A magnetically induced self-assembly of Ru@Fe3O4/rGO cathode for diclofenac degradation in electro-Fenton process.

In this study, a novel magnetic nanocomposite of Ru@Fe3O4/rGO was successfully synthesized by a simple hydro-thermal method. The Ru@Fe3O4/rGO particles were assembled and immobilized for innovative magnetically assembled electrode (MAE) without any binder, and the electrode was further applied in heterogeneous electro-Fenton (hetero-EF) process for the degradation of diclofenac (DCF). The results showed that rGO could remarkably enhance the conductivity and catalyze the two-electron oxygen reduction, which greatly improved the generation of H2O2. In addition, the mixture valence of Fe and Ru species might provide rich reaction sites and enhance electron transfer by synergy. Thus, the Ru@Fe3O4/rGO MAE exhibited a stable and high electrocatalytic activity in the hetero-EF process for DCF degradation over a wide pH range from 2 to 9 owing to the higher electroactive surface area (EASA) and lower charge/mass-transfer resistance. The DCF degradation efficiency could reach about 100% within 90 min under pH 5 and current 40 mA, and the Ru@Fe3O4/rGO MAE showed high stability and reusability after five cycles. Theoretically, 1O2 and •OH were the main reactive oxygen species (ROS) participating in DCF degradation in the Ru@Fe3O4/rGO MAE hetero-EF process. Furthermore, according to the LC-MS/MS intermediates, the possible DCF degradation pathway was deduced including dechlorination, hydroxylation and ring opening attacked by ROS. Eleven intermediates were detected during DCF degradation in the MAE hetero-EF process, and the ecological risk of DCF degradation in Ru@Fe3O4/rGO MAE hetero-EF process was significantly reduced. This study provides new insights into the magnetically assembled electrode of Ru@Fe3O4/rGO and displays a new practical application prospect of the materials for high-efficient removal and degradation of DCF from wastewater.

Paper-based device for the selective determination of doxycycline antibiotic based on the turn-on fluorescence of bovine serum albumin-coated copper nanoclusters.

An enhanced ratiometric fluorescence sensor was built for on-site visual detection of doxycycline (DOX) through the interaction with bovine serum albumin on the surface of red emissive copper nanoclusters. Upon the addition of weakly fluorescent DOX, the red fluorescence from copper nanoclusters gradually decreased through the inner-filter effect (IFE), while a green fluorescence appears and significantly increases, forming an interesting fluorescent isosbestic point, which was assigned to DOX due to sensitization effect of bovine serum albumin. On the basis of this ratiometric fluorescence, the system possessed good limit of detection (LOD) of 45 nM and excellent selectivity for DOX over other tetracyclines. Based on these findings, a paper-based sensor has been fabricated for distinct visual detection of trace DOX and combined with smartphone color recognizer for quantitative detection of DOX (LOD = 83 nM). This method shows broad application prospects in environmental monitoring and food safety.

Oxygenic Hybrid Semiconducting Nanoparticles for Enhanced Photodynamic Therapy.

Photodynamic nanotheranostics has shown great promise for cancer therapy; however, its therapeutic efficacy is limited due to the hypoxia of tumor microenvironment and the unfavorable bioavailability of existing photodynamic agents. We herein develop hybrid core-shell semiconducting nanoparticles (SPN-Ms) that can undergo O2 evolution in hypoxic solid tumor to promote photodynamic process. Such oxygenic nanoparticles are synthesized through a one-pot surface growth reaction and have a unique multilayer structure cored and coated with semiconducting polymer nanoparticles (SPNs) and manganese dioxide (MnO2) nanosheets, respectively. The SPN core serves as both NIR fluorescence imaging and photodynamic agent, while the MnO2 nanosheets act as a sacrificing component to convert H2O2 to O2 under hypoxic and acidic tumor microenvironment. As compared with the uncoated SPN (SPN-0), the oxygenic nanoparticles (SPN-M1) generate 2.68-fold more 1O2 at hypoxic and acidic conditions under NIR laser irradiation at 808 nm. Because of such an oxygen-evolution property, SPN-M1 can effectively eradicate cancer cells both in vitro and in vivo. Our study thus not only reports an in situ synthetic method to coat organic nanoparticles but also develops a tumor-microenvironment-sensitive theranostic nanoagent to overcome hypoxia for amplified therapy.

