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1.
Anal Chem ; 96(42): 16499-16504, 2024 Oct 22.
Artículo en Inglés | MEDLINE | ID: mdl-39383474

RESUMEN

Accurate diagnosis of highly aggressive and deadly tumors is essential for effective treatment and improved patient outcomes, and microRNAs (miRNAs) have emerged as crucial biomarkers for their roles in tumor initiation, progression, and metastasis. Herein, we present an on-site visualization colorimetric assay for tumor-associated miRNAs using ruthenium nanoparticle decorated titanium dioxide nanoribbon (Ru@TiO2) as a peroxidase-like (POD) nanozyme. Remarkably, the Ru@TiO2 nanozyme can catalyze the oxidation of chromogenic substrates through its POD-like activity, which is effectively inhibited by pyrophosphate generated during the rolling circle amplification process, thereby enabling miRNA detection through a visible colorimetric readout. This approach provides a highly sensitive and specificity assay for miRNAs in diluted human serum with a detection limit of 100 pM. It shows great potential for clinical diagnostics and biological research, offering a promising tool for early cancer diagnosis and molecular diagnostics.


Asunto(s)
Colorimetría , MicroARNs , Rutenio , Titanio , Titanio/química , Humanos , MicroARNs/análisis , MicroARNs/sangre , MicroARNs/metabolismo , Rutenio/química , Neoplasias/diagnóstico , Nanopartículas del Metal/química , Peroxidasa/metabolismo , Peroxidasa/química , Límite de Detección , Catálisis , Oxidación-Reducción , Biomarcadores de Tumor/sangre
2.
Small ; 20(2): e2306169, 2024 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-37670217

RESUMEN

Halloysite nanotubes (HNTs) have emerged as a highly regarded choice in biomedical research due to their exceptional attributes, including superior loading capacity, customizable surface characteristics, and excellent biocompatibility. HNTs feature tubular structures comprising alumina and silica layers, endowing them with a large surface area and versatile surface chemistries that facilitate selective modifications. Moreover, their substantial pore volume and wide range of pore sizes enable efficient entrapment of diverse functional molecules. This comprehensive review highlights the broad biomedical application spectrum of HNTs, shedding light on their potential as innovative and effective therapeutic agents across various diseases. It emphasizes the necessity of optimizing drug delivery techniques, developing targeted delivery systems, rigorously evaluating biocompatibility and safety through preclinical and clinical investigations, exploring combination therapies, and advancing scientific understanding. With further advancements, HNTs hold the promise to revolutionize the pharmaceutical industry, opening new avenues for the development of transformative treatments.


Asunto(s)
Nanotubos , Arcilla/química , Nanotubos/química , Sistemas de Liberación de Medicamentos/métodos
3.
Small ; 20(13): e2307294, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-37963858

RESUMEN

The pursuit of stable and efficient electrocatalysts toward seawater oxidation is of great interest, yet it poses considerable challenges. Herein, the utilization of Cr-doped CoFe-layered double hydroxide nanosheet array is reported on nickel-foam (Cr-CoFe-LDH/NF) as an efficient electrocatalyst for oxygen evolution reaction in alkaline seawater. The Cr-CoFe-LDH/NF catalyst can achieve current densities of 500 and 1000 mA cm -2 with remarkably low overpotentials of only 334 and 369 mV, respectively. Furthermore, it maintains at least 100 h stability when operated at 500 mA cm-2.

4.
Small ; 20(28): e2311055, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38295001

RESUMEN

Through inducing interlayer anionic ligands and functionally modifying conductive carbon-skeleton on the transition metal chalcogenides (TMCs) parent to achieve atomic-level defect-manipulation and nanoscopic-level architecture design is of great significance, which can broaden interlayer distance, optimize electronic structure, and mitigate structural deformation to endow high-efficiency battery performance of TMCs. Herein, an intriguing 3D biconcave hollow-tyre-like anode constituted by carbon-packaged defective-rich SnSSe nanosheet grafting onto Aspergillus niger spores-derived hollow-carbon (ANDC@SnSSe@C) is reported. Systematically experimental investigations and theoretical analyses forcefully demonstrate the existence of anion Se ligand and outer-carbon all-around encapsulation on the ANDC@SnSSe@C can effectively yield abundant structural defects and Na+-reactivity sites, accelerate rapid ion migration, widen interlayer spacing, as well as relieve volume expansion, thus further resolving the critical issues throughout the charge-discharge processes. As anticipated, as-fabricated ANDC@SnSSe@C anode contributes extraordinary reversible capacity, wonderful cyclic lifespan with 83.4% capacity retention over 2000 cycles at 20.0 A g-1, and exceptional rate capability. A series of correlated kinetic investigations and ex situ characterizations deeply reveal the underlying springheads for the ion-transport kinetics, as well as synthetically elucidate phase-transformation mechanism of the ANDC@SnSSe@C. Furthermore, the ANDC@SnSSe@C-based sodium ion full cell and hybrid capacitor offer high-capacity contribution and remarkable energy-density output, indicative of its great practicability.

