Polysaccharides templates for assembly of nanosilver

Accepted Manuscript Title: Polysaccharides Templates for Assembly of Nanosilver Author: Hossam. E. Emam Hanan B. Ahmed PII: DOI: Reference:

S0144-8617(15)00843-7 http://dx.doi.org/doi:10.1016/j.carbpol.2015.08.095 CARP 10298

To appear in: Received date: Revised date: Accepted date:

19-7-2015 19-8-2015 30-8-2015

Please cite this article as: Emam, Hm. E., and Ahmed, H. B.,Polysaccharides Templates for Assembly of Nanosilver, Carbohydrate Polymers (2015), http://dx.doi.org/10.1016/j.carbpol.2015.08.095 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

1

Polysaccharides Templates for Assembly of Nanosilver Hossam. E. Emam 1, ∗, Hanan B. Ahmed 2

2

4

1 2

Textile Research Division, National Research Centre, Dokki, Cairo 12311, Egypt

Chemistry Department, Faculty of Science, Helwan University, Ain-Helwan, Cairo

5

11795, Egypt

6

Corresponding author Tel.: +20 201008002487

E-mail address: [email protected] (Hossam E. Emam).

cr

7

∗

ip t

3

9

Abstract

us

8

Polysaccharides are particularly attractive in biomedical applications due to its

11

biodegradability and biocompatibility. In addition to its ecofriendly effects and easy

12

processing into different hydrogel shapes, made polysaccharides used on a large scale

13

as suitable media for preparation of silver nanoparticles (AgNPs). In spite of, most of

14

polysaccharides are water insoluble, but, it has shown to be quite efficient capping

15

agents and/or nanoreactor matrices for production of AgNPs. Several methods have

16

been developed to get the benefit of multi-functionality for polysaccharides'

17

macromolecules in preparation of AgNPs. Therefore, recently, preparation of

18

nanosilver using different polysaccharides have been the focus of an exponentially

19

increasing number of works devoted to develop nanocomposites by blending AgNPs

20

with different polysaccharides matrices. The current review represents a wide survey

21

for the published studies which interested in using of polysaccharides in nanosilver

22

preparations.

23

Keywords: Polysaccharides, AgNPs, Stabilizing agent, Reducer, Templates.

24

I. Introduction

Ac ce pt e

d

M

an

10

25

Noble metal nanoparticles are characterized by unique electronic, optical,

26

mechanical, magnetic and chemical properties rather than the bulk materials becomes

27

recently the subject of focused research in the last decade. These unique properties are

28

attributed to large volume to surface area ratio which leads manifold applications in

29

solar energy conversion, catalysis, medicine and water treatment for instance

30

(Hutchinson, 2008; Kamat, 2002; Li et al., 2001). 1

Page 1 of 24

Generation of metal nanoparticles includes three main stages, namely the

32

reduction reaction of metal ions to free atoms, nucleation and growth. Recent studies

33

showed that, the reaction kinetics and experimental conditions play important roles

34

for the nucleation and growth stages. Reduction of metal salt precursors to the

35

elemental metal nanoparticles plays a crucial role, and generally requires a reducing

36

agent and a stabilizer one, in order to obtain shape and size controlled metal

37

nanoparticles (MNPs). Therefore, all of afore mentioned methods in the literatures

38

used for synthesis of nanometals become an attractive field for research in order to

39

transform the sized controllable nanoparticles potential applications to reality (Knoll

40

and Keilmann, 1999; Sengupta et al., 2005; Wiley et al., 2007).

cr

ip t

31

A fact has been achieved that the size, morphology, despersibility, and

42

physicochemical properties of the metal NPs are strongly affected by the experimental

43

conditions, reaction kinetics between metal ions with reducer, and stabilizer

44

(Sengupta et al., 2005). Some commonly used chemical reductants for preparation of

45

nanosilver are borohydride, ascorbate, hydrazine, and elemental hydrogen (Shirtcliffe

46

et al., 1999; Nickel et al., 2000; Chou and Ren, 2000; Evanoff et al., 2004; Sondi et

47

al., 2003; Merga et al., 2007; Ahmadi et al., 1996). Some of the commonly used

48

methods for surface protection of MNPs are self-assembled monolayers, as the most

49

popular is citrate and thiol-functionalized organic substrates (Ullman, 1996),

50

encapsulation in H2O pools of reverse microemulsions (Petit, 1993) and dispersion in

