Development of silver nanoparticles‐loaded calcium alginate beads embedded in gelatin scaffolds for use as wound dressings

Silver nanoparticles (AgNPs)‐loaded calcium alginate beads embedded in gelatin scaffolds were developed to sustain and maintain the release of silver (Ag⁺) ions over an extended time period. The UV irradiation technique was used to reduce Ag⁺ ions in alginate solution to AgNPs. The average sizes of AgNPs ranged between ca 20 and ca 22 nm. The AgNPs‐loaded calcium alginate beads were prepared by electrospraying of a sodium alginate solution containing AgNPs into calcium chloride (CaCl₂) solution. The AgNPs‐loaded calcium alginate beads were then embedded into gelatin scaffolds. The release characteristics of Ag⁺ ions from both the AgNPs‐loaded calcium alginate beads and the AgNPs‐loaded calcium alginate beads embedded in gelatin scaffolds were determined in either deionized water or phosphate buffer solution at 37 °C for 7 days. Moreover, the AgNPs‐loaded calcium alginate beads embedded in gelatin scaffolds were tested for their antibacterial activity and cytotoxicity. © 2014 Society of Chemical Industry     

Silver Nanoparticles Impair Cognitive Functions and Modify the Hippocampal Level of Neurotransmitters in a Coating-Dependent Manner

Due to their potent antibacterial properties, silver nanoparticles (AgNPs) are widely used in industry and medicine. However, they can cross the brain–blood barrier, posing a risk to the brain and its functions. In our previous study, we demonstrated that oral administration of bovine serum albumin (BSA)-coated AgNPs caused an impairment in spatial memory in a dose-independent manner. In this study, we evaluated the effects of AgNPs coating material on cognition, spatial memory functioning, and neurotransmitter levels in rat hippocampus. AgNPs coated with BSA (AgNPs(BSA)), polyethylene glycol (AgNPs(PEG)), or citrate (AgNPs(Cit)) or silver ions (Ag⁺) were orally administered at a dose of 0.5 mg/kg b.w. to male Wistar rats for a period of 28 days, while the control (Ctrl) rats received 0.2 mL of water. The acquisition and maintenance of spatial memory related to place avoidance were assessed using the active allothetic place avoidance task, in which rats from AgNPs(BSA), AgNPs(PEG), and Ag⁺ groups performed worse than the Ctrl rats. In the retrieval test assessing long-term memory, only rats from AgNPs(Cit) and Ctrl groups showed memory maintenance. The analysis of neurotransmitter levels indicated that the ratio between serotonin and dopamine concentration was disturbed in the AgNPs(BSA) rats. Furthermore, treatment with AgNPs or Ag⁺ resulted in the induction of peripheral inflammation, which was reflected by the alterations in the levels of serum inflammatory mediators. In conclusion, depending on the coating material used for their stabilization, AgNPs induced changes in memory functioning and concentration of neurotransmitters.     

Comparison of adsorptive features between silver ion and silver nanoparticles on nanoporous materials

The removal of Ag⁺ or AgNPs released from nano-products or effluent of WTP is important to reduce the potential risk of AgNPs. In this work, we prepared bimodal nanoporous silica (BNS) to compare the removal efficiency of Ag⁺ and AgNP with unimodal nanoporous silica (NS). To determine the adsorption capacity of Ag⁺ and AgNPs on NS and BNS, isotherm and kinetics studies was carried out at different concentrations. The results showed BNS with a bimodal nanoporous structure and a large external surface showed a higher uptake capacity and faster adsorption rate.     

