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SYNTHESIS OF SILVER NANOPARTICLES, MULTIFUNCTIONAL PROPERTIES AND APPLICATIONS IN BIOMEDICINE AND ENVIRONMENT.

Byline: S. Shaheen, M.A. Iqbal, S. Kanwal, H.Z. Batool, S. Ashraf and M. Furqan

Keywords: synthesis, nano particles, silver, properties, antibacterial activity, bio medical application, photonics.

INTRODUCTION

The prefix nano comes from "nanos" which is Greek word and indicates one billionth parts or 10-9 units. Nano technology is a fast growing field as it produces nano particles including nano products that can have wide range of properties differing from larger matter. It also includes synthesis and development of various nano materials. Nano particles refer those particles which size range from 1 to 100 nm. Particles in this range show properties which differ from the bulk materials both chemically and physically, mainly because of huge surface and volume ratio. One of the techniques to synthesize nano particles is top down where size of the material is made to decrease. The other one is bottom up which breaks up large sized particles to make nano materials. Nano technology is the science of very small and is used to manipulate matter at very small scale. This technique not only affects a specific area but it also simply means the production of extremely small products.

With the help of this technology, new nano sized materials can be synthesized for their application at atomic and molecular scales. (Pal et al., 2011) The classification of nano particles requires its dimensions. 1D structure includes thin films that are widely used in engineering and electronics such as storage system, biological and chemicals sensors, and many optical devices. Carbon nano tubes are example of two dimensional nano particles that are one nano meter in diameter and length is abouy100 nm. Because of high current density of carbon nano tubes i.e., billion amperes/m2, it behaves as a supper conductor. Due to this mechanical strength of CNT's, it is 60 times greater than other best steel. Fullerenes are example of three dimensional nano particles. They display remarkable physical properties.e.g. when extreme pressure is applied on them, the shape changes but as some of pressure is released they regain the original shape. They are also used in the production of solar cells.

Synthesis of noble metal Nps is an area of immense attention, for the reason that their applications in the field of optics, electronics, biotechnology and environmental sciences. Gold and silver Nps are widely utilized for the production of steady dispersion of nano particles to be used in optoelectronic devices, such as, photography, and photonics and also in catalysis of biological systems. Silver nano (Ag Nps) particles have got more attention because of remarkable anti microbial properties. Beside this they exhibit broad spectrum of fungical and bactericide activities. They are used in industry to produce soaps, food, paste, plastic and textiles. Other than this, they show exceptional thermal and optoelectronic properties to be employed in electronic components, photonics and catalysis. Due to this reason special attention is being paid in the fabrication of silver nano particles using different techniques (Song et al., 2016).

Now a days, a huge research is going on in the field of nanocomposites, which are defined as the materials formed by the combination of more than one Nps in order to gain the finest properties of all components. In nanocomposites, nanoparticles (clay, metal, carbon nanotubes) act as fillers in a matrix, usually polymer matrix (Nguyen-Tri et al., 2018).At present, silver nano particles are synthesized using different approaches which include many physical, chemical and biological techniques. All techniques have their own limitations and delimitations that depend on the availability of resources and produce nano particles with different sizes (Natsuki et al., 2015): All of these methods are discussed in detail below.

Methods used for the synthesis of silver nano particles

Chemical Methods: Chemical methods are mostly utilized for the synthesis of silver Nps and among them the most common approach is chemical reduction method by organic and inorganic compounds. It produces stable nano particles in water and organic solvents. Production of nano particles mainly depend on the temperature during the fabrication process. Some of them can be performed at room temperature however for high reaction ratio; most of them have elevated temperature (Jiang et al., 2006).

Chemical Reduction Method: Mainly the chemical reduction process in solution involves three main components, (i) Metal precursor (ii) reducing agent (iii) capping agent. In order to produce nano particles with uniform size distribution, it is required that nuclei must be produced at the same time. Only in this way all nuclei will have similar size and same subsequence growth. Nucleation and nuclei growth can be controlled by the adjustment of different reaction factors, such as, pH to reduce the effect of stabilizing agent and reaction temperature (Evanoff and Chumanov, 2004).

