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We investigated the impacts of spherical and triangular-plate-shaped lipid-coated silver nanoparticles (AgNPs) designed to prevent surface oxidation and silver ion (Ag+) dissolution in a small-scale microcosm to examine the role of shape and surface functionalization on biological interactions. Exposures were conducted in microcosms consisting of algae, bacteria, crustaceans, and fish embryos. Each microcosm was exposed to one of five surface chemistries within each shape profile (at 0, 0.1, or 0.5 mg Ag/L) to investigate the role of shape and surface composition on organismal uptake and toxicity. The hybrid lipid-coated AgNPs did not result in any significant release of Ag+ and had the most significant toxicity to D. magna, the most sensitive species, although the bacterial population growth rate was reduced in all exposures. Despite AgNPs resulting in increasing algal growth over the experiment, we found no correlation between algal growth and the survival of D. magna, suggesting that the impacts of the AgNPs on bacterial survival influenced algal growth rates. No significant impacts on zebrafish embryos were noted in any exposure. Our results demonstrate that the size, shape, and surface chemistry of AgNPs can be engineered to achieve specific goals while mitigating nanoparticle risks.

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Nanosized Ag and CeO2 particles obtained through the hydrothermal method were physically mixed to obtain composite antibacterial agents. The comparative experiments of antibacterial properties showed that the antibacterial activity of the nanocomposites was improved compared to the nanoparticles alone, which indicated that the synergistic antibacterial effect existed between Ag and CeO2. On the one hand, ICP-MS results showed that the existence of CeO2 suppressed the silver ion release rate and provided the composite with the ability of antibrowning; on the other, EPR data indicated that more hydroxyl radicals (·OH) were generated by the interfacial interaction between nanosized Ag and nanosized CeO2. Hence, for the Ag-CeO2 composite antibacterial agent, hydroxyl radicals played an important role in causing bacterial death.

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A robust method to prepare silver nanoclusters (AgNCs) inside a methacrylic acid-ethyl acrylate (MAA-EA) nanogel is proposed, where AgNCs were produced within the nanogel scaffold via UV-photoreduction. The impact of UV irradiation time on the formation of AgNCs and their application in biolabeling and antimicrobial properties were examined. The AgNCs formation is described by two stages; (1) Agn (n = 2-8) nanoclusters formation between 0 and 25 min, and (2) larger silver nanoparticles (AgNPs) formed via aggregation inside the nanogel. The antimicrobial performance depended on the size and concentration of silver ions (Ag+). A maximum inhibitory concentration (MIC) of 1.1 ppm was observed for antimicrobial test with yeast, and a MIC of 11 and 22 ppm was recorded for Escherichia. coli and Staphylococcus aureus respectively. Combining with the green illumination property of AgNCs (emitted at 525 nm) with dead yeast, it could be used for biolabeling. By tuning the size through photoirradiation, the nanogel templated AgNCs is a promising candidate for antimicrobial and biolabeling applications.

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The ability of silver nanoparticles (AgNPs) to be used as drug nanocarriers has helped rapidly to invent novel strategies to treat diseases, such as cancer. The nanoparticles may offer a valuable tool to novel pH-sensitive drug delivery systems in the present scenario because of their undergoing mechanisms associated with the regulated dissolution, aggregation, and generation of oxygen radicals as well. These processes could be monitored by electrochemical (bio)sensors that are less money and time-consuming compared to other analytical approaches, however, with comparable analytical performance. In this paper, synthesized and microscopically characterized gallic acid-coated AgNPs (GA-AgNPs) are investigated using spectral and electrochemical methods. To investigate the Ag+ release, a 21-day ageing experiment is performed spectrophotometrically, finding that the peak maximum of GA-AgNPs spectra diminished by 24.5%. The highest Ag+ content was electrochemically determined in the supernatant solution after centrifugation (6.97 µmol·L-1), while no significant concentration of silver ions in solution after redispersion was observed (1.26 µmol·L-1). The interaction experiment indicates a stabilization of GA-AgNPs in the presence of long-chain dsDNA as well as a mutual electrostatic interaction with DNA sugar-phosphate backbone. This interaction mechanism is confirmed by FTIR analysis, showing a shift (1049 to 1061 cm-1 and 913 to 964 cm-1) specific to DNA phosphate bands. Finally, doxorubicin-loaded GA-AgNPs are monitored for the specific drug release in the physiological and more reactive weakly acidic microenvironment. Hereby, electrochemical (bio)sensing of GA-AgNPs undergoing mechanisms shows a huge potential to be used for monitoring of drug delivery systems at cancer therapy.

