance and applications in detecting biological molecules, bacteria, and cells. Furthermore, this review focuses on the improvement of the detection performance and enhancement of the applicability of graphene-based electrochemical sensors. We hope that this article will provide a reference for the future development of electrochemical sensors based on 3D graphene composites.

Deep Red Light Driven Hydrogen Evolution by Heterojunction Polymer Dots for Diabetic Wound Healing.

We describe small heterojunction polymer dots (Pdots) with deep-red light catalyzed H2 generation for diabetic skin wound healing. The Pdots with donor/acceptor heterojunctions showed remarkably enhanced photocatalytic activity as compared to the donor or acceptor nanoparticles alone. We encapsulate the Pdots and ascorbic acid into liposomes to form Lipo-Pdots nanoreactors, which selectively scavenge ⋅OH radicals in live cells and tissues under 650 nm light illumination. The antioxidant capacity of the heterojunction Pdots is ~10 times higher than that of the single-component Pdots described previously. Under a total light dose of 360 J/cm2, the Lipo-Pdots nanoreactors effectively scavenged ⋅OH radicals and suppressed the expression of pro-inflammatory cytokines in skin tissues, thereby accelerating the healing of skin wounds in diabetic mice. This study provides a feasible solution for safe and effective treatment of diabetic foot ulcers.

Fe Single-Atom Catalyst for Efficient and Rapid Fenton-Like Degradation of Organics and Disinfection against Bacteria.

The Fenton-like reaction has great potential in water treatment. Herein, an efficient and reusable catalytic system is developed based on atomically dispersed Fe catalyst by anchoring Fe atoms on nitrogen-doped porous carbon (Fe SA/NPCs). The catalyst of Fe SA/NPCs exhibits enhanced performance in activating peroxymonosulfate (PMS) for organic pollutant degradation and bacterial inactivation. The Fe SA/NPCs + PMS system demonstrates a high turnover frequency of 39.31 min-1 in Rhodamine B (RhB) degradation as well as a strong bactericidal activity that can completely sterilize an Escherichia coli culture within 5 min. Meanwhile, the degradation activity of RhB by Fe SA/NPCs is improved up to 28 to 371-fold in comparison with the controls. Complete degradation of RhB can be achieved in 30 s by the Fe SA/NPCs + PMS system, demonstrating an efficiency much higher than most traditional Fenton-like processes. Experiments with different radical scavengers and density functional theory calculations have revealed that singlet oxygen (1 O2 ) generated on the N-coordinated single Fe atom (Fe-N4 ) sites is the key reactive species for the effective and rapid pollutant degradation and bacterial inactivation. This work innovatively affords a promising single-Fe-atom catalyst/PMS system for applying Fenton-like reactions in water treatment.

Microemulsion-Confined Biomineralization of PEGylated Ultrasmall Fe3O4 Nanocrystals for T2-T1 Switchable MRI of Tumors.

Ultrasmall superparamagnetic iron oxide nanoparticles (USPIONs) are a novel T1 contrast agent with good biocompatibility and switchable imaging signal that have not been widely applied for magnetic resonance imaging (MRI) because it is difficult to induce their relatively close ideal agglomeration. Here, by combining the microemulsion method with the biomineralization principle, a pH-responsive T2-T1 switchable MRI nanoprobe was constructed via the microemulsion-confined biomineralization of PEGylated USPIONs (PEG-USPIONs). The size of the formed CaCO3-coated PEG-USPION conjugates (PEG-USPIONs@CaCO3 nanoprobe) was uniform and controllable, and the preparation method was simple. The PEG-USPIONs inside the nanoconjugates agglomerate more tightly, and the T1-MRI signal of the nanoprobe is converted to the T2-MRI signal. When exposed to the acidic environment of the tumor tissue or internal organelles, the CaCO3-coating of the nanoprobes is dissolved, and free PEG-USPIONs are released, thus realizing the T1-weighted imaging of the tumors. The suitability of the PEG-USPIONs@CaCO3 nanoprobe for tumor MRI detection was successfully demonstrated using a mouse model bearing a subcutaneous 4T1 xenograft.

Measuring Cellular Uptake of Polymer Dots for Quantitative Imaging and Photodynamic Therapy.