Cobalt Phosphide Double-Shelled Nanocages: Broadband Light-Harvesting Nanostructures for Efficient Photothermal Therapy and Self-Powered Photoelectrochemical Biosensing.

Ultra-broadband light-absorbing materials are highly desired for effective solar-energy harvesting. Herein, novel cobalt phosphide double-shelled nanocages (CoP-NCs) are synthesized. Uniquely, these CoP-NCs are able to nonselectively absorb light spanning the full solar spectrum, benefiting from its electronic properties and hollow nanostructure. They promise a wide range of applications involving solar energy utilization. As proof-of-concept demonstrations, CoP-NCs are employed here as effective photothermal agents to ablate cancer cells by utilizing their ability of near-infrared heat conversion, and as photoactive material for self-powered photoelectrochemical sensing by taking advantage of their ability of photon-to-electricity conversion.

Ternary Chalcogenide Nanosheets with Ultrahigh Photothermal Conversion Efficiency for Photoacoustic Theranostics.

2D materials (TDMs) have been explored for photonic theranostics. To achieve deep-tissue penetration, near-infrared (NIR) light is essential for photoacoustic (PA) theranostics. However, because the absorption profiles of existing TDMs are generally featureless with no obvious NIR absorption peaks, their PA signals and therapeutic efficacies are limited. This paper herein reports the synthesis and application of ternary chalcogenide nanosheets (Ta2 NiS5 -P) for PA theranostics. In contrast to the current TDMs for such application, Ta2 NiS5 -P has a ternary instead of binary composition. This difference brings in the strong and featured NIR for Ta2 NiS5 -P. To the best of the knowledge, this is the first example using ternary chalcogenide nanosheets for such application; moreover, the photothermal conversion efficiency of Ta2 NiS5 -P is the highest (35%) among all the reported TDMs based on the same calculation method. These advantages allow Ta2 NiS5 -P to passively target, effectively delineate, and completely eradicate the tumor of living mice after systemic administration.

Visualizing gaseous nitrogen dioxide by ratiometric fluorescence of carbon nanodots-quantum dots hybrid.

A novel nanohybrid ratiometric fluorescence probe for on-site and visual determination of nitrogen dioxide (NO2) has been designed. The hybrid probe comprises blue-colored fluorescence carbon nanodots (CDs) and red-colored emission CdTe quantum dots (QDs). Such hybridized probe exhibits dual emission bands centered at 460 and 665 nm, respectively. The blue fluorescence of CDs is insensitive to the analyte, whereas the red emission of QDs is specifically quenched by the analyte, resulting in a distinguishable color change from orange-red to blue upon exposure to NO2. The limit of detection for nitrogen dioxide is estimated to be 19 nM in aqueous solution. More importantly, the nanohybrid probe has been successfully applied in visual detection of gaseous NO2 with a detection limit of 1 ppm, suggesting its potential application for NO2 sensing.

Manipulating the Surface Chemistry of Quantum Dots for Sensitive Ratiometric Fluorescence Detection of Sulfur Dioxide.

Herein, we report a novel approach to the rapid visual detection of gaseous sulfur dioxide (SO2) by manipulating the surface chemistry of 3-aminopropyltriethoxysilane (APTS)-modified quantum dots (QDs) using fluorescent coumarin-3-carboxylic acid (CCA) for specific reaction with SO2. The CCA molecules are attached to the surface amino groups of the QDs through electrostatic attraction, thus the fluorescence of CCA is greatly suppressed because of the formation of an ion-pair complex between the ATPS-modified QDs and CCA. Such an interaction is vulnerable to SO2 because SO2 can readily react with surface amino groups to form strong charge-transfer complexes and subsequently release the strongly fluorescent CCA molecules. The mechanism has been carefully verified through a series of control experiments. Upon exposure to different amounts of SO2, the fluorescent color of the nanoparticle-based sensor displays continuously changes from red to blue. Most importantly, the approach owns high selectivity for SO2 and a tolerance of interference, which enables the sensor to detect SO2 in a practical application. Using this fluorescence-based sensing method, we have achieved a visual detection limit of 6 ppb for gaseous SO2.