5.
Small ; 20(31): e2400141, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38431944

RESUMEN

Seawater electrolysis holds tremendous promise for the generation of green hydrogen (H2). However, the system of seawater-to-H2 faces significant hurdles, primarily due to the corrosive effects of chlorine compounds, which can cause severe anodic deterioration. Here, a nickel phosphide nanosheet array with amorphous NiMoO4 layer on Ni foam (Ni2P@NiMoO4/NF) is reported as a highly efficient and stable electrocatalyst for oxygen evolution reaction (OER) in alkaline seawater. Such Ni2P@NiMoO4/NF requires overpotentials of just 343 and 370 mV to achieve industrial-level current densities of 500 and 1000 mA cm-2, respectively, surpassing that of Ni2P/NF (470 and 555 mV). Furthermore, it maintains consistent electrolysis for over 500 h, a significant improvement compared to that of Ni2P/NF (120 h) and Ni(OH)2/NF (65 h). Electrochemical in situ Raman spectroscopy, stability testing, and chloride extraction analysis reveal that is situ formed MoO4 2-/PO4 3- from Ni2P@NiMoO4 during the OER test to the electrode surface, thus effectively repelling Cl- and hindering the formation of harmful ClO-.

6.
Small ; 20(28): e2311431, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38366284

RESUMEN

Renewable electricity-driven seawater splitting presents a green, effective, and promising strategy for building hydrogen (H2)-based energy systems (e.g., storing wind power as H2), especially in many coastal cities. The abundance of Cl- in seawater, however, will cause severe corrosion of anode catalyst during the seawater electrolysis, and thus affect the long-term stability of the catalyst. Herein, seawater oxidation performances of NiFe layered double hydroxides (LDH), a classic oxygen (O2) evolution material, can be boosted by employing tungstate (WO4 2-) as the intercalated guest. Notably, insertion of WO4 2- to LDH layers upgrades the reaction kinetics and selectivity, attaining higher current densities with ≈100% O2 generation efficiency in alkaline seawater. Moreover, after a 350 h test at 1000 mA cm-2, only trace active chlorine can be detected in the electrolyte. Additionally, O2 evolution follows lattice oxygen mechanism on NiFe LDH with intercalated WO4 2-.

7.
Inorg Chem ; 63(41): 19322-19331, 2024 Oct 14.
Artículo en Inglés | MEDLINE | ID: mdl-39361814

RESUMEN

Exploring high-performance and low-platinum-based electrocatalysts to accelerate the oxygen reduction reaction (ORR) at the air cathode of zinc-air batteries remains crucial. Herein, by combining electroless deposition and carbothermal reduction, a nitrogen-doped carbon-supported highly dispersed PtSn alloy nanocatalyst (PtSn/NC) was prepared for a high-efficiency ORR process. Electrochemical measurements show that PtSn/NC exhibits excellent electrocatalytic ORR activity with a half-wave potential of 0.850 V versus reversible hydrogen electrode (RHE), which is higher than that of commercial Pt/C (0.815 V). The PtSn/NC-based (20 µgPt cm-2) rechargeable Zn-air battery exhibited astonishing performance with a maximum power density of up to 150.1 mW cm-2, as well as excellent rate performance and charge/discharge stability. Physical characterization reveals that carbothermal reduction could compel the transformation of Sn oxide into metallic Sn, which then alloys with the deposited Pt atoms to form the PtSn nanoalloy, in which electrons are transferred from Sn atoms to neighboring Pt atoms, thereby improving the ability of Pt-based active sites to catalyze the ORR process in PtSn/NC by optimizing the unoccupied d-band of Pt atoms. This work provides a reliable and innovative route for the rational design of highly dispersed Pt-based alloy ORR electrocatalysts.

