RESUMEN
Developing an activity detection platform for hyaluronidase (HAase) is crucial for diagnosing and treating cancer. However, traditional detection of HAase is based on changes in the flow rate caused by viscosity or requires complex modifications and processing, which limits the detection accuracy and sensitivity. Herein, hyaluronic acid (HA)-modified mesoporous-based heterochannels (mesoporous carbon-doped γ-Fe2O3 nanoparticles/anodized aluminum oxide, MC-γ-Fe2O3/AAO) featuring ordered 3D transport frameworks and a photothermal property were developed for high performance HAase detection. The HA molecules on the surface of the mesoporous layer provide abundant active sites for HAase detection. An improved ionic current was realized after enzymatic hydrolysis reactions between HA and HAase due to enhanced surface charges and more hydrophilicity, leading to highly sensitive and accurate HAase detection. Notably, the detection performance can be further upgraded with the assistance of the photothermal property of γ-Fe2O3. An amplified detection current signal was achieved owing to a synergistic effect between ion currents and photoresponsive currents. A wide linear detection range from 1 to 50 U/mL and a low detection limit of 0.348 U/mL were obtained, achieving a 2% improvement under illumination. Importantly, the heterochannels have also been successfully applied for HAase detection in fetal bovine serum samples, manifesting considerable application prospects. This work provides a new strategy in constructing photoresponsive nanochannels with a photothermal property for a highly efficient biosensing platform.
RESUMEN
Developing ionic diode membranes featuring asymmetric structures is in high demand for salinity gradient energy harvesting. These membranes offer benefits in mitigating ion concentration polarization, thereby promoting ion permeability. However, most reported works focus on the role of heterogeneous charge-based bipolar ionic diode membranes for ion concentration polarization suppression, with comparatively less attention given to maintaining ion selectivity. Herein, unipolar ionic diode nanofluidic mesoporous silica membranes featuring stepped mesochannels were developed via a micellar sequential oriented interfacial self-assembly strategy as a salinity gradient energy harvester. Due to the asymmetric mesochannels and unipolar structure (both sides carry negative charge), the ionic diode membranes exhibit a strong rectification ratio of â¼15.91 to facilitate unidirectional ion transport while maintaining excellent cation selectivity (cation transfer number of â¼0.85). Besides, the vertically aligned mesochannels significantly reduce ion transport resistance, generating a high ionic flux. Consequently, the unipolar ionic diode nanofluidic membranes demonstrate a power output of 5.88 W/m2 between artificial sea and river water. The unipolar feature gives notable enhancements of 296% and 144% in power output compared to the symmetric membrane and bipolar ionic diode membrane, respectively. This work opens up new routes for designing ionic diode membranes for salinity gradient energy harvesting.
RESUMEN
Surgery remains the standard treatment for spinal metastasis. However, uncontrolled intraoperative bleeding poses a significant challenge for adequate surgical resection and compromises surgical outcomes. In this study, we develop a thrombin (Thr)-loaded nanorobot-hydrogel hybrid superstructure by incorporating nanorobots into regenerated silk fibroin nanofibril hydrogels. This superstructure with superior thixotropic properties is injected percutaneously and dispersed into the spinal metastasis of hepatocellular carcinoma (HCC) with easy bleeding characteristics, before spinal surgery in a mouse model. Under near-infrared irradiation, the self-motile nanorobots penetrate into the deep spinal tumor, releasing Thr in a controlled manner. Thr-induced thrombosis effectively blocks the tumor vasculature and reduces bleeding, inhibiting tumor growth and postoperative recurrence with Au nanorod-mediated photothermal therapy. Our minimally invasive treatment platform provides a novel preoperative therapeutic strategy for HCC spinal metastasis effectively controlling intraoperative bleeding and tumor growth, with potentially reduced surgical complications and enhanced operative outcomes.
