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1.
J Mater Chem B ; 12(16): 3908-3916, 2024 Apr 24.
Artículo en Inglés | MEDLINE | ID: mdl-38567452

RESUMEN

The fabrication of shape-selective coinage metal nanoclusters (MNCs) has promising applications due to their exceptional physical and chemical molecule-like properties. However, the stability of the specific geometry of the nanoclusters, such as their cubic shapes, is unclear and has been unraveled by assessing the nanoclusters' interactions with different environments. In this work, we investigate the morphological stability of cubic structured, coinage metal nanoclusters of varying sizes ranging from 14 to 1099 atoms. The impact of solvent environments like water and the presence of ionic liquids (IL) on the stabilization of the MNCs were assessed using molecular dynamics (MD) simulations. In general, smaller MNCs composed of less than 256 atoms encountered structural distortion easily compared to the larger ones, which preserved their cubic morphology with minimal surface aberrations in water. However, in the presence of 4M 1-butyl-1,1,1-trimethyl ammonium methane sulfonate [N1114][C1SO3] IL solution, the overall cubic shape of the MNCs was successfully preserved. Strikingly, it is observed that in contrast to the noble MNCs like Au and Ag, the cubic morphology for Cu MNCs with sizes less than 256 atoms exhibited significant stability even in the absence of IL.


Asunto(s)
Cobre , Nanopartículas del Metal , Simulación de Dinámica Molecular , Cobre/química , Nanopartículas del Metal/química , Líquidos Iónicos/química , Tamaño de la Partícula , Propiedades de Superficie , Agua/química
2.
Sci Rep ; 14(1): 9027, 2024 04 19.
Artículo en Inglés | MEDLINE | ID: mdl-38641640

RESUMEN

Copper-doped ZnO nanoparticles with the formula Zn1-x(Cu)O, where x = 0.0, 0.03, 0.05, and 0.07 were produced using the co-precipitation process. Physical, chemical, and structural properties were properly examined. Powdered X-ray diffraction (P-XRD) patterns revealed the formation of hexagonal wurtzite crystal structure in all samples, through atomic substitutional incorporation in the Cu-doped ZnO lattice. The presence of Cu ions and their dissolution in the host ZnO crystal structure was supported by FT-IR spectra. HR-TEM images were used to assess the average size, morphology, and shape regularity of the synthesized samples. The form and homogeneity of the ZnO changed when Cu ions were substituted, as evidenced by FE-SEM/EDX analysis. The presence of copper signals in the Cu-doped samples indicates that the doping was successful. The decrease in zeta potential with an increased copper doping percentage designates that the nanoparticles (NPs) are more stable, which could be attributed to an increase in the ionic strength of the aqueous solution. The synthesized NPs were evaluated for their substantial in vitro antioxidant properties. In addition, the antimicrobial efficacy of the materials was tested against pathogenic microorganisms. Regarding the anti-diabetic activity, the 7Cu ZnO sample showed the highest inhibitory effect on the α-amylase enzyme. No variations were observed in the activities of the acetylcholinesterase enzyme (AChE) and proteinase enzymes with ZnO and samples doped with different concentrations of Cu. Therefore, further studies are recommended to reveal the in-vitro anti-diabetic activity of the studied doped samples. Finally, molecular docking provided valuable insights into the potential binding interactions of Cu-doped ZnO with α-amylase, FabH of E. coli, and Penicillin-binding proteins of S. aureus. These outcomes suggest that the prepared materials may have an inhibitory effect on enzymes and hold promise in the battle against microbial infections and diabetes.


Asunto(s)
Óxido de Zinc , Óxido de Zinc/farmacología , Óxido de Zinc/química , Simulación del Acoplamiento Molecular , Espectroscopía Infrarroja por Transformada de Fourier , Cobre/química , Escherichia coli , Staphylococcus aureus , Acetilcolinesterasa , Iones/farmacología , alfa-Amilasas
3.
Front Cell Infect Microbiol ; 14: 1301351, 2024.
Artículo en Inglés | MEDLINE | ID: mdl-38655284