8.
Angew Chem Int Ed Engl ; 63(30): e202406441, 2024 Jul 22.
Artículo en Inglés | MEDLINE | ID: mdl-38742483

RESUMEN

Transition-metal carbides with metallic properties have been extensively used as electrocatalysts due to their excellent conductivity and unique electronic structures. Herein, NbC nanoparticles decorated carbon nanofibers (NbC@CNFs) are proposed as an efficient and robust catalyst for electrochemical synthesis of ammonia from nitrate/nitrite reduction, which achieves a high Faradaic efficiency (FE) of 94.4 % and a large ammonia yield of 30.9 mg h-1 mg-1 cat.. In situ electrochemical tests reveal the nitrite reduction at the catalyst surface follows the *NO pathway and theoretical calculations reveal the formation of NbC@CNFs heterostructure significantly broadens density of states nearby the Fermi energy. Finite element simulations unveil that the current and electric field converge on the NbC nanoparticles along the fiber, suggesting the dispersed carbides are highly active for nitrite reduction.

9.
Angew Chem Int Ed Engl ; 63(1): e202316522, 2024 Jan 02.
Artículo en Inglés | MEDLINE | ID: mdl-37994225

RESUMEN

Seawater electrolysis is an attractive way of making H2 in coastal areas, and NiFe-based materials are among the top options for alkaline seawater oxidation (ASO). However, ample Cl- in seawater can severely corrode catalytic sites and lead to limited lifespans. Herein, we report that in situ carbon oxyanion self-transformation (COST) from oxalate to carbonate on a monolithic NiFe oxalate micropillar electrode allows safeguard of high-valence metal reaction sites in ASO. In situ/ex situ studies show that spontaneous, timely, and appropriate COST safeguards active sites against Cl- attack during ASO even at an ampere-level current density (j). Our NiFe catalyst shows efficient and stable ASO performance, which requires an overpotential as low as 349 mV to attain a j of 1 A cm-2 . Moreover, the NiFe catalyst with protective surface CO3 2- exhibits a slight activity degradation after 600 h of electrolysis under 1 A cm-2 in alkaline seawater. This work reports effective catalyst surface design concepts at the level of oxyanion self-transformation, acting as a momentous step toward defending active sites in seawater-to-H2 conversion systems.

10.
Small ; 19(23): e2301146, 2023 06.
Artículo en Inglés | MEDLINE | ID: mdl-36879476

RESUMEN

The severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2)-caused COVID-19 pandemic has rapidly escalated into the largest global health emergency, which pushes to develop detection kits for the detection of COVID-19 with high sensitivity, specificity, and fast analysis. Here, aptamer-functionalized MXene nanosheet is demonstrated as a novel bionanosensor that detects COVID-19. Upon binding to the spike receptor binding domain of SARS-CoV-2, the aptamer probe is released from MXene surface restoring the quenched fluorescence. The performances of the fluorosensor are evaluated using antigen protein, cultured virus, and swab specimens from COVID-19 patients. It is evidenced that this sensor can detect SARS-CoV-2 spike protein at final concentration of 38.9 fg mL-1 and SARS-CoV-2 pseudovirus (limit of detection: 7.2 copies) within 30 min. Its application for clinical samples analysis is also demonstrated successfully. This work offers an effective sensing platform for sensitive and rapid detection of COVID-19 with high specificity.


Asunto(s)
COVID-19 , Humanos , COVID-19/diagnóstico , SARS-CoV-2 , Pandemias , Oligonucleótidos
11.
Small ; 19(17): e2208036, 2023 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-36717274

RESUMEN

Electrochemical nitrate (NO3 - ) reduction reaction (NO3 - RR) is a potential sustainable route for large-scale ambient ammonia (NH3 ) synthesis and regulating the nitrogen cycle. However, as this reaction involves multi-electron transfer steps, it urgently needs efficient electrocatalysts on promoting NH3  selectivity. Herein, a rational design of Co nanoparticles anchored on TiO2  nanobelt array on titanium plate (Co@TiO2 /TP) is presented as a high-efficiency electrocatalyst for NO3 - RR. Density theory calculations demonstrate that the constructed Schottky heterostructures coupling metallic Co with semiconductor TiO2  develop a built-in electric field, which can accelerate the rate determining step and facilitate NO3 - adsorption, ensuring the selective conversion to NH3 . Expectantly, the Co@TiO2 /TP electrocatalyst attains an excellent Faradaic efficiency of 96.7% and a high NH3  yield of 800.0 µmol h-1  cm-2  under neutral solution. More importantly, Co@TiO2 /TP heterostructure catalyst also presents a remarkable stability in 50-h electrolysis test.