51

polymeric matrixes (Zahran et al., 2014a; Zahran et al., 2014b; Hebeish et al., 2010).

an

M

d

Ac ce pt e

52

us

41

Polysaccharides, due to their ability for chelating different metal ions it could

53

act as stabilizing agents. The polymer-metal ion complex can then be reduced under

54

different experimental conditions, to produce MNPs with small size and narrow size

55

distribution. Additionally, polysaccharides could also be characterized by good

56

reducibility, as its building blocks contain different functional groups and thus can

57

play the dual roles of NPs generators and protecting agents. This dual function of the

58

polysaccharide can be an advantage in the green and cost effective syntheses of MNPs

59

since it avoids the usage of harmful and toxic chemicals which limited the use of

60

MNPs for biological or medical applications.

61

Silver Nanoparticles (AgNPs)

2

Page 2 of 24

Different metal nanoparticles (i.e., Ag, Au, Pd, Pt, Rh, Ir, etc.) with diameter

63

more than 10 nm are characterized by high stability due to their chemical inertness,

64

however, when the size decreased to 2-4, they become easily oxidized in air. Different

65

metal nanoparticles could be physically, biologically or chemically prepared in

66

suitable solvent, in the presence of protective/capping/stabilizing agent such like

67

polymers, surfactants or strong coordination ligands.

ip t

62

Controlling the factors which influence shape and size of nanoparticles is of

69

empirical significance to modulate the catalytic, optical and/or biological properties of

70

the manufactured nanometals. Generally, there are two different ways for

71

morphological controlling of precious nanoparticles :(i) template-directed preparation,

72

in which metal ions are reduced and nanoparticles grow within the template,

73

therefore, the shape and sizes of the so-obtained nanoparticles are controlled by the

74

morphological properties of the template; (ii) growth-directed preparation, in which,

75

shape-selective nanometals are prepared by using suitable metal precursor, reducing

76

agent, protecting agent and controlling reaction kinetics.

M

an

us

cr

68

Silver materials are any silver- containing materials with special activities due

78

to their nano-sized characters. Also Nano-silver referred to commercial products

79

which contain metallic silver in size range of 5-50 nm or ionic silver with special

80

medical applications (Panyala et al. 2008).

Ac ce pt e

81

d

77

An impressive number of methods for synthesizing AgNPs have been described

82

in literatures, as generally AgNPs could be applicable in different medical purposes

83

(medical textiles, cosmetics, pharmaceutical products, etc…….) or in other industrial

84

applications (electronics, catalysis, etc…...). A new concept referred to green

85

synthesis of AgNPs has recently been introduced, where the used reactants and

86

solvents are described as non-toxic and benign compounds to the environment, and

87

the so-obtained nanosilver colloids could be applicable in different biological

88

purposes (Emam et al., 2015; Zahran et al., 2014a; Zahran et al., 2014b; El-Rafie et

89

al., 2014; Hebeish et al., 2010). The chemical reduction of silver salts is one of the

90

most widespread methods used for the synthesis of silver nanoparticles. In this way,

91

the metal salts are dissociated to metal ions, and then reduced by a reducer to form

92

metal nanoparticles that are stabilized by suitable capping agent.

3

Page 3 of 24

Great numbers of reducing agents include salts such as sodium borohydride

94

(Guoping et al., 2012) or sodium citrate (Harriman et al., 1987) and gases such as

95

carbon monoxide and hydrogen (Ershov and Abkhalimov, 2007) have been studied in

96

literatures. Silver nanoparticles with high surface energy and high surface are tuned to

97

aggregate or agglomerate. Recently, preparation of stable AgNPs is accomplished

98

using protective coordinates, which provide electrostatic and/or steric protection like

99

polymers and surfactants (Zahran et al., 2014a; Zahran et al., 2014b, El-Rafie et al.,

100

2014). Also, stabilization of nanoparticles through immobilization is another

101

demonstrated stabilization way (White et al., 2010).

cr

ip t

93

The stability of the particles depends on the method in which the stabilizers are

103

anchored to the manufactured nanoparticles. According to the nature of capping agent

104

used, stabilization anchorage proceeds through three main mechanisms: (i) steric

105

stabilization due to the presence of bulky groups, (ii) electrostatic stabilization, which

106

arises from electrostatic attraction between opposing charges, or (iii) stabilization by

107

ligands (organo-metallic or covalent bonds) (Castonguay and Kakkar, 2010; Richter et

108

al., 2009; Scott et al., 2005).