RESUMEN
Enantioselective sensing and separation represent formidable challenges across a diverse range of scientific domains. The advent of hybrid chiral membranes offers a promising avenue to address these challenges, capitalizing on their unique characteristics, including their heterogeneous structure, porosity, and abundance of chiral surfaces. However, the prevailing fabrication methods typically involve the initial preparation of achiral porous membranes followed by subsequent modification with chiral molecules, limiting their synthesis flexibility and controllability. Moreover, existing chiral membranes struggle to achieve coupled-accelerated enantioseparation (CAE). Here, we report a replacement strategy to controllably produce mesoscale and chiral silica-carbon (MCSC) hybrid membranes that comprise chiral pores by interfacial superassembly on a macroporous alumina (AAO) membrane, in which both ion- and enantiomers can be effectively and selectively transported across the membrane. As a result, the heterostructured hybrid membrane (MCSC/AAO) exhibits enhanced selectivity for cations and enantiomers of amino acids, achieving CAE for amino acids with an isoelectric point (pI) exceeding 7. Interestingly, the MCSC/AAO system demonstrates enhanced pH-sensitive enantioseparation compared to chiral mesoporous silica/AAO (CMS/AAO) with significant improvements of 78.14, 65.37, and 14.29% in the separation efficiency, separation factor, and permeate flux, respectively. This work promises to advance the synthesis of two or more component-integrated chiral nanochannels with multifunctional properties and allows a better understanding of the origins of the homochiral hybrid membranes.
RESUMEN
Ion-selective nanochannel membranes assembled from two-dimensional (2D) nanosheets hold immense promise for power conversion using salinity gradient. However, they face challenges stemming from insufficient surface charge density, which impairs both permselectivity and durability. Herein, we present a novel vacancy-engineered, oxygen-deficient NiCo layered double hydroxide (NiCoLDH)/cellulose nanofibers-wrapped carbon nanotubes (VOLDH/CNF-CNT) composite membrane. This membrane, featuring abundant angstrom-scale, cation-selective nanochannels, is designed and fabricated through a synergistic combination of vacancy engineering and interfacial super-assembly. The composite membrane shows interlayer free-spacing of ~3.62â Å, which validates the membrane size exclusion selectivity. This strategy, validated by DFT calculations and experimental data, improves hydrophilicity and surface charge density, leading to the strong interaction with K+ ions to benefit the low ion transport resistance and exceptional charge selectivity. When employed in an artificial river water|seawater salinity gradient power generator, it delivers a high-power density of 5.35â W/m2 with long-term durability (20,000s), which is almost 400 % higher than that of the pristine NiCoLDH membrane. Furthermore, it displays both pH- and temperature-sensitive ion transport behavior, offering additional opportunities for optimization. This work establishes a basis for high-performance salinity gradient power conversion and underscores the potential of vacancy engineering and super-assembly in customizing 2D nanomaterials for diverse advanced nanofluidic energy devices.
RESUMEN
Bioinspired nanochannel-based sensors have elicited significant interest because of their excellent sensing performance, and robust mechanical and tunable chemical properties. However, the existing designs face limitations due to material constraints, which hamper broader application possibilities. Herein, a heteromembrane system composed of a periodic mesoporous organosilica (PMO) layer with three-dimensional (3D) network nanochannels is constructed for glutathione (GSH) detection. The unique hierarchical pore architecture provides a large surface area, abundant reaction sites and plentiful interconnected pathways for rapid ionic transport, contributing to efficient and sensitive detection. Moreover, the thioether groups in nanochannels can be selectively cleaved by GSH to generate hydrophilic thiol groups. Benefiting from the increased hydrophilic surface, the proposed sensor achieves efficient GSH detection with a detection limit of 1.2 µM by monitoring the transmembrane ionic current and shows good recovery ranges in fetal bovine serum sample detection. This work paves an avenue for designing and fabricating nanofluidic sensing systems for practical and biosensing applications.
Asunto(s)
Glutatión , Límite de Detección , Compuestos de Organosilicio , Glutatión/química , Glutatión/análisis , Glutatión/sangre , Porosidad , Compuestos de Organosilicio/química , Animales , Bovinos , Técnicas Biosensibles/métodos , Membranas Artificiales , Técnicas Electroquímicas/métodosRESUMEN
In the field of sustainable chemistry, it is still a significant challenge to realize efficient light-powered space-confined catalysis and propulsion due to the limited solar absorption efficiency and the low mass and heat transfer efficiency. Here, novel semiconductor TiO2 nanorockets with asymmetric, hollow, mesoporous, and double-layer structures are successfully constructed through a facile interfacial superassembly strategy. The high concentration of defects and unique topological features improve light scattering and reduce the distance for charge migration and directed charge separation, resulting in enhanced light harvesting in the confined nanospace and resulting in enhanced catalysis and self-propulsion. The movement velocity of double-layered nanorockets can reach up to 10.5 µm s-1 under visible light, which is approximately 57 and 119% higher than that of asymmetric single-layered TiO2 and isotropic hollow TiO2 nanospheres, respectively. In addition, the double-layered nanorockets improve the degradation rate of the common pollutant methylene blue under sustainable visible light with a 247% rise of first-order rate constant compared to isotropic hollow TiO2 nanospheres. Furthermore, FEA simulations reveal and confirm the double-layered confined-space enhanced catalysis and self-propulsion mechanism.
