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1.
Phys Chem Chem Phys ; 26(30): 20399-20408, 2024 Jul 31.
Artigo em Inglês | MEDLINE | ID: mdl-39016092

RESUMO

In carbon dioxide electrochemical reduction (CO2ER), since isolated catalysts encounter challenges in meeting the demands of intricate processes for producing multi-carbon (C2+) products, tandem catalysis is emerging as a promising approach. Nevertheless, there remains an insufficient theoretical understanding of designing tandem catalysts. Herein, we utilized density functional theory (DFT) to screen 80 tandem catalysts for efficient CO2ER to C2 products systematically, which combines the advantages of nitrogen-doped carbon-supported transition metal single-atom catalysts (M-N-C) and copper clusters. Three crucial criteria were designed to select structures for generation and transfer of *CO and facilitate C-C coupling. The optimal Cu/RuN4-pl catalyst exhibited an excellent ethanol production capacity. Additionally, the relationship between CO adsorption strength and transfer energy barrier was established, and the influence of the electronic structure on its adsorption strength was studied. This provided a novel and well-considered solution and theoretical guidance for the design of rational composition and structurally superior tandem catalysts.

2.
Inorg Chem ; 62(48): 19677-19689, 2023 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-37977192

RESUMO

We report the synthesis and comprehensive characterization of organic-inorganic hybrid salts formed by bis-cationic N,N'-bis(2-(trimethylammonium)ethylene)perylene-3,4,9,10-tetracarboxylic acid bisimide (PTCD2+) and Keggin-type [XW12O40]n- (X = Si, n = 4; X = P, n = 3) polyoxometalates. (PTCD)3[PW12O40]2·3DMSO·2H2O (2) and (PTCD)2[SiW12O40]·DMSO·2H2O (3) were structurally characterized by single crystal X-ray diffraction. The cations in both structures exhibited infinite chainlike arrangements through π-π interactions, contrasting with the previously reported cation-anion stacking observed in naphthalene diimide derivatives. A detailed theoretical study employing topological analysis of the electron density distribution within the quantum theory of atoms in molecules approach provided further insights into this structural dualism. Atomic force microscopy analyses revealed the formation of self-assembled supramolecular structures on graphite from molecular monolayers (3 nm of thick) to submicrometer aggregates for 2. Hyperspectral Raman spectroscopy imaging revealed that such heterostructures are likely formed by an enhanced π-π interactions. Both complexes demonstrated interesting electrochemical behavior, photoluminescence and X-ray-induced luminescence. Electron spin resonance analysis confirmed charge separation in both compounds, with enhanced efficiency observed in compound 2. Our findings of these perylene-based organic-inorganic hybrid salts offer the potential for their application in optoelectronic devices and functional materials.

3.
Inorg Chem ; 61(3): 1571-1589, 2022 Jan 24.
Artigo em Inglês | MEDLINE | ID: mdl-34982539

RESUMO

δ-Bi2O3:M (M = S, Se, and Re) with an oxygen-defective fluorite-type structure is obtained by a coprecipitation method starting from the bismuth oxido cluster [Bi38O45(OMc)24(dmso)9]·2dmso·7H2O (A) in the presence of additives such as Na2SO4, Na2SeO4, NH4ReO4, Na2SeO3·5H2O, and Na2SO3. The coprecipitation of the starting materials with aqueous NaOH results in the formation of alkaline reaction mixtures, and the cubic bismuth(III)-based oxides Bi14O20(SO4) (1c), Bi14O20(SeO4) (2c), Bi14O20(ReO4.5) (3c), Bi12.25O16.625(SeO3)1.75 (4c), and Bi10.51O14.765(SO3)0.49(SO4)0.51 (5c) are obtained after microwave-assisted heating; formation of compound 5c is the result of partial oxidation of sulfur. The compounds 1c, 2c, 4c, and 5c absorb UV light only, whereas compound 3c absorbs in the visible-light region of the solar spectrum. Thermal treatment of the as-prepared metastable bismuth(III) oxide chalcogenates 1c and 2c at T = 600 °C provides a monotropic phase transition into their tetragonal polymorphs Bi14O20(SO4) (1t) and Bi14O20(SeO4) (2t), while compound 3c is transformed into the tetragonal modification of Bi14O20(ReO4.5) (3t) after calcination at T = 700 °C. Compounds of the systems Bi2O3-SOx (x = 2 and 3) and Bi2O3-Re2O7 are thermally stable up to T = 800 °C, whereas compounds of the system Bi2O3-SeO3 completely lose SeO3. Thermal treatment of 4c and 5c in air results in the oxidation of the tetravalent to hexavalent sulfur and selenium, respectively, upon heating to T = 400-500 °C. The as-prepared cubic bismuth(III)-based oxides 1c-5c were studied with regard to the photocatalytic decomposition of rhodamine B under visible-light irradiation with compound 3c showing the highest turnover and efficiency.