109

II. Polysaccharides mediated for AgNPs

d

M

an

us

102

Silver salts are historically known as antimicrobial agent, and recently, it has

111

been reported that, silver nanocrystals is distinguished by its excellent antimicrobial

112

action rather than ionic form (Emam et al., 2014a). Besides, silver has been used for

113

ages in wound treatment. Recently, upcoming resistances of pathogens against

114

antibiotics (especially in medical care) led to an increase of silver incorporation into

115

medical matrices and nowadays a variety of applications are in different local and

116

international markets.

117

Ac ce pt e

110

In the view of the large numbers of available natural polymers, this review has

118

focused on the usage of polysaccharides derived from natural sources, i.e. polymeric

119

carbohydrate structures that have been intensely investigated in the context of medical

120

applications. Recent years have witnessed the implementation of AgNPs using

121

polysaccharides as biodegradable and biocompatible polymers that directly emerge in

122

biocidal materials. Such polymers in solutions are considered as hydrogels and can be

123

described as effective capping agents for AgNPs. Polysaccharides have been used as

124

composite matrices due to several characteristics of relevance for biological and

4

Page 4 of 24

125

medical applications, namely: biocompatibility, bifunctionility, sensitivity to external

126

stimuli. In addition to their ability for coordinating with metal ions, polysaccharides

127

could be used as reducers and capping agents for preparation of AgNPs. The polymer-metal ion complex can be reduced under controllable experimental

129

conditions, resulting in small sized nanoparticles. Once metal ions reduced to produce

130

nano-sized species; polysaccharide building blocks will impair nanoparticles clotting

131

(Fig. 1). So, the net produced matrix can be designed to perform different functions,

132

depending on the properties of the loaded inorganic nanoparticles and, on the other

133

hand, this product can be easily adapted to bio-systems due to their potential

134

biocompatibility

135

polyfunctional compounds, as it includes different functional groups, so, they can

136

serve as a springboard for the creation of multimodal and multifunctional systems

137

through the addition of reactive and bioactive groups.

138

contain hydroxyl groups and a hemi-acetal reducing end that are capable of reducing

139

precursor salts. The oxidation of polysaccharides hydroxyl groups to carbonyl groups

140

plays an important role in the reduction of metal salts (Mata et al., 2009). Others

141

contain amino reducing end groups, capable of complexing and stabilizing metallic

142

nanoparticles (Nadkarni et al., 1994). Carbohydrates with such amino groups bind

143

tightly to the surface of the AgNPs providing them with hydrophilic surfaces (Kemp

144

et al., 2009a). Monitoring the change in reducing end groups provides an excellent

145

way of measuring the exact amount of polysaccharides which acts in reducing and

146

complexing metal ions. High alkalinity results in polysaccharides depolymerization,

147

alkaline hydrolysis, and/or oxidizing destruction (Nadezhda et al., 2012), producing

148

fragments with high reducibility. Thus, recent researches were interested in using

149

polysaccharides for synthesis of AgNPs under alkaline conditions. Therefore this

150

review summarizes the employment of different polysaccharides in synthesizing of

151

AgNPs. As a final note, the challenging field comprising the green manufacturing of

152

AgNPs using polysaccharides will be put in perspective.

low-toxicity.

Polysaccharides

could

be

described

as

us

and

cr

ip t

128

Ac ce pt e

d

M

an

Some of polysaccharides

153

5

Page 5 of 24

153 154

Figure 1: Schematic diagram presented the action of polysaccharides as reducing and stabilizing agent for silver nanoparticles.

M

an

us

cr

ip t

155

Ac ce pt e

d

Reduction step

Stabilization step

6

Page 6 of 24

156 157

Heparin, Schizophyllan and Hyaluronic acid (HA) Silver-heparin

nanocomposites

have

been

manufactured

using

2,6-

diaminopyridinyl heparin (DAPHP), which acts as both reducer and protecting agent

159

(Kemp et al., 2009a; Kemp et al., 2009b). The reducing end of heparin was

160

chemically modified by 2,6-diaminopyridine (DAP) to give DAPHP, envisaging its

161

application as chelating and stabilizing for AgNPs. A narrow size distribution of

162

particles was observed for Ag-DAPHP nanoparticles, due to the stable coordination

163