Electrochemical method: It was observed that size of selective nano scale of transit on metal particle could be seen electrochemically using tetra alkyl ammonium sales stabilizer of metal cluster in a nano aqueous solution. Since then process of electrolysis has been used for the reduction of material ions. It is a heterogeneous process. There are two general types of electrochemical methods; Potentiometeric (no current, equilibrium potential) and voltametric (current measured as a function of application potential). Main function of this method is an electrode which provides an interface where process of change transfer occurs. These processes are reported to be better than other chemical methods to produce nano particles because of low cost, ease to handling, higher quality and modest equipments (Guzman et al., 2008)

Pyrolysis: One of useful methods for the synthesis of silver nano particles is spray pyrolysis. Although this method can produce silver nano particles successfully, yet, the requirement of the use of stabilizer for the protection of the synthesized nano particles from agglomeration is necessary. The drawback of pyrolysis method is that it is very expensive and not friendly to environment (Natsuki et al., 2015).

Physical methods: These methods usually involve process of evaporation and condensation which is carried out in a tube furnace and certain atmospheric pressure. Various types of nano particles like, Au, Pb, Cu and fluorine (F) have been produced by using this technique. Although Ag Nps can be produced by the use of tube furnace, it has several draw backs e.g.; tube furnace occupies large spaces around the source material and require much larger time to become thermally stabilize and require power consumption of more than several kilowatts but many physical methods have advantages above chemical methods because that they do not make use chemicals which are toxic. The process of ions formation for nano particles is usually faster rather than other methods (Abbasi et al., 2016;Panwar et al., 2017)which includes laser ablation (Baiee et al., 2018; Gellini et al., 2018; Sportelli et al., 2018).

Bio-based methods: Nano particles prepared by biological methods are better to those prepared by chemical and physical methods in several ways. Though chemical and physical methods produce larger quantities of nano particles with a well defined shape and size in a short time, yet they are costly, complicated and produce toxic base materials which are dangerous for environment and human wellbeing. With the help of biological methods, there is no need of using expensive chemicals. These methods are also supported in a way that the micro organisms used in the process inhabit ambient conditions of varying temperature, pressure and pH. The nanoparticles produced by this process has greater surface area and high catalytic reactivity. Biosynthesis of nano particles take place when the micro organism capture ion from there surrounding environment and turn these metal ions into the required metal through enzyme which is generated by the cell activities.

This process can be characterized into extra cellular and intra cellular synthesis regarding the location of the particles, that is, where they are formed the intra cellular process takes place and ions transport into the microbial cell to form nanoparticles (Velez et al., 2018).

Table 1: Chemical methods to synthesize Ag Nps.

Reducing agent###Capping agent###Size of nano particle###Characterization###Shape of nano###Colour of###References

###(Shanmugasundaram###techniques###particle###solution

###and Balagurunathan)

Chemical reduction method

Hydrazine hydrate###Sodium###9-30###UV-Visible, TEM,###Spherical###Pale###(Guzman et al.,

###citrate, Sodium dodecyle###EDX,XRD###yellow to###2008)

###sulphate(SDS)###pale red

Hydrazin, formalyne,###SDS###Below 20 at###UV-Visible, SEM, DLS###(Szczepanowicz et

ascorbic acid###20-25AdegC temperature###al., 2010)

Sodium citrate###Sodium citrate###30 at high tem.###FESEM,UV-###Spherical###(Zhou and Wang,

###Visible,DLS###2012)

Tri-sodium citrate###Sodium borohydride###25 At high tem.###UV-Visible, HRTEM,###Spherical###Greenish###(Bonsak et al., 2011)

###(NaBH4)###AFM###brown

Sodium borohydrade,###NaBH4###-###UV-Visible, SEM###Triangular###(Rashid et al., 2013)

trisodium citrate

AgNO3, sodium###3 and 100 nm###UV-vis spectrometry,###spherical and###(Gakiya-Teruya et

citrate###dynamic light scattering###cylinder###al., 2019)

###(DLS

Nano composite

silver nitrate with###sodium citrate ,hydrogen###UV-vis, DTC showed a###nanocomposite###bright###(Reynoso-Garcia et

Dithiocarbamate###peroxide and sodium###plasmonic absorption###(NC) of###yellow###al., 2018)

Ligand###borohydride###band###spherical Ag###and blue

###NPs and PA###colors

###polymer NPs

of 1-vinyl-1,2,4-###radical-initiated###2 to 6 nm###TEM,SEM,FTIR,UV###(Reynoso-Garcia et

triazole and N-###polymerization###al., 2018)

vinylpyrrolidone

Trisodiumcitrate,AgN###68 nm###SEM ,TEM,EDX,XPS###(Ahari et al.)