4.
Sensors (Basel) ; 21(12)2021 Jun 16.
Artigo em Inglês | MEDLINE | ID: mdl-34208587

RESUMO

Electrochemical sensors play a significant role in detecting chemical ions, molecules, and pathogens in water and other applications. These sensors are sensitive, portable, fast, inexpensive, and suitable for online and in-situ measurements compared to other methods. They can provide the detection for any compound that can undergo certain transformations within a potential window. It enables applications in multiple ion detection, mainly since these sensors are primarily non-specific. In this paper, we provide a survey of electrochemical sensors for the detection of water contaminants, i.e., pesticides, nitrate, nitrite, phosphorus, water hardeners, disinfectant, and other emergent contaminants (phenol, estrogen, gallic acid etc.). We focus on the influence of surface modification of the working electrodes by carbon nanomaterials, metallic nanostructures, imprinted polymers and evaluate the corresponding sensing performance. Especially for pesticides, which are challenging and need special care, we highlight biosensors, such as enzymatic sensors, immunobiosensor, aptasensors, and biomimetic sensors. We discuss the sensors' overall performance, especially concerning real-sample performance and the capability for actual field application.


Assuntos
Técnicas Biossensoriais , Nanocompostos , Técnicas Eletroquímicas , Água , Qualidade da Água
5.
Small ; 15(19): e1805228, 2019 May.
Artigo em Inglês | MEDLINE | ID: mdl-30932320

RESUMO

Direct covalent functionalization of large-area single-layer hexagonal boron nitride (hBN) with various polymer brushes under mild conditions is presented. The photopolymerization of vinyl monomers results in the formation of thick and homogeneous (micropatterned, gradient) polymer brushes covalently bound to hBN. The brush layer mechanically and chemically stabilizes the material and allows facile handling as well as long-term use in water splitting hydrogen evolution reactions.

6.
Analyst ; 144(10): 3297-3306, 2019 May 13.
Artigo em Inglês | MEDLINE | ID: mdl-30968075

RESUMO

Graphene oxide (GO) films are deposited on flexible Kapton substrates and selectively modified to conductive reduced graphene oxide (rGO) electrodes using laser patterning. Based on this, we design, fabricate, and test a flexible sensor integrating laser-reduced GO with silver plasmonic nanostructures. The fabricated device results in dual transduction channels: for electrochemical and plasmonic nanostructure-based surface-enhanced Raman spectroscopy (SERS) detection. The spectroscopic analysis verifying the formation of rGO and the modification by silver nanostructures is performed by Raman, energy dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS). The morphological investigation is followed by optical and scanning electron microscopy imaging. In addition to pristine silver nanostructures, the Raman spectroscopy results show the formation of species such as Ag2O, Ag2CO3, and Ag2SOx. A dual-channel sensor device based on electrochemical and plasmonic detection is fabricated as a demonstration of our Ag-rGO flexible concept architecture. The dual-channel device performance is successfully demonstrated in the electrochemical and SERS detection of 4-nitrobenzenethiol (4-NBT) using the same device. Our results show that without Ag nanostructures the sensitivity in the electrochemical and optical channels is not sufficient to detect 4-NBT. The performance and stability of the silver modified device are also verified. This work demonstrates an inexpensive, highly efficient, and greener way that is compatible with solution-processing technology for the production of flexible GO-based electrochemical and SERS detection devices integrated with plasmonic nanostructures.