RESUMEN
Copper ions (Cu2+), as a crucial trace element, play a vital role in living organisms. Thus, the detection of Cu2+ is of great significance for disease prevention and diagnosis. Nanochannel devices with an excellent nanoconfinement effect show great potential in recognizing and detecting Cu2+ ions. However, these devices often require complicated modification and treatment, which not only damages the membrane structure, but also induces nonspecific, low-sensitivity and non-repeatable detection. Herein, a 2D MXene-carboxymethyl chitosan (MXene/CMC) freestanding membrane with ordered lamellar channels was developed by a super-assembly strategy. The introduction of CMC provides abundant space charges, improving the nanoconfinement effect of the nanochannel. Importantly, the CMC can chelate with Cu2+ ions, endowing the MXene/CMC with the ability to detect Cu2+. The formation of CMC-Cu2+ complexes decreases the space charges, leading to a discernible variation in the current signal. Therefore, MXene/CMC can achieve highly sensitive and stable Cu2+ detection based on the characteristics of nanochannel composition. The linear response range for Cu2+ detection is 10-9 to 10-5 M with a low detection limit of 0.095 nM. Notably, MXene/CMC was successfully applied for Cu2+ detection in real water and fetal bovine serum samples. This work provides a simple, highly sensitive and stable detection platform based on the properties of the nanochannel composition.
Asunto(s)
Quitosano , Nitritos , Oligoelementos , Elementos de Transición , Cobre , Quitosano/química , Iones/químicaRESUMEN
Since Cu2+ ions play a pivotal role in both ecosystems and human health, the development of a rapid and sensitive method for Cu2+ detection holds significant importance. Fluorescent mesoporous silica materials (FMSMs) have garnered considerable attention in the realm of chemical sensing, biosensing, and bioimaging due to their distinctive structure and easily functionalized surfaces. As a result, numerous Cu2+ sensors based on FMSMs have been devised and extensively applied in environmental and biological Cu2+ detection over the past few decades. This review centers on the recent advancements in the methodologies for preparing FMSMs, the mechanisms underlying sensing, and the applications of FMSMs-based sensors for Cu2+ detection. Lastly, we present and elucidate pertinent perspectives concerning FMSMs-based Cu2+ sensors.
RESUMEN
The utilization of sustained and green energy is believed to alleviate increasing menace of global environmental concerns and energy dilemma. Interfacial assembly of 2D graphene-derived ion channels (2D-GDICs) with tunable ion/fluid transport behavior enables efficient harvesting of renewable green energy from ubiquitous water, especially for osmotic energy harvesting. In this review, various interfacial assembly strategies for fabricating diverse 2D-GDICs are summarized and their ion transport properties are discussed. This review analyzes how particular structure and charge density/distribution of 2D-GDIC can be modulated to minimize internal resistance of ion/fluid transport and enhance energy conversion efficiency, and highlights stimuli-responsive functions and stability of 2D-GDIC and further examines the possibility of integrating 2D-GDIC with other energy conversion systems. Notably, the presented preparation and applications of 2D-GDIC also inspire and guide other 2D materials to fabricate sophisticated ion channels for targeted applications. Finally, potential challenges in this field is analyzed and a prospect to future developments toward high-performance or large-scale real-word applications is offered.
