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1.
Nat Mater ; 22(10): 1182-1188, 2023 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-37592031

RESUMEN

Since the first discovery of the fatigue phenomenon in the late 1830s, efforts to fight against fatigue failure have continued. Here we report a fatigue resistance phenomenon in nano-TiB2-decorated AlSi10Mg enabled by additive manufacturing. This fatigue resistance mechanism benefits from the three-dimensional dual-phase cellular nanostructure, which acts as a strong volumetric nanocage to prevent localized damage accumulation, thus inhibiting fatigue crack initiation. The intrinsic fatigue strength limit of nano-TiB2-decorated AlSi10Mg was proven to be close to its tensile strength through the in situ fatigue tests of a defect-free microsample. To demonstrate the practical applicability of this mechanism, printed bulk nano-TiB2-decorated AlSi10Mg achieved fatigue resistance more than double those of other additive manufacturing Al alloys and surpassed those of high-strength wrought Al alloys. This strategy of additive-manufacturing-assisted nanostructure engineering can be extended to the development of other dual-phase fatigue-resistant metals.

2.
Inorg Chem ; 63(5): 2327-2339, 2024 Feb 05.
Artículo en Inglés | MEDLINE | ID: mdl-38270093

RESUMEN

As a hydrogen carrier and a vital component in fertilizer production, ammonia (NH3) is set to play a crucial role in the planet's future. While its industrial production feeds half of the global population, it uses fossil fuels and emits greenhouse gases. To tackle this issue, photocatalytic nitrogen fixation using visible light is emerging as an effective alternative method. This strategy avoids carbon dioxide (CO2) emissions and harnesses the largest share of sunlight. In this work, we successfully incorporated a 5-nitro isophthalic acid linker into MOF-808 to introduce structural defects and open metal sites. This has allowed modulation of the electronic structure of the MOF and effectively reduced the band gap energy from 3.8 to 2.6 eV. Combination with g-C3N4 enhanced further NH3 production, as these two materials possess similar band gap energies, and g-C3N4 has shown excellent performance for this reaction. The nitro groups serve as acceptors, and their integration into the MOF structure allowed effective interaction with the free electron pairs on N-(C)3 in the g-C3N4 network nodes. Based on DFT calculations, it was concluded that the adsorption of N2 molecules on open metal sites caused a decrease in their triple bond energy. The modified MOF-808 showed superior performance compared with the other MOFs studied in terms of N2 photoreduction under visible light. This design concept offers valuable information about how to engineer band gap energy in MOF structures and their combination with appropriate semiconductors for solar-powered photocatalytic reactions, such as N2 or CO2 photoreduction.

3.
World J Microbiol Biotechnol ; 40(8): 252, 2024 Jun 24.
Artículo en Inglés | MEDLINE | ID: mdl-38913279

RESUMEN

This study explores the biosynthesis of silver nanoparticles (AgNPs) using the Streptomyces tuirus S16 strain, presenting an eco-friendly alternative to mitigate the environmental and health risks of chemical synthesis methods. It focuses on optimizing medium culture conditions, understanding their physicochemical properties, and investigating their potential photothermal-based antibacterial application. The S16 strain was selected from soils contaminated with heavy metals to exploit its ability to produce diverse bioactive compounds. By employing the combination of Response Surface Methodology (RSM) and Artificial Neural Network (ANN)-Genetic Algorithm (GA) strategies, we optimized AgNPs synthesis, achieving an improvement of nearly 2.45 times the initial yield under specific conditions (Bennet's medium supplemented with glycerol [5 g/L] and casamino-acid [3 g/L] at 30 °C for 72 h). A detailed physicochemical characterization was conducted. Notably, the AgNPs were well dispersed, and a carbonaceous coating layer on their surface was confirmed using energy-dispersive X-ray spectroscopy. Furthermore, functional groups were identified using Fourier-transform infrared spectroscopy, which helped enhance the AgNPs' stability and biocompatibility. AgNPs also demonstrated efficient photothermal conversion under light irradiation (0.2 W/cm2), with temperatures increasing to 41.7 °C, after 30 min. In addition, treatment with light irradiation of E. coli K-12 model effectively reduced the concentration of AgNPs from 105 to 52.5 µg/mL, thereby enhancing the efficacy of silver nanoparticles in contact with the E. coli K-12.