There is a great deal of interest in the development of nanoparticles for biomedicine. The question of how many nanoparticles are taken up by cells is important for biomedical applications. Here, we describe a fluorescence method for the quantitative measurement of the cellular uptake of polymer dots (Pdots) and a further estimation of intracellular Pdots photosensitizer for fluorescence imaging and photodynamic therapy. The approach relies on the high brightness, excellent stability, minimal aggregation quenching, and metalloporphyrin doping properties of the Pdots. We correlated the single-cell fluorescence brightness obtained from fluorescence spectrometry, confocal microscopy, and flow cytometry with the number of endocytosed Pdots, which was validated by inductively coupled plasma mass spectrometry. Our results indicated that, on average, ∼1.3 million Pdots were taken up by single cells that were incubated for 4 h with arginine 8-Pdots (40 µg/mL, ∼20 nm diameter). The absolute number of endocytosed Pdots of individual cells could be estimated from confocal microscopy by comparing the single-cell brightness with the average intensity. Furthermore, we investigated the cell viability as a result of an intracellular Pdots photosensitizer, from which the half maximal inhibitory concentration was determined to be ∼7.2 × 105 Pdots per cell under the light dose of 60 J/cm2. This study provides an effective method for quantifying endocytosed Pdots, which can be extended to investigate the cellular uptake of various conjugated polymer carriers in biomedicine.

Three-dimensional graphene oxide foams loaded with AuPd alloy: a sensitive electrochemical sensor for dopamine.

The authors describe a chemical sensor for dopamine (DA). It is based on the use of three-dimensional graphene oxide (3D rGO) loaded with varying amounts of AuPd bimetallic nanoparticles (3D rGO/AuPd NPs). The 3D rGO acts as an effective substrate providing a large surface area and allowing fast electron transfer. The interaction between 3D rGO and surface AuPd NPs increases the activity of the sensing material. These composites were fabricated as the active layer on an indium tin oxide for DA determination. The electrode showed the best performance at a working potential of 0.25 V (vs. the saturated calomel reference electrode) and a scan rate of 100 mVs-1. The best electrode exhibits good sensitivity (4670 µA·mM-1·cm-2), a wide linear response (0.5 µM to 135 µM), and a low detection limit (0.2 µM). It is also selective, easily reproducible, and stable. It was applied to the determination of DA in spiked human serum and in clinical DA hydrochloride injections. The excellent performance of this electrode is attributed to the efficient electron transfer and large specific surface area of 3D rGO and to the high electrocatalytic activity of AuPd NPs due to the synergistic effect between the 3D rGO substrate and the AuPd alloy NPs. Graphical abstract An three-dimensional reduced graphene oxide (3D rGO) foam was loaded with AuPd bimetallic nanoparticles and applied to dopamine (DA) detection in human serum and an injection fluid.

A Dendritic Supramolecular Complex as Uniform Hybrid Micelle with Dual Structure for Bimodal In Vivo Imaging.

In this study, a uniform complex dual micelle bearing a gadolinium-substituted polyoxometalate core, a hydrophobic middle, and a biocompatible organic shell, which exhibits a uniform size and definite molecular weight and chemical composition, is constructed through a simple two-step process for use as a fluorescence and magnetic resonance imaging (MRI) contrast agent. A paramagnetic polyoxometalate cluster, K13 [Gd(ß2 -SiW11 O39 )2 ], is first encapsulated with a cationic 3-generation dendron (D-3) bearing triethylene glycol monomethyl ether terminal groups through ionic substitution. The formed electrostatic complex, (D-3)13 [Gd(ß2 -SiW11 O39 )2 ] (D-GdSiW), which displays an ambivalent micellar structure, is then demonstrated to act as a suitable carrier for the uptake of cationic fluorescent dyes, forming a loaded complex. The dye-loaded complex D-GdSiW-D is thus proven to display high relaxivity as a contrast agent, maintaining its structural stability under physiological conditions with low cell cytotoxicity. Confocal laser scanning microscopic observation also demonstrates the fluorescence imaging property of the prepared complex upon consumption by MCF-7 cells. Both in vivo fluorescence imaging and MRI further confirm that the complex micelle with dual micellar structure may be a suitable liver-specific contrast agent for clinical diagnosis.

Incorporation of Porphyrin to π-Conjugated Backbone for Polymer-Dot-Sensitized Photodynamic Therapy.