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To reduce the high operational costs of water treatment because of membrane biofouling, next-generation materials are being developed to counteract microbial growth. These modern anti-biofouling strategies are based on new membrane materials or membrane surface modifications. In this study, antimicrobial films comprising rGO, rGO-CuO, rGO-Ag, and rGO-CuO-Ag were synthesized, evaluated, and tested for potential biofouling control using Pseudomonas aeruginosa PAO1 as the model bacterium. The combined rGO-CuO-Ag film displayed enhanced reduction (10-log reduction) in biofouling in comparison to the rGO film (control), followed by the rGO-Ag film (8-log reduction) and rGO-CuO film (0-log reduction). This demonstrated that the use of mixed antimicrobial agents is more effective in reducing biofouling than that of a single agent. The rGO-CuO-Ag film exhibited consistent, controlled, and moderate release of silver (Ag) ions. The release of Ag ions produced a long-lasting antimicrobial effect. These results underscore the potential applications of combined antimicrobial surface-based agents in practice and further research.

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Silver nanoparticles (Ag-NPs) can be considered as a cost-effective alternative to antibiotics. In the presence of Fe(III)-citrate and Ag+, Klebsiella oxytoca DSM 29614 produces biogenic Ag-NPs embedded in its peculiar exopolysaccharide (EPS). K. oxytoca DSM 29614 was cultivated in a defined growth medium-containing citrate (as sole carbon source) and supplemented with Ag+ and either low or high Fe(III) concentration. As inferred from elemental analysis, transmission and scanning electron microscopy, Fourier transform infrared spectrometry and dynamic light scattering, Ag-EPS NPs were produced in both conditions and contained also Fe. The production yield of high-Fe/Ag-EPS NPs was 12 times higher than the production yield of low-Fe/Ag-EPS NPs, confirming the stimulatory effect of iron. However, relative Ag content and Ag+ ion release were higher in low-Fe/Ag-EPS NPs than in high-Fe/Ag-EPS NPs, as revealed by emission-excitation spectra by luminescent spectrometry using a novel ad hoc established phycoerythrin fluorescence-based assay. Interestingly, high and low-Fe/Ag-EPS NPs showed different and growth medium-dependent minimal inhibitory concentrations against Staphylococcus aureus ATCC 29213 and Pseudomonas aeruginosa ATCC 15442. In addition, low-Fe/Ag-EPS NPs exert inhibition of staphylococcal and pseudomonal biofilm formation, while high-Fe/Ag-EPS NPs inhibits staphylococcal biofilm formation only. Altogether, these results, highlighting the different capability of Ag+ release, support the idea that Fe/Ag-EPS NPs produced by K. oxytoca DSM 29614 can be considered as promising candidates in the development of specific antibacterial and anti-biofilm agents.Key points • Klebsiella oxytoca DSM 29614 produces bimetal nanoparticles containing Fe and Ag.• Fe concentration in growth medium affects nanoparticle yield and composition.• Phycoerythrin fluorescence-based assay was developed to determine Ag+release.• Antimicrobial efficacy of bimetal nanoparticle parallels Ag+ions release.

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OBJECTIVE: To synthetize calcium aluminate (C3A) and silver-containing C3A particles (C3A+Ag) testing their effects on the properties of a MTA-based endodontic sealer in comparison to an epoxy resin- and a calcium silicate-based sealer. METHODS: Pure C3A and C3A+Ag particles were synthesized by a chemical method and characterized using XRD to identify crystalline phases. SEM/EDS analysis investigated morphology, particle size, and elemental composition of particles. Setting time, flow, radiopacity, water sorption and solubility of commercial and modified sealers were evaluated according to ISO 6876/2012. The pH and ions release were measured using a pHmeter and a microwave induced plasma optical emission spectrometer. The inhibition of biofilm growth was evaluated by confocal laser scanning microscopy (CLSM). Data were rank transformed and analyzed by ANOVA and Tukey test (P<0.05). RESULTS: The C3A particles showed an irregular grain agglomerated structure with voids and pores. In C3A+Ag particles, Ag modified the material morphology, confirming the deposition of Ag. The physicochemical properties of the modified MTA-based sealer were similar to the commercial material, except for the significant increase in Ca+2 release. However, there was no Ag release. Setting time, flow, radiopacity, water sorption and solubility were adequate for all materials. All the materials showed alkaline pH. Antibiofilm effect was improved in the presence of C3A particles, while the biofilm inhibition was lower in the presence of Ag. SIGNIFICANCE: The modified sealer presented improved antibiofilm properties and calcium release, without dramatic effects on the other characteristics. It is expected a positive effect in its antimicrobial behavior.