Asunto(s)
Antibacterianos , Nanopartículas del Metal , Metales Pesados , Redes Neurales de la Computación , Plata , Microbiología del Suelo , Plata/farmacología , Plata/química , Nanopartículas del Metal/química , Antibacterianos/farmacología , Antibacterianos/química , Algoritmos , Streptomyces/metabolismo , Streptomyces/efectos de la radiación , Pruebas de Sensibilidad Microbiana , Contaminantes del Suelo , Escherichia coli/efectos de los fármacos , Espectroscopía Infrarroja por Transformada de Fourier
4.
Small ; 19(49): e2303697, 2023 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-37612799

RESUMEN

Despite many efforts devoted toward the design of covalent organic frameworks (COFs) at the framework level by selecting the building blocks, their organization in the nano to meso regimes is often neglected. Moreover, the importance of processability for their applications has recently emerged and the synthesis of COF nanostructures without agglomeration is still a challenge. Herein, the first example of hybrid COF-polymer particles for which polymers are used to manipulate the 2D COF growth along a specific direction is reported. The study examines how the nature, chain-end functionality, and molar mass of the polymer influence the shaping of hybrid 2D boronate ester-linked COF-polymer particles. Catechol-poly(N-butyl acrylate) leads to the self-assembly of crystallites into quasi-spherical structures while catechol-poly(N-isopropylacrylamide) mediates the synthesis of raspberry-like COF-polymer particles with radial grain orientation. Scanning and transmission electron microscopies (SEM and TEM) and 4D-STEM-ACOM (automated crystal orientation mapping) highlight the single-crystal character of these domains with one plane family throughout the particles. Interestingly, the presence of PNIPAm on the particle surface allows their drying without co-crystallization and enables their resuspension. Kinetic investigations show that catechol-PnBuA acts as a modulator and catechol-PNIPAm induces a template effect, introducing supramolecular self-assembly properties into particles to create new morphologies with higher structural complexity, beyond the framework level.

5.
Inorg Chem ; 61(3): 1735-1744, 2022 Jan 24.
Artículo en Inglés | MEDLINE | ID: mdl-35001621

RESUMEN

The orthorhombic phase of KNbO3 perovskite has been applied for nitrogen (N2) photoreduction to ammonia (NH3). However, this material suffers from a low surface area and low ammonia production efficiency under UV light irradiation. To eliminate these barriers, we used a metal-organic framework (MOF), named as TMU-5 ([Zn(OBA)(BPDH)0.5]n·1.5DMF, where H2OBA = 4,4'-oxybis(benzoic acid) and BPDH = 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene), for the synthesis of the KNbO3@TMU-5 hybrid material. KNbO3@TMU-5 achieved a NH3 production rate of 39.9 µmol·L-1·h-1·g-1 upon UV light irradiation, as compared to 20.5 µmol·L-1·h-1·g-1 recorded for KNbO3 under similar experimental conditions. Using different characterization techniques especially gas adsorption, cyclic voltammetry, X-ray photoelectron spectroscopy, photocurrent measurements, and Fourier transform infrared spectroscopy, it has been found that the higher photoactivity of KNbO3@TMU-5 in ammonia production is due to its higher surface area, higher electron-hole separation efficiency, and higher density of negative charges on Nb sites. This work shows that hybridization of conventional semiconductors (SCs) with photoactive MOFs can improve the photoactivity of the SC@MOF hybrid material in different reactions, especially kinetically complex reactions like photoconversion of nitrogen to ammonia.

