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Nowadays, bacteria resistance to many antibiotics is a huge problem, especially in clinics and other parts of the healthcare system. This critical health issue requires a dynamic approach to produce new types of antibacterial coatings to combat various pathogen microbes. In this research, we prepared a new type of carbon quantum dots based on phloroglucinol using the bottom-up method. Polyurethane composite films were produced using the swell-encapsulation-shrink method. Detailed electrostatic force and viscoelastic microscopy of carbon quantum dots revealed inhomogeneous structure characterized by electron-rich/soft and electron-poor/hard regions. The uncommon photoluminescence spectrum of carbon quantum dots core had a multipeak structure. Several tests confirmed that carbon quantum dots and composite films produced singlet oxygen. Antibacterial and antibiofouling efficiency of composite films was tested on eight bacteria strains and three bacteria biofilms.
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The cost of treatment of antibiotic-resistant pathogens is on the level of tens of billions of dollars at the moment. It is of special interest to reduce or solve this problem using antimicrobial coatings, especially in hospitals or other healthcare facilities. The bacteria can transfer from medical staff or contaminated surfaces to patients. In this paper, we focused our attention on the antibacterial and antibiofouling activities of two types of photodynamic polyurethane composite films doped with carbon polymerized dots (CPDs) and fullerene C60. Detailed atomic force, electrostatic force and viscoelastic microscopy revealed topology, nanoelectrical and nanomechanical properties of used fillers and composites. A relationship between the electronic structure of the nanocarbon fillers and the antibacterial and antibiofouling activities of the composites was established. Thorough spectroscopic analysis of reactive oxygen species (ROS) generation was conducted for both composite films, and it was found that both of them were potent antibacterial agents against nosocomial bacteria (Klebsiela pneumoniae, Proteus mirabilis, Salmonela enterica, Enterococcus faecalis, Enterococcus epidermis and Pseudomonas aeruginosa). Antibiofouling testing of composite films indicated that the CPDs/PU composite films eradicated almost completely the biofilms of Pseudomonas aeruginosa and Staphylococcus aureus and about 50% of Escherichia coli biofilms.
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In this study, nanochitosan dots (ChiDs) were synthesized using gamma rays and encapsulated in bacterial cellulose (BC) polymer matrix for antibiofilm potential in photodynamic therapy. The composites were analyzed for structural changes using SEM, AFM, FTIR, XRD, EPR, and porosity measurements. Additionally, ChiD release was assessed. The results showed that the chemical composition remained unaltered, but ChiD agglomerates embedded in BC changed shape (1.5-2.5 µm). Bacterial cellulose fibers became deformed and interconnected, with increased surface roughness and porosity and decreased crystallinity. No singlet oxygen formation was observed, and the total amount of released ChiD was up to 16.10%. Antibiofilm activity was higher under green light, with reductions ranging from 48 to 57% under blue light and 78 to 85% under green light. Methicillin-resistant Staphylococcus aureus was the most sensitive strain. The new photoactive composite hydrogels show promising potential for combating biofilm-related infections.
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Carbon quantum dots as a novel type of carbon nanomaterials have attracted the attention of many researchers because of their unique optical, antibacterial, and anticancer properties as well as their biocompatibility. In this study, for the first time, carbon quantum dots were prepared from o-phenylenediamine dissolved in toluene by a solvothermal route. Subsequently, the prepared carbon quantum dots were encapsulated into polyurethane films by a swelling-encapsulation-shrink method. Analyses of the results obtained by different characterization methods (AFM, TEM, EDS, FTIR, photoluminescence, and EPR) indicate the significant influence of the precursor on structural, chemical, and optical properties. Antibacterial and cytotoxicity tests showed that these dots did not have any antibacterial potential, because of the low extent of reactive oxygen species production, and showed low dark cytotoxicity. By investigating the cellular uptake, it was established that these dots penetrated the HeLa cells and could be used as probes for bioimaging.