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Biomedical polymers are an integral component in a wide range of medical devices because of their many desirable properties. However, extensive use of polymer materials in medical devices has been associated with an increasing incidence of patient infections. Efforts to address this issue have included incorporating antimicrobial additives to develop novel antimicrobial polymeric materials. Silver, with its high toxicity towards bacteria, oligodynamic effect and good thermal stability, has been employed as an additive for polymeric medical devices. In the present study, commercially available elemental (Biogate) and ionic (Ultrafresh 16) silver additives were incorporated into a Polyamide 11 (PA 11) matrix using a compression press. These polymer composites were evaluated for their antimicrobial and ion-release properties. Elemental silver composites were shown to retain their antimicrobial properties for extended periods and actively released silver ions for 84 days; whereas ionic silver composites lost their ion-release activity and, therefore, their antibacterial activity after 56 days. Bacterial log reduction units of 3.87 for ionic silver and 2.41 for elemental silver were identified within 24 h, when tested in accordance with the ISO 22196 test standard; this indicates that ionic silver is more efficient for short-term applications than elemental silver.

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Understanding the mechanism of nanosilver-dependent antibacterial activity against microorganisms helps optimize the design and usage of the related nanomaterials. In this study, we prepared four kinds of 10 nm-sized silver nanoparticles (AgNPs) with dictated surface chemistry by capping different ligands, including citrate, mercaptopropionic acid, mercaptohexanoic acid, and mercaptopropionic sulfonic acid. Their surface-dependent chemistry and antibacterial activities were investigated. Owing to the weak bond to surface Ag, short carbon chain, and low silver ion attraction, citrate-coated AgNPs caused the highest silver ion release and the strongest antibacterial activity against Escherichia coli, when compared to the other tested AgNPs. The study on the underlying antibacterial mechanisms indicated that cellular membrane uptake of Ag, NAD+/NADH ratio increase, and intracellular reactive oxygen species (ROS) generation were significantly induced in both AgNP and silver ion exposure groups. The released silver ions from AgNPs inside cells through a Trojan-horse-type mechanism were suggested to interact with respiratory chain proteins on the membrane, interrupt intracellular O2 reduction, and induce ROS production. The further oxidative damages of lipid peroxidation and membrane breakdown caused the lethal effect on E. coli. Altogether, this study demonstrated that AgNPs exerted antibacterial activity through the release of silver ions and the subsequent induction of intracellular ROS generation by interacting with the cell membrane. The findings are helpful in guiding the controllable synthesis through the regulation of surface coating for medical care purpose.

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Silver is the most famous bactericidal element known from ancient times. Its antibacterial and antifungal effects are typically associated with the Ag ionization and concentration of Ag+ ions in a bacterial culture. Herein we thoroughly studied the influence of surface topography and roughness on the rate of Ag+ ion release. We considered two types of biocompatible and bioactive TiCaPCON-Ag films with 1 and 2 at. % of Ag and nine types of Ti surfaces with an average roughness varying in the range from 5.4 × 10-2 to 12.6 µm and different topographic features obtained through polishing, sandblasting, laser treatment, and pulsed electrospark deposition. It is demonstrated that the Ag+ ion release rates do not depend on the Ag content in the films as the main parameter, and it is other factors, such as the state of Ag agglomeration, surface topography and roughness, as well as kinetics of surface oxidation, that play a critical role. The obtained results clearly show a synergistic effect of the Ag content in the film and surface topography and roughness on Ag+ ion release. By changing the surface topographical features at a constant content of bactericidal element, we showed that the Ag+ ion release can be either accelerated by 2.5 times or almost completely suppressed. Despite low Ag+ ion concentration in physiological solution (<40 ppb), samples with specially fabricated surface reliefs (flakes or holes) showed a pronounced antibacterial effect already after 3 h of immersion in E. coli bacterial culture. Thus, our results open up new possibilities for the production of cost-effective, scalable, and biologically safe implants with pronounced antibacterial characteristics for future applications in the orthopedic field.