6.
Molecules ; 27(9)2022 May 05.
Artículo en Inglés | MEDLINE | ID: mdl-35566301

RESUMEN

The mechanical and physical properties of zirconium carbide (ZrC) are limited to its ability to deteriorate in oxidizing environments. Low refractory oxides are typically formed as layers on ZrC surfaces when exposed to the slightest concentrations of oxygen. However, this carbide has a wide range of applications in nuclear reactor lines and nozzle flaps in the aerospace industry, just to name a few. To develop mechanically strong and oxygen-resistant ZrC materials, the need for studying and characterizing the oxidized layers, with emphasis on the interfacial structure between ZrC and the oxidized phases, cannot be understated. In this paper, the ZrC(111)//c-ZrO2 (111) interface was studied by both finite temperature molecular dynamic simulation and DFT. The interfacial mechanical properties were characterized by the work of adhesion which revealed a Zr|OO|Zr|OO//ZrC(111) interface model as the most stable with an oxygen layer from ZrO2 being deposited on the ZrC(111) surface. Further structural analysis at the interface showed a crack in the first ZrO2 layer at the interfacial region. Investigations of the electronic structure using the density of state calculations and Bader charge analysis revealed the interfacial properties as local effects with no significant impacts in the bulk regions of the interface slab.

7.
Int J Mol Sci ; 22(4)2021 Feb 09.
Artículo en Inglés | MEDLINE | ID: mdl-33572104

RESUMEN

In this paper, we present a versatile template-directed colloidal self-assembly method for the fabrication in aqueous phase of composition-tuned mesoporous RuO2@TiO2-SiO2 catalysts. Randomly methylated ß-cyclodextrin/Pluronic F127 supramolecular assemblies were used as soft templates, TiO2 colloids as building blocks, and tetraethyl orthosilicate as a silica source. Catalysts were characterized at different stages of their synthesis using dynamic light scattering, N2-adsorption analysis, powder X-ray diffraction, temperature programmed reduction, high-resolution transmission electron microscopy, high-angle annular bright-field and dark-field scanning transmission electron microscopy, together with EDS elemental mapping. Results revealed that both the supramolecular template and the silica loading had a strong impact on the pore characteristics and crystalline structure of the mixed oxides, as well as on the morphology of the RuO2 nanocrystals. Their catalytic performance was then evaluated in the aqueous phase hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) under mild conditions (50 °C, 50 bar H2). Results showed that the cyclodextrin-derived catalyst displayed almost quantitative LA conversion and 99% GVL yield in less than one hour. Moreover, this catalyst could be reused at least five times without loss of activity. This work offers an effective approach to the utilization of cyclodextrins for engineering the surface morphology of Ru nanocrystals and pore characteristics of TiO2-based materials for catalytic applications in hydrogenation reactions.


Asunto(s)
Tecnología Química Verde/métodos , Lactonas/química , Ácidos Levulínicos/química , Rutenio/química , Catálisis , Ingeniería Química/métodos , Ciclodextrinas/química , Hidrogenación , Microscopía Electrónica de Transmisión , Nanopartículas/química , Nanopartículas/ultraestructura , Porosidad , Prueba de Estudio Conceptual , Dióxido de Silicio/química , Propiedades de Superficie , Titanio/química , Difracción de Rayos X
8.
Nanotechnology ; 30(3): 035301, 2019 Jan 18.
Artículo en Inglés | MEDLINE | ID: mdl-30452388

RESUMEN

In this paper we report on the fabrication and electrical characterization of InAs-on-nothing metal-oxide-semiconductor field-effect transistor composed of a suspended InAs channel and raised InAs n+ contacts. This architecture is obtained using 3D selective and localized molecular beam epitaxy on a lattice mismatched InP substrate. The suspended InAs channel and InAs n+ contacts feature a reproducible and uniform shape with well-defined 3D sidewalls. Devices with 1 µm gate length present a saturation drain current (I Dsat) of 300 mA mm-1 at V DS = 0.8 V and a trans-conductance (GM ) of 120 mS mm-1 at V DS = 0.5 V. In terms of electrostatic control, the devices display a minimal subthreshold swing of 110 mV dec-1 at V DS = 0.5 V and a small drain induced barrier lowering of 50 mV V-1.