Graphene oxide supported gold nanoclusters for the sensitive and selective detection of nitrite ions.

The research progress on the selective and sensitive fluorescent detection of nitrite anions has greatly relied on the development of new fluorescent materials. Herein, a novel nanohybrid exhibiting dual emissions in blue and red wavelength ranges is fabricated for the rapid, on-site, and sensitive detection of nitrite anions. Such a nanohybrid system consists of graphene oxide (GO-C6NH2) and gold nanoclusters (HSA-Au NCs), which have been hybridized by electrostatic attraction and hydrogen bonding interaction. The nanohybrid has been completely characterized with respect to its fluorescence properties, photostability, and morphology. It has been found that red fluorescence of gold nanoclusters selectively responds to nitrite, whereas the blue fluorescence of graphene oxide remains constant, resulting in a distinct fluorescence color evolution from red to blue. Therefore, we apply the nanohybrid for the detection of nitrite anions by a fluorescence ratiometric method and estimate a detection limit of 46 nM, lower than the allowable level (∼21 µM) in drinking water set by U.S. Environmental Protection Agency. The method has been further validated by applying it for the determination of nitrite anions in real samples, including tap water, lake water, and cured meat.

Oxidative cleavage-based near-infrared fluorescent probe for hypochlorous acid detection and myeloperoxidase activity evaluation.

A near-infrared (NIR) fluorescent probe was synthesized and demonstrated to be highly selective in reaction with hypochlorous acid (HOCl), an endogenous reactive oxygen species (ROS) produced by myeloperoxidase in neutrophils. The reaction with HOCl resulted in the NIR fluorescence quenching at 774 nm and the absorbance decreasing at 710 nm, accompanied by the appearance of a new absorption band at 520 nm. The reaction mechanism was carefully examined and proposed to proceed by initial formation of chlorohydrins and subsequent degradation. This NIR fluorescent probe was successfully applied as a selective and sensitive indicator for HOCl on the basis of either colorimetry or fluorometry, which showed detection limits of 0.13 and 0.70 µM, respectively. In addition, the molecular probe was further demonstrated for NIR fluorescence imaging of HOCl in cells and for evaluating the enzymatic activity of myeloperoxidase in the HOCl generation by measuring absorbance change.

Selective visual detection of trace trinitrotoluene residues based on dual-color fluorescence of graphene oxide-nanocrystals hybrid probe.

Herein, for the detection of highly explosive 2,4,6-trinitrotoluene (TNT) instantly and on-site, a fluorescence ratiometric probe using a dual-emission nanohybrid has been developed. The nanohybrid comprises blue-colored fluorescent graphene oxide (FGO) being conjugated with red-emitting manganese-doped ZnS nanocrystals (ZnS:Mn NCs), the latter being functionalized with hexamethylenediamine. The blue fluorescence of FGO is insensitive to TNT and is used as an internal reference, whereas the red fluorescence of ZnS:Mn NCs can be selectively quenched by TNT through electron transfer, resulting in a unique red-purple-blue color response as the amount of TNT is increased. Thus, the probe could be used for the quantitative measurement of TNT based on the fluorescence ratiometric method. We demonstrated that the nanohybrid probe exhibited high visual detection sensitivity and reliability in comparison with single-color fluorescence quenching probes. A fluorescence test paper was prepared using the nanohybrid probe and was demonstrated to detect TNT residues directly on various surfaces including rubber, a person's fingers and manila envelopes with a visual detection limit as low as 5.68 ng mm(-2), showing its promising application for security screening.

Programmed Nanocloak of Commensal Bacteria-Derived Nanovesicles Amplify Strong Immunoreactivity against Tumor Growth and Metastatic Progression.