黑曲霉负载银纳米颗粒的制备及其抗菌性能

采用非酶还原法,以黑曲霉菌原位还原银氨离子制备一种新型银纳米颗粒（AgNPs）/菌体复合抗菌材料,着重考察了反应温度与pH值对还原过程和所得复合材料的抗菌性能及稳定性的影响。结果表明,在温度为30℃、60℃和pH 9.5、11.5条件下,能够合成出粒径为6.9～8.2 nm的近球形AgNPs。该AgNPs均匀地分布在菌体表面上,对E.coli显示出高的抗菌性能：最小抑菌浓度(MIC)为217～434 mg·L^-1（以菌粉总质量表示）或8～20 mg Ag·L^-1（以银含量表示）。提高反应温度有利于提高菌体银负载量,但AgNPs粒径增大,抗菌性能有所下降;提高反应pH值有利于提高还原速率,而对抗菌性能影响不显著。复合材料中AgNPs与菌体结合牢固,单位质量复合材料释出的Ag⁺含量为1.7～6.8 mg·g^-1,提高反应温度和pH值后Ag⁺的释出均减少。     

Silver-doped biphasic calcium phosphate/alginate microclusters with antibacterial property and controlled doxorubicin delivery

Biphasic calcium phosphate (BCP) based materials possessed with both excellent biocompatibility and antibacterial activity show potential advantages for biomedical applications. Here, the silver-doped BCP/Alginate (_AgBA) microclusters were first fabricated using the double-emulsions method. First, BCP nanoparticles were incorporated into the alginate network to form BCP/Alginate microclusters via the emulsion process. Then, silver nanoparticles (AgNPs) were in situ involved in BCP/Alginate networks to obtain the final _AgBA microclusters. Transmission electron microscopy and scanning electron microscopy confirmed that BCP nanoparticles and AgNPs were uniformly distributed in _AgBA microclusters. The morphology of _AgBA microclusters could be regulated by adjusting emulsion power, and microclusters using the medium powder (500 W) showed a regular spherical shape. Furthermore, CCK-8 analysis identified that _AgBA microclusters were cytocompatible culturing with human bone marrow-derived mesenchymal stem cells. Qualitative antibacterial tests exhibited the excellent inhibition effects of _AgBA microclusters against Staphylococcus aureus (Gram-positive) and Escherichia coli. (Gram-negative). Lastly, the doxorubicin (DOX)-loaded _AgBA microclusters presented adjustable loading efficiency of DOX and controllable release profiles. The cumulative release could reach 73.3% after 72 h in PBS. The above results raised a new route for antibacterial microclusters development for biomedical applications.     

<Emphasis Type="Italic">Brassica rapa</Emphasis> var. <Emphasis Type="Italic">japonica</Emphasis> Leaf Extract Mediated Green Synthesis of Crystalline Silver Nanoparticles and Evaluation of Their Stability,Cytotoxicity and Antibacterial Activity

Silver nanoparticles (AgNPs) were successfully synthesized from the reduction of Ag⁺ using AgNO₃ solution as a precursor and Brassica rapa var. japonica leaf extract as a reducing and capping agent. This study was aimed at synthesis of AgNPs, exhibiting less toxicity with high antibacterial activity. The characterization of AgNPs was carried out using UV–Vis spectrometry, energy dispersive X-ray spectrometry, fourier transform infrared spectrometry, field emission scanning electron microscopy, X-ray diffraction, atomic absorption spectrometry, and transmission electron microscopy analyses. The analyses data revealed the successful synthesis of nano-crystalline Ag possessing more stability than commercial AgNPs. The cytotoxicity of Brassica AgNPs was compared with commercial AgNPs using in vitro PC12 cell model. Commercial AgNPs reduced cell viability to 23% (control 97%) and increased lactate dehydrogenase activity at a concentration of 3 ppm, whereas, Brassica AgNPs did not show any effects on both of the cytotoxicity parameters up to a concentration level of 10 ppm in PC12 cells. Moreover, Brassica AgNPs exhibited antibacterial activity in terms of zone of inhibition against E. coli (11.1?±?0.5 mm) and Enterobacter sp. (15?±?0.5 mm) which was higher than some previously reported green-synthesised AgNPs. Thus, this finding can be a matter of interest for the production and safe use of green-AgNPs in consumer products.     