9.
Phys Chem Chem Phys ; 19(9): 6569-6578, 2017 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-28203655

RESUMEN

Spinel Co2SnO4 nanoparticles are synthesized by a facile hydrothermal route in alkaline solution using SnCl4 and CoCl2 as precursors. The structure, morphology and chemical composition of the nanoparticles are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray (EDX), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). The catalytic performance of the Co2SnO4 nanoparticles is thoroughly evaluated for peroxymonosulfate (PMS) activation for removal of rhodamine B (RhB) and pentachlorophenol (PCP) from water. The influence of different process parameters on the RhB degradation efficiency is examined and the catalytic stability is evaluated. Under optimized conditions, the Co2SnO4/PMS system is very efficient with a full degradation of RhB and PCP in less than 10 min at room temperature, as revealed by high performance liquid chromatography (HPLC) analysis. Quenching experiments suggested that sulfate radicals (SO4˙-) are the main active species in the degradation process. Moreover, the Co2SnO4 catalyst is stable without any apparent activity loss after 5 cycling runs.

10.
Sensors (Basel) ; 16(10)2016 Oct 18.
Artículo en Inglés | MEDLINE | ID: mdl-27763533

RESUMEN

Perturbations in glucose homeostasis is critical for human health, as hyperglycemia (defining diabetes) leads to premature death caused by macrovascular and microvascular complications. However, the simple and accurate detection of glucose in the blood at low cost remains a challenging task, although it is of great importance for the diagnosis and therapy of diabetic patients. In this work, carbon quantum dots decorated with copper oxide nanostructures (CQDs/Cu2O) are prepared by a simple hydrothermal approach, and their potential for electrochemical non-enzymatic glucose sensing is evaluated. The proposed sensor exhibits excellent electrocatalytic activity towards glucose oxidation in alkaline solutions. The glucose sensor is characterized by a wide concentration range from 6 µM to 6 mM, a sensitivity of 2.9 ± 0.2 µA·µM-1·cm-2, and a detection limit of 6 µM at a signal-to-noise ratio S/N = 3. The sensors are successfully applied for glucose determination in human serum samples, demonstrating that the CQDs/Cu2O-based glucose sensor satisfies the requirements of complex sample detection with adapted potential for therapeutic diagnostics.

11.
Nanotechnology ; 25(47): 475705, 2014 Nov 28.
Artículo en Inglés | MEDLINE | ID: mdl-25379772

RESUMEN

Polyanilines (PANI)/reduced graphene oxide (RGO) nanocomposites are chemically synthesized. Their structure and morphology are characterized by scanning and transmission electron microscopies, x-ray diffraction and Raman spectroscopy. In addition, the nanocomposites' electrical, thermal and thermoelectric (TE) transport characteristics are investigated as a function of RGO content. The power factor and figure of merit (ZT) of PANI/RGO hybrids are deduced from measurements of the electrical conductivity (σ), Seebeck coefficient (α) and thermal conductivity (κ). Experimental results reveal that the properties of PANI/RGO composites are inherently dependent on the volume fraction of RGO. It is observed that electrical percolation follows a 2D conduction process which takes place for samples having 0.099 vol% RGO content. Unlike electrical conductivity, the thermal conductivity of PANI/RGO increases only slightly with the RGO fraction and is successfully fitted using a modified MG-EMA model which provides an interfacial (PANI/RGO nanoplatelets) resistance (Rk) of 4.9 × 10(-10) m(2) K W(-1). This low Rk value is attributed to good interactions between the planar geometry of RGO platelets and PANI aromatic rings through π-π stackings as evidenced by Raman spectroscopy and x-ray studies. Compared to that of pure PANI, the TE performance of PANI/RGO composites exhibits a ZT enhancement of two orders of magnitude.

12.
ACS Appl Mater Interfaces ; 16(12): 14852-14863, 2024 Mar 27.
Artículo en Inglés | MEDLINE | ID: mdl-38501567

RESUMEN

Among semiconductor nanomaterials, titanium dioxide is at the forefront of heterogeneous photocatalysis, but its catalytic activity greatly suffers from the loss of photoexcited charge carriers through deleterious recombination processes. Here, we investigate the impact of an external electric field (EEF) applied to conventional P25 TiO2 nanopowder with or without Au nanoparticles (NPs) to circumvent this issue. The study of two redox reactions in the gas phase, water splitting and toluene degradation, reveals an enhancement of the photocatalytic activity with rather modest electric fields of a few volt/centimeters only. Such an improvement arises from the electric-field-induced quenching of the green emission in anatase, allowing the photoexcited charge carriers to be transferred to the adsorbed reactants instead of pointless radiative recombinations. Applying an EEF across a trap-rich metal oxide material, such as TiO2, which, when impregnated with Au NPs, leads, respectively, to 12- and 6-fold enhancements in the production of hydrogen and the oxidation of toluene for an electric field of 8 V/cm, without any electrolysis, is a simple and elegant strategy to meet higher photocatalytic efficiencies.