The photosensitizers used in photodynamic therapy are mainly based on porphyrin derivatives. However, clinical applications encounter several limitations regarding photosensitizers such as their low absorption coefficients, poor water-solubility, and leaching from delivery carriers. Here, we describe covalent incorporation of porphyrin in conjugated polymer backbone for development of efficient polymer-dot photosensitizer. Spectroscopic characterizations revealed that the light-harvesting polymer dominantly transfer the excitation energy to the porphyrin unit, yielding efficient singlet oxygen generation for photodynamic therapy. The polymer dots (Pdots) also possess excellent stability that overcomes the photosensitizer leaching problem as encountered in other nanoparticle carriers. In vitro cytotoxicity and photodynamic efficacy of the Pdots were evaluated in MCF-7 cells by in vitro assay, indicating that the Pdots can efficiently damage cancer cells. In vivo photodynamic therapy by using the Pdots was further investigated with xenograft tumors in Balb/c nude mice, which show that the tumors were significantly inhibited or eradicated in certain cases. The high-yield singlet oxygen generation and excellent stability of porphyrin-incorporated Pdots are promising for photodynamic treatment of malignant tumors.

One-Step Synthesis of Single-Layer MnO2 Nanosheets with Multi-Role Sodium Dodecyl Sulfate for High-Performance Pseudocapacitors.

A template-free, one-step and one-phase synthesis of single-layer MnO2 nanosheets has been developed via a redox reaction between KMnO4 and sodium dodecyl sulfate (SDS). The successful formation of single-layer MnO2 nanosheets has been confirmed by the characteristic absorption around 374 nm and the typical thickness of ~0.95 nm. The slow redox reaction controlled by the gradual hydrolysis of SDS is found to be the key factor for the successful formation of single-layer nanosheets. SDS not only serves as the precursor of dodecanol to reduce KMnO4 , but also aids the formation of single-layer MnO2 nanosheets as a structure-inducing agent. The resultant single-layer MnO2 nanosheets possess superior specific capacitance, which can be attributed to the extended surface and high porosity of MnO2 nanosheets on the electrode. The MnO2 nanosheets also show excellent durability, retaining 91% of the starting capacitance after 10 000 charge/discharge cycles. Moreover, the symmetric pseudocapacitor based on the synthesized single-layer MnO2 nanosheets exhibits a high specific capacitance, indicating great potential for real energy storage. Therefore, it has been demonstrated for the first time that a single readily available reagent, SDS, can play multiple roles in reducing KMnO4 to conveniently yield single-layer MnO2 nanosheets as a high-performance pseudocapacitive material.

Graphene carrier for magneto-controllable bioelectrocatalysis.

A magnetically driven fuel-free graphene carrier loaded with redox-active cargo-ferrocene as an electron mediator is fabricated for magneto-controllable bioelectrocatalysis. The activation and deactivation of redox-active cargo's redox activity by magnetically driven positioning of the graphene carrier with loaded ferrocene near and away from the conductive support can be employed for magneto-switchable bioelectrocatalyzed oxidation of glucose by glucose oxidase between active and inactive electrocatalytic states, respectively.

Conjugated polymer dots for ultra-stable full-color fluorescence patterning.

Stable full-color fluorescence patterning are achieved by multicolor polymer-dot inks. The fluorescent patterns show extraordinary stability upon various treatments, offering a superior combination of bright fluorescence, excellent photostability, chemical resistance, and eco-friendship.

Unravelling the correlation between the aspect ratio of nanotubular structures and their electrochemical performance to achieve high-rate and long-life lithium-ion batteries.

The fundamental understanding of the relationship between the nanostructure of an electrode and its electrochemical performance is crucial for achieving high-performance lithium-ion batteries (LIBs). In this work, the relationship between the nanotubular aspect ratio and electrochemical performance of LIBs is elucidated for the first time. The stirring hydrothermal method was used to control the aspect ratio of viscous titanate nanotubes, which were used to fabricate additive-free TiO2 -based electrode materials. We found that the battery performance at high charging/discharging rates is dramatically boosted when the aspect ratio is increased, due to the optimization of electronic/ionic transport properties within the electrode materials. The proof-of-concept LIBs comprising nanotubes with an aspect ratio of 265 can retain more than 86 % of their initial capacity over 6000 cycles at a high rate of 30 C. Such devices with supercapacitor-like rate performance and battery-like capacity herald a new paradigm for energy storage systems.

A novel pH-activated AIEgen probe for dynamic lysosome tracking and high-efficiency photodynamic therapy.

A novel AIEgen molecular probe (N-3QL) with typical AIE effects, good biocompatibility, lysosome targeting, pH activation, excellent photostability, and high brightness was synthesized using two simple synthetic steps. Spectroscopic and cytotoxicity experiments indicate that N-3QL can not only be used for the dynamic monitoring of cancer cell lysosomes, but also for photodynamic therapy (PDT) ablation of cancer cells.