RESUMEN

Bacterial infections emerge as a significant contributor to mortality and morbidity worldwide. Emerging extended-spectrum ß-lactamase (ESBL) Escherichia coli strains provide a greater risk of bacteremia and mortality, are increasingly resistant to antibiotics, and are a major producer of ESBLs. E. coli bacteremia-linked mastitis is one of the most common bacterial diseases in animals, which can affect the quality of the milk and damage organ functions. There is an elevated menace of treatment failure and recurrence of E. coli bacteremia necessitating the adoption of rigorous alternative treatment approaches. In this study, Se-Boil-CuO multimetallic nanoparticles (MMNPs) were synthesized as an alternate treatment from Talaromyces haitouensis extract, and their efficiency in treating ESBL E. coli was confirmed using standard antimicrobial assays. Scanning electron microscopy, UV-visible spectroscopy, and dynamic light scattering were used to validate and characterize the mycosynthesized Se-BiO-CuO MMNPs. UV-visible spectra of Se-BiO-CuO MMNPs showed absorption peak bands at 570, 376, and 290 nm, respectively. The average diameters of the amorphous-shaped Se-BiO-CuO MMNPs synthesized by T. haitouensis extract were approximately 66-80 nm, respectively. Se-BiO-CuO MMNPs (100 µg/mL) showed a maximal inhibition zone of 18.33 ± 0.57 mm against E. coli. Se-BiO-CuO MMNPs also exhibited a deleterious impact on E. coli killing kinetics, biofilm formation, swimming motility, efflux of cellular components, and membrane integrity. The hemolysis assay also confirms the biocompatibility of Se-BiO-CuO MMNPs at the minimum inhibitory concentration (MIC) range. Our findings suggest that Se-BiO-CuO MMNPs may serve as a potential substitute for ESBL E. coli bacteremia.


Asunto(s)
Antibacterianos , Cobre , Escherichia coli , Pruebas de Sensibilidad Microbiana , beta-Lactamasas , Escherichia coli/efectos de los fármacos , beta-Lactamasas/metabolismo , Animales , Cobre/química , Cobre/farmacología , Antibacterianos/farmacología , Antibacterianos/química , Nanopartículas del Metal/química , Infecciones por Escherichia coli/tratamiento farmacológico , Infecciones por Escherichia coli/microbiología , Nanopartículas/química
4.
Nature ; 628(8009): 765-770, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38658685

RESUMEN

Solar fuels offer a promising approach to provide sustainable fuels by harnessing sunlight1,2. Following a decade of advancement, Cu2O photocathodes are capable of delivering a performance comparable to that of photoelectrodes with established photovoltaic materials3-5. However, considerable bulk charge carrier recombination that is poorly understood still limits further advances in performance6. Here we demonstrate performance of Cu2O photocathodes beyond the state-of-the-art by exploiting a new conceptual understanding of carrier recombination and transport in single-crystal Cu2O thin films. Using ambient liquid-phase epitaxy, we present a new method to grow single-crystal Cu2O samples with three crystal orientations. Broadband femtosecond transient reflection spectroscopy measurements were used to quantify anisotropic optoelectronic properties, through which the carrier mobility along the [111] direction was found to be an order of magnitude higher than those along other orientations. Driven by these findings, we developed a polycrystalline Cu2O photocathode with an extraordinarily pure (111) orientation and (111) terminating facets using a simple and low-cost method, which delivers 7 mA cm-2 current density (more than 70% improvement compared to that of state-of-the-art electrodeposited devices) at 0.5 V versus a reversible hydrogen electrode under air mass 1.5 G illumination, and stable operation over at least 120 h.


Asunto(s)
Cobre , Electrodos , Cobre/química , Energía Solar , Cristalización
5.
J Nanobiotechnology ; 22(1): 205, 2024 Apr 24.
Artículo en Inglés | MEDLINE | ID: mdl-38658965

RESUMEN

The elevated level of hydrogen sulfide (H2S) in colon cancer hinders complete cure with a single therapy. However, excessive H2S also offers a treatment target. A multifunctional cascade bioreactor based on the H2S-responsive mesoporous Cu2Cl(OH)3-loaded hypoxic prodrug tirapazamine (TPZ), in which the outer layer was coated with hyaluronic acid (HA) to form TPZ@Cu2Cl(OH)3-HA (TCuH) nanoparticles (NPs), demonstrated a synergistic antitumor effect through combining the H2S-driven cuproptosis and mild photothermal therapy. The HA coating endowed the NPs with targeting delivery to enhance drug accumulation in the tumor tissue. The presence of both the high level of H2S and the near-infrared II (NIR II) irradiation achieved the in situ generation of photothermic agent copper sulfide (Cu9S8) from the TCuH, followed with the release of TPZ. The depletion of H2S stimulated consumption of oxygen, resulting in hypoxic state and mitochondrial reprogramming. The hypoxic state activated prodrug TPZ to activated TPZ (TPZ-ed) for chemotherapy in turn. Furthermore, the exacerbated hypoxia inhibited the synthesis of adenosine triphosphate, decreasing expression of heat shock proteins and subsequently improving the photothermal therapy. The enriched Cu2+ induced not only cuproptosis by promoting lipoacylated dihydrolipoamide S-acetyltransferase (DLAT) heteromerization but also performed chemodynamic therapy though catalyzing H2O2 to produce highly toxic hydroxyl radicals ·OH. Therefore, the nanoparticles TCuH offer a versatile platform to exert copper-related synergistic antitumor therapy.