O3

Micro emulsion

Hydrazine hydrate###2-ethyle hexyl,###2-5 at room temprature###UV-Visible, TEM###Spherical###(Zhang et al., 2007)

###Sulfosuccinate

Photo chemical process###(X-Ray radiolysis)

X-Ray###28 at 1atm. pressure###Spherical###(Remita et al., 2007)

UV light###4- 10 in 20 min at 1###UV-Visible, TEM###Spherical###(Bakar et al., 2007)

###atm. Pressure

Xe-Hg lamp###0.75 -1.12 in 60 sec.###UV-Visible,###Spherical###(Zaarour et al.,

###2014)

Sol gel method

Material###Reducing agent###Stabilizer###Size of nano###Characterizat###Shape of###References

###particle(Shanmugasun###ion###nano

###daram and###techniques###particle

###Balagurunathan)

Silica powder at###Ethanol, distilled water,###Nitric acid (HNO3)###20-40###XRD, TEM,###Spherical###(Duhan et al.,

300AdegC###Nitric acid###FTIR###2010)

Silica powder at###Tetra butyl (C16H36O4T2###16 +- 0.6###UV-Visible,###Spherical###(Farasat et al.,

700AdegC###TNBT), metallic tin powder###SEM, XRD,###2011)

###TEM

Silica powder at###Water alcohol###12-20###SEM, XRD,###Spherical###(Serezhkina et al.,

600AdegC###TEM###2003)

Nanocomposite

titanium###isopropyl alcohol,###acetic acid###(XRD),###(Mohallem et al.,

isopropoxide and###(EDS), TEM###2018)

silver nitrate 400AdegC###UV-Vis

Table 2: Variation in color and pH value by changing PVP-Ag.

PVP-Ag###pH###Color###Reference

250 ppm###5.6###Green

500 ppm###5.8###Light brown###(Zieliska et al., 2009)

1000 ppm###5.7###Brown

Table 3: Variation in color and particle size by changing pH value.

PVP-Ag###Size###PH###Color###Reference

250 ppm###36 nm###5.3###Green###(Zieliska et al.,

250ppm###44 nm###5.6###Green###2009)

250 ppm###140 nm###9.1###yellow

Table 4: Physical method to synthesize Ag Nps

Laser ablation (Nd:YAG Laser)

Wavelength###Stabilizer###Size of nano particle###Characterization###Shape of###Reference

(Shanmugasundaram###(Shanmugasundaram###techniques###nano

and Balagurunathan)###and Balagurunathan)###particle

Second harmonic 532###Polyvinyl alcohol###5-45###UV-Visible, TEM###Spherical###(Hue, 2008)

1064###Sodium chloride###5-50###UV-Visible, TEM###Ellipsoidal###(Bae et al.,

###2002)

1064###De-ionized water###34 at 50AdegC###SEM, XRD###Spherical###(Tyurnina et

###al., 2013)

Second harmonic 532###Chitosan, EG###10.5 for chitosan, 22.08###UV-Visible, TEM###Spherical###(Tajdidzadeh

###ethylene glycol###EG and DW (27.41 nm)###et al., 2014)

###and distilled water

###at 60C DW

1064 andSecond harmonic###water, methanol,###12-33###UV-Visible, TEM###Irregular###(Jeon and

532###and isopropanol###Yeh, 1998)

1064 with 10ns pulse###Nitric acid###2-5nm###UV-Visible, TEM###Spherical###(Pyatenko et

duration###with pale###al., 2004)

###yellow color

###of solution

Precursor###Capping###Reducing###Size of nano particle###Characterization###Shape of###References

###agent###agent###(Shanmugasundaram###techniques###nano

###and Balagurunathan)###particle

Sputtering process

DC###Ultra high###7.5 cm###5x10-6 m bar at 50 mA###TEM###3.8-5.9###(Asanithi et

Magnetron###purity argon###spherical###al., 2012)

###99.9%

Alpha CD###Carboxylic###.06 Mm bar for 20 s###XRD, IH-NMR###2-10###(Zhu et al.,

###acid###2013)

Table: 5 the particle size of silver nanoparticles and their corresponding volume fraction

Samples###Volume###Particle size (Shanmugasundaram###Standard deviation for particle size###References