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A general model of an oxidative dissolution of silver particle suspensions was developed that rigorously considers the bulk and surface solute transport. A two-step surface reaction scheme was proposed that comprises the formation of the silver oxide phase by direct oxidation and the acidic dissolution of this phase leading to silver ion release. By considering this, a complete set of equations is formulated describing oxygen and silver ion transport to and from particles' surfaces. These equations are solved in some limiting cases of nanoparticle dissolution in dilute suspensions. The obtained kinetic equations were used for the interpretation of experimental data pertinent to the dissolution kinetics of citrate-stabilized silver nanoparticles. In these kinetic measurements the role of pH and bulk suspension concentration was quantitatively evaluated by using the atomic absorption spectrometry (AAS). It was shown that the theoretical model adequately reflects the main features of the experimental results, especially the significant increase in the dissolution rate for lower pH. Also the presence of two kinetic regimes was quantitatively explained in terms of the decrease in the coverage of the fast dissolving oxide layer. The overall silver dissolution rate constants characterizing these two regimes were determined.

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The rapid development of silver nanoparticles (AgNPs) based products has raised increasing concerns in view of their potential hazardous risks to the environment and human health. The roles of the released silver ions in AgNPs induced cytotoxicities are being hotly debated. Using rat cerebral astrocytes, the neurotoxicological effects of AgNPs and silver ions were investigated. Acute toxicity based on Alamar Blue assay showed that silver ions were considerably more toxic than AgNPs. Comparative studies indicated that AgNPs increased caspase activities and induced cell apoptosis under cytotoxic level of exposures, while silver ions compromised cell membrane integrity and dominantly caused cell necrosis. Cellular internalization of silver provided the basis for the cytotoxicities of these two silver species. In contrast to silver ions, intracellular reactive oxygen species (ROS) generation occurred in time- and concentration-dependent manners in astrocytes upon AgNPs stimulation, which caused subsequent c-Jun N-terminal kinases (JNK) phosphorylation and promoted the programmed cell death. Non-cytotoxic level of AgNPs exposure increased multiple cytokines secretion from the astrocytes, indicating that AgNPs were potentially involved in neuroinflammation. This effect was independent of silver ions as well. The distinct toxicological effects caused by AgNPs and silver ions provided the solid proofs for the particle-specific effects which should be concerned regarding the accurate assessment of AgNPs exposure risks.

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Biodegradable, antimicrobial composite of various silver ion concentrations was synthesized using zeta potential and isoelectric point measurements, for a controlled release of silver ions, and in addition to assess the effect of protein adsorption with the increase of the silver ion concentration. The interaction between hydroxyapatite (HAp) and silver incorporated hydroxyapatite (AgHAp) with gelatin was increased by optimally adjusting the zeta potential and isoelectric point of the ceramic (HAp and AgHAp), and bio-polymer individually. The electrostatic interactions between the ceramic and biopolymer were confirmed, through shifts in N-H stretching, decrease in the swelling ratio, and increase in the degradation temperature observed by the derivative thermo-gravimetric analysis (DTG). These results substantiate that, the zeta potential is a novel tool to increase the ceramic-biopolymer interaction. Increasing electrostatic interaction between the biopolymer and ceramic, decreases the release of silver ions in the simulated body fluid, due to the controlled degradation of the biopolymer. The isoelectric point decreases with the increase of the silver ion concentration, which evidenced the change in the net surface charge. With the increase of the silver ion concentration, the protein adsorption decreases due to an increase in hydrophilic character of the composite. This study examines the minimum concentration of silver ion essential for maximum protein adsorption, antimicrobial and hemocompatibility. This study provides a novel route to control the release of silver ions by enhancing the ceramic-polymer interaction and estimate the silver ion concentration suitable for protein adsorption. The prepared composite is nontoxic, degradable, and antimicrobial, with the controlled release of silver ions in the simulated body fluid.

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Commercial use of silver nanoparticles (AgNPs) will lead to a potential route for human exposure via potable water. Coagulation followed by sedimentation, as a conventional technique in the drinking water treatment facilities, may become an important barrier to prevent human from AgNP exposures. This study investigated the removal of AgNP suspensions by four regular coagulants. In the aluminum sulfate and ferric chloride coagulation systems, the water parameters slightly affected the AgNP removal. However, in the poly aluminum chloride and polyferric sulfate coagulation systems, the optimal removal efficiencies were achieved at pH 7.5, while higher or lower of pH could reduce the AgNP removal. Besides, the increasing natural organic matter (NOM) would reduce the AgNP removal, while Ca(2+) and suspended solids concentrations would also affect the AgNP removal. In addition, results from the transmission electron microscopy and X-ray diffraction showed AgNPs or silver-containing nanoparticles were adsorbed onto the flocs. Finally, natural water samples were used to validate AgNP removal by coagulation. This study suggests that in the case of release of AgNPs into the source water, the traditional water treatment process, coagulation/sedimentation, can remove AgNPs and minimize the silver ion concentration under the well-optimized conditions.

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