7.
Phys Chem Chem Phys ; 21(19): 10125-10134, 2019 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-31062795

RESUMO

Raman spectroscopy is the tool of choice in the physicochemical investigation of carbon nanomaterials. However, Raman analysis of graphene oxide (GO) is lagging in comparison to the rich information gained in the case of carbon nanotubes and graphene. Here, we carried out a joint current sensing atomic force microscopy (CSAFM) and Raman spectroscopy investigation of laser-reduced GO. Reduced graphene oxide (rGO) was obtained under different laser powers in the range from 0.1 to 10 mW (532 nm). We compare the Raman spectra and the electrical conductivity at the nanoscale obtained by current sensing atomic force microscopy. Our analysis shows that three bands in the second-order region (2D, D + G, 2G), in the range from 2500 to 3200 cm-1, are uniquely sensitive to the degree of reduction. Moreover, we found that the changes in peak area ratios AD+G/AD and A2G/AD show a direct correlation with the electrical resistance of rGO. We establish an optical micro-spectroscopy way to assess the degree of reduction in laser-reduced GO. These new insights provide a convenient and useful way to investigate the reduction of rGO from the fitting analysis of Raman spectra, becoming a useful tool in fundamental research and the development of rGO-based microdevices.

8.
Inorg Chem ; 57(14): 8540-8549, 2018 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-29949355

RESUMO

The "controlled" synthesis of metastable γ-Bi2O3 by solution based approaches was reported several times recently, but the formation of Bi12SiO20 in the presence of trace amounts of silicates renders the results to be questionable. Here, the preparation of the Sillenite γ-Bi2O3 and the Sillenite-type Bi12SiO20 starting from the polynuclear bismuth oxido cluster [Bi38O45(O2CC3H5)24(DMSO)9] is reported. γ-Bi2O3 crystallizes after calcination at 800 °C of the silicate-free hydrolysis product "[Bi38O45(OH)24]" on a silver sheet. Corrosion of the substrate causes contamination with silver, which is not incorporated into the Bi-O lattice, and was removed by treatment with an aqueous KCN-solution. Bi12SiO20 was obtained after hydrothermal treatment of the bismuth oxido cluster in the presence of NaOH in glass vessels or Na2SiO3 in a Teflon-lined reactor vessel followed by calcination at 600 °C. PXRD studies, scanning electron microscopy, nitrogen adsorption measurements, IR- and Raman spectroscopy, diffuse UV-vis spectroscopy, and DSC were used for characterization. The phase transition of γ-Bi2O3 to give α-Bi2O3 occurred slowly in the temperature range of 348-510 °C ( Δ Hγ→α = 6.57 kJ·mol-1). The silver-containing γ-Bi2O3 exhibits slightly increased Raman modes compared to the silver-free sample due to the SERS effect. In the diffuse UV-vis spectrum γ-Bi2O3 exhibits an absorption edge at λ = 485 nm ( E g = 2.76 eV), and the contamination with silver results in an additional absorption edge at λ = 572 nm. Silver-free γ-Bi2O3 exhibits an absorption edge at λ = 460 nm ( E g = 2.83 eV) and Bi12SiO20 at λ = 422 nm ( E g = 3.16 eV). The photocatalytic activity of the compounds was investigated in the decomposition of aqueous rhodamine B under visible light irradiation, showing silver-containing γ-Bi2O3 to be slightly more effective compared to Bi12SiO20 and significantly more effective than the silver-free γ-Bi2O3.