13.
iScience ; 27(2): 108865, 2024 Feb 16.
Artículo en Inglés | MEDLINE | ID: mdl-38313056

RESUMEN

Deciphering the fossil record of cyanobacteria is crucial to understand their role in the chemical and biological evolution of the early Earth. They profoundly modified the redox conditions of early ecosystems more than 2.4 Ga ago, the age of the Great Oxidation Event (GOE), and provided the ancestor of the chloroplast by endosymbiosis, leading the diversification of photosynthetic eukaryotes. Here, we analyze the morphology, ultrastructure, chemical composition, and metals distribution of Polysphaeroides filiformis from the 1040-1006 Ma Mbuji-Mayi Supergroup (DR Congo). We evidence trilaminar and bilayered ultrastructures for the sheath and the cell wall, respectively, and the preservation of Ni-tetrapyrrole moieties derived from chlorophyll in intracellular inclusions. This approach allows an unambiguous interpretation of P. filiformis as a branched and multiseriate photosynthetic cyanobacterium belonging to the family of Stigonemataceae. It also provides a possible minimum age for the emergence of multiseriate true branching nitrogen-fixing and probably heterocytous cyanobacteria.

14.
Langmuir ; 29(41): 12688-96, 2013 Oct 15.
Artículo en Inglés | MEDLINE | ID: mdl-24083658

RESUMEN

In this Article, we report on the encapsulation of decyl-modified silicon nanoparticles (decyl-SiNPs) into ∼80 nm lipid nanocapsules (LNCs). The decyl-SiNPs were produced by thermal hydrosilylation of hydride-terminated SiNPs (H-SiNPs) liberated from porous silicon. Various techniques, including Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), UV-vis absorption, dynamic light scattering (DLS), and photoluminescence (PL), were used to characterize their size, shape, colloidal, and optical properties. The results indicate that these nanocapsules feature controllable size, good dispersity, high loading rate of SiNPs, colloidal stability in various media, and bright PL. The PL of decyl-SiNPs loaded LNCs was stable upon heating to 80 °C, but was sensitive to basic solutions due to proton-gated emission of the SiNPs arranged at the LNCs interface between the oil phase and the hydrophilic polyethylene glycol moieties of the surfactant. These luminescent nanocapsules are therefore promising candidates as cellular probes for fluorescence imaging. In addition, it was found that TEM imaging of small-sized decyl-SiNPs could be greatly improved by preliminary negative staining of TEM grids with phosphotungstic acid.


Asunto(s)
Lípidos/química , Nanopartículas/química , Silicio/química , Hidrodinámica , Tamaño de la Partícula , Porosidad , Propiedades de Superficie
15.
ACS Appl Mater Interfaces ; 15(50): 58345-58355, 2023 Dec 20.
Artículo en Inglés | MEDLINE | ID: mdl-38063412

RESUMEN

Seawater electrolysis represents a viable alternative for large-scale synthesis of hydrogen (H2), which is recognized as the most promising clean energy source, without relying on scarce fresh water. However, high energy cost and harmful chlorine chemistry in seawater limited its development. Herein, an effective catalyst based on a ruthenium nanoparticle-Ti3C2 MXene composite loaded on nickel foam (RuO2-Ti3C2/NF) with an open, fine, and homogeneous nanostructure was devised and synthesized by electrodeposition for high performance and stable overall seawater splitting. To drive a current density of 100 mA cm-2, the RuO2-Ti3C2/NF electrode required a small overpotential of 85 and 351 mV for HER and OER in 1 M KOH with only a slight increase in 1 M KOH seawater (156 and 378 mV for, respectively, HER and OER). An assembled RuO2-Ti3C2/NF-based two-electrode cell required an overpotential of only 1.84 V to acquire 100 mA cm-2 in 1 M KOH seawater and maintained its activity for over 25 h. This low cell voltage effectively prevented chlorine electrochemical evolution without anode protection. These promising results open up new avenues for the effective conversion of abundant seawater resources to hydrogen fuel.