Asunto(s)
Cobre , Ácido Hialurónico , Sulfuro de Hidrógeno , Mitocondrias , Nanopartículas , Terapia Fototérmica , Profármacos , Tirapazamina , Terapia Fototérmica/métodos , Sulfuro de Hidrógeno/metabolismo , Sulfuro de Hidrógeno/farmacología , Animales , Cobre/química , Cobre/farmacología , Ratones , Humanos , Mitocondrias/metabolismo , Mitocondrias/efectos de los fármacos , Profármacos/farmacología , Profármacos/química , Tirapazamina/farmacología , Tirapazamina/química , Nanopartículas/química , Ácido Hialurónico/química , Línea Celular Tumoral , Neoplasias del Colon/terapia , Neoplasias del Colon/metabolismo , Neoplasias del Colon/tratamiento farmacológico , Ratones Endogámicos BALB C , Antineoplásicos/farmacología , Antineoplásicos/química , Ratones Desnudos
6.
ACS Sens ; 9(4): 1906-1915, 2024 Apr 26.
Artículo en Inglés | MEDLINE | ID: mdl-38565844

RESUMEN

As a carcinogenic and highly neurotoxic hazardous gas, benzene vapor is particularly difficult to be distinguished in BTEX (benzene, toluene, ethylbenzene, xylene) atmosphere and be detected in low concentrations due to its chemical inertness. Herein, we develop a depth-related pore structure in Cu-TCPP-Cu to thermodynamically and kinetically enhance the adsorption of benzene vapor and realize the detection of ultralow-temperature benzene gas. We find that the in-plane π electronic nature and proper pore sizes in Cu-TCPP-Cu can selectively induce the adsorption and diffusion of BTEX. Interestingly, the theoretical calculations (including density functional theory (DFT) and grand canonical Monte Carlo (GCMC) simulations) exhibit that benzene molecules are preferred to adsorb and array as a consecutive arrangement mode in the Cu-TCPP-Cu pore, while the TEX (toluene, ethylbenzene, xylene) dominate the jumping arrangement model. The differences in distribution behaviors can allow adsorption and diffusion of more benzene molecules within limited room. Furthermore, the optimal pore-depth range (60-65 nm) of Cu-TCPP-Cu allows more exposure of active sites and hinders the gas-blocking process. The optimized sensor exhibits ultrahigh sensitivity to benzene vapor (155 Hz/µg@1 ppm), fast response time (less than 10 s), extremely low limit of detection (65 ppb), and excellent selectivity (83%). Our research thus provides a fundamental understanding to design and optimize two-dimensional metal-organic framework (MOF)-based gas sensors.


Asunto(s)
Benceno , Cobre , Límite de Detección , Estructuras Metalorgánicas , Termodinámica , Benceno/análisis , Benceno/química , Cobre/química , Estructuras Metalorgánicas/química , Adsorción , Cinética , Teoría Funcional de la Densidad , Gases/análisis , Gases/química
7.
ACS Appl Mater Interfaces ; 16(15): 18534-18550, 2024 Apr 17.
Artículo en Inglés | MEDLINE | ID: mdl-38574189

RESUMEN

The metastasis and recurrence of cancer are related to immunosuppression and hypoxia in the tumor microenvironment. Activating immune activity and improving the hypoxic environment face essential challenges. This paper reports on a multifunctional nanomaterial, HSCCMBC, that induces immunogenic cell death through powerful photodynamic therapy/chemodynamic therapy synergistic antitumor effects. The tumor microenvironment changed from the immunosuppressive type to immune type, activated the immune activity of the system, decomposed hydrogen peroxide to generate oxygen based on Fenton-like reaction, and effectively increased the level of intracellular O2 with the assistance of 3-bromopyruvate, a cell respiratory inhibitor. The structure and composition of HSCCMBC were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, infrared spectroscopy, etc. Oxygen probe RDPP was used to investigate the oxygen level inside and outside the cell, and hydroxyl radical probe tetramethylbenzidine was used to investigate the Fenton-like reaction ability. The immunofluorescence method investigated the expression of various immune markers and hypoxia-inducing factors in vitro and in vivo after treatment. In vitro and in vivo experiments indicate that HSCCMBC is an excellent antitumor agent and is expected to be a candidate drug for antitumor immunotherapy.


Asunto(s)
Nanopartículas , Neoplasias , Humanos , Dióxido de Silicio/farmacología , Cobre/química , Carbono/farmacología , Muerte Celular Inmunogénica , Neoplasias/tratamiento farmacológico , Oxígeno/química , Hipoxia , Línea Celular Tumoral , Peróxido de Hidrógeno/química , Microambiente Tumoral , Nanopartículas/química
8.
Mikrochim Acta ; 191(5): 284, 2024 04 23.
Artículo en Inglés | MEDLINE | ID: mdl-38652331