9.
Nano Lett ; 17(10): 6027-6033, 2017 10 11.
Artigo em Inglês | MEDLINE | ID: mdl-28925710

RESUMO

Tip-enhanced Raman spectroscopy (TERS) has been rapidly improved over the past decade and opened up opportunities to study phonon properties of materials at the nanometer scale. In this Letter, we report on TERS of an ultrathin MoS2 flake on a nanostructured Au on silicon surface forming a two-dimensional (2D) crystal/plasmonic heterostructure. Au nanostructures (shaped in triangles) are prepared by nanosphere lithography, and then MoS2 is mechanically exfoliated on top of them. The TERS spectra acquired under resonance conditions at 638 nm excitation wavelength evidence strain changes spatially localized to regions as small as 25 nm in TERS imaging. We observe the highest Raman intensity enhancement for MoS2 on top of Au nanotriangles due to the strong electromagnetic confinement between the tip and a single triangle. Our results enable us to determine the local strain in MoS2 induced during heterostructure formation. The maximum frequency shift of E2g mode is determined to be (4.2 ± 0.8) cm-1, corresponding to 1.4% of biaxial strain induced in the MoS2 layer. We find that the regions of maximum local strain correspond to the regions of maximum topographic curvature as extracted from atomic force microscopy measurements. This tip-enhanced Raman spectroscopy study allows us to determine the built-in strain that arises when 2D materials interact with other nanostructures.

10.
Sci Total Environ ; 935: 173262, 2024 Jul 20.
Artigo em Inglês | MEDLINE | ID: mdl-38768719

RESUMO

Growing concerns about pesticide residues in agriculture are pushing the scientific community to develop innovative and efficient methods for detecting these substances at low concentrations down to the molecular level. In this context, surface-enhanced Raman spectroscopy (SERS) is a powerful analytical method that has so far already undergone some validation for its effectiveness in pesticide detection. However, despite its great potential, SERS faces significant difficulties obtaining reproducible and accurate pesticide spectra, particularly for some of the most widely used pesticides, such as malathion, chlorpyrifos, and imidacloprid. Those inconsistencies can be attributed to several factors, such as interactions between pesticides and SERS substrates and the variety of substrates and solvents used. In addition, differences in the equipment used to obtain SERS spectra and the lack of standards for control experiments further complicate the reproducibility and reliability of SERS data. This review systematically discusses the problems mentioned above, including a comprehensive analysis of the challenges in precisely evaluating SERS spectra for pesticide detection. We not only point out the existing limitations of the method, which can be traced in previous review works, but also offer practical recommendations to improve the quality and comparability of SERS spectra, thereby expanding the potential applications of the method in such an essential field as pesticide detection.

11.
Adv Mater ; 36(32): e2404411, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38837809

RESUMO

Antibiotic-resistant pathogens have become a global public health crisis, especially biofilm-induced refractory infections. Efficient, safe, and biofilm microenvironment (BME)-adaptive therapeutic strategies are urgently demanded to combat antibiotic-resistant biofilms. Here, inspired by the fascinating biological structures and functions of phages, the de novo design of a spiky Ir@Co3O4 particle is proposed to serve as an artificial phage for synergistically eradicating antibiotic-resistant Staphylococcus aureus biofilms. Benefiting from the abundant nanospikes and highly active Ir sites, the synthesized artificial phage can simultaneously achieve efficient biofilm accumulation, extracellular polymeric substance (EPS) penetration, and superior BME-adaptive reactive oxygen species (ROS) generation, thus facilitating the in situ ROS delivery and enhancing the biofilm eradication. Moreover, metabolomics found that the artificial phage obstructs the bacterial attachment to EPS, disrupts the maintenance of the BME, and fosters the dispersion and eradication of biofilms by down-regulating the associated genes for the biosynthesis and preservation of both intra- and extracellular environments. The in vivo results demonstrate that the artificial phage can treat the biofilm-induced recalcitrant infected wounds equivalent to vancomycin. It is suggested that the design of this spiky artificial phage with synergistic "penetrate and eradicate" capability to treat antibiotic-resistant biofilms offers a new pathway for bionic and nonantibiotic disinfection.


Assuntos
Antibacterianos , Bacteriófagos , Biofilmes , Espécies Reativas de Oxigênio , Biofilmes/efeitos dos fármacos , Antibacterianos/farmacologia , Antibacterianos/química , Espécies Reativas de Oxigênio/metabolismo , Staphylococcus aureus/efeitos dos fármacos , Staphylococcus aureus/fisiologia , Biocatálise , Matriz Extracelular de Substâncias Poliméricas/metabolismo , Matriz Extracelular de Substâncias Poliméricas/química , Farmacorresistência Bacteriana/efeitos dos fármacos , Animais
12.
Nanomaterials (Basel) ; 14(5)2024 Mar 06.
Artigo em Inglês | MEDLINE | ID: mdl-38470809

