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International Journal of
eISSN: 2573-2838

Biosensors & Bioelectronics

Research Article Volume 5 Issue 5

Synthesis and characterization of silver nanoparticles and their application as an antibacterial agent

Jose Vega-Baudrit,1,2 Stephanie Marin Gamboa,1 Ericka Rodriguez Rojas,1 Veronica Vega Martinez1

1National University Heredia, Costa Rica
2National Nanotechnology Laboratory, Costa Rica

Correspondence: Jose Vega-Baudrit, Chemistry School, National University Heredia, Costa Rica

Received: September 15, 2019 | Published: October 22, 2019

Citation: Gamboa SM, Rojas ER, Martínez VV, et al. Synthesis and characterization of silver nanoparticles and their application as an antibacterial agent. Int J Biosen Bioelectron. 2019;5(5):166-173. DOI: 10.15406/ijbsbe.2019.05.00172

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Abstract

A great interest for the study of nanoscale chemical species has been studied. This review presents the main methods of chemical reduction for the preparation of silver nanoparticles, such as the preparation of silver particles using NaBH4 and ascorbic acid as a reducing and stabilizing agent, the preparation of silver particles using PVP as a reducing agent and the preparation of silver particles using DMF as a reducing agent. In addition, the main methods of characterization of silver nanoparticles are presented according to the size and morphology of the nanoparticles and the properties of surface and stability. Finally, the applicability of silver nanoparticles as an antibacterial agent is demonstrated.

Keywords: silver nanoparticles, chemical reduction method, particle size, AFM, DLS, SEM, TEM, EDS, FTIR, antibacterial agent

Abbreviations

EDS, energy dispersive X-ray spectroscopy; FT-IR, infrared spectroscopy or Fourier transform; DLS, dynamic light scattering; PCS, photon correlation spectroscopy

Introduction

At present a great interest has been visualized by the study of chemical species of nanometric size (Figure 1), this due to the applicability that has been demonstrated in chemical research areas due to its great variety of properties. Their scale of size and their metallic character makes them even more interesting in their practical application due to their biological, optical, catalytic properties, etc.1 In the nanoparticles of metals, the optical properties focus on the mass oscillation of the free conduction electrons as a result of the interaction with the electromagnetic radiation, the electric field that is formed induces the formation of a dipole in the nanoparticle which is what attributes its restorative force due to the attempt to compensate for this effect, developing in parallel the study of properties and their multiple applications.2 Silver has many uses, but undoubtedly one of the most interesting is its use as a disinfectant agent for antibacterial purposes. Due to the great boom that has existed in nanotechnology, different physical, chemical and biological methods have been developed for obtaining silver nanoparticles, so this paper seeks to describe some of the methods, their characterization and paying special attention to their capacity as an antibacterial agent.3

Figure 1 Photos of silver nanoparticles in the image nanowires, nanocubes, nanopyramides, nanoprisms.4

Chemical synthesis of silver nanoparticles

The nanoparticles have been of great scientific value since they came to reduce the gap between the bulk materials and the atomic / molecular structures, the nanoparticles of silver are the most attractive due to the high surface area by volume ratio, the surface of the Nano particles are so important and should be controlled since a change in the size of the surface can generate a change in the physical and chemical properties of the nanoparticles.4 But what does the properties of these nano particles depend on? What can we control so that the properties of them vary? When the particles reach a size between 1-100nm their properties are different at the electrical, chemical and physical levels, so it is evident that the properties are directly related to the size, so that by changing their size and shape, control is achieved of properties such as: temperature, redox potential, its color, conductivity, chemical stability, electrical qualities, optics, etc.5 Extensive studies have shown that the size, morphology, stability and properties specifically of the nano silver particles are greatly influenced by the experimental conditions of their synthesis, the kinetics of the reaction, the interaction of the ions with the reducing agents and the absorption processes of the stabilizing agent used.5 so that the specific control regarding its shape, size, distribution of the desired silver nano particle falls on the synthesis method that is selected.6 Most chemical syntheses are based on the reduction reactions of metallic silver salts, but first you must select the shape of the nano particle that is sought, if it is spherical, if it is triangular, cubic, pyramidal, rods, cylinders, (Figure 2) once the form is known, then the method that best fits the nanoparticle shape is selected, since the speed of the reaction and the interaction with the stabilizers define the shape of the nano particle (Figure 3). It should be known, what happens in a nanoparticle synthesis process? As mentioned above requires a precise control in the synthesis to control the size and shape in order to obtain a set of particles with a certain property. In a synthesis by the general we have the following components which must be known to manipulate and work them: metallic precursor, reducing agent (solvent) and stabilizing agent (Figure 4). In addition, two very important formation processes are taken into account, one is nucleation, in which a high activation energy is required for the agglomeration of the atoms and the other is that of growth where, on the contrary, a low energy of Activation for ordering in the formation of particles, is in these points of the synthesis where the shape and size are totally dependent on the speed of both processes which are controlled by parameters such as concentration, temperature, reducing power and the pH.7 On the other hand, the stabilizing agent plays a very important role in the synthesis because with its help the nanoparticles are protected in such a way that an unexpected agglomeration is prevented in the step of controlling their size and shape (Figure 5).