RESUMEN

A dual-mode (colorimetric/fluorescence) nanoenzyme-linked immunosorbent assay (NLISA) was developed based on Au-Cu nanocubes generating Prussian blue nanoparticles (PBNPs). It is expected that this method can be used to detect the residues of sulfonamides in the field, and solve the problem of long analysis time and high cost of the traditional method. Sulfadimethoxine (SDM) was selected as the proof-of-concept target analyte. The Au-Cu nanocubes were linked to the aptamer by amide interaction, and the Au-Cu nanocubes, SDM and antibody were immobilized on a 96-well plate using the sandwich method. The assay generates PBNPs by oxidising the Cu shells on the Au-Cu nanocubes in the presence of hydrochloric acid, Fe3+ and K3[Fe (CN)6]. In this process, the copper shell undergoes oxidation to Cu2+ and subsequently Cu2 + further quenches the fluorescence of the carbon point. PBNPs exhibit peroxidase-like activity, oxidising 3,3',5,5'-tetramethylbenzidine (TMB) to OX-TMB in the presence of H2O2, which alters the colorimetric signal. The dual-mode signals are directly proportional to the sulfadimethoxine concentration within the range 10- 3~10- 7 mg/mL. The limit of detection (LOD) of the assay is 0.023 ng/mL and 0.071 ng/mL for the fluorescent signal and the colorimetric signal, respectively. Moreover, the assay was successfully applied to determine sulfadimethoxine in silver carp, shrimp, and lamb samples with satisfactory results.


Asunto(s)
Carbono , Colorimetría , Cobre , Ferrocianuros , Sulfadimetoxina , Ferrocianuros/química , Sulfadimetoxina/análisis , Sulfadimetoxina/química , Cobre/química , Colorimetría/métodos , Carbono/química , Límite de Detección , Oro/química , Puntos Cuánticos/química , Fluorometría/métodos , Nanopartículas del Metal/química , Aptámeros de Nucleótidos/química , Nanopartículas/química , Animales , Ensayo de Inmunoadsorción Enzimática/métodos
9.
Biosens Bioelectron ; 256: 116275, 2024 Jul 15.
Artículo en Inglés | MEDLINE | ID: mdl-38603839

RESUMEN

Constructing relatively inexpensive nanomaterials to simulate the catalytic performance of laccase is of great significance in recent years. Although research on improving laccase-like activity by regulating ligands of copper (amino acids or small organic molecules, etc.) have achieved remarkable success. There are few reports on improving laccase-like activity by adjusting the composition of metal Cu. Here, we used perovskite hydroxide AB(OH)6 as a model to evaluate the relationship between Cu based alloys and their laccase-like activity. We found that when the Cu/Mn alloy ratio of the perovskite hydroxide A point is greater than 1, the laccase-like activity of the binary alloy perovskite hydroxide is higher than that of the corresponding single Cu. Based on the measurements of XPS and ICP-MS, we deduced that the improvements of laccase-like activity mainly attribute to the ratio of Cu+/Cu2+and the content of Cu. Moreover, two types of substrates (toxic pollutants and catechol neurotransmitters) were used to successfully demonstrated such nanozymes' excellent environmental protecting function and biosensing property. This work will provide a novel approach for the construction and application of laccase-like nanozymes in the future.


Asunto(s)
Técnicas Biosensibles , Cobre , Lacasa , Óxidos , Titanio , Lacasa/química , Lacasa/metabolismo , Técnicas Biosensibles/métodos , Cobre/química , Titanio/química , Óxidos/química , Hidróxidos/química , Compuestos de Calcio/química , Restauración y Remediación Ambiental/métodos , Catecoles/análisis , Catecoles/química , Materiales Biomiméticos/química , Catálisis
10.
Food Chem ; 448: 139127, 2024 Aug 01.
Artículo en Inglés | MEDLINE | ID: mdl-38608399

RESUMEN

To address the food safety issues caused by toxins, we established a fluorescent copper nanocluster biosensor based on magnetic aptamer for the visual and quantitative detection of ZEN. Specifically, we utilized the docking-aided rational tailoring (DART) strategy to analyze intermolecular force and interaction sites between zearalenone (ZEN) and the aptamer, and optimize the long-chain aptamer step by step to enhance the binding affinity by 3.4 times. The magnetic bead-modified aptamer underwent conformational changes when competing with complementary sequences to bind with ZEN. Then, the released complementary sequences will be amplified in template-free mode with the presence of the terminal deoxynucleotidyl transferase (TdT), and generating T-rich sequences as the core sequences for the luminescence of copper nanoclusters. The luminescence could be visualized and quantitatively detected through ultraviolet irradiation. The proposed label-free aptasensor exhibited high sensitivity and specificity, with a low limit of detection (LOD) of 0.1 ng/mL.