RESUMO

Tungsten diselenide (WSe2) has emerged as a promising ambipolar semiconductor material for field-effect transistors (FETs) due to its unique electronic properties, including a sizeable band gap, high carrier mobility, and remarkable on-off ratio. However, engineering the contacts to WSe2 remains an issue, and high contact barriers prevent the utilization of the full performance in electronic applications. Furthermore, it could be possible to tune the contacts to WSe2 for effective electron or hole injection and consequently pin the threshold voltage to either conduction or valence band. This would be the way to achieve complementary metal-oxide-semiconductor devices without doping of the channel material.This study investigates the behaviour of two-dimensional WSe2 field-effect transistors with multi-layer palladium diselenide (PdSe2) as a contact material. We demonstrate that PdSe2 contacts favour hole injection while preserving the ambipolar nature of the channel material. This consequently yields high-performance p-type WSe2 devices with PdSe2 van der Waals contacts. Further, we explore the tunability of the contact interface by selective laser alteration of the WSe2 under the contacts, enabling pinning of the threshold voltage to the valence band of WSe2, yielding pure p-type operation of the devices.

13.
ACS Sens ; 9(4): 1809-1819, 2024 04 26.
Artigo em Inglês | MEDLINE | ID: mdl-38587867

RESUMO

While most of the research in graphene-based materials seeks high electroactive surface area and ion intercalation, here, we show an alternative electrochemical behavior that leverages graphene's potential in biosensing. We report a novel approach to fabricate graphene/polymer nanocomposites with near-record conductivity levels of 45 Ω sq-1 and enhanced biocompatibility. This is realized by laser processing of graphene oxide in a sandwich structure with a thin (100 µm) polyethylene terephthalate film on a textile substrate. Such hybrid materials exhibit high conductivity, low polarization, and stability. In addition, the nanocomposites are highly biocompatible, as evidenced by their low cytotoxicity and good skin adhesion. These results demonstrate the potential of graphene/polymer nanocomposites for smart clothing applications.


Assuntos
Grafite , Lasers , Têxteis , Grafite/química , Humanos , Técnicas Eletroquímicas/métodos , Nanocompostos/química , Condutividade Elétrica , Polietilenotereftalatos/química , Animais , Materiais Biocompatíveis/química , Técnicas Biossensoriais/métodos
14.
Mater Today Bio ; 22: 100784, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37731959

RESUMO

Smart implants are increasingly used to treat various diseases, track patient status, and restore tissue and organ function. These devices support internal organs, actively stimulate nerves, and monitor essential functions. With continuous monitoring or stimulation, patient observation quality and subsequent treatment can be improved. Additionally, using biodegradable and entirely excreted implant materials eliminates the need for surgical removal, providing a patient-friendly solution. In this review, we classify smart implants and discuss the latest prototypes, materials, and technologies employed in their creation. Our focus lies in exploring medical devices beyond replacing an organ or tissue and incorporating new functionality through sensors and electronic circuits. We also examine the advantages, opportunities, and challenges of creating implantable devices that preserve all critical functions. By presenting an in-depth overview of the current state-of-the-art smart implants, we shed light on persistent issues and limitations while discussing potential avenues for future advancements in materials used for these devices.