12.
Small ; 19(30): e2300620, 2023 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-37058080

RESUMEN

Electroreduction of nitrite (NO2 - ) to valuable ammonia (NH3 ) offers a sustainable and green approach for NH3 synthesis. Here, a Cu3 P@TiO2 heterostructure is rationally constructed as an active catalyst for selective NO2 - -to-NH3 electroreduction, with rich nanosized Cu3 P anchored on a TiO2 nanoribbon array on Ti plate (Cu3 P@TiO2 /TP). When performed in the 0.1 m NaOH with 0.1 m NaNO2 , the Cu3 P@TiO2 /TP electrode obtains a large NH3 yield of 1583.4 µmol h-1  cm-2 and a high Faradaic efficiency of 97.1%. More importantly, Cu3 P@TiO2 /TP also delivers remarkable long-term stability for 50 h electrolysis. Theoretical calculations indicate that intermediate adsorption/conversion processes on Cu3 P@TiO2 interfaces are synergistically optimized, substantially facilitating the conversion of NO2 - -to-NH3 .

13.
Small ; 19(24): e2300291, 2023 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-36919558

RESUMEN

Synthesis of green ammonia (NH3 ) via electrolysis of nitric oxide (NO) is extraordinarily sustainable, but multielectron/proton-involved hydrogenation steps as well as low concentrations of NO can lead to poor activities and selectivities of electrocatalysts. Herein, it is reported that oxygen-defective TiO2 nanoarray supported on Ti plate (TiO2- x /TP) behaves as an efficient catalyst for NO reduction to NH3 . In 0.2 m phosphate-buffered electrolyte, such TiO2- x /TP shows competitive electrocatalytic NH3 synthesis activity with a maximum NH3 yield of 1233.2 µg h-1  cm-2 and Faradaic efficiency of 92.5%. Density functional theory calculations further thermodynamically faster NO deoxygenation and protonation processes on TiO2- x (101) compared to perfect TiO2 (101). And the low energy barrier of 0.7 eV on TiO2- x (101) for the potential-determining step further highlights the greatly improved intrinsic activity. In addition, a Zn-NO battery is fabricated with TiO2- x /TP and Zn plate to obtain an NH3 yield of 241.7 µg h-1  cm-2 while providing a peak power density of 0.84 mW cm-2 .

14.
Small ; 19(42): e2303424, 2023 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-37330654

RESUMEN

Ammonia (NH3 ) is an indispensable feedstock for fertilizer production and one of the most ideal green hydrogen rich fuel. Electrochemical nitrate (NO3 - ) reduction reaction (NO3 - RR) is being explored as a promising strategy for green to synthesize industrial-scale NH3 , which has nonetheless involved complex multi-reaction process. This work presents a Pd-doped Co3 O4 nanoarray on titanium mesh (Pd-Co3 O4 /TM) electrode for highly efficient and selective electrocatalytic NO3 - RR to NH3 at low onset potential. The well-designed Pd-Co3 O4 /TM delivers a large NH3 yield of 745.6 µmol h-1 cm-2 and an extremely high Faradaic efficiency (FE) of 98.7% at -0.3 V with strong stability. These calculations further indicate that the doping Co3 O4 with Pd improves the adsorption characteristic of Pd-Co3 O4 and optimizes the free energies for intermediates, thereby facilitating the kinetics of the reaction. Furthermore, assembling this catalyst in a Zn-NO3 - battery realizes a power density of 3.9 mW cm-2 and an excellent FE of 98.8% for NH3 .

15.
Inorg Chem ; 62(30): 11746-11750, 2023 Jul 31.
Artículo en Inglés | MEDLINE | ID: mdl-37449955

RESUMEN

Constructing efficient and low-cost oxygen evolution reaction (OER) catalysts operating in seawater is essential for green hydrogen production but remains a great challenge. In this study, we report an iron doped cobalt carbonate hydroxide nanowire array on nickel foam (Fe-CoCH/NF) as a high-efficiency OER electrocatalyst. In alkaline seawater, such Fe-CoCH/NF demands an overpotential of 387 mV to drive 500 mA cm-2, superior to that of CoCH/NF (597 mV). Moreover, it achieves excellent electrochemical and structural stability in alkaline seawater.

16.
Inorg Chem ; 62(38): 15352-15357, 2023 Sep 25.
Artículo en Inglés | MEDLINE | ID: mdl-37695036

RESUMEN

Electrocatalytic nitrite (NO2-) reduction offers the potential to synthesize high-value ammonia (NH3) while simultaneously removing NO2- pollution from aqueous solutions, but it requires high-efficiency catalysts to drive the complex six-electron reaction. Herein, cobalt-nanoparticle-decorated 3D porous nitrogen-doped carbon network (Co@NC) is proven as a high-efficiency catalyst for the selective electroreduction of NO2- to NH3. Such Co@NC attains a large NH3 yield of 922.7 µmol h-1 cm-2 and a high Faradaic efficiency of 95.4% under alkaline conditions. Furthermore, it shows remarkable electrochemical stability during cyclic electrolysis.