Figure 2 TEM images of silver NP (triangular (left), hemispherical (medium) and cubic (right) Ag nanoplates compatible in Cu-TEM grids and their structural models Study of styrene oxidation in three forms of nanoparticles silver.4

Figure 3 Study of the oxidation of styrene in three forms of nanoparticles (triangular, nano spherical and cubic plates) of silver The results of the graph show that the speed of the cubic nanoparticles is 14 times more than the triangular ones and 4 times more than the hemispherical ones.4

Figure 4 General mechanism of formation of silver nanoparticles from the chemical reduction in solution of AgNO3 salt.8

Figure 5 Silver nanoparticle synthesis method where starch functions as a stabilizing agent8

Methods of synthesis of silver nano particles

There is a wide range of methods for the synthesis of silver nanoparticles (Table 1), where the participants we select in the reaction depend, so will the shape and characteristics of the Nanoparticles, then we will detail some of the chemical synthesis methods existing, where in its vast majority from Silver Nitrate are obtained Silver Acetate and Silver Citrate, which are recrystallized and purified to be used as precursors of silver nanoparticles. Different studies show that when silver citrate is used as a silver precursor, the solution was transparent and stable over time (for at least 3 months). While when using silver nitrate or silver acetate the resulting colloidal solution was unstable and silver precipitated after 1 day.5

Method

Reducing Agent or Solvent

Stabilizer or surfactant

Particle size

Shape

Chemical

Trisodium citrate

Trisodium citrate

30-6Onm

Spherical

Chemical

NaBH4

Citrato

7nm

Spherical

Chemical

Ethyleneglycol

PVP

17±2nm

Spherical

Chemical

Paraffin

Oleylamine

10- l4nm

Spherical

Chemical

B-D-giucuose

Starch

 

Different

Chemical

DMF

APS/PVP

 

Different

Chemical

Hydrazine hydrate

AOl

2-5 nm

Spherical

Chemical

Ethyleneglycol

PVP

30-50nm

Cubic

Chemical

Pentanediol

PVP

 

Cubic

Chemical

Sodium Tartaric

PVP

 

Bars

Chemical

Ethyleneglycol

 

30-40nm

Wires

Chemical

Ethylene glycol

PVP

 

Bars

Chemical

UV Radiation

PVP/PEG

 

Sphere/Prism

Chemical

Hydrazine hydrate

PVP

50- 200nm

Triangular

Wet- Chemical

Sodium borohydride/sodium citrate

 

4 ± 2 nm

Bars

Chemical Solution

Ascorbicacid

CTAB

 

Wires

Wet-Chemical

Ascorbicacid

 

30-40nm

Wires

Physical

Electrical arc discharge

Sodium Citrate

14-27 nm

Spherical

Physical

D(-100, UV

D(- 100

3Onm

Spherical

Green

Extractos Vegetales

Vegetable extracts

30-40 nm

Spherical

Biological

Bacillus sp

Bacillus sp.

5-15 nm

Spherical

Biological

Lactobacilius

Lactobacilius Proteins

6- 15.7nm

Spherical

Biological

Shewaneila oneidensis

Shewaneila oneidensis

2-11 nm

Spherical

Biological

Fungus T. viride

Trichoderma viride

5-40 nm

Spherical

Biological

Cassia angustifoila

Cassia angustifoila

9-31 nm

Spherical

Biological

Daucus Carota

Daucus Carota

2Onm

Spherical

Biological

Bacillus Strain CS 11

Bacillus Strain CS 12

42-92 nm

Spherical

Biological

Aspergililus niger

AspergiHius niger

1-20 nm

Spherical

Biological

Arbutus unedo leaf extract

Arbutus unedo leaf extract

3-20 nm

Spherical

Biological

Leaf extracts from Eucalyptus macrocarpa

Eucalyptus macrocarpa

38 ± 2 nm

Cubic

Photochemical

Carboxymethylated chitosan (CMCTS)

CMCTS

2-8 nm

Cubic

Microwavelechnique

Ethyleneglycol

PVP

 

Wires

Microwave-Assisted

Ethylene glycol monoalkyl ethers

PVP

 

Prism

Photo chemical reduction (X-ray radiolysis)

X-ray

 

28 nm

Spherical

Electrochemical (Poiloiprocess)

Electrolysis cathode: titanium anode: Pt

PVP

11 nm

Spherical

Table 1 Synthesis of silver nanoparticles using different synthesis methods to obtain nanoparticles with different characteristics and sizes