16.
Nanomaterials (Basel) ; 12(19)2022 Sep 23.
Artículo en Inglés | MEDLINE | ID: mdl-36234441

RESUMEN

A clay-based TiO2 nanocomposite material was synthesized by a facile method, to investigate its structure and photocatalytic efficiency. The supported TiO2 nanoparticles were generated using a sol-gel method, and subsequently, mixed with a suspension of sepiolite. The material was recovered in powder form (Mc-80) and then calcined to properly arrange the crystal lattice of the TiO2 particles for use in heterogeneous photocatalysis (Mc-80-500). A powder X-ray diffractogram of Mc-80-500 revealed a dispersion of anatase and rutile phase TiO2 particles on the clay surface, exhibiting a size in the order of 4-8 nm. TEM images of Mc-80-500 confirmed the presence of isolated TiO2 beads on the surface of the fibrous sepiolite. The specific surface area of Mc-80-500 was larger than that of raw sepiolite and that of free TiO2 nanoparticles. Mc-80-500 was found to be more efficient in heterogeneous photocatalysis compared to other TiO2 materials based on sepiolite. Total depollution of a reactive dye (Orange G) was achieved after 1 h irradiation time, which is relatively quick compared to previous reports. The photocatalyst material can be washed with distilled water without chemical additives or calcination, and can be reused several times for photocatalysis, without loss of efficiency.

17.
Geobiology ; 20(5): 599-622, 2022 09.
Artículo en Inglés | MEDLINE | ID: mdl-35712885

RESUMEN

The morphogenesis of most carbonaceous microstructures that resemble microfossils in Archean (4-2.5 Ga old) rocks remains debated. The associated carbonaceous matter may even-in some cases-derive from abiotic organic molecules. Mineral growths associated with organic matter migration may mimic microbial cells, some anatomical features, and known microfossils-in particular those with simple spheroid shapes. Here, spheroid microstructures from a chert of the ca. 3.4 Ga Strelley Pool Formation (SPF) of the Pilbara Craton (Western Australia) were imaged and analyzed with a combination of high-resolution in situ techniques. This provides new insights into carbonaceous matter distributions and their relationships with the crystallographic textures of associated quartz. Thus, we describe five new types of spheroids and discuss their morphogenesis. In at least three types of microstructures, wall coalescence argues for migration of carbonaceous matter onto abiotic siliceous spherulites or diffusion in poorly crystalline silica. The nanoparticulate walls of these coalescent structures often cut across multiple quartz crystals, consistent with migration in/on silica prior to quartz recrystallization. Sub-continuous walls lying at quartz boundaries occur in some coalescent vesicles. This weakens the "continuous carbonaceous wall" criterion proposed to support cellular inferences. In contrast, some clustered spheroids display wrinkled sub-continuous double walls, and a large sphere shows a thick sub-continuous wall with pustules and depressions. These features appear consistent with post-mortem cell alteration, although abiotic morphogenesis remains difficult to rule out. We compared these siliceous and carbonaceous microstructures to coalescent pyritic spheroids from the same sample, which likely formed as "colloidal" structures in hydrothermal context. The pyrites display a smaller size and only limited carbonaceous coatings, arguing that they could not have acted as precursors to siliceous spheroids. This study revealed new textural features arguing for abiotic morphogenesis of some Archean spheroids. The absence of these features in distinct types of spheroids leaves open the microfossil hypothesis in the same rock. Distinction of such characteristics could help addressing further the origin of other candidate microfossils. This study calls for similar investigations of metamorphosed microfossiliferous rocks and of the products of in vitro growth of cell-mimicking structures in presence of organics and silica.


