A light-assisted in situ embedment of silver nanoparticles to prepare functionalized fabrics.

This article presents a simple, one-step, in situ generation of silver nanoparticle-functionalized fabrics with antibacterial properties, circumventing the conventional, multistep, time-consuming methods. Silver nanoparticle formation was studied with a library of capping agents (branched polyethylenimine [BPEI] of molecular weight [Mw] 10,000 and 25,000, polyvinylpyrrolidone, polyethylene glycol, polyvinylalcohol and citrate) mixed with silver nitrate. The mixture was then exposed to an assortment of light wavelengths (ultraviolet, infrared and simulated solar light) for studying the light-assisted synthesis of nanoparticles. The formation of nanoparticles corresponded with the reducing capabilities of the polymers wherein BPEI gave the best response. Notably, the irradiation wavelengths had little effect on the formation of the nanoparticle when the total irradiation energy was kept constant. The feasibility of utilizing this method for in situ nanoparticle synthesis on textile fabrics (towel [100% cotton], gauze [100% cotton], rayon, felt [100% polyester] and microfiber [15% nylon, 85% polyester]) was verified by exposing the fabrics soaked in an aqueous solution of 1% (w/v) AgNO3 and 1% (w/v) BPEI (Mw 25,000) to light. The formation of nanoparticles on fabrics and their retention after washing was verified using scanning electron microscopy and quantified by inductively coupled plasma optical emission spectrometry. The functional property of the fabric as an antibacterial surface was successfully demonstrated using model bacteria such as Staphylococcus aureus, Enterococcus faecalis and Escherichia coli. The successful generation of silver nanoparticle-functionalized textile fabrics without the use of caustic chemicals, solvents and excessive heating presents a major step towards realizing a scalable green chemistry for industrial generation of functionalized fabrics for a wide range of applications.

Voltammetric Study of the Influence of Various Phosphate Anions on Silver Nanoparticle Oxidation.

The antibacterial properties of silver are strongly controlled by the redox couple of silver/silver(I). This work reports the influence of phosphate anions on silver nanoparticle oxidation, which is important given the abundance of phosphate species in biological systems. The three different species of anions were found to have a varying degree of influence on silver oxidation with the order PO4 (3-)>HPO4 (2-)>H2PO4 (-). It was found that in the presence of phosphate anions, the silver oxidation potential shifts to a less positive value, which indicated the increasing ease of the oxidation reaction of silver. Given that the interplay between silver and its cation is crucial to its antibacterial properties and significant concentrations of the HPO4 (2-) anion are present at biological pH (near neutral), it is essential that the influence of the dibasic anion (HPO4 (2-)) on silver oxidation dynamics be considered for biological systems.

'Nano-impacts': An Electrochemical Technique for Nanoparticle Sizing in Optically Opaque Solutions.

Typical laser-dependent methods such as nanoparticle tracking analysis (NTA) and dynamic light scattering (DLS) are not able to detect nanoparticles in an optically opaque medium due to scattering or absorption of light. Here, the electrochemical technique of 'nano-impacts' was used to detect nanoparticles in solution in the presence of high levels of alumina particulates causing a milky white suspension. Using the 'nano-impacts' method, silver nanoparticles were successfully detected and sized in the model opaque medium. The results obtained compared well with those using transmission electron microscopy (TEM), an ex situ method for nanoparticle size determination. The ability to use the 'nano-impacts' method in media unmeasurable to competitor techniques confers a significant advantage on the electrochemical approach.

Anodic stripping voltammetry of silver nanoparticles: aggregation leads to incomplete stripping.

The influence of nanoparticle aggregation on anodic stripping voltammetry is reported. Dopamine-capped silver nanoparticles were chosen as a model system, and melamine was used to induce aggregation in the nanoparticles. Through the anodic stripping of the silver nanoparticles that were aggregated to different extents, it was found that the peak area of the oxidative signal corresponding to the stripping of silver to silver(I) ions decreases with increasing aggregation. Aggregation causes incomplete stripping of the silver nanoparticles. Two possible mechanisms of 'partial oxidation' and 'inactivation' of the nanoparticles are proposed to account for this finding. Aggregation effects must be considered when anodic stripping voltammetry is used for nanoparticle detection and quantification. Hence, drop casting, which is known to lead to aggregation, is not encouraged for preparing electrodes for analytical purposes.

The influence of the capping agent on the oxidation of silver nanoparticles: nano-impacts versus stripping voltammetry.