Preparation and characterization of poly(styrene)/metal composites via reversible addition-fragmentation chain transfer (RAFT) polymerization

The expectant dithiocarbamate group end-functional poly(styrene) (PS) with a controlled molecular weight and low molecular weight distribution was synthesized conveniently via reversible addition-fragmentation chain transfer (RAFT) polymerization and was used to prepare polymer/metal composites with coordination chemistry. By the self-assembly technique, PS coordinated with the rare earth metal in N,N-dimethylformamide (DMF) to generate the fluorescent Eu–PS and Sm–PS complexes. Furthermore, PS-coated spherical silver nanoparticles (AgNPs) were prepared by reducing Ag⁺ to Ag⁰ under ultrasound irradiation in the presence of DMF and H₂O. The well core/shell structure of the AgNPs was characterized by transmission electron microscopy (TEM).     

A Novel Approach to Prepare Poly(Vinyl Acetate)/Ag Nanocomposite for Effective Antimicrobial Coating Applications

Polyvinyl acetate nanocomposites were successfully prepared based on silver nanoparticles. First, silver nanoparticles were directly prepared during the in situ emulsion polymerization of vinyl acetate monomer using AgNO₃ as a source of Ag⁺ ions and poly(vinyl alcohol) was used for dual functions as emulsifier for emulsion polymerization and as a stabilizing agent, trisodium citrate (C₆H₅O₇Na₃) was used as reducing agent for Ag⁺ ions during the polymerization process. The prepared polyvinyl acetate/Ag nanocomposites were assessed using X-ray diffraction, scanning electron microscopy, Fourier transform infrared, transmission electron microscopy, and ultraviolet spectra. The antibacterial properties of the prepared polyvinyl acetate/Ag nanocomposites were investigated as antimicrobial activity against pathogenic bacteria, i.e., Staphylococcus aureus (G^+ve bacteria) and Escherichia coli (G^?ve bacteria). These polyvinyl acetate nanocomposites could be used as a promising material for enhanced and continuous antibacterial applications as coating and packaging materials.     

Synthesis and Mechanism of Spherical Ag-doped Polypyrrole Assisted by Complexing Agents

Highly dispersed Ag-doped Polypyrrole (PPy) spherical composites can be efficiently synthesized via oxidative polymerization of pyrrole with FeCl₃ in an aqueous Ag⁺-containing solution in the presence of trisodium citrate, followed by concentrated ammonia treatment. However, the formation mechanisms involved in how to control the shape and how to get the metallic Ag⁰ need further investigation. In order to elucidate the formation mechanisms, the intermediates in different reaction stage were collected and investigated. Combining the experimental phenomenon and the structure characterization of the samples, it was found that citrate ions make a role of complexing Ag⁺ to produce [Ag₃(C₆H₅O₇)_n+1]^3n? complexes in the early reaction stage, then mainly play a role of steric stabilizer of AgCl micelles and are responsible for the shape tailoring of PPy composite as well as the reduction of Ag⁺ in the process of ammonia treatment. Evidently, negative-charged AgCl micelles become the main nucleation sites of pyrrole polymerization through the electrostatic attraction between the negative and positive ions. Concentrated ammonia is adopted to eliminate AgCl cores from the precursor of Ag-doped PPy composites obtained by chemical redox reaction and provides an accelerated reaction condition for reduction of Ag⁺ by reductants (citrate ion or pyrrole monomer). Ag-containing micelles induction method is a facial chemical method to obtain uniform Ag-doped composites and can be broadened to design other Ag-containing functional materials.