RESUMEN
Heterogeneous membranes play a crucial role in osmotic energy conversion by effectively reducing concentration polarization. However, most heterogeneous membranes mitigate concentration polarization through an asymmetric charge distribution, resulting in compromised ion selectivity. Herein, hetero-nanochannels with asymmetric wettability composed of 2D mesoporous carbon and graphene oxide are constructed. The asymmetric wettability of the membrane endows it with the ability to suppress the concentration polarization without degrading the ion selectivity, as well as achieving a diode-like ion transport feature. As a result, enhanced osmotic energy harvesting is achieved with a power density of 6.41 W m-2 . This represents a substantial enhancement of 102.80-137.85% when compared to homogeneous 2D membranes, surpassing the performance of the majority of reported 2D membranes. Importantly, the membrane can be further used for high-performance ionic power harvesting by regulating ion transport, exceeding previously reported data by 89.1%.
RESUMEN
Autonomously self-propelled nanoswimmers represent the next-generation nano-devices for bio- and environmental technology. However, current nanoswimmers generate limited energy output and can only move in short distances and duration, thus are struggling to be applied in practical challenges, such as living cell transportation. Here, we describe the construction of biodegradable metal-organic framework based nanobots with chemically driven buoyancy to achieve highly efficient, long-distance, directional vertical motion to "find-and-fetch" target cells. Nanobots surface-functionalized with antibodies against the cell surface marker carcinoembryonic antigen are exploited to impart the nanobots with specific cell targeting capacity to recognize and separate cancer cells. We demonstrate that the self-propelled motility of the nanobots can sufficiently transport the recognized cells autonomously, and the separated cells can be easily collected with a customized glass column, and finally regain their full metabolic potential after the separation. The utilization of nanobots with easy synthetic pathway shows considerable promise in cell recognition, separation, and enrichment.
RESUMEN
Chemotherapy remains as the first-choice treatment option for triple-negative breast cancer (TNBC). However, the limited tumor penetration and low cellular internalization efficiency of current nanocarrier-based systems impede the access of anticancer drugs to TNBC with dense stroma and thereby greatly restricts clinical therapeutic efficacy, especially for TNBC bone metastasis. In this work, biomimetic head/hollow tail nanorobots were designed through a site-selective superassembly strategy. We show that nanorobots enable efficient remodeling of the dense tumor stromal microenvironments (TSM) for deep tumor penetration. Furthermore, the self-movement ability and spiky head markedly promote interfacial cellular uptake efficacy, transvascular extravasation, and intratumoral penetration. These nanorobots, which integrate deep tumor penetration, active cellular internalization, near-infrared (NIR) light-responsive release, and photothermal therapy capacities into a single nanodevice efficiently suppress tumor growth in a bone metastasis female mouse model of TNBC and also demonstrate potent antitumor efficacy in three different subcutaneous tumor models.
Asunto(s)
Hipertermia Inducida , Nanopartículas , Neoplasias de la Mama Triple Negativas , Animales , Humanos , Ratones , Femenino , Neoplasias de la Mama Triple Negativas/terapia , Neoplasias de la Mama Triple Negativas/patología , Biomimética , Línea Celular Tumoral , Fototerapia , Microambiente TumoralRESUMEN
Micro-/nanomotors with advanced motion manipulation have recently received mounting interest; however, research focusing on the motion regulation strategies is still limited, as the simple construction and composition of micro-/nanomotors restrict the functionality. Herein, a multifunctional TiO2-SiO2-mesoporous carbon nanomotor is synthesized via an interfacial superassembly strategy. This nanomotor shows an asymmetric matchstick-like structure, with a head composed of TiO2 and a tail composed of SiO2. Mesoporous carbon is selectively grown on the surface of TiO2 through surface-charge-mediated assembly. The spatially anisotropic distribution of the photocatalytic TiO2 domain and photothermal carbon domain enables multichannel control of the motion, where the speed can be regulated by energy input and the directionality can be regulated by wavelength. Upon UV irradiation, the nanomotor exhibits a head-leading self-diffusiophoretic motion, while upon NIR irradiation, the nanomotor exhibits a tail-leading self-thermophoretic motion. As a proof-of-concept, this mechanism-switchable nanomotor is employed in wavelength-regulated targeted cargo delivery on a microfluidic chip. From an applied point of view, this nanomotor holds potential in biomedical applications such as active drug delivery and phototherapy. From a fundamental point of view, this research can provide insight into the relationship between the nanostructures, propulsion mechanisms, and motion performance.