Overexpression of FERM Domain Containing Kindlin 2 (FERMT2) in Fibroblasts Correlates with EMT and Immunosuppression in Gastric Cancer.

The mesenchymal feature, dominated by epithelial mesenchymal transition (EMT) and stromal cell activation, is one of the main reasons for the aggressive nature of tumors, yet it remains poorly understood. In gastric cancer (GC), the fermitin family homolog-2 (FERMT2) is involved in macrophage signaling, promoting migration and invasion. However, the function of FERMT2 in fibroblasts remains unclear. Here, we demonstrated that downregulation of FERMT2 expression can block EMT in GC cells by inhibiting fibroblast activation in vitro. Furthermore, we found that, in addition to the known pathways, fibroblast-derived FERMT2 promotes M2-like macrophage growth and that in human GC samples, there is a strong positive correlation between FERMT2 and CD163 and CD206 levels. Notably, high FERMT2 expression was significantly associated with poor clinical outcomes and was upregulated in patients with advanced disease. Taken together, our results provide evidence that the fibroblast-FERMT2-EMT-M2 macrophage axis plays a critical role in the GC mesenchymal phenotype and may be a promising target for the treatment of advanced GC.

Semiconducting polymer dots for multifunctional integrated nanomedicine carriers.

The expansion applications of semiconducting polymer dots (Pdots) among optical nanomaterial field have long posed a challenge for researchers, promoting their intelligent application in multifunctional nano-imaging systems and integrated nanomedicine carriers for diagnosis and treatment. Despite notable progress, several inadequacies still persist in the field of Pdots, including the development of simplified near-infrared (NIR) optical nanoprobes, elucidation of their inherent biological behavior, and integration of information processing and nanotechnology into biomedical applications. This review aims to comprehensively elucidate the current status of Pdots as a classical nanophotonic material by discussing its advantages and limitations in terms of biocompatibility, adaptability to microenvironments in vivo, etc. Multifunctional integration and surface chemistry play crucial roles in realizing the intelligent application of Pdots. Information visualization based on their optical and physicochemical properties is pivotal for achieving detection, sensing, and labeling probes. Therefore, we have refined the underlying mechanisms and constructed multiple comprehensive original mechanism summaries to establish a benchmark. Additionally, we have explored the cross-linking interactions between Pdots and nanomedicine, potential yet complete biological metabolic pathways, future research directions, and innovative solutions for integrating diagnosis and treatment strategies. This review presents the possible expectations and valuable insights for advancing Pdots, specifically from chemical, medical, and photophysical practitioners' standpoints.

Enhanced fluorescence properties of polyfluorene-based polymer dots through an ascorbic acid-photoaging treatment for living cell imaging.

The polymer dots (Pdots) prepared by the conjugated polymer (PFO, poly (9,9-dihexylfluorene-2,7-diyl)) have high fluorescence intensity and are often used in biological fluorescence imaging. However, due to the chain defects, the PFO Pdots suffer from stability issues such as photoinactivation and photobleaching. To solve this problem, we drew inspiration from the preparation process of organic planar light-emitting devices and added an optimization processing after Pdots was prepared. We used illumination as the driving force to activate defects on its chain, and ascorbic acid as a reducing substance to restore the chain defects of the polymer to a more stable state. Through this method, we increased the fluorescence intensity by nearly 1.9 times, and significantly improving their long and short-term stability. In addition, it ensures other properties remain unchanged. This optimization scheme is also fully compatible with the entire biological imaging process, ensuring that other important properties such as cytotoxicity do not undergo unnecessary changes. Furthermore, we conducted material characterization and theoretical simulation, revealing that the optimization scheme mainly serves to repair C-9 alkyl defects on the polyfluorene unit. This study has improved and enhanced the fluorescence performance of PFO Pdots, and also provides a way to optimize the treatment of other similar conjugated polymer material systems.

Self-assembly of three-dimensional liver organoids: virtual reconstruction via endocytosed polymer dots for refactoring the fine structure.