###fraction###and Balagurunathan)###(Shanmugasundaram and Balagurunathan)

15 min###1.0 x 10-8###6.33###1.93###(Zamiri et

30 min###1.6 x 10-8###5.18###1.65###al., 2011)

45 min###2.4 x 10-8###4.84###1.09

Chitosan-Based (Katas et al., 2018, Rehan et al., 2018) nanocomposites of silver are synthesized by bio based method and have many potential applications in bio medicine(Marques-Hueso et al., 2018). Biogenic synthesis of platinum based (Pt/Ag, Pt/Au and Pt/Ag/Au) nanocomposites is formed by using biomass of Streptomyces (Shanmugasundaram and Balagurunathan, 2018).

Use of bacteria: For the first time in history silver particles were synthesized by using bacteria in 2000(Bhattacharya and Gupta, 2005). It was reported that stable silver NPs of size 40 nm could be produced by bio reduction of colloidal silver ions with a culture supernatant of nonpathogenic bacterium, bacilluslicheniformis (Joerger et al., 2000; Kalimuthu et al., 2008).

Fungi: In the list of microorganisms to synthesize nano particle, fungi is recent addition. Its use is encouraged as it secretes enzymes and is used in laboratory very easily. In 2001, by using fungus and vetrrticillium were used to synthesize Ag Nps. When fungus biomass was exposed to colloidal Ag+ ions, it resulted in the reduction of metal ions to produce silver nano particles of size25 +- 12 nm (Mukherjee et al., 2001).

Use of yeast: A few reports exist, in which silver nano particles are produced by yeast. Using yeast strain MKY3 silver nano particles were synthesized with size range of 2-5 nm extracellularly (Kowshik et al., 2002).

Use of plants: In biosynthesis plant or some important parts like stem and leaves are used to synthesize nano particles. Living plant(Ahmed et al., 2016)like aloe vera (Logaranjan et al., 2016; Tippayawat et al., 2016)and Andean black berry fruit extract are not only used to produce Ag Nps, but also reduce toxic effect of silver(Kumar et al., 2017).

In Situ Polymerization Method: This method was used to fabricate the nanocomposite coatings with organic matrices, which were conducting polymer (Asmussen and Vallo, 2016; Taormina et al., 2018).

Nano polymer composite.

opolymer of 1-vinyl-###N-vinylpyrrolidone###metal###1 to 12###Spheric###powder X-ray diffraction,###(Pozdnyakov

1,2,4-triazole###as a stabilizer###nanoparticles###nm###form###transmission electron###et al., 2017)

###microscopy

1-Vinyl-1,2,4-triazole###ethyl alcohol###metal###17-125###SEM, FTIR, X-ray###(Pozdnyakov

and Acrylonitrile###precursor.###nm###diffractio###et al., 2019)

Table 6: Biological methods to synthesize Ag Nps.

Material###Temperature(AdegC)###Size of nano###Shape of particle/###Location###Time (hour)###Characterization###Reference

###particle###color of solution###Technique

Bacteria

Bacillus cereus###30-40###42-92###Pale yellow to###Extra/inter###24###UV-Visible###(Das et al., 2014)

###brown###cellular

Bacillus cereus###20-40###Spherical###Extra cellular###24###UV-Visible###(Sunkar and

###Nachiyar, 2012)

Fungi

Fusariumoxysporu###20-50###Spherical###Extracellular###28###FTIR###(Duran et al., 2005)

m

Verticillium###25+-12###intracellular###Electron###(Mukherjee et al.,

###microscopy###2001)

###analysis

Yeast

yeast strain MKY3###30###2-5###Spherical###Extracellular###9-10###photoelectron###(Kowshik et al.,

###spectroscopy,###2002)

###TEM ,XRD

Plant

Azadirachtaindica###34###brown color of###15###UV-Visible,###(Ahmed et al., 2016)

###soln.###min###FTIR, DLS

Solanumtricobatu,S###35###41-53###Irregular shape,###48###UV-Visible,###(Logeswari et al.,

yzygiumcumini,###Orange color of###FTIR,XRD,###2015)

Centellaasiatica###soln.###AFM

Applications: Silver nano particles show great area of interest owing to their exceptional properties, to be utilized into numerous antimicrobial applications, cosmetics industry, biosensors, electronic components, composite materials and many more(Caro et al., 2010). Furthermore, they are also extensively used in fields like, drug delivery, medical imaging, (Joerger et al., 2000) and low cost paper batteries (Hu et al., 2009). Some of the properties and applications of Ag Nps are discussed below.

