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Short peptides are attractive building blocks for the fabrication of self-assembled materials with significant biological, chemical, and physical properties. The microscopic and macroscopic properties of assemblies are usually closely related to the dimensionality of formed hydrogen bond networks. Here, two completely different supramolecular architectures connected by distinct hydrogen bond networks were obtained by simply adding a hydroxyl group to switch from cyclo-tryptophan-alanine (cyclo-WA) to cyclo-tryptophan-serine (cyclo-WS). While hydroxyl-bearing cyclo-WS molecules provided an additional hydrogen bond donor that links to adjacent molecules, forming a rigid three-dimensional network, cyclo-WA arranged into a water-mediated zipper-like structure with a softer two-dimensional layer template. This subtle alteration resulted in a 14-fold enhancement of Young's modulus values in cyclo-WS compared to cyclo-WA. Both cyclo-dipeptides exhibit biocompatibility, high fluorescence, and piezoelectricity. The demonstrated role of dimensionality of hydrogen bond networks opens new avenues for rational design of materials with precise morphologies and customizable properties for bioelectronic applications.
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Peptide-based nanomaterials can serve as promising drug delivery agents, facilitating the release of active pharmaceutical ingredients while reducing the risk of adverse reactions. We previously demonstrated that Cyclo-Histidine-Histidine (Cyclo-HH), co-assembled with cancer drug Epirubicin, zinc, and nitrate ions, can constitute an attractive drug delivery system, combining drug self-encapsulation, enhanced fluorescence, and the ability to transport the drug into cells. Here, we investigated both computationally and experimentally whether Cyclo-HH could co-assemble, in the presence of zinc and nitrate ions, with other cancer drugs with different physicochemical properties. Our studies indicated that Methotrexate, in addition to Epirubicin and its epimer Doxorubicin, and to a lesser extent Mitomycin-C and 5-Fluorouracil, have the capacity to co-assemble with Cyclo-HH, zinc, and nitrate ions, while a significantly lower propensity was observed for Cisplatin. Epirubicin, Doxorubicin, and Methorexate showed improved drug encapsulation and drug release properties, compared to Mitomycin-C and 5-Fluorouracil. We demonstrated the biocompatibility of the co-assembled systems, as well as their ability to intracellularly release the drugs, particularly for Epirubicin, Doxorubicin, and Methorexate. Zinc and nitrate were shown to be important in the co-assembly, coordinating with drugs and/or Cyclo-HH, thereby enabling drug-peptide as well as drug-drug interactions in successfully formed nanocarriers. The insights could be used in the future design of advanced cancer therapeutic systems with improved properties.
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Antineoplásicos , Neoplasias , Epirubicina/uso terapêutico , Histidina/química , Mitomicina , Nitratos , Antineoplásicos/uso terapêutico , Antineoplásicos/química , Doxorrubicina/uso terapêutico , Doxorrubicina/química , Peptídeos/química , Fluoruracila/uso terapêutico , Zinco , Neoplasias/tratamento farmacológicoRESUMO
Bacterial infections are of major medical concern due to antibiotic resistance. Carbon quantum dots (CDs) have emerged as potentially excellent biomaterials for multifunctional applications due to their low toxicity, outstanding water solubility, high fluorescence, and high biocompatibility. All of these properties allow CDs to be exceptional biomaterials for inhibiting the growth of bacteria and stopping biofilm formation due to their strong binding affinity, cell wall penetration, and solubilizing biofilm in water. Here, we describe a strategy for one-pot synthesis of histidine-derived zinc-doped N-doped CDs (Zn-NCDs) by a hydrothermal method for inhibiting the growth of both Gram-positive and Gram-negative bacteria without harming mammalian cells. The NCDs and Zn-NCDs showed uniform sizes (â¼6 nm), crystallinity, good photostability, high quantum yield (76%), and long decay time (â¼5 ns). We also studied their utilization for live cell bio-imaging and the antimicrobial properties towards the Gram-positive Staphylococcus aureus and the Gram-negative Pseudomonas aeruginosa. Importantly, the Zn-NCDs could penetrate the biofilm and bacterial cell wall to effectively inhibit the growth of bacteria and subsequently inhibit biofilm formation. Thus, the structure, chemical composition, and low toxicity properties of the newly-developed Zn-NCDs exemplify a promising novel method for the preparation of nano-level antibacterial drugs.