17.
Inorg Chem ; 62(1): 25-29, 2023 Jan 09.
Artículo en Inglés | MEDLINE | ID: mdl-36537850

RESUMEN

Electrochemical nitrate (NO3-) reduction is a potential approach to produce high-value ammonia (NH3) while removing NO3- pollution, but it requires electrocatalysts with high efficiency and selectivity. Herein, we report the development of Fe3O4 nanoparticles decorated TiO2 nanoribbon array on titanium plate (Fe3O4@TiO2/TP) as an efficient electrocatalyst for NO3--to-NH3 conversion. When operated in 0.1 M phosphate-buffered saline and 0.1 M NO3-, such Fe3O4@TiO2/TP achieves a prominent NH3 yield of 12394.3 µg h-1 cm-2 and a high Faradaic efficiency of 88.4%. In addition, it exhibits excellent stability during long-time electrolysis.


Asunto(s)
Nanopartículas , Nanotubos de Carbono , Nitratos , Amoníaco
18.
Inorg Chem ; 62(32): 12644-12649, 2023 Aug 14.
Artículo en Inglés | MEDLINE | ID: mdl-37534956

RESUMEN

Electrochemical nitrite (NO2-) reduction is recognized as a promising strategy for synthesizing valuable ammonia (NH3) and degrading NO2- pollutants in wastewater. The six-electron process for the NO2- reduction reaction is complex and necessitates a highly selective and stable electrocatalyst for efficient conversion of NO2- to NH3. Herein, a FeP nanoparticle-decorated TiO2 nanoribbon array on a titanium plate (FeP@TiO2/TP) is proposed as an efficient catalyst for NH3 production under ambient conditions. In 0.1 M NaOH with 0.1 M NO2-, such a FeP@TiO2/TP affords a large NH3 yield of 346.6 µmol h-1 cm-2 and a high Faradaic efficiency of 97.1%. Additionally, it demonstrates excellent stability and durability during long-term cycling tests and electrolysis experiments.

19.
Inorg Chem ; 62(20): 7976-7981, 2023 May 22.
Artículo en Inglés | MEDLINE | ID: mdl-37144756

RESUMEN

Seawater electrolysis driven by renewable electricity is deemed a promising and sustainable strategy for green hydrogen production, but it is still formidably challenging. Here, we report an iron-doped NiS nanosheet array on Ni foam (Fe-NiS/NF) as a high-performance and stable seawater splitting electrocatalyst. Such Fe-NiS/NF catalyst needs overpotentials of only 420 and 270 mV at 1000 mA cm-2 for the oxygen evolution reaction and hydrogen evolution reaction in alkaline seawater, respectively. Furthermore, its two-electrode electrolyzer needs a cell voltage of 1.88 V for 1000 mA cm-2 with 50 h of long-term electrochemical durability in alkaline seawater. Additionally, in situ electrochemical Raman and infrared spectroscopy were employed to detect the reconstitution process of NiOOH and the generation of oxygen intermediates under reaction conditions.

20.
Nanotechnology ; 35(10)2023 Dec 21.
Artículo en Inglés | MEDLINE | ID: mdl-38055973

RESUMEN

Seawater splitting is a compelling avenue to produce abundant hydrogen, which requires high-performance and cost-effective catalysts. Constructing bimetallic transition metal phosphides is a feasible strategy to meet the challenge. Here, an amorphous Co-Mo-P film supported on nickel foam (Co-Mo-P/NF) electrode is developed with bifunctional properties for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline seawater. Corresponding results indicate that the introduction of Mo can improve the active sites and regulate the intrinsic activity. Such a Co-Mo-P/NF behaves with prominent electrocatalytic activity towards both HER and OER, demanding low overpotentials of 193 and 352 mV at 100 mA cm‒2in alkaline seawater, respectively. Furthermore, the assembled electrolyzer demands a pronounced overall seawater splitting activity with a low cell voltage of 1.76 V to deliver 100 mA cm-2presenting excellent durability without obvious attenuation after 24 h continuous stability test. This work expands the horizon to develop transition metal-phosphorus electrocatalysts with robust and efficient activity for overall seawater splitting.

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