Synthesis method 1: preparation of silver particles using NaBH4 and Ac. ascorbic as a reducing and stabilizing agent

From Silver Nitrate used as a precursor of silver nanoparticles, using ascorbic acid (99%), sodium borohydride as reducing agents also working silver nanoparticles with a concentration between 250-500mg/dm3 by the addition of silver as a precursor (silver citrate, silver nitrate or silver acetate) drop wise to an aqueous solution of sodium borohydride (Figure 6) silver nanoparticles were obtained by injecting NaBH4 solution into an aqueous solution of AgNO3 in the presence of citrate (Figure 7). In addition, a subsequent treatment to these nanospheres, using AgNO3, but now with ascorbic acid as a reducing agent, nanoparticles are obtained in the form of a rod / cable.5 The formation of these can be confirmed by means of a silver spectrum for the colloids that used silver citrate since a strong plasmon band is observed near 396nm, which confirms that the silver ions were reduced to Ag° in phase watery (Figure 8).

Figure 6 Method of chemical synthesis of nanospheres and silver nanobars.8

Figure 7 A. Preparation of a silver colloid in aqueous solution using sodium borohydride as a reducing agent.5 B. TEM image of silver nanobars.4

Figure 8 UV-VIS spectrum for a yellow silver colloid.5

Synthesis method 2: preparation of silver particles using PVP as a reducing

By means of this method of synthesis of silver, particles with various forms are obtained, simply other factors must be controlled (Figure 9). Using an aqueous solution and PVP as a stabilizing agent, the silver precursor is added, for example, to about 150mL of deionized water containing 5g of PVP for the formation of the silver colloid in a concentration of 250-500mg/dm3, adding drop wise to the silver nitrate or silver citrate solution and stirring for 1h.5 The poly (vinyl pyrrolidone) polymer (PVP) is one of the most widely used stabilizing agents for metallic nanoparticles. Thus, one of the first syntheses consisted in the photo reduction of AgNO3 in the presence of PVP as a stabilizing agent using 243nm UV radiation. With this method, silver nanoparticles between 15 and 22nm can be obtained depending on the molar ratio between AgNO3 and PVP. Subsequently, different methods have been described in which PVP acts as a stabilizing agent for silver nanoparticles synthesized by reducing silver salts with different chemical reducing agents such as potassium bitartrate or DMF and even using microwaves and the PVP itself as a reducing agent. PVP has also been used as a stabilizing agent in the reaction of AgNO3 with polyols (Polyol method) that leads to the synthesis of nanospheres, nanocubes, nano bars or silver nanowires. In general, the study of the parameters that affect the reactions and, especially, the concentration of the stabilizing polymer, allow exercising a great control over the size and shape of the silver nanoparticles.8

Figure 9 Different silver nanostructures synthesized by the reduction of silver nitrate in ethylene glycol, using polyvinylpyrrolidone as a stabilizing agent.8

Synthesis method 3: preparation of silver particles using DMF as a reducing

In this case, dimethylformamide (DMF) has been used as a solvent and as a reducing agent against silver salts under different reaction conditions (Figure 10). Thus, nanoparticles of different sizes have been achieved using aminopropyltriethoxysilane (APS) or polyvinylpyrrolidone (PVP) as stabilizing agents. When the PVP polymer is used as the stabilizing agent, silver nanoparticles (spherical or prisms) can be obtained. When APS is used, silver nanoparticles surrounded by a layer of silica are obtained. As mentioned above, the aggregation of the nanoparticles in solution can be prevented by the use of stabilizing agents. The process of forming the nanoparticles is usually similar to that described above, that is reduction of a silver salt in the presence of a reducing agent. However, the use of these agents allows, on the one hand, to avoid the aggregation of nanoparticles in organic solvents and, on the other hand, to exert precise control over their size, shape and monodispersity by modifying the reaction conditions.

Figure 10 Synthesis of silver nanoparticles using DMF as a reducing agent.8

Synthesis method 4: green method, preparation of silver particles using natural precursors

Green sources include a wide range of natural precursors that include plant extracts, bacteria, and enzymes. One of the most common sources of antioxidants used for the synthesis of silver nanoparticles is fruit juices, as they can act as coating agents and reducers. One of the examples is the pomegranate that as a rich source of polyphenols has been the target of many studies for the determination of its constituents and the attribution of its properties to its available components in the shell, mesocarp, aril and juice. New biosynthetic sources were used to obtain Ag nanoparticles, in the solution phase, the pomegranate shell extract forms a complex of natural silver, which at high temperature (300°C) is transformed into silver nanoparticles (Figure 11). However, the same complex ends in bulk metallic silver at 600°C resulting in well dispersed silver nanoparticles. In addition, the solid state reaction of a natural precursor with the silver salt exposed to high tem