     

Novel antibacterial composite of coal/LLDPE loaded with silver ions

A novel antibacterial composite of coal/LLDPE (linear low density polyethylene) loaded with silver ions (ACCPE) was prepared by means of solid–liquid phase adsorption and extrusion. The composite was characterized by IR, XRD and SEM, and the mechanical, rheological, and Ag⁺‐releasing, and antibacterial properties of the composite were investigated. We discover that the ACCPE shows favorable mechanical properties, features a higher processability and antibacterial activity, and the coal and silver ion possess superimposed effect on antibacterial activity against Escherichia coli. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Poly(2‐acrylamido glycolic acid‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid): Synthesis,characterization, and retention properties for environmentally impacting metal ions

Poly(2‐acrylamido glycolic acid‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) [P(AGA‐co‐APSA)] was synthesized by radical polymerization in an aqueous solution. The water‐soluble polymer, containing secondary amide, hydroxyl, carboxylic, and sulfonic acid groups, was investigated, in view of their metal‐ion‐binding properties, as a polychelatogen with the liquid‐phase polymer‐based retention technique under different experimental conditions. The investigated metal ions were Ag⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Pb²⁺, and Cr³⁺, and these were studied at pHs 3, 5, and 7. P(AGA‐co‐APSA) showed efficient retention of all metal ions at the pHs studied, with a minimum of 60% for Co(II) at pH 3 and a maximum close to 100% at pH 7 for all metal ions. The maximum retention capacity (n metal ion/n polymer) ranged from 0.22 for Cd²⁺ to 0.34 for Ag⁺. The antibacterial activity of Ag⁺, Cu²⁺, Zn²⁺, and Cd²⁺ polymer–metal complexes was studied, and P(AGA‐co‐APSA)–Cd²⁺ presented selective antibacterial activity for Staphylococcus aureus with a minimum inhibitory concentration of 2 μg/mL. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Activity of antibacterial compounds immobilised on montmorillonite

The activities of antibacterial compounds, such as cetylpyridinium (CP), cetyltrimethylammonium (CTA), silver ions and metallic silver, immobilised on montmorillonite (MMT), were tested in Escherichia coli and Enterococcus faecium bacteria. The results of bacterial growth tests were confirmed by determination of the minimum inhibition concentrations (MICs). Unlike CP and CTA, the intercalated silver ions were easily released from MMT by ion-exchange with Na⁺ and acted as very effective antibacterial substances in the long term. Their bactericidal and bacteriostatic effects were determined. Generally, antibacterial compounds are effective when they are released from an inorganic carrier. Metallic silver was prepared by reduction of intercalated Ag⁺ with sodium borohydride. Antibacterial effects of metallic silver were not observed.     

Amino‐terminated polylactide micelles with an external poly(ethylene oxide) corona as carriers of drug‐loaded anionic liposomes

Micelles were prepared from a mixture of NH₂‐terminated poly(l ‐lactide) and poly(d ,l ‐lactide)‐block‐poly(ethylene oxide) (molar ratio of 3:7). The micelles were complexed with bilayer lipid vesicles (liposomes) composed of anionic palmitoyloleoylphosphatidylserine and zwitterionic dioleoylphosphatidylcholine in a molar ratio of 3:7. The micelles and micelle–liposome complexes were characterized using dynamic light scattering, laser electrophoresis, fluorimetry, transmission electron microscopy, enzymatic hydrolysis and cell viability with the following main findings. (i) Average diameter of micelle cores was found to be 70 ± 10 nm. (ii) Each micelle carried ca 20 000 amino groups. (iii) In a pH 7 solution the impact of the protonated NH₂ groups in the total surface of micelles was negligible owing to their screening by bulky poly(ethylene oxide) blocks. (iv) The micelles were stable in slightly acidic and neutral aqueous solutions, but aggregated in slightly alkaline solutions. (v) The micelles showed no cytotoxicity up to 0.04 mg mL^?1 concentration (the maximum concentration in the experiment). (vi) Each micelle adsorbed ca 30 anionic liposomes loaded with the antitumor antibiotic doxorubicin; the liposomes retained their integrity upon binding with micelles. (vii) The initial micelles and the micelle–liposome complexes showed two‐week stability to enzymatic hydrolysis. © 2018 Society of Chemical Industry     