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Nowadays, it is a great challenge to develop new medicines for treating various infectious diseases. The treatment of these diseases is of utmost interest to further prevent the development of multi-drug resistance in different pathogens. Carbon quantum dots, as a new member of the carbon nanomaterials family, can potentially be used as a highly promising visible-light-triggered antibacterial agent. In this work, the results of antibacterial and cytotoxic activities of gamma-ray-irradiated carbon quantum dots are presented. Carbon quantum dots (CQDs) were synthesized from citric acid by a pyrolysis procedure and irradiated by gamma rays at different doses (25, 50, 100 and 200 kGy). Structure, chemical composition and optical properties were investigated by atomic force microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, UV-Vis spectrometry and photoluminescence. Structural analysis showed that CQDs have a spherical-like shape and dose-dependent average diameters and heights. Antibacterial tests showed that all irradiated dots had antibacterial activity but CQDs irradiated with dose of 100 kGy had antibacterial activity against all seven pathogen-reference bacterial strains. Gamma-ray-modified CQDs did not show any cytotoxicity toward human fetal-originated MRC-5 cells. Moreover, fluorescence microscopy showed excellent cellular uptake of CQDs irradiated with doses of 25 and 200 kGy into MRC-5 cells.
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Development of new types of antimicrobial coatings is of utmost importance due to increasing problems with pathogen transmission from various infectious surfaces to human beings. In this study, new types of highly potent antimicrobial polyurethane composite films encapsulated by hydrophobic riboflavin-based carbon polymer dots are presented. Detailed structural, optical, antimicrobial, and cytotoxic investigations of these composites were conducted. Low-power blue light triggered the composites to eradicate Escherichia coli in 30 min, whereas the same effect toward Staphylococcus aureus was reached after 60 min. These composites also show low toxicity against MRC-5 cells. In this way, RF-CPD composites can be used for sterilization of highly touched objects in the healthcare industry.
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Due to their low cost and possible green synthesis, high stability and resistance to photobleaching, graphene quantum dots (GQDs) can be considered as one of the class of carbon nanomaterials which may have great potential as an agent for photosensitized oxygen activation. In such a way, GQDs can be used as a theranostic agent in photodynamic therapy. In this work pristine GQDs, GQDs irradiated with gamma rays and GQDs doped with N and N, S atoms are produced using a simple, green approach. By using different techniques (AFM, HR-TEM, SEM-EDS, FTIR, XRD, PL and UV-Vis) we investigated structural and optical properties of the new types of GQDs. We showed that GQDs functionalized with thiourea (GQDs-TU) completely lost the ability to produce singlet oxygen (1O2) upon photoexcitation while functionalization with urea (GQDs-U) improves the capability of GQDs to produce 1O2 upon the same conditions. Thus, presented GQDs modification with urea seems like a promising approach for the production of the efficient photosensitizer. On the opposite, GQDs-TU are efficient OH quencher. Due to high singlet oxygen production and low cytotoxicity below 100⯵g/mL against HeLa cells, GQDs-U is a good candidate as an agent in photodynamic therapy at this concentration.