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Pontos Quânticos , Animais , Pontos Quânticos/química , Antibacterianos/farmacologia , Histidina , Carbono/química , Bactérias Gram-Negativas , Bactérias Gram-Positivas , Zinco/química , Água , Biofilmes , Materiais Biocompatíveis/farmacologia , MamíferosRESUMO
Carbon quantum dots (CQDs) are one of the most promising types of fluorescent nanomaterials due to their exceptional water solubility, excellent optical properties, biocompatibility, chemical inertness, excellent refractive index, and photostability. Nitrogen-containing CQDs, which include amino acid based CQDs, are especially attractive due to their high quantum yield, thermal stability, and potential biomedical applications. Recent studies have attempted to improve the preparation of amino acid based CQDs. However, the highest quantum yield obtained for these dots was only 44%. Furthermore, the refractive indices of amino acid derived CQDs were not determined. Here, we systematically explored the performance of CQDs prepared from all 20 coded amino acids using modified hydrothermal techniques allowing more passivation layers on the surface of the dots to optimize their performance. Intriguingly, we obtained the highest refractive indices ever reported for any CQDs. The values differed among the amino acids, with the highest refractive indices found for positively charged amino acids including arginine-CQDs (â¼2.1), histidine-CQDs (â¼2.0), and lysine-CQDs (â¼1.8). Furthermore, the arginine-CQDs reported here showed a nearly 2-fold increase in the quantum yield (â¼86%) and a longer decay time (â¼8.0 ns) compared to previous reports. In addition, we also demonstrated that all amino acid based CQD materials displayed excitation-dependent emission profiles (from UV to visible) and were photostable, water-soluble, noncytotoxic, and excellent for high contrast live cell imaging or bioimaging. These results indicate that amino acid based CQD materials are high-refractive-index materials applicable for optoelectronic devices, bioimaging, biosensing, and studying cellular organelles in vivo. This extraordinary RI may be highly useful for exploring cellular elements with different densities.
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Pontos Quânticos , Refratometria , Aminoácidos , Pontos Quânticos/química , Carbono/química , Água , ArgininaRESUMO
Molten metals have prospective applications as soft fluids with unique physical and chemical properties, yet materials based on them are still in their infancy and have great potential. Ultrasonic irradiation of molten metals in liquid media induces acoustic cavitation and dispersion of the liquid metal into micrometric and nanometric spheres. This review focuses on the synthesis of mmetallic materials via sonochemistry from molten metals with low melting point (< 420 á´¼C): Ga, Hg, In, Sn, Bi, Pb, and Zn, which can be melted in organic or inorganic media or water and of aqueous solutions of metallic ions to form two immiscible liquid phases. Organic molecule entrapment, polymer solubilization, chiral imprinting, and catalyst incorporation within metals or metallic particles were recently developed to provide novel hybrid nanomaterials for several applications including catalysis, fuel cells, and biomass-to-biofuel conversion. In all cases where molten metal was sonicated in an organic solvent, in addition to a solid precipitant, an interesting supernatant was obtained that contained metal-doped carbon dots (M@C-dots). Some of these M@C-dots were found to exhibit highly effective antimicrobial activity, promote neuronal tissue growth, or have utility in lithium-ion rechargeable batteries. The economic feasibility and commercial scalability of molten metal sonochemistry attract fundamental interest in the reaction mechanisms, as the versatility and controllability of the structure and material properties invite exploration of various applications.
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Ultrasonic irradiation of molten metals in liquid media causes dispersion of the metals into suspensions of micro- and nanoparticles that can be separated. This is applicable mainly to low-mp elemental metals or alloys, but higher mp elemental metals or alloys were also reported. Among metals, mercury and gallium exhibit especially-low melting points and are thus considered as liquid metals (LMs). Sonication of mercury in aqueous solutions of certain metal ions can cause simultaneous reduction of the ions and reactions between the metals. Gallium can be melted and sonicated in warm water, as well as in aqueous solutions of various solutes such as metal ions and organic compounds, which opened a wide window of interactions between the gallium particles and the solutes. Sonication of molten metals in organic liquids, such as polyethylene glycol (PEG) 400, forms carbon dots (C-dots) doped with nanoparticles of these metals. This review article summarizes the various interactions and reactions that occur upon sonication of metals in liquid media.