Recent discoveries in commensal microbiota demonstrate the great promise of intratumoral bacteria as attractive molecular targets of tumors in improving cancer treatment. However, direct leveraging of in vivo antibacterial strategies such as antibiotics to potentiate cancer therapy often leads to uncertain effectiveness, mainly due to poor selectivity and potential adverse effects. Here, building from the clinical discovery that patients with breast cancer featured rich commensal bacteria, we developed an activatable biointerface by encapsulating commensal bacteria-derived extracellular vesicles (BEV) with a responsive nanocloak to potentiate immunoreactivity against intratumoral bacteria and breast cancer. We show that the interfacially cloaked BEV (cBEV) not only overcame serious systemic side responses but also demonstrated heightened immunogenicity by intercellular responsive immunogenicity, facilitating dendritic cell maturation through activating the cGAS-STING pathway. As a preventive measure, vaccination with nanocloaked cBEVs achieved strong protection against bacterial infection, largely providing prophylactic efficiency against tumor challenges. When treated in conjunction with immune checkpoint inhibitor anti-PD-L1 antibodies, the combined approach elicited a potent tumor-specific immune response, synergistically inhibiting tumor progression and mitigating lung metastases.

Non-discriminating engineered masking of immuno-evasive ligands on tumour-derived extracellular vesicles enhances tumour vaccination outcomes.

The success of personalized cancer immunotherapy depends on the initial tumour antigenic presentation to dendritic cells and macrophages. Tumour-derived extracellular vesicles (TEVs) contain abundant tumour antigenic molecules. The presence of anti-phagocytotic signals such as cluster of differentiation 47 (CD47) on the surface of the TEVs, however, leads to evasion of the same dendritic cells and macrophages. Here we show that iron oxide hydroxide nanocomposites can successfully mask TEV surfaces and unblock phagocytosis without affecting extracellular vesicles' elicited immune goals. After internalization, the mask disintegrates in the lysosome, releasing the tumour antigenic cargo. This triggers antigen presentation and promotes dendritic cell activation and maturation and macrophage reprogramming in animal models, leading to a drastic reduction of tumour volume and metastasis, and in human malignant pleural effusion clinical samples. This straightforward masking strategy eliminates the ubiquitous anti-phagocytosis block found in clinical samples and can be applied universally across all patient-specific TEVs as tumour antigenic agents for enhanced immunotherapy.

White light powered antimicrobial nanoagents for triple photothermal, chemodynamic and photodynamic based sterilization.

Antibacterial nanoagents have been increasingly developed due to their favorable biocompatibility, cost-effective raw materials, and alternative chemical or optical properties. Nevertheless, there is still a pressing need for antibacterial nanoagents that exhibit outstanding bacteria-binding capabilities and high antibacterial efficiency. In this study, we constructed a multifunctional cascade bioreactor (GCDCO) as a novel antibacterial agent. This involved incorporating carbon dots (CDs), cobalt sulfide quantum dots (CoSx QDs), and glucose oxidase (GOx) to enhance bacterial inhibition under sunlight irradiation. The GCDCO demonstrated highly efficient antibacterial capabilities attributed to its favorable photothermal properties, photodynamic activity, as well as the synergistic effects of hyperthermia, glucose-augmented chemodynamic action, and additional photodynamic activity. Within this cascade bioreactor, CDs played the role of a photosensitizer for photodynamic therapy (PDT), capable of generating ˙O2- even under solar light irradiation. The CoSx QDs not only functioned as a catalytic component to decompose hydrogen peroxide (H2O2) and generate hydroxyl radicals (˙OH), but they also served as heat generators to enhance the Fenton-like catalysis process. Furthermore, GOx was incorporated into this cascade bioreactor to internally supply H2O2 by consuming glucose for a Fenton-like reaction. As a result, GCDCO could generate a substantial amount of reactive oxygen species (ROS), leading to a significant synergistic effect that greatly induced bacterial death. Furthermore, the in vitro antibacterial experiment revealed that GCDCO displayed notably enhanced antibacterial activity against E. coli (99+ %) when combined with glucose under simulated sunlight, surpassing the efficacy of the individual components. This underscores its remarkable efficiency in combating bacterial growth. Taken together, our GCDCO demonstrates significant potential for use in the routine treatment of skin infections among diabetic patients.

Baiting bacteria with amino acidic and peptidic corona coated defect-engineered antimicrobial nanoclusters for optimized wound healing.