Silver‐loaded lyocell fibers modified by tempo‐mediated oxidation

The purpose of this research was to accomplish antimicrobial properties in lyocell fibers by Ag⁺ ions sorption from aqueous silver nitrate solution. Sorption properties of lyocell fibers were improved by the selective TEMPO‐mediated oxidation, i.e. oxidation with sodium hypochlorite and catalytic amount of sodium bromide and 2,2,6,6‐tetramethylpiperidine‐1‐oxy radical (TEMPO). The most suitable experimental conditions for the selective TEMPO‐mediated oxidation were determined by changing oxidation conditions: concentration of sodium hypochlorite, as well as duration of sorption. The obtained results showed that the maximum sorption capacity (0.809 mmol of Ag⁺ ions per gram of fibers) of modified lyocell fibers was obtained for the sample modified with 4.84 mmol NaClO per gram of cellulose, during 1 h. The antifungal activity of the TEMPO‐oxidized lyocell fibers with silver ions against fungi from the Candida family, Candida albicans (ATCC 24433), and antibacterial activity against two strains: Staphylococcus aureus (ATCC 25923) and Escherichia coli (ATCC 25922) were confirmed in vitro. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Efficiency of silver‐based antibacterial additives and its influence in thermoplastic elastomers

Styrene‐butylene/ethylene‐styrene‐based thermoplastic elastomers (TPE) are polymers with soft touch properties that are widely used for manufacturing devices that involve hand contact. However, when contaminated with microorganisms these products can contribute to spreading diseases. The incorporation of antibacterial additives can help maintain low bacteria counts. This work evaluated the antibacterial action of TPE loaded with silver ions and silver nanoparticles. The additives nanosilver on fumed silica (NpAg_silica), silver phosphate glass (Ag⁺_phosphate), and bentonite organomodified with silver (Ag⁺_bentonite) were added to the TPE formulation. The compounds were evaluated for tensile and thermal properties and antimicrobial activity against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). All the additives eliminated over 90% of E. coli, but only NpAg_silica killed more than 80% of S. aureus population. The better effect of NpAg_silica was attributed to the additive's high specific surface area, which promoted greater contact with bacteria cells. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43956.     

Antibacterial activity of organomontmorillonites and organovermiculites prepared using chlorhexidine diacetate

Organoclays with antibacterial activity were prepared from cation exchanged Ag⁺, Cu^2 + and Zn^2 + forms of montmorillonite and vermiculite using five concentrations of chlorhexidine diacetate. The samples were characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The antibacterial activity against Enterococcus faecalis, Escherichia coli and Pseudomonas aeruginosa was evaluated by finding the minimum inhibitory concentration (MIC). All prepared organomontmorillonites and organovermiculites showed the best antibacterial activity against an E. coli bacterial strain.     

Synthesis of High‐Temperature‐Stable TiO2 and its Application on Ag+‐Activated Ceramic Tile

The main purpose of study was to provide a common synergy using Ag⁺‐doped calcium phosphate powder and high‐temperature‐stable TiO₂ for antibacterial and photocatalytic tile applications. Thermally stable SiO₂‐modified TiO₂ active layer was deposited on Ag⁺‐activated ceramic tiles by spray coating. The results showed that a nearly 100% cleanability degree was detected for SiO₂‐modified TiO₂ (TS)‐coated antibacterial tiles when compared uncoated and unmodified TiO₂‐coated tiles. Antibacterial tests and colorimetric analyses indicated that ceramic tiles provide both antibacterial and photocatalytic properties simultaneously.     