RESUMEN
Light-responsive nanochannels have attracted extensive attention due to their noninvasive external field control and intelligent ion regulation. However, the limited photoresponsive current and the low photoelectric conversion efficiency still restrict their development. Here, a light-controlled nanochannel composed of 4-aminothiophenol and gold nanoparticles-modified mesoporous titania nanopillar arrays and alumina oxide (4-ATP-Au-MTI/AAO) is fabricated by the interfacial super-assembly strategy. Inspired by the process of electron transfer between photosystem I and photosystem II, the efficient electron transfer between TiO2, AuNPs, and 4-ATP under light is achieved by coupling the photoresponsive materials and functional molecules. Under illumination, 4-ATP is oxidized to p-nitrothiophenol (PNTP), which brings about changes in the wettability of the nanochannel, resulting in significant improvement (252.8%) of photoresponsive current. In addition, under the action of the reductant, the nanochannels can be restored to the initial dark state, enabling multiple reversible cycles. This work opens a new route for the fabrication of high-performance light-controlled nanochannels by coupling light-responsive materials and light-responsive molecules, which may guide the development of photoelectric conversion nanochannel systems.
RESUMEN
Capturing the abundant salinity gradient power into electric power by nanofluidic systems has attracted increasing attention and has shown huge potential to alleviate the energy crisis and environmental pollution problems. However, not only the imbalance between permeability and selectivity but also the poor stability and high cost of traditional membranes limit their scale-up realistic applications. Here, intertwined "soft-hard" nanofibers/tubes are densely super-assembled on the surface of anodic aluminum oxide (AAO) to construct a heterogeneous nanochannel membrane, which exhibits smart ion transport and improved salinity gradient power conversion. In this process, one-dimensional (1D) "soft" TEMPO-oxidized cellulose nanofibers (CNFs) are wrapped around "hard" carbon nanotubes (CNTs) to form three-dimensional (3D) dense nanochannel networks, subsequently forming a CNF-CNT/AAO hybrid membrane. The 3D nanochannel networks constructed by this intertwined "soft-hard" nanofiber/tube method can significantly enhance the membrane stability while maintaining the ion selectivity and permeability. Furthermore, benefiting from the asymmetric structure and charge polarity, the hybrid nanofluidic membrane displays a low membrane inner resistance, directional ionic rectification characteristics, outstanding cation selectivity, and excellent salinity gradient power conversion performance with an output power density of 3.3 W/m2. Besides, a pH sensitive property of the hybrid membrane is exhibited, and a higher power density of 4.2 W/m2 can be achieved at a pH of 11, which is approximately 2 times more compared to that of pure 1D nanomaterial based homogeneous membranes. These results indicate that this interfacial super-assembly strategy can provide a way for large-scale production of nanofluidic devices for various fields including salinity gradient energy harvesting.
RESUMEN
To improve the accuracy of early warning on coal spontaneous combustion (CSC), this paper, on the basis of the principle of preferential selection of index gases in CSC process, carries out fitting analysis of the variation curve of index gas data with coal temperature by combining logistic fitting model, then establishes a CSC graded warning system based on positive pressure beam tube monitoring, and determines CO, O2, φ(CO)/φ(O2), C2H4, C2H6, φ(C2H4)/φ(C2H6) as the index gases for predicting and forecasting CSC, and accurately divides the CSC process into seven levels of early warning: safe, gray, blue, yellow, orange, red, and black. Applying the CSC positive pressure beam tube monitoring system to Dongtan coal mine and analyzing the error by manual sampling and sampling by positive pressure beam tube system, we find that the error is less than 0.1%. Monitoring of several working faces, we get that the CO and CH4 concentrations of 14,320 working face are higher than the normal level at the beginning of mining, and the 100 × CO/ΔO2 value is higher than the gray warning threshold of 0.1, and the warning level is gray warning. After taking timely preventive measures against coal oxidation and warming, the CO and CH4 concentrations return to the normal level and the warning level drops to the safe level. This paper improves the monitoring, identifying and early warning capabilities of underground CSC in its early stage.