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This review article summarizes the comprehensive work that was done in our laboratory in recent years, as-well-as other reports, on the various aspects of sonochemistry of molten gallium. The low mp (29.8 °C) of gallium enables its melting in warm water, aqueous solutions and organic liquids. This opened a new research direction that focused on the chemical and physical properties of gallium particles that were formed in such media. It includes their interactions with water and with organic and inorganic solutes in aqueous solutions and with carbon nanoparticles. Formation of nanoparticles of liquid gallium alloys was also reported.
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The design of novel cancer drug nanocarriers is critical in the framework of cancer therapeutics. Nanomaterials are gaining increased interest as cancer drug delivery systems. Self-assembling peptides constitute an emerging novel class of highly attractive nanomaterials with highly promising applications in drug delivery, as they can be used to facilitate drug release and/or stability while reducing side effects. Here, we provide a perspective on peptide self-assembled nanocarriers for cancer drug delivery and highlight the aspects of metal coordination, structure stabilization, and cyclization, as well as minimalism. We review particular challenges in nanomedicine design criteria and, finally, provide future perspectives on addressing a portion of the challenges via self-assembling peptide systems. We consider that the intrinsic advantages of such systems, along with the increasing progress in computational and experimental approaches for their study and design, could possibly lead to novel classes of single or multicomponent systems incorporating such materials for cancer drug delivery.
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Antineoplásicos , Nanoestruturas , Neoplasias , Humanos , Sistemas de Liberação de Medicamentos , Neoplasias/tratamento farmacológico , Nanoestruturas/química , Peptídeos/química , Portadores de FármacosRESUMO
Tissue engineering (TE) is a rapidly expanding field aimed at restoring or replacing damaged tissues. In spite of significant advancements, the implementation of TE technologies requires the development of novel, highly biocompatible three-dimensional tissue structures. In this regard, the use of peptide self-assembly is an effective method for developing various tissue structures and surface functionalities. Specifically, the arginine-glycine-aspartic acid (RGD) family of peptides is known to be the most prominent ligand for extracellular integrin receptors. Due to their specific expression patterns in various human tissues and their tight association with various pathophysiological conditions, RGD peptides are suitable targets for tissue regeneration and treatment as well as organ replacement. Therefore, RGD-based ligands have been widely used in biomedical research. This review article summarizes the progress made in the application of RGD for tissue and organ development. Furthermore, we examine the effect of RGD peptide structure and sequence on the efficacy of TE in clinical and preclinical studies. Additionally, we outline the recent advancement in the use of RGD functionalized biomaterials for the regeneration of various tissues, including corneal repair, artificial neovascularization, and bone TE.
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Carbon quantum dots (CDs) are a class of emerging carbonaceous nanomaterials that have received considerable attention due to their excellent fluorescent properties, extremely small size, ability to penetrate cells and tissues, ease of synthesis, surface modification, low cytotoxicity, and superior water dispersion. In light of these properties, CDs are extensively investigated as candidates for bioimaging probes, efficient drug carriers, and disease diagnostics. Functionalized CDs represent a promising therapeutic candidate for ocular diseases. Here, this work reviews the potential use of functionalized CDs in the diagnosis and treatment of eye-related diseases, including the treatment of macular and anterior segment diseases, as well as targeting Aß amyloids in the retina.