Asunto(s)
Aptámeros de Nucleótidos , Técnicas Biosensibles , Cobre , Zearalenona , Zearalenona/análisis , Zearalenona/química , Cobre/química , Técnicas Biosensibles/instrumentación , Aptámeros de Nucleótidos/química , Contaminación de Alimentos/análisis , Límite de Detección , Simulación del Acoplamiento Molecular , Nanopartículas del Metal/química , Fluorescencia
11.
J Colloid Interface Sci ; 666: 434-446, 2024 Jul 15.
Artículo en Inglés | MEDLINE | ID: mdl-38608638

RESUMEN

Bacterial infections are among the most significant causes of death in humans. Chronic misuse or uncontrolled use of antibiotics promotes the emergence of multidrug-resistant superbugs that threaten public health through the food chain and cause environmental pollution. Based on the above considerations, copper selenide nanosheets (CuSe NSs) with photothermal therapy (PTT)- and photodynamic therapy (PDT)-related properties have been fabricated. These CuSe NSs possess enhanced PDT-related properties and can convert O2 into highly toxic reactive oxygen species (ROS), which can cause significant oxidative stress and damage to bacteria. In addition, CuSe NSs can efficiently consume glutathione (GSH) at bacterial infection sites, thus further enhancing their sterilization efficacy. In vitro antibacterial experiments with near-infrared (NIR) irradiation have shown that CuSe NSs have excellent photothermal bactericidal properties. These experiments also showed that CuSe NSs exerted excellent bactericidal effects on wounds infected with methicillin-resistant Staphylococcus aureus (MRSA) and significantly promoted the healing of infected wounds. Because of their superior biological safety, CuSe NSs are novel copper-based antimicrobial agents that are expected to enter clinical trials, serving as a modern approach to the major problem of treating bacterially infected wounds.


Asunto(s)
Antibacterianos , Cobre , Staphylococcus aureus Resistente a Meticilina , Pruebas de Sensibilidad Microbiana , Nanoestructuras , Terapia Fototérmica , Cobre/química , Cobre/farmacología , Antibacterianos/farmacología , Antibacterianos/química , Staphylococcus aureus Resistente a Meticilina/efectos de los fármacos , Animales , Nanoestructuras/química , Ratones , Especies Reactivas de Oxígeno/metabolismo , Humanos , Propiedades de Superficie , Tamaño de la Partícula , Selenio/química , Selenio/farmacología , Farmacorresistencia Bacteriana/efectos de los fármacos , Infecciones Estafilocócicas/tratamiento farmacológico
12.
Toxicon ; 242: 107707, 2024 May 06.
Artículo en Inglés | MEDLINE | ID: mdl-38579983

RESUMEN

This research presents the synthesis and characterization of Cu-doped Fe3O4 (Cu-Fe3O4) nanoparticles as a magnetically recoverable and reusable detoxifying agent for the efficient and long-lasting neutralization of bacterial toxins. The nanoparticles were synthesized using the combustion synthesis method and characterized through SEM, XRD, BET, TGA, and VSM techniques. The detoxification potential of Cu-Fe3O4 was compared with traditional formaldehyde (FA) in detoxifying epsilon toxin (ETx) from Clostridium perfringens Type D, the causative agent of enterotoxemia in ruminants. In vivo residual toxicity tests revealed that Cu-Fe3O4 could detoxify ETx at a concentration of 2.0 mg mL-1 within 4 days at room temperature (RT) and 2 days at 37 °C, outperforming FA (12 and 6 days at RT and 37 °C, respectively). Characterization studies using dynamic light scattering (DLS) and circular dichroism (CD) highlighted lower conformational changes in Cu-Fe3O4-detoxified ETx compared to FA-detoxified ETx. Moreover, Cu-Fe3O4-detoxified ETx exhibited exceptional storage stability at 4 °C and RT for 6 months, maintaining an irreversible structure with no residual toxicity. The particles demonstrated remarkable reusability, with the ability to undergo five continuous detoxification batches. This study provides valuable insights into the development of an efficient and safe detoxifying agent, enabling the production of toxoids with a native-like structure. The magnetically recoverable and reusable nature of Cu-Fe3O4 nanoparticles offers practical advantages for easy recovery and reuse in detoxification reactions.


Asunto(s)
Toxinas Bacterianas , Cobre , Formaldehído , Formaldehído/química , Cobre/química , Animales , Toxinas Bacterianas/química , Toxinas Bacterianas/toxicidad , Clostridium perfringens , Nanopartículas de Magnetita/química
13.
Anal Chem ; 96(16): 6493-6500, 2024 Apr 23.
Artículo en Inglés | MEDLINE | ID: mdl-38595323

RESUMEN

Mitochondria play a crucial role in maintaining cellular homeostasis, and the depolarization of mitochondrial membrane potential (MMP) is an important signal of apoptosis. Additionally, protein misfolding and aggregation are closely related to diseases including neurodegenerative diseases, diabetes, and cancers. However, the interaction between MMP changes and disease-related protein aggregation was rarely studied. Herein, we report a novel "turn-on" fluorescent probe MitoRhB that specifically targets to mitochondria for Cu2+ detection in situ. The fluorescence lifetime (τ) of MitoRhB exhibits a positive correlation with MMP changes, allowing us to quantitatively determine the relative MMP during SOD1 (A4 V) protein aggregation. Finally, we found that (1) the increasing concentrations of copper will accelerate the depolarization of mitochondria and reduce MMP; (2) the depolarization of mitochondria can intensify the degree of protein aggregation, suggesting a new routine of copper-induced cell death mediated through abnormal MMP depolarization and protein aggregation.