In vitro culture of organoids holds considerable promise for the treatment of diseases or the provision of artificial organs. Traditional 2D differentiation from mesenchymal stem cells (MSCs) faces challenges in replicating the development of embryonic organs at the cellular level; conversely, the cultivation of 3D organoids exhibits potential for application. It is crucial for clinicians and technology researchers to acquire insights into organoid tissue differentiation, autonomous morphogenesis, as well as 3D assembly processes in vitro. In this investigation, novel 3D organoids capable of engendering complex liver-like tissues in vitro were cultured, and a class of high-luminance semiconductor polymer dots (Pdots) was employed to monitor the self-assembly process of 3D liver organoid tissues and cellular interaction and migration dynamics. Three-dimensional liver-bud (3D-LB) organoid tissues were derived through the interplay of induced MSCs, Wharton's Jelly, and human umbilical vein endothelial cells (HUVECs), and their structural characteristics were determined during the liver-bud organoid development; ultimately, the co-cultured organoid spatial cellular clusters resembling a truffle were successfully replicated. Utilizing R8-Pdots with remarkable resolution and biocompatibility, the structural elements of functional and vascularized organs derived from liver organoid tissues were adeptly reconstituted, and this investigation shall contribute to a further understanding of human hepato-developmental physiology and liver-disease modeling.

Bioinspired MoS2 Nanosheet-Modified Carbon Fibers for Synergetic Bacterial Elimination and Wound Disinfection.

Bacterial infection is one of the most frequent wound complications and has become a major public health concern. Increasing resistance to antibiotics has been noted with these agents broadly used in wound management. It is an urgent demand to develop alternative antibacterial strategies with a reduced chance of resistance. Herein, a Nepenthes-mimicking nanosheet array of MoS2 on carbon fibers (CF-MoS2 ) is proposed to achieve dual bactericidal activities. First, the sharp edges of synthesized surfaces are capable of inducing physical disruption of cell membranes, demonstrating mechanical antibacterial activity like their natural counterparts. Second, in the presence of near-infrared light, bioinspired CF-MoS2 nanosheets are able to cause the death of damaged bacteria owing to their inherent photothermal properties. Such dual-functional modes endow the surfaces with nearly 100% killing efficiency for highly concentrated Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). Furthermore, their potential to be applied as wound dressings for photothermal treatment of infectious wounds is also investigated in vivo. Bioinspired CF-MoS2 dressings show advantages of synergistic disinfection and efficient promotion of wound regeneration. It is foreseen that this high-performance and multifunctional CF-MoS2 could afford a feasible broad-spectrum treatment for non-antibiotic disinfection.

Janus biomass aerogel for Highly-Efficient steam Generation, Desalination, degradation of organics and water disinfection.

Solar-driven water purification has been deemed as a cheap, green and renewable technology to mitigate water shortage and pollution. Herein, a biomass aerogel with hydrophilic-hydrophobic Janus structure has been prepared as solar water evaporator, which is achieved by partially modifying hydrothermal-treated loofah sponge (HLS) with reduced graphene oxide (rGO). It's a rare design philosophy that HLS serves as a substrate with large pores and hydrophilic properties to ensure continuous and effective water transport, and the hydrophobic layer with rGO modification guarantees good salt resistance in seawater desalination with high photothermal conversion efficiency. As a result, the obtained Janus aerogel, p-HLS@rGO-12, exhibits impressive solar-driven evaporation rates of 1.75 kg m-2h-1 and 1.54 kg m-2h-1 for pure water and seawater respectively, with good cycling stability in the evaporation process. Furthermore, p-HLS@rGO-12 also demonstrates outstanding photothermal degradation of rhodamine B (greater than98.8 % in 2 h) and sterilization of E. coli (nearly 100 % in 2 h). This work offers an unusual approach to achieve highly efficient solar-driven steam generation, seawater desalination, organic pollutant degradation, and water disinfection simultaneously. The prepared Janus biomass aerogel holds great potential application in the field of seawater desalination and wastewater purification.

Assembly of graphene sheets into 3D macroscopic structures.

Integration of graphene sheets, 2D nanoscale building blocks, into 3D macroscopic assemblies and ultimately into a functional system is essential to explore the advanced properties of individual graphene sheets for macroscopic applications. This Concept paper summarizes different ways, such as flow-directed assembly, layer-by-layer deposition, template-directed method, and leavening strategy to assemble graphene sheets into the layered and porous 3D macroscopic structures. The obtained structures show unique properties, such as flexible network, high specific surface area, and outstanding electrical and mechanical properties. Furthermore, the functional systems based on such graphene 3D macroscopic structures have shown enhanced performance in the applications of energy storage, catalysis, environmental remediation, and sensing.