Nuclear Magnetic Resonance Investigation of the Effect of pH on Micelle Formation by the Amino Acid‐Based Surfactant Undecyl l‐Phenylalaninate

Micelle formation by the anionic amino acid‐based surfactant undecyl l ‐phenylalaninate (und‐Phe) was investigated as a function of pH in solutions containing either Na⁺, l ‐arginine, l ‐lysine, or l ‐ornithine counterions. In each mixture, the surfactant's critical micelle concentration (CMC) was the lowest at low pH and increased as solutions became more basic. Below pH 9, surfactant solutions containing l ‐arginine and l ‐lysine had lower CMC than the corresponding solutions with Na⁺ counterions. Nuclear magnetic resonance (NMR) diffusometry and dynamic light scattering studies revealed that und‐Phe micelles with Na⁺ counterions had hydrodynamic radii of approximately 15 Å throughout the investigated pH range. Furthermore, l ‐arginine, l ‐lysine, and l ‐ornithine were found to bind most strongly to the micelles below pH 9 when the counterions were cationic. Above pH 9, the counterions became zwitterionic and dissociated from the micelle surface. In und‐Phe/l ‐arginine solution, counterion dissociation was accompanied by a decrease in the hydrodynamic radius of the micelle. However, in experiments with l ‐lysine and l ‐ornithine, micelle radii remained the same at low pH when counterions were bound and at high pH when they were not. This result suggested that l ‐arginine is attached perpendicular to the micelle surface through its guanidinium functional group with the remainder of the molecule extending into solution. Contrastingly, l ‐lysine and l ‐ornithine likely bind parallel to the micelle surface with their two amine functional groups interacting with different surfactant monomers. This model was consistent with the results from two‐dimensional ROESY (rotating frame Overhauser enhancement spectroscopy) NMR experiments. Two‐dimensional NMR also showed that in und‐Phe micelles, the aromatic rings on the phenylalanine headgroups were rotated toward the hydrocarbon core of micelle.     

Formation and Growth of Micelles in Dilute Aqueous CTAB Solutions in the Presence of NaNO<Subscript>3</Subscript> and NaClO<Subscript>3</Subscript>

Self-assembly of cetyltrimethylammonium bromide (CTAB) in aqueous solution, in the presence of two inorganic salts viz, NaNO₃ and NaClO₃ was investigated by steady-state fluorescence, electrical conductance, surface tension, viscosity, dynamic light scattering (DLS) and cryogenic transmission microscopy (cryo-TEM). The counterions located at short enough distances to CTA⁺ micellar surface experience a very strong electrostatic attraction and thus become condensed. This counterion condensation plays a significant role in deciding the effective charge on the micelle, their screening interaction and structural transition of the micelles. In the present work, the probable mechanism of the salts' action in aqueous solution of CTAB is explained. The critical micelle concentration (CMC), area per molecule (Ų), micelle hydrodynamic diameter (D _h ), and aggregation number (N _agg) of CTAB micelles in the absence and presence of the salts are reported. The addition of both salts followed the lyotropic series and showed a remarkable decrease in CMC. A detailed investigation of the structural transitions from spherical to rod or even to entangled wormlike structures is presented from cryoTEM.     

Silver Nanoparticles Loaded Thermoresponsive Hybrid Nanofibrous Hydrogel as a Recyclable Dip‐Catalyst with Temperature‐Tunable Catalytic Activity

Silver nanoparticles (AgNPs) loaded thermoresponsive nanofibrous hydrogel is fabricated by electrospinning the aqueous solution containing the metal nanoparticles and poly((N‐isopropylacrylamide)‐co‐(N‐hydroxymethylacrylamide)) copolymer, followed by heat treatment. To avoid negative effect of the stabilizer or the residual reductant on their performances, the AgNPs of less than 5 nm size are synthesized through reducing Ag⁺ ions in the spinning solution by UV irradiation. The prepared nanofibrous hydrogel with desirable stability in aqueous medium has significant thermoresponsive property, and can reach its swelling or deswelling equilibrium state within 15 s with the medium temperature changing between 25 and 50 °C alternately. The smart nanofibrous hydrogel as a dip‐catalyst has the catalysis for the reduction of 4‐nitrothiophenol to 4‐aminothiophenol by NaBH₄, and its catalytic activity can be rapidly tuned by temperature. Moreover, it can be facilely recycled from the reaction system at least four times, without any loss of its catalytic activity.