Asunto(s)
Cobre , Colorantes Fluorescentes , Potencial de la Membrana Mitocondrial , Agregado de Proteínas , Potencial de la Membrana Mitocondrial/efectos de los fármacos , Cobre/química , Cobre/metabolismo , Humanos , Colorantes Fluorescentes/química , Mitocondrias/metabolismo , Mitocondrias/química , Superóxido Dismutasa-1/metabolismo , Superóxido Dismutasa-1/química , Células HeLa
14.
Anal Chem ; 96(16): 6202-6208, 2024 Apr 23.
Artículo en Inglés | MEDLINE | ID: mdl-38598750

RESUMEN

New strategies for accurate and reliable detection of adenosine triphosphate (ATP) with portable devices are significant for biochemical analysis, while most recently reported approaches cannot satisfy the detection accuracy and independent of large instruments simultaneously, which are unsuitable for fast, simple, and on-site ATP monitoring. Herein, a unique, convenient, and label-free point-of-care sensing strategy based on novel copper coordination polymer nanoflowers (CuCPNFs) was fabricated for multimode (UV-vis, photothermal, and RGB values) onsite ATP determination with high selectivity, sensitivity, and accuracy. The resulting CuCPNFs with a 3D hierarchical structure exhibit the ATP-triggered decomposition behavior because the competitive coordination between ATP and the copper ions of CuCPNFs can result in the formation of ATP-Cu, which reveals preeminent peroxidase mimics activity and can accelerate the oxidation of 3, 3', 5, 5'-tetramethylbenzidine (TMB) to form oxTMB. During this process, the detection system displayed not only color changes but also a strong NIR laser-driven photothermal effect. Thus, the photothermal and color signal variations are easily monitored by a portable thermometer and a smartphone. This multimode point-of-care platform can meet the requirements of onsite, without bulky equipment, accuracy, and reliability all at once, greatly enhancing its application in practice and paving a new way in ATP analysis.


Asunto(s)
Adenosina Trifosfato , Cobre , Polímeros , Cobre/química , Adenosina Trifosfato/análisis , Polímeros/química , Sistemas de Atención de Punto , Humanos , Nanoestructuras/química , Límite de Detección , Colorimetría , Bencidinas/química , Pruebas en el Punto de Atención
15.
J Environ Sci (China) ; 143: 12-22, 2024 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-38644010

RESUMEN

Selective catalytic NH3-to-N2 oxidation (NH3-SCO) is highly promising for abating NH3 emissions slipped from stationary flue gas after-treatment devices. Its practical application, however, is limited by the non-availability of low-cost catalysts with high activity and N2 selectivity. Here, using defect-rich nitrogen-doped carbon nanotubes (NCNT-AW) as the support, we developed a highly active and durable copper-based NH3-SCO catalyst with a high abundance of cuprous (Cu+) sites. The obtained Cu/NCNT-AW catalyst demonstrated outstanding activity with a T50 (i.e. the temperature to reach 50% NH3 conversion) of 174°C in the NH3-SCO reaction, which outperformed not only the Cu catalyst supported on N-free O-functionalized CNTs (OCNTs) or NCNT with less surface defects, but also those most active Cu catalysts in open literature. Reaction kinetics measurements and temperature-programmed surface reactions using NH3 as a probe molecule revealed that the NH3-SCO reaction on Cu/NCNT-AW follows an internal selective catalytic reaction (i-SCR) route involving nitric oxide (NO) as a key intermediate. According to mechanistic investigations by X-ray photoelectron spectroscopy, Raman spectroscopy, and X-ray absorption spectroscopy, the superior NH3-SCO performance of Cu/NCNT-AW originated from a synergy of surface defects and N-dopants. Specifically, surface defects promoted the anchoring of CuO nanoparticles on N-containing sites and, thereby, enabled efficient electron transfer from N to CuO, increasing significantly the fraction of SCR-active Cu+ sites in the catalyst. This study puts forward a new idea for manipulating and utilizing the interplay of defects and N-dopants on carbon surfaces to fabricate Cu+-rich Cu catalysts for efficient abatement of slip NH3 emissions via selective oxidation.