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Grafite , Neoplasias/tratamento farmacológico , Fotoquimioterapia , Fármacos Fotossensibilizantes , Pontos Quânticos , Oxigênio Singlete/química , Tioureia , Grafite/química , Grafite/farmacologia , Células HeLa , Humanos , Neoplasias/metabolismo , Neoplasias/patologia , Fármacos Fotossensibilizantes/química , Fármacos Fotossensibilizantes/farmacologia , Pontos Quânticos/química , Pontos Quânticos/uso terapêutico , Tioureia/química , Tioureia/farmacologiaRESUMO
Due to controversial reports concerning antibacterial activity of different graphene based materials it is very important to investigate their antibacterial action on a wide range of Gram-positive and Gram-negative bacteria. In this paper we have investigated the structure induced phototoxic antibacterial activity of four types of graphene based materials: graphene oxide (GO), graphene quantum dots (GQDs), carbon quantum dots (CQDs) and nitrogen doped carbon quantum dots (N-CQDs). Antibacterial activity was tested on 19 types of bacteria. It is found that nanometer-size CQDs and N-CQDs are the most potent agents whereas micrometer-size GO has very poor antibacterial activity. Electron paramagnetic resonance measurements confirmed photodynamic production of singlet oxygen for all types of used quantum dots. Detailed analysis has shown that N-CQDs are an excellent photodynamic antibacterial agent for treatment of bacterial infections induced by Enterobacter aerogenes (E. aerogenes), Proteus mirabilis (P. mirabilis), Staphylococcus saprophyticus (S. saprophyticus), Listeria monocytogenes (L. monocytogenes), Salmonella typhimurium (S. typhimurium) and Klebsiella pneumoniae.
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Electrochemically exfoliated graphene is functionalized graphene with potential application in biomedicine. Two most relevant biological features of this material are its electrical conductivity and excellent water dispersibility. In this study we have tried to establish the correlation between graphene structure and its antibacterial properties. The exfoliation process was performed in a two electrode-highly oriented pyrolytic graphite electrochemical cell. Solution of ammonium persulfate was used as an electrolyte. Exfoliated graphene sheets were dispersed in aqueous media and characterized by atomic force microscopy, scanning electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, X photoelectron spectroscopy, X-ray diffraction, electron paramagnetic resonance, zeta potential, contact angle measurements and surface energy. Antibacterial assays have shown lack of the significant antibacterial activity. Major effect on bacteria was slight change of bacteria morphology. Membrane remained intact despite significant change of chemical content of membrane components.
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Herein, the ability of gamma irradiation to enhance the photoluminescence properties of graphene quantum dots (GQDs) was investigated. Different doses of γ-irradiation were used on GQDs to examine the way in which their structure and optical properties can be affected. The photoluminescence quantum yield was increased six times for the GQDs irradiated with high doses compared to the nonirradiated material. Both photoluminescence lifetime and values of optical band gap were increased with the dose of applied gamma irradiation. In addition, the exploitation of the gamma-irradiated GQDs as photosensitizers was examined by monitoring the production of singlet oxygen under UV illumination. The main outcome was that the GQDs irradiated at lower doses act as better photoproducers than the ones irradiated at higher doses. These results corroborate that the structural changes caused by gamma irradiation have a direct impact on GQD ability to produce singlet oxygen and their photostability under prolonged UV illumination. This makes low-dose irradiated GQDs promising candidates for photodynamic therapy.
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Raios gama , Grafite/química , Luminescência , Fotoquimioterapia/métodos , Pontos Quânticos/química , Espectroscopia de Ressonância de Spin Eletrônica , Microscopia de Força Atômica , Tamanho da Partícula , Fármacos Fotossensibilizantes/farmacologia , Oxigênio Singlete/química , Espectrofotometria Ultravioleta , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
The excellent photoluminescent properties of graphene quantum dots (GQD) makes them suitable candidates for biomedical applications, but their cytotoxicity has not been extensively studied. Here we show that electrochemically produced GQD irradiated with blue light (470 nm, 1W) generate reactive oxygen species, including singlet oxygen, and kill U251 human glioma cells by causing oxidative stress. The cell death induced by photoexcited GQD displayed morphological and/or biochemical characteristics of both apoptosis (phosphatidylserine externalization, caspase activation, DNA fragmentation) and autophagy (formation of autophagic vesicles, LC3-I/LC3-II conversion, degradation of autophagic target p62). Moreover, a genetic inactivation of autophagy-essential LC3B protein partly abrogated the photodynamic cytotoxicity of GQD. These data indicate potential usefulness of GQD in photodynamic therapy, but also raise concerns about their possible toxicity.