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Nanoestruturas , Pontos Quânticos , Carbono , Diagnóstico por Imagem , Portadores de Fármacos , Corantes Fluorescentes , HumanosRESUMO
Carbon dots (CDs) are a novel type of carbon-based nanomaterial that has gained considerable attention for their unique optical properties, including tunable fluorescence, stability against photobleaching and photoblinking, and strong fluorescence, which is attributed to a large number of organic functional groups (amino groups, hydroxyl, ketonic, ester, and carboxyl groups, etc.). In addition, they also demonstrate high stability and electron mobility. This article reviews the topic of doped CDs with organic and inorganic atoms and molecules. Such doping leads to their functionalization to obtain desired physical and chemical properties for biomedical applications. We have mainly highlighted modification techniques, including doping, polymer capping, surface functionalization, nanocomposite and core-shell structures, which are aimed at their applications to the biomedical field, such as bioimaging, bio-sensor applications, neuron tissue engineering, drug delivery and cancer therapy. Finally, we discuss the key challenges to be addressed, the future directions of research, and the possibilities of a complete hybrid format of CD-based materials.
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A microporous carboxylate metal-organic framework MIL-100 Fe was prepared as submicron particles by microwave-assisted hydrothermal synthesis (Fe-MOF-MW). This product was explored, for the first time, for the preparation of polylactic acid (PLA) mixed matrix membranes. The produced MOF was characterised by powder X-ray diffraction (PXRD), environmental scanning electron microscopy (ESEM) as well as by thermogravimetric analysis (TGA) and nitrogen adsorption/desorption. The effect of different Fe-MOF-MW concentrations (0.1 and 0.5 wt%) on the membrane properties and performance were evaluated. These membranes were used in the pervaporation process for the separation of methanol/methyl tert-butyl-ether mixtures at the azeotropic point. The influence of the feed temperature and vacuum pressure on the membrane performance was evaluated and the results were compared with PLA pristine membranes. Moreover, the produced membranes have been characterised in terms of morphology, MOF dispersion in the polymeric membrane matrix, wettability, thickness, mechanical resistance and swelling propensity. The presence of Fe-MOF-MW was found to have a beneficial effect in improving the selectivity of mixed matrix membranes towards methanol at both concentrations. The highest selectivity was obtained for the PLA membranes embedded with 0.5 wt% of Fe-MOF-MW and tested at the temperature of 25 °C and vacuum pressure of 0.09 mbar.
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The current study explores the formation of active eco-friendly materials capable of preventing microbial contamination using in situ ultrasonic grafting of vanillin, curcumin and a curcumin-vanillin mixture on the surfaces of carboxymethylcellulose (CMC) and chitosan films. Spectroscopic, microscopic, physical and mechanical studies revealed that the films grafted with curcumin-vanillin mixture demonstrate improved mechanical properties and higher degree of order. The bioactivity of the prepared films was tested on food model, fresh-cut melons and films with a deposited curcumin-vanillin mixture showed superior antibacterial properties. For instance, this mixture-grafted on CMC films demonstrated a total inhibition of yeast/mold proliferation during 12 days. The HR-SEM studies of the mixture-grafted films revealed the presence of crystalline structures. Cooperative crystallization effect between the curcumin (the crystal maker) and the volatile vanillin is suggested to be responsible for the observed effects. According to our knowledge, this is the first usage of co-crystallization method in surface deposition. The results point out to a general strategy of combining a crystal maker agent with a volatile active agent during in situ sonochemical deposition to form bioactive materials that can be further used for food packaging, agriculture, pharmacology and more.
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Benzaldeídos/química , Curcumina/química , Polissacarídeos/química , Cristalização , Teste de Materiais , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
Carbon-based nanomaterials are gaining more and more interest because of their wide range of applications. Carbon dots (CDs) have shown exclusive interest due to unique and novel physicochemical, optical, electrical, and biological properties. Since their discovery, CDs became a promising material for wide range of research applications from energy to biomedical and tissue engineering applications. At same time several new methods have been developed for the synthesis of CDs. Compared to many of these methods, the sonochemical preparation is a green method with advantages such as facile, mild experimental conditions, green energy sources, and feasibility to formulate CDs and doped CDs with controlled physicochemical properties and lower toxicity. In the last five years, the sonochemically synthesized CDs were extensively studied in a wide range of applications. In this review, we discussed the sonochemical assisted synthesis of CDs, doped CDs and their nanocomposites. In addition to the synthetic route, we will discuss the effect of various experimental parameters on the physicochemical properties of CDs; and their applications in different research areas such as bioimaging, drug delivery, catalysis, antibacterial, polymerization, neural tissue engineering, dye absorption, ointments, electronic devices, lithium ion batteries, and supercapacitors. This review concludes with further research directions to be explored for the applications of sonochemical synthesized CDs.