Asunto(s)
Amoníaco , Cobre , Oxidación-Reducción , Cobre/química , Amoníaco/química , Catálisis , Nanotubos de Carbono/química , Contaminantes Atmosféricos/química , Temperatura , Modelos Químicos
16.
J Phys Chem B ; 128(14): 3350-3359, 2024 Apr 11.
Artículo en Inglés | MEDLINE | ID: mdl-38564809

RESUMEN

Secondary coordination sphere (SCS) interactions have been shown to play important roles in tuning reduction potentials and electron transfer (ET) properties of the Type 1 copper proteins, but the precise roles of these interactions are not fully understood. In this work, we examined the influence of F114P, F114N, and N47S mutations in the SCS on the electronic structure of the T1 copper center in azurin (Az) by studying the hyperfine couplings of (i) histidine remote Nε nitrogens and (ii) the amide Np using the two-dimensional (2D) pulsed electron paramagnetic resonance (EPR) technique HYSCORE (hyperfine sublevel correlation) combined with quantum mechanics/molecular mechanics (QM/MM) and DLPNO-CCSD calculations. Our data show that some components of hyperfine tensor and isotropic coupling in N47SAz and F114PAz (but not F114NAz) deviate by up to ∼±20% from WTAz, indicating that these mutations significantly influence the spin density distribution between the CuII site and coordinating ligands. Furthermore, our calculations support the assignment of Np to the backbone amide of residue 47 (both in Asn and Ser variants). Since the spin density distributions play an important role in tuning the covalency of the Cu-Scys bond of Type 1 copper center that has been shown to be crucial in controlling the reduction potentials, this study provides additional insights into the electron spin factor in tuning the reduction potentials and ET properties.


Asunto(s)
Nativos Alasqueños , Azurina , Azurina/genética , Azurina/química , Cobre/química , Nitrógeno/química , Mutación , Espectroscopía de Resonancia por Spin del Electrón/métodos , Amidas
17.
Carbohydr Polym ; 332: 121935, 2024 May 15.
Artículo en Inglés | MEDLINE | ID: mdl-38431402

RESUMEN

A novel cellulose composite (denoted as PEI@MMA-1) with porous interconnected structure was prepared by adsorbing methyl cellulose (MC) onto microcrystalline cellulose (MCC) and cross-linking polyethyleneimine (PEI) with MCC by the action of epichlorohydrin, which had the excellent adsorption property, wettability and elasticity. The performances of PEI@MMA-1 composite for removing tetracycline (TC), Cu2+ and coexistent pollutant (TC and Cu2+ mixture) were systematically explored. For single TC or Cu2+ contaminant, the maximum adsorption capacities were 75.53 and 562.23 mg/g at 30 °C, respectively, while in the dual contaminant system, they would form complexes and Cu2+ could play a "bridge" role to remarkably promote the adsorption of TC with the maximum adsorption capacities of 281.66 and 253.58 mg/g for TC and Cu2+. In addition, the adsorption kinetics, isotherms and adsorption mechanisms of single-pollutant and dual-pollutant systems have been thoroughly investigated. Theoretical calculations indicated that the amide group of TC molecule with the assistance of Cu2+ interacted with the hydroxyl group of PEI@MMA-1 composite to enhance the TC adsorption capacity. Cycle regeneration and fixed bed column experiments revealed that the PEI@MMA-1 possessed the excellent stability and utility. Current PEI@MMA-1 cellulose composite exhibited a promising application for remediation of heavy metals and antibiotics coexistence wastewater.


Asunto(s)
Celulosa/análogos & derivados , Cobre , Polietileneimina/análogos & derivados , Contaminantes Químicos del Agua , Cobre/química , Adsorción , Contaminantes Químicos del Agua/química , Tetraciclina/química , Antibacterianos , Iones , Cinética
18.
Carbohydr Polym ; 332: 121923, 2024 May 15.
Artículo en Inglés | MEDLINE | ID: mdl-38431418

RESUMEN

Bacterial cellulose (BC) produced by Acetobacter xylinum has great advantages in wound dressing. However, the structural limitation under static culture, and lack of antibacterial properties restrict its application, especially for infectious wound healing. The present study reported an original wound dressing, which was composed of a Janus BC membrane with antibacterial nano-sized copper oxide (CuO) through polydopamine (PDA) conjugation to promote wound healing under infectious condition. The finished product (CuO/PDA/BC membrane) exhibited favorable air permeability, high hydrophilicity and good mechanical properties, as well as strong antibacterial effects by the sustained release of CuO and photothermal effect of CuO/PDA. Furthermore, CuO/PDA/BC membrane inhibited inflammatory response and promoted wound healing in an infectious wound model in vivo. These results suggested that our CuO/PDA/BC membrane had great potential as wound dressing for infectious wound healing.