Optical Properties and Applications: When light falls on the metal surface of Ag Nps, a strong interaction occurs, which results in the oscillations of conduction electrons on the surface at specific wavelengths also known as Surface Plasmon Resonance (SPR). Due to this property, Ag NPs are very efficient in absorbing and scattering of light and exhibit a color that depends on the shape and size of these particles. Using SPR effect, Ag NPs gain very high sensitivity and measurements can be conducted in real time. With the help of Localized Surface Plasmon Resonance (LSPR), it is possible to monitor the quantity of chemical species and dynamical processes that occur inside a cell. The LSPR biosensors also provide a path to sensitive bio detection experiments with simple, light, small and low cost instrumentation (El-Nour et al., 2010).

Biological Properties and Applications: Silver Nps are extensively used everywhere in industry including in food containers, detergents, cosmetics and in various other products to stop the increase of germs. It is because silver provides large surface area for contact with bacteria, to get attached with cell membrane and penetrate inside the bacteria at nanometer scale (Liau et al., 1997; Rai et al., 2009). Once Ag Nps get inside cell of bacteria, release Ag+ which has lower pH and can create free radicals to increase antibacterial activity. As Ag Nps show evidence of immense toxicity to broad range of microorganisms, they along with their nano composites(Jaworski et al., 2018; Song et al., 2016) find numerous applications in the field of biology(Cheng et al., 2016) such as, antibacterial agents and DNA sequencing.

Catalytic Properties and Applications: Use of metallic Nps and nanocomposites as catalysts (Mousavi et al., 2016) is an emerging field and researches are going on to obtain basic insight to key features that control the activity, selectivity and life time of catalysts at nanoscale. Metal Nps have a high surface area which increases catalytic activity because of occurring of more reactions at one time. Catalysts can be used in two different ways in catalytic process: either they can be the site of catalysis or they can act as a support for catalytic processes. Silver Nps/nano composite(Alshehri et al., 2016; Mitsudome et al., 2012) are used as catalysts in various chemical processes like, methanol oxidation to deformaldehyde and ethylene to ethylene oxide.

Medical Applications: Silver Nps find broad range of use in medicine and are incorporated for burn treatment coating stainless steel materials, medical devices, coating dental materials, and for personal health care. AgNps are constantly being used to improve today's therapies. It can also be used in purification of water, wound caring and drug delivery due to their antimicrobial behavior (Pal et al., 2011). On the other hand, these particles are also used in antibacterial cream, dressings, endotracheal tubes for the increment of efficiency. Silver compounds like silver proteinate and silver nitrate are being used to dilute solution of eye drops (Natsuki et al., 2015; Nguyen-Tri et al., 2018)

DISCUSSIONS

Invention of nanotechnology has changed our life altogether. The main focus is to produce Nps which show their enormous applications in variety of fields and are cheap and environment friendly at the same time. Although, noble metals have widely been used for a variety of purposes, silver Nps are under great attention in the way that they are antiviral, anti-inflammatory and anti-angiogenic and continuously been used in biomedical applications, such as, diagnosis of cancer and drug delivery, etc. That is why; they are produced using various physical, chemical and biological methods. Some of the methods and brief applications of these Nps have been discussed in this review article.

Conclusions: In this review, the synthesis routes of silver Nps, including chemical, physical and biological synthesis are discussed in detail along with tables. Then the unique properties and applications of silver Nps in different fields are discussed briefly. The main advantage of biological synthesis over other methods is that it avoids toxic reagents. Thus, Nps produced in this way are more stable than those produced chemically. However, the drawback is that the process of purification may result in pathogenic and potential bacteria which can cause contamination. That is why biological synthesis also needs caution while using in medical applications. Researchers are being done to synthesize Ag Nps using different reducing and capping agents such as protein, carbohydrates, bacteria, fungi and yeast as they are ecofriendly. The extensive utilization of Ag Nps in biological field is of great interest nowadays and is growing rapidly.

Ag Nps provide large surface area for contact with these microorganisms, hence, increasing the anti-bactericidal activities. Due to this compatibility they are widely used in biomedical industry including drug delivery, diagnosis, sunscreen lotions and human health care.

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