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Materiais Biocompatíveis/química , Materiais Biocompatíveis/síntese química , Carbono/química , Pontos Quânticos/química , Sonicação , Engenharia Tecidual , Animais , Materiais Biocompatíveis/farmacologia , Catálise , HumanosRESUMO
We report the osteogenic potential of silver (Ag), gold (Au), or silver-gold doped hydroxyapatite nanoparticles (Ag-Au-HA) in zebrafish (ZF) jawbone regeneration (JBR) model. The hydroxyapatite (HA, Ca10(PO4)6(OH)2), Ag-HA, Au-HA, and Ag-Au-HA nanomaterials were synthesized by the co-precipitation procedure. The surface structures of Ag-HA, Au-HA, HA, and Ag-Au-HA were analysed by scanning electron microscopy, transmission-electron microscopy (TEM), x-ray diffraction, Fourier transform infrared (FTIR), UV-vis, energy dispersive x-ray spectroscopy (EDS), elemental mapping, and laser fluorescent spectroscopy. The TEM and EDS analysis confirmed that the Ag and Au are associated with the surface of HA nanoparticle. The chemical structure of HA, Ag-HA, Au-HA, and Ag-Au-HA nanoparticles was validated by FTIR and EDS analysis. We observed that Ag and Au are associated with HA nanoparticles by electrostatic, wander wall, and electrostatic and H-bonding interaction. The effect of Ag-HA, Au-HA, and Ag-Au-HA nanoparticles on bone regeneration was confirmed by ZF JBR model. The significant growth of ZF bone regeneration was observed in Ag-Au-HA nanoparticles as compared with HA, Ag-HA, and Au-HA nanoparticles. These results indicating a therapeutic potential of Ag-Au-HA compositions suggest these nanomaterials would be excellent for bone regeneration and fracture healing.
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Regeneração Óssea , Durapatita/química , Ouro/química , Arcada Osseodentária/fisiopatologia , Nanocompostos/química , Prata/química , Animais , Cristalografia por Raios X , Consolidação da Fratura , Ligação de Hidrogênio , Lasers , Microscopia Eletrônica de Varredura , Microscopia Eletrônica de Transmissão , Nanopartículas , Nanoestruturas , Osteogênese/efeitos dos fármacos , Espectrofotometria , Espectroscopia de Infravermelho com Transformada de Fourier , Eletricidade Estática , Engenharia Tecidual/métodos , Raios Ultravioleta , Peixe-ZebraRESUMO
Furfural is a versatile biomass-derived platform compound used for the synthesis of several strategic chemicals. The sonochemically synthesized Zn doped CuO nanoparticles (NPs) were used for the production of furfural. The catalytic activity of the Zn doped CuO NPs was examined, as a model, during the dehydration reaction of xylose to furfural. In addition to that, we have also compared the catalytic activity of the Zn doped CuO NP with ZnO NPs, ZnO bulk, CuO NPs, CuO bulk, etc. This nanoscale catalyst (Zn doped CuO NP) has a large surface area, which enhances its catalytic activity and enables it to completely convert the xylose to furfural at 150⯰C within 12â¯h without any trace of by-products, as confirmed by HPLC, 13C NMR and 1H NMR. HPLC analysis demonstrated that the yield of furfural is up to 86â¯mol %, compared to the 45â¯mol % obtained with ZnO NPs, ZnO bulk, CuO NPs, CuO bulk, etc. as catalysts.