Asunto(s)
Celulosa , Indoles , Polímeros , Infección de Heridas , Humanos , Celulosa/farmacología , Celulosa/química , Cobre/farmacología , Cobre/química , Cicatrización de Heridas , Antibacterianos/farmacología , Antibacterianos/química , Óxidos/farmacología
19.
Sci Rep ; 14(1): 5589, 2024 03 07.
Artículo en Inglés | MEDLINE | ID: mdl-38453990

RESUMEN

The utilization of plants for the production of metallic nanoparticles is gaining significant attention in research. In this study, we conducted phytochemical screening of Alstonia scholaris (A. scholaris) leaves extracts using various solvents, including chloroform, ethyl acetate, n-hexane, methanol, and water. Our findings revealed higher proportions of flavonoids and alkaloids in both solvents compared to other phytochemical species. In the methanol, extract proteins, anthraquinone and reducing sugar were not detected. On the other hand, the aqueous extract demonstrated the presence of amino acids, reducing sugar, phenolic compounds, anthraquinone, and saponins. Notably, ethyl acetate and chloroform extracts displayed the highest levels of bioactive compounds among all solvents. Intrigued by these results, we proceeded to investigate the antibacterial properties of the leaf extracts against two major bacterial strains, Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). All extracts exhibited significant zones of inhibition against both bacterial isolates, with S. aureus showing higher susceptibility compared to E. coli. Notably, the methanol extract displayed the most potent I hibitory effect against all organisms. Inspired by the bioactivity of the methanol extract, we employed it as a plant-based material for the green synthesis of copper nanoparticles (Cu-NPs). The synthesized Cu-NPs were characterized using Fourier infrared spectroscopy (FT-IR), UV-visible spectroscopic analysis, and scanning electron microscopy (SEM). The observed color changes confirmed the successful formation of Cu-NPs, while the FTIR analysis matched previously reported peaks, further verifying the synthesis. The SEM micrographs indicated the irregular shapes of the surface particles. From the result obtained by energy dispersive X-ray spectroscopic analysis, Cu has the highest relative abundance of 67.41 wt%. Confirming the purity of the Cu-NPs colloid. These findings contribute to the growing field of eco-friendly nanotechnology and emphasize the significance of plant-mediated approaches in nanomaterial synthesis and biomedical applications.


Asunto(s)
Acetatos , Alstonia , Antiinfecciosos , Nanopartículas del Metal , Cobre/química , Espectroscopía Infrarroja por Transformada de Fourier , Staphylococcus aureus , Escherichia coli , Metanol/farmacología , Cloroformo/farmacología , Extractos Vegetales/farmacología , Extractos Vegetales/química , Antiinfecciosos/farmacología , Antibacterianos/química , Nanopartículas del Metal/química , Fitoquímicos/farmacología , Solventes/farmacología , Azúcares/farmacología , Antraquinonas/farmacología , Pruebas de Sensibilidad Microbiana
20.
Molecules ; 29(5)2024 Feb 21.
Artículo en Inglés | MEDLINE | ID: mdl-38474457

RESUMEN

This study presents a simple and energy-efficient self-assembly LAG synthetic method for novel water-soluble copper(I) complexes [Cu(terpy)(PTA)][PF6] (1) and [Cu(terpy)(PTA)2][PF6] (2). They were characterized by FT-IR, 1H, and 31P{1H} NMR spectroscopy, elemental analysis, and single-crystal/powder X-ray diffraction (for 2). The X-ray analysis of compound 2 indicates a bidentate coordination mode of terpyridine to the metal center. Variable-temperature NMR tests indicate dynamic properties for terpyridine in the case of both compounds, as well as for the PTA ligands in the case of 2. Additionally, compounds 1 and 2 exhibit interesting cytotoxic activity, which was tested on normal human dermal fibroblasts (NHDFs), human lung carcinoma (A549), human breast adenocarcinoma (MCF-7), and human cervix carcinoma (HeLa) established cell lines. In comparison to the other tested compounds, complexes 1 and 2 seem to have significantly lower IC50 values against cancer cells (A549, HeLa, MCF-7), indicating their potential as prospective anticancer agents. Moreover, both compounds show no significant toxicity towards normal skin cells (NHDFs), suggesting a certain selectivity in their action on cancer cells. Cisplatin as a reference compound also exhibited considerable cytotoxicity against cancer cells but with a low level of selectivity, which could lead to unwanted effects on normal cells. Remarkably, compounds 1 and 2 exhibit up to 30 times the cytotoxic activity of cisplatin, with a six-fold lower toxicity to normal cells. They also interact strongly with human serum albumin, suggesting potential therapeutic applications. Overall, these compounds hold significant promise as potential chemotherapeutic agents.


Asunto(s)
Adamantano/análogos & derivados , Antineoplásicos , Carcinoma , Complejos de Coordinación , Compuestos Organofosforados , Femenino , Humanos , Cisplatino/farmacología , Cobre/química , Línea Celular Tumoral , Agua , Estudios Prospectivos , Espectroscopía Infrarroja por Transformada de Fourier , Complejos de Coordinación/química , Antineoplásicos/farmacología , Ligandos
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