Keeping steps ahead of the bacteria in the race for more efficacious antibacterial strategies is increasingly difficult with the advent of bacterial resistance genes. Herein, we engineered copper sulfide nanoclusters (CuSx NCs) with variable sulfur defects for enhanced dual-treatment of bacterial infections by manipulating photothermal effects and Fenton-like activity. Next, by encasing CuSx NCs with a complex mixture of amino acids and short peptides derived from Luria-Bertani bacterial culture media as a protein corona, we managed to coax E. Coli to take up these CuSx NCs. As a whole, Amino-Pep-CuSx NCs was perceived as a food source and actively consumed by bacteria, enhancing their effective uptake by at least 1.5-fold greater than full length BSA protein BSA-corona CuSx NCs. Through strategically using defect-engineering, we successfully fine-tune photothermal effect and Fenton-like capacity of CuSx NCs. Increased sulfur defects lead to reduced but sufficient heat generation under solar-light irradiation and increased production of toxic hydroxyl radicals. By fine-tuning sulfur defects during synthesis, we achieve CuSx NCs with an optimal synergistic effect, significantly enhancing their bactericidal properties. These ultra-small and biodegradable CuSx NCs can rapidly break down after treatment for clearance. Thus, Amino-Pep-CuSx NCs demonstrate effective eradication of bacteria both in vitro and in vivo because of their relatively high uptake, optimal balanced photothermal and chemodynamic outcomes. Our study offers a straightforward and efficient method to enhance bacterial uptake of next generation of antibacterial agents.

2D/2D Heterojunction of BiOBr/BiOI Nanosheets for In Situ H2 O2 Production and Activation toward Efficient Photocatalytic Wastewater Treatment.

The presence of toxic organic pollutants in aquatic environments poses significant threats to human health and global ecosystems. Photocatalysis that enables in situ production and activation of H2 O2 presents a promising approach for pollutant removal; however, the processes of H2 O2 production and activation potentially compete for active sites and charge carriers on the photocatalyst surface, leading to limited catalytic performance. Herein, a hierarchical 2D/2D heterojunction nanosphere composed of ultrathin BiOBr and BiOI nanosheets (BiOBr/BiOI) is developed by a one-pot microwave-assisted synthesis to achieve in situ H2 O2 production and activation for efficient photocatalytic wastewater treatment. Various experimental and characterization results reveal that the BiOBr/BiOI heterojunction facilitates efficient electron transfer from BiOBr to BiOI, enabling the one-step two-electron O2 reduction for H2 O2 production. Moreover, the ultrathin BiOI provides abundant active sites for H2 O2 adsorption, promoting in situ H2 O2 activation for •O2 - generation. As a result, the BiOBr/BiOI hybrid exhibits excellent activity for pollutant degradation with an apparent rate constant of 0.141 min-1 , which is 3.8 and 47.3 times that of pristine BiOBr and BiOI, respectively. This work expands the range of the materials suitable for in situ H2 O2 production and activation, paving the way toward sustainable environmental remediation using solar energy.

Efficient ratiometric fluorescence probe based on dual-emission quantum dots hybrid for on-site determination of copper ions.

Of various chemosensory protocols, the color change observed by the naked eye is considered to be a conceivable and on-site way to indicate the presence of an analyte. We herein designed a ratiometric fluorescence probe by hybridizing dual-emission quantum dots (QDs) and demonstrated its efficiency for on-site visual determination of copper ions. The hybrid probe comprises two sizes of cadmium telluride QDs emitting red and green fluorescence, respectively, in which the red-emitting ones are embedded in silica nanoparticles and the green-emitting ones are covalently linked onto the surface. The fluorescence of the embedded QDs is insensitive to the analyte, whereas the green emissive QDs are functionalized to be selectively quenched by the analyte. Upon exposure to different amounts of copper ions, the variations of the dual emission intensity ratios display continuous color changes from green to red, which can be clearly observed by the naked eye. The limit of detection for copper is estimated to be 1.1 nM, much lower than the allowable level of copper (~20 µM) in drinking water set by U.S. Environmental Protection Agency. The probe is demonstrated for the determination of copper ions in lake water and mineral water samples, especially for visually monitoring copper residues on herb leaves. This prototype ratiometric probe is simple, fully self-contained, and thus potentially attractive for visual identification without the need for elaborate equipment.

Sensitive detection of trace hemoglobin using fluorescence method based on functionalized quantum dots.