The influence of capping agents on the oxidation of silver nanoparticles was studied by using the electrochemical techniques of anodic stripping voltammetry and anodic particle coulometry ("nano-impacts"). Five spherical silver nanoparticles each with a different capping agent (branched polyethylenimine (BPEI), citrate, lipoic acid, polyethylene glycol (PEG) and polyvinylpyrrolidone (PVP)) were used to perform comparative experiments. In all cases, regardless of the capping agent, complete oxidation of the single nanoparticles was seen in anodic particle coulometry. The successful quantitative detection of the silver nanoparticle size displays the potential application of anodic particle coulometry for nanoparticle characterisation. In contrast, for anodic stripping voltammetry using nanoparticles drop casting, it was observed that the capping agent has a very significant effect on the extent of silver oxidation. All five samples gave a low oxidative charge corresponding to partial oxidation. It is concluded that the use of anodic stripping voltammetry to quantify nanoparticles is unreliable, and this is attributed to nanoparticle aggregation.

Electrochemical quantification of iodide ions in synthetic urine using silver nanoparticles: a proof-of-concept.

Typical urinary iodide concentrations range from 0.3 µM to 6.0 µM. The conventional analytical method is based on the Sandell-Kolthoff reaction. It involves the toxic reagent, arsenic acid, and a waiting time of 30 minutes for the iodide ions to reduce the cerium(iv) ions. In the presented work, an alternative fast electrochemical method based on a silver nanoparticle modified electrode is proposed. Cyclic voltammetry was performed with a freshly modified electrode in presence of iodide ions and the voltammetric peaks corresponding to the oxidation of silver to silver iodide and the reverse reaction were recorded. The peak height of the reduction signal of silver iodide was used to plot a calibration line for the iodide ions. Two calibration plots for the iodide ions were obtained, one in 0.1 M sodium nitrate (a chloride-ion free environment to circumvent any interference from the other halides) and another in synthetic urine (which contains 0.2 M KCl). In both of the calibration plots, linear relationships were found between the reduction peak height and the iodide ion concentration of 0.3 µM to 6.0 µM. A slope of 1.46 × 10(-2) A M(-1) and a R(2) value of 0.999 were obtained for the iodide detection in sodium nitrate. For the synthetic urine experiments, a slope of 3.58 × 10(-3) A M(-1) and a R(2) value of 0.942 were measured. A robust iodide sensor with the potential to be developed into a point-of-care system has been validated.

Electrochemical studies of silver nanoparticles: a guide for experimentalists and a perspective.

This perspective summarises four different electrochemical techniques that have been established and frequently used to characterize various properties of silver nanoparticles. These are based on drop casting (I), in situ nanoparticle sticking and stripping (II), transfer sticking and stripping (III) or nanoparticle impacts (IV). The specific characteristics of the different methodologies are explained and contrasted with each other with the focus being on the respective benefits and limitations together with essential insights for experimentalists.

Electrochemical detection of chloride levels in sweat using silver nanoparticles: a basis for the preliminary screening for cystic fibrosis.

Cystic fibrosis is a common disease which has an associated characteristic symptom of high sweat chloride content. Thus, chloride ion quantification in sweat is important towards the screening of cystic fibrosis. Electrochemical methods, being cost effective and convenient, can be exploited for this. The electrochemical oxidation of silver nanoparticles in the absence of chloride ions gives one voltammetric signal related to the oxidation of silver to silver ions. The presence of chloride ions in the solution causes the appearance of an additional signal at a lower potential which is related to the oxidation of silver to silver chloride. This signal has a peak height which correlates linearly with the concentration of chloride ions from 2 mM to 40 mM when the electrochemical experiments are performed on silver nanoparticle modified screen printed electrodes. Thus, reliable quantification was found to be achievable. Furthermore, chloride ion levels of diluted synthetic sweat samples are measured accurately with the modified electrodes. Thus, the detection of the chloride ion concentration with a silver nanoparticle modified electrode provides a proof-of-concept for a point-of-care system for preliminary screening of cystic fibrosis.

The anodic stripping voltammetry of nanoparticles: electrochemical evidence for the surface agglomeration of silver nanoparticles.

Analytical expressions for the anodic stripping voltammetry of metallic nanoparticles from an electrode are provided. First, for reversible electron transfer, two limits are studied: that of diffusionally independent nanoparticles and the regime where the diffusion layers originating from each particle overlap strongly. Second, an analytical expression for the voltammetric response under conditions of irreversible electron transfer kinetics is also derived. These equations demonstrate how the peak potential for the stripping process is expected to occur at values negative of the formal potential for the redox process in which the surface immobilised nanoparticles are oxidised to the corresponding metal cation in the solution phase. This work is further developed by considering the surface energies of the nanoparticles and its effect on the formal potential for the oxidation. The change in the formal potential is modelled in accordance with the equations provided by Plieth [J. Phys. Chem., 1982, 86, 3166-3170]. The new analytical expressions are used to investigate the stripping of silver nanoparticles from a glassy carbon electrode. The relative invariance of the stripping peak potential at low surface coverages of silver is shown to be directly related to the surface agglomeration of the nanoparticles.