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There is a growing need for biocompatible nanocomposites that may efficiently interact with biological tissues through multiple modalities. Carbon dots (CDs) could serve as biocompatible fluorescence nanomaterials for targeted tissue/cell imaging. Important goals toward this end are to enhance the fluorescence quantum yields of the CDs and to increase their targetability to cells. Here, sonochemistry was used to develop a one-pot synthesis of CDs, including metal-doped CDs (M@CDs), demonstrating how various experimental parameters, such as sonication time, temperature, and power of sonication affect the size of the CDs (2-10â¯nm) and their fluorescence properties. The highest measured quantum yield of emission was â¼16%. Similarly, we synthesized CDs doped with different metals (M@CDs) including Ga, Sn, Zn, Ag, and Au. The interaction of M@CDs with neuron-like cells was examined and showed efficient uptake and low cytotoxicity. Moreover, the influence of the M@CDs on the improvement of neurites during initiation and elongation growth phases were compared with pristine CDs. Our research demonstrates the use of M@CDs for imaging and for neuronal interactions. The M@CD nanocomposites are promising due to their biocompatibility, photo-stability and potential selective affinity, paving the way for multifunctional biomedical applications.
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Materiais Biocompatíveis/química , Materiais Biocompatíveis/farmacologia , Carbono/química , Corantes Fluorescentes/química , Metais/química , Neurônios/efeitos dos fármacos , Pontos Quânticos/química , Animais , Diferenciação Celular/efeitos dos fármacos , Proliferação de Células/efeitos dos fármacos , Neurônios/citologia , Células PC12 , RatosRESUMO
The in vivo delivery of therapeutic nanoparticles (NPs) represents a potentially powerful tool that can significantly alter the biological effects of pharmaceutically active compounds. Here, we report on sensitization of tumors to chemotherapy by ammonium trichloro(dioxoethylene-o,o')tellurate (AS101) encapsulated in NPs, termed AS101-NPs, developed as a composite with the biocompatible and biodegradable copolymer of poly(d,l-lactic-co-glycolic acid)-block-poly(ethylene glycol) (PLGA-b-PEG). AS101 is a potent immunomodulating agent (both in vitro and in vivo) currently undergoing phase II clinical trials for antitumor activity and sensitization of tumors to chemotherapy. Approaches that can control the pharmacokinetic parameters to regulate its clearance from the administered drug delivery system and minimize side effects are of prodigious importance. A strategy to synthesize AS101-NPs by nanoprecipitation is presented, along with their physical characterization. The influence of AS101 encapsulation on its properties was evaluated in vivo. The AS101-NPs demonstrated a significantly enhanced peritoneal macrophage count compared with AS101 administered in vivo at a conventional dosage in mouse models. Moreover, AS101 inhibited B16 melanoma lung metastasis in mice when given intraperitoneally, before or after tumor cell inoculation. A bell-shaped dose-response was observed. The frequency of AS101 administration appears to be an important factor for achieving an optimal antimetastatic effect.
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In this work, we describe a low-cost, two-step synthesis of composites of nitrogen-doped carbon quantum dots (NCDs) with γ-Fe2O3 (NCDs/γ-Fe2O3), which is based on a hydrothermal cum co-precipitation method. The product is a fine powder of particles having an average diameter of 9 ± 3 nm. The physical and chemical properties of NCDs/γ-Fe2O3 were studied, as well as the superconducting quantum interference device and Mossbauer analysis of the magnetic properties of these nanocomposites. The interaction of NCDs/γ-Fe2O3 nanocomposites with neuron-like cells was examined, showing efficient uptake and low toxicity. Our research demonstrates the use of the nanocomposites for imaging and for controlling the cellular motility. The NCDs/γ-Fe2O3 nanocomposites are promising because of their biocompatibility, photostability, and potential selective affinity, paving the way for multifunctional biomedical applications.
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Concentrated suspensions of silver and copper salts in silicone oil were heated to 200⯰C and irradiated with ultrasonic energy for different time durations. Characterization of the products was done using X-ray powder diffraction. In most cases, metallic Ag or Cu were obtained, together with their oxide forms Ag2O and Cu2O. The salts, used as precursors, do not dissolve in silicone oil but rather form a heterogeneous system, and we assume that local heating, caused by the acoustic cavitation, enhanced their thermal decomposition and the formation of metallic particles. It was found that the presence of silver particles enhances the formation of metallic copper. This phenomenon was observed in the experiment with the acetate salts mixture.