15.
ACS Nano ; 17(3): 2943-2957, 2023 02 14.
Artigo em Inglês | MEDLINE | ID: mdl-36688804

RESUMO

The microenvironments with high reactive-oxygen-species (ROS) levels, inflammatory responses, and oxidative-stress effects in diabetic ulcer wounds, leading to poor proliferation and differentiation of stem cells, severely inhibit their efficient healing. Here, to overcome the unbalanced multielectron reactions in ROS catalysis, we develop a cobalt selenide-based biocatalyst with an amorphous Ru@CoSe nanolayer for ultrafast and broad-spectrum catalytic ROS-elimination. Owing to the enriched electrons and more unoccupied orbitals of Ru atoms, the amorphous Ru@CoSe nanolayer-equipped biocatalyst displays excellent catalase-like kinetics (maximal reaction velocity, 23.05 µM s-1; turnover number, 2.00 s-1), which exceeds most of the currently reported metal compounds. The theoretical studies show that Ru atoms act as "regulators" to tune the electronic state of the Co sites and modulate the interaction of oxygen intermediates, thus improving the reversible redox properties of active sites. Consequently, the Ru@CoSe can efficiently rescue the proliferation of mesenchymal stem cells and maintain their angiogenic potential in the oxidative stress environment. In vivo experiments reveal the superior ROS-elimination ability of Ru@CoSe on the inflammatory diabetic wound. This study offers an effective nanomedicine for catalytic ROS-scavenging and ultrafast healing of inflammatory wounds and also provides a strategy to design biocatalytic metal compounds via bringing amorphous catalytic structures.


Assuntos
Diabetes Mellitus , Cicatrização , Humanos , Espécies Reativas de Oxigênio , Cicatrização/fisiologia , Estresse Oxidativo , Metais , Oxigênio
16.
Commun Chem ; 6(1): 166, 2023 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-37580376

RESUMO

Metallic nanoparticles are widely explored for boosting light-matter coupling, optoelectronic response, and improving photocatalytic performance of two-dimensional (2D) materials. However, the target area is restricted to either top or bottom of the 2D flakes. Here, we introduce an approach for edge-specific nanoparticle decoration via light-assisted reduction of silver ions and merging of silver seeds. We observe arrays of the self-limited in size silver nanoparticles along tungsten diselenide WSe2 nanoribbon edges. The density of nanoparticles is tunable by adjusting the laser fluence. Scanning electron microscopy, atomic force microscopy, and Raman spectroscopy are used to investigate the size, distribution, and photo-response of the deposited plasmonic nanoparticles on the quasi-one-dimensional nanoribbons. We report an on-surface synthesis path for creating mixed-dimensional heterostructures and heterojunctions with potential applications in opto-electronics, plasmonics, and catalysis, offering improved light matter coupling, optoelectronics response, and photocatalytic performance of 2D materials.

17.
ACS Appl Mater Interfaces ; 15(32): 38946-38955, 2023 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-37466067

RESUMO

The concept of wearables is rapidly evolving from flexible polymer-based devices to textile electronics. The reason for this shift is the ability of textiles to ensure close contact with the skin, resulting in comfortable, lightweight, and compact "always with you" sensors. We are contributing to this polymer-textile transition by introducing a novel and simple way of laser intermixing of graphene with synthetic fabrics to create wearable sensing platforms. Our hybrid materials exhibit high electrical conductivity (87.6 ± 36.2 Ω/sq) due to the laser reduction of graphene oxide and simultaneous laser-induced graphene formation on the surface of textiles. Furthermore, the composite created between graphene and nylon ensures the durability of our materials against sonication and washing with detergents. Both of these factors are essential for real-life applications, but what is especially useful is that our free-form composites could be used as-fabricated without encapsulation, which is typically required for conventional laser-scribed materials. We demonstrate the exceptional versatility of our new hybrid textiles by successfully recording muscle activity, heartbeat, and voice. We also show a gesture sensor and an electrothermal heater embedded within a single commercial glove. Additionally, the use of these textiles could be extended to personal protection equipment and smart clothes. We achieve this by implementing self-sterilization with light and laser-induced functionalization with silver nanoparticles, which results in multifunctional antibacterial textiles. Moreover, incorporating silver into such fabrics enables their use as surface-enhanced Raman spectroscopy sensors, allowing for the direct analysis of drugs and sweat components on the clothing itself. Our research offers valuable insights into simple and scalable processes of textile-based electronics, opening up new possibilities for paradigms like the Internet of Medical Things.