Asunto(s)
Fósiles , Sedimentos Geológicos , Sedimentos Geológicos/química , Minerales , Cuarzo , Dióxido de Silicio
18.
ACS Nano ; 16(2): 3081-3091, 2022 Feb 22.
Artículo en Inglés | MEDLINE | ID: mdl-35156366

RESUMEN

Oriented attachment of colloidal quantum dots allows the growth of two-dimensional crystals by design, which could have striking electronic properties upon progress on manipulating their conductivity. Here, we explore the origin of doping in square and epitaxially fused PbSe quantum dot superlattices with low-temperature scanning tunneling microscopy and spectroscopy. Probing the density of states of numerous individual quantum dots reveals an electronic coupling between the hole ground states of the quantum dots. Moreover, a small amount of quantum dots shows a reproducible deep level in the band gap, which is not caused by structural defects in the connections but arises from unpassivated sites at the {111} facets. Based on semiconductor statistics, these distinct defective quantum dots, randomly distributed in the superlattice, trap electrons, releasing a concentration of free holes, which is intimately related to the interdot electronic coupling. They act as acceptor quantum dots in the host quantum dot lattice, mimicking the role of dopant atoms in a semiconductor crystal.

19.
Biomater Adv ; 134: 112697, 2022 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-35581073

RESUMEN

The widespread of bacterial infections including biofilms drives the never-ending quest for new antimicrobial agents. Among the great variety of nanomaterials, carbon dots (CDs) are the most promising antibacterial material, but still require the adjustment of their surface properties for enhanced activity. In this contribution, we report a facile functionalization method of carbon dots (CDs) by tetraalkylammonium moieties using diazonium chemistry to improve their antibacterial activity against Gram-positive and Gram-negative bacteria. CDs were modified by novel diazonium salts bearing tetraalkylammonium moieties (TAA) with different alkyl chains (C2, C4, C9, C12) for the optimization of antibacterial activity. Variation of the alkyl chain allows to reach the significant antibacterial effect for CDs-C9 towards Gram-positive Staphylococcus aureus (S. aureus) (MIC = 3.09 ± 1.10 µg mL-1) and Gram-negative Escherichia coli (E. coli) (MIC = 7.93 ± 0.17 µg mL-1) bacteria. The antibacterial mechanism of CDs-C9 is ascribed to the balance between the positive charge and hydrophobicity of the alkyl chains. TAA moieties are responsible for enhanced adherence on the bacterial cell membrane, its penetration and disturbance of physiological metabolism. CDs-C9 were not effective in the generation of reactive oxygen species excluding the oxidative damage mechanism. In addition, CDs-C9 effectively promoted the antibiofilm treatment of S. aureus and E. coli biofilms outperforming previously-reported CDs in terms of treatment duration and minimal inhibitory concentration. The good biocompatibility of CDs-C9 was demonstrated on mouse fibroblast (NIH/3T3), HeLa and U-87 MG cell lines for concentrations up to 256 µg mL-1. Collectively, our work highlights the correlation between the surface chemistry of CDs and their antimicrobial performance.


Asunto(s)
Antibacterianos , Infecciones Estafilocócicas , Animales , Antibacterianos/farmacología , Carbono/química , Escherichia coli , Bacterias Gramnegativas , Bacterias Grampositivas/metabolismo , Ratones , Staphylococcus aureus
20.
Nanomaterials (Basel) ; 12(7)2022 Mar 29.
Artículo en Inglés | MEDLINE | ID: mdl-35407246

RESUMEN

Germanane is a two-dimensional material consisting of stacks of atomically thin germanium sheets. It's easy and low-cost synthesis holds promise for the development of atomic-scale devices. However, to become an electronic-grade material, high-quality layered crystals with good chemical purity and stability are needed. To this end, we studied the electrical transport of annealed methyl-terminated germanane microcrystallites in both high vacuum and ultrahigh vacuum. Scanning electron microscopy of crystallites revealed two types of behavior which arise from the difference in the crystallite chemistry. While some crystallites are hydrated and oxidized, preventing the formation of good electrical contact, the four-point resistance of oxygen-free crystallites was measured with multiple tips scanning tunneling microscopy, yielding a bulk transport with resistivity smaller than 1 Ω·cm. When normalized by the crystallite thickness, the resistance compares well with the resistance of hydrogen-passivated germanane flakes found in the literature. Along with the high purity of the crystallites, a thermal stability of the resistance at 280 °C makes methyl-terminated germanane suitable for complementary metal oxide semiconductor back-end-of-line processes.

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