The fluorescence quenching of quantum dots by hemoglobin has been demonstrated to depend on surface functionalization, and this property has been utilized to construct a novel fluorescent method for rapid, sensitive, and selective detection of trace hemoglobin in urine at microgram level. This method shows low interference and high selectivity for hemoglobin with a limit of detection of 4.3 µg L(-1) in water and 66.1 µg L(-1) in urine, which are lower than those of currently used methods in labs and clinics. Spike and recovery tests in raw, acidified, and alkalized urine samples exhibit good recovery rates for the spiked concentrations close to the limit of detection.

Rare-earth-doped indium oxide nanosphere-based gas sensor for highly sensitive formaldehyde detection at a low temperature.

Formaldehyde (HCHO) is widely viewed as a carcinogenic volatile organic compound in indoor air pollution that can seriously threaten human health and life. Thus, there is a critical need to develop gas sensors with improved sensing performance, including outstanding selectivity, low operating temperature, high responsiveness, and short recovery time, for HCHO detection. Currently, doping is considered an effective strategy to raise the sensing performance of gas sensors. Herein, various rare earth elements-doped indium oxide (RE-In2O3) nanospheres were fabricated as gas sensors for improved HCHO detection via a facile and environmentally solvothermal method. Such RE-In2O3 nanosphere-based sensors exhibited remarkable gas-sensing performance, including a high selectivity and stability in air. Compared with pure, Yb-, Dy-doped In2O3 and different La ratios doped into In2O3, 6% La-doped In2O3 (La-In2O3) nanosphere-based sensors demonstrated a high response value of 210 to 100 ppm at 170 °C, which was around 16 times higher than that of the pure In2O3 sensor, and also exhibited a detection limit of 10.9 ppb, and a response time of 30 s to 100 ppm HCHO with a recovery time of 160 s. Finally, such superior sensing performance of the 6% La-In2O3 sensors was proposed to be attributed to the synergistic effect of the large specific surface area and enhanced surface oxygen vacancies on the surface of In2O3 nanospheres, which produced chemisorbed oxygen species to release electrons and provided abundant reaction sites for HCHO gas. This study sheds new light on designing nanomaterials to build gas sensors for HCHO detection.

Simultaneous detection and removal of 2,4,6-trinitrophenyl phenol and dichromate by metal-organic framework.

2,4,6-trinitrophenyl phenol (TNP) and dichromate (Cr2O72-) have serious toxicological effects on environment. Therefore, it is very important to detect and remove TNP and Cr2O72- in environmental matrix. In this work, a dual-functional UiO type metal-organic framework (Zr-Sti) was synthesized for simultaneous detection and removal of those pollutants in aqueous solution. As for detection, Zr-Sti exhibited sensitive and selective fluorescence response to TNP and Cr2O72- with detection limit below µM level, and possible mechanism behind was proposed and partially supported by experiment data. In addition, adsorption capacity of the prepared Zr-Sti for TNP and Cr2O72- was further investigated to evaluate its performance in pollutant removal from aqueous solution, and the mechanism behinds the obtained high removal efficiency was proposed. These results together with the satisfied recovery for simultaneous detection of TNP and Cr2O72- in real sample, indicate the potential of the prepared Zr-Sti material in the field of environment monitoring and remediation.

Advances in Extracellular Vesicle Nanotechnology for Precision Theranostics.

Extracellular vesicles (EVs) have increasingly been recognized as important cell surrogates influencing many pathophysiological processes, including cellular homeostasis, cancer progression, neurologic disease, and infectious disease. These behaviors enable EVs broad application prospects for clinical application in disease diagnosis and treatment. Many studies suggest that EVs are superior to conventional synthetic carriers in terms of drug delivery and circulating biomarkers for early disease diagnosis, opening up new frontiers for modern theranostics. Despite these clinical potential, EVs containing diverse cellular components, such as nucleic acids, proteins, and metabolites are highly heterogeneous and small size. The limitation of preparatory, engineering and analytical technologies for EVs poses technical barriers to clinical translation. This article aims at present a critical overview of emerging technologies in EVs field for biomedical applications and challenges involved in their clinic translations. The current methods for isolation and identification of EVs are discussed. Additionally, engineering strategies developed to enhance scalable production and improved cargo loading as well as tumor targeting are presented. The superior clinical potential of EVs, particularly in terms of different cell origins and their application in the next generation of diagnostic and treatment platforms, are clarified.