Asunto(s)
Minas de Carbón , Combustión Espontánea , Carbón Mineral/análisis , Gases/análisis , Minería , TemperaturaRESUMEN
Photo-regulated nanofluidic devices have attracted great attention in recent years due to their adjustable ion transport in real time. However, most of the photo-responsive nanofluidic devices can only adjust the ionic current unidirectionally, and cannot simultaneously increase or decrease the current signal intelligently by one device. Herein, a mesoporous carbon-titania/ anodized aluminum hetero-channels (MCT/AAO) is constructed by super-assembly strategy, which exhibits dual-function of cation selectivity and photo response. The polymer and TiO2 nanocrystals jointly build the MCT framework. Polymer framework with abundant negatively charged sites endows MCT/AAO with excellent cation selectivity, and TiO2 nanocrystals are responsible for the photo-regulated ion transport. High photo current densities of 1.8 mA m-2 (increase) and 1.2 mA m-2 (decrease) are realized by MCT/AAO benefiting from the ordered hetero-channels. Significantly, MCT/AAO can also achieve the bidirectionally adjustable osmotic energy by alternating the configurations of concentration gradient. Theoretical and experimental results reveal that the superior photo-generated potential is responsible for the bidirectionally adjustable ion transport. Consequently, MCT/AAO performs the function of harvesting ionic energy from the equilibrium electrolyte solution, which greatly expands its practical application field. This work provides a new strategy in constructing dual-functional hetero-channels toward bidirectionally photo-regulated ionic transport and energy harvesting.
RESUMEN
BACKGROUND: Dipeptidyl peptidase-IV (DPP-IV), α-glucosidase, and α-amylase play a prominent role in regulating postprandial blood sugar levels, which are regarded as key targets for the treatment of type 2 diabetes mellitus (T2DM). The present study aimed to characterize bioactive compounds as potent crucial sugar metabolism enzyme inhibitors from sugarcane leaves by virtual screening. In total, 41 sugarcane leaf-derived compounds were used for the screening of multiple targets. Subsequently, the molecular mechanism and activity validation in vitro of the interaction between enzymes and compound were carried out. RESULTS: Flavonoid compound schaftoside was identified by molecular simulation and showed significant DPP-IV (0.1050 ± 1.22 mmol L-1 ), α-glucosidase (0.078 ± 0.06 mmol L-1 ), and α-amylase (0.3067 ± 0.35 mmol L-1 ) inhibitory effects. The residues ARG125 and TYR662 of DPP-IV may play crucial roles in inhibiting the activity of DPP-IV. Multiple hydrogen bonds and electrostatic interactions were exhibited between schaftoside and α-glucosidase. Molecular modeling revealed that schaftoside displays strong binding with the catalytic triad (ASP197, ASP300, and GLU233) of α-amylase. CONCLUSION: Our findings demonstrate that schaftoside from sugarcane leaves might be an edible for T2DM treatment." © 2023 Society of Chemical Industry.
Asunto(s)
Diabetes Mellitus Tipo 2 , Inhibidores de la Dipeptidil-Peptidasa IV , Saccharum , Humanos , Hipoglucemiantes/farmacología , Hipoglucemiantes/química , alfa-Glucosidasas/química , Inhibidores de la Dipeptidil-Peptidasa IV/farmacología , Inhibidores de la Dipeptidil-Peptidasa IV/química , Simulación del Acoplamiento Molecular , Diabetes Mellitus Tipo 2/tratamiento farmacológico , Saccharum/metabolismo , Dipeptidil Peptidasa 4/química , alfa-Amilasas/química , Hojas de la Planta/metabolismo , Inhibidores de Glicósido Hidrolasas/químicaRESUMEN
Carbendazim, a systemic fungicide, is one of the most commonly detected pesticides in cowpeas. Pickled cowpea is a fermented vegetable product with unique flavor favored in China. The dissipation and degradation of carbendazim were investigated in the pickled process. The degradation rate constant of carbendazim in pickled cowpeas was 0.9945 and the half-life of the carbendazim was 14.06 ± 0.82 d. Seven transformation products (TPs) were identified in the pickled process. Furthermore, the toxicity of some TPs show more harmful to three aquatic organisms (TP134) and rats (all the identified TPs) than carbendazim. And most of the TPs posed more development toxicity and mutagenicity than carbendazim. 4 out of 7 TPs were discovered in the real pickled cowpea samples. These results shed light on the degradation and biotransformation of the carbendazim in the pickled process, to better understand the potential health risk of pickled food and evaluate the environmental pollution.