18.
ACS Nano ; 17(17): 16501-16516, 2023 09 12.
Artigo em Inglês | MEDLINE | ID: mdl-37616178

RESUMO

The healing of tendon injury is often hindered by peritendinous adhesion and poor regeneration caused by the accumulation of reactive oxygen species (ROS), development of inflammatory responses, and the deposition of type-III collagen. Herein, an extracellular vesicles (EVs)-cloaked enzymatic nanohybrid (ENEV) was constructed to serve as a multifaceted biocatalyst for ultrasound (US)-augmented tendon matrix reconstruction and immune microenvironment regulation. The ENEV-based biocatalyst exhibits integrated merits for treating tendon injury, including the efficient catalase-mimetic scavenging of ROS in the injured tissue, sustainable release of Zn2+ ions, cellular uptake augmented by US, and immunoregulation induced by EVs. Our study suggests that ENEVs can promote tenocyte proliferation and type-I collagen synthesis at an early stage by protecting tenocytes from ROS attack. The ENEVs also prompted efficient immune regulation, as the polarization of macrophages (Mφ) was reversed from M1φ to M2φ. In a rat Achilles tendon defect model, the ENEVs combined with US treatment significantly promoted functional recovery and matrix reconstruction, restored tendon morphology, suppressed intratendinous scarring, and inhibited peritendinous adhesion. Overall, this study offers an efficient nanomedicine for US-augmented tendon regeneration with improved healing outcomes and provides an alternative strategy to design multifaceted artificial biocatalysts for synergetic tissue regenerative therapies.


Assuntos
Vesículas Extracelulares , Traumatismos dos Tendões , Animais , Ratos , Espécies Reativas de Oxigênio , Colágeno Tipo I , Tendões
19.
Polymers (Basel) ; 15(24)2023 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-38139874

RESUMO

Flexible electronics have sparked significant interest in the development of electrically conductive polymer-based composite materials. While efforts are being made to fabricate these composites through laser integration techniques, a versatile methodology applicable to a broad range of thermoplastic polymers remains elusive. Moreover, the underlying mechanisms driving the formation of such composites are not thoroughly understood. Addressing this knowledge gap, our research focuses on the core processes determining the integration of reduced graphene oxide (rGO) with polymers to engineer coatings that are not only flexible and robust but also exhibit electrical conductivity. Notably, we have identified a particular range of laser power densities (between 0.8 and 1.83 kW/cm2), which enables obtaining graphene polymer composite coatings for a large set of thermoplastic polymers. These laser parameters are primarily defined by the thermal properties of the polymers as confirmed by thermal analysis as well as numerical simulations. Scanning electron microscopy with elemental analysis and X-ray photoelectron spectroscopy showed that conductivity can be achieved by two mechanisms-rGO integration and polymer carbonization. Additionally, high-speed videos allowed us to capture the graphene oxide (GO) modification and melt pool formation during laser processing. The cross-sectional analysis of the laser-processed samples showed that the convective flows are present in the polymer substrate explaining the observed behavior. Moreover, the practical application of our research is exemplified through the successful assembly of a conductive wristband for wearable devices. Our study not only fills a critical knowledge gap but also offers a tangible illustration of the potential impact of laser-induced rGO-polymer integration in materials science and engineering applications.

20.
Nanomaterials (Basel) ; 13(5)2023 Mar 02.
Artigo em Inglês | MEDLINE | ID: mdl-36903801

RESUMO

Structural electronics, as well as flexible and wearable devices are applications that are possible by merging polymers with metal nanoparticles. However, using conventional technologies, it is challenging to fabricate plasmonic structures that remain flexible. We developed three-dimensional (3D) plasmonic nanostructures/polymer sensors via single-step laser processing and further functionalization with 4-nitrobenzenethiol (4-NBT) as a molecular probe. These sensors allow ultrasensitive detection with surface-enhanced Raman spectroscopy (SERS). We tracked the 4-NBT plasmonic enhancement and changes in its vibrational spectrum under the chemical environment perturbations. As a model system, we investigated the sensor's performance when exposed to prostate cancer cells' media over 7 days showing the possibility of identifying the cell death reflected in the environment through the effects on the 4-NBT probe. Thus, the fabricated sensor could have an impact on the monitoring of the cancer treatment process. Moreover, the laser-driven nanoparticles/polymer intermixing resulted in a free-form electrically conductive composite that withstands over 1000 bending cycles without losing electrical properties. Our results bridge the gap between plasmonic sensing with SERS and flexible electronics in a scalable, energy-efficient, inexpensive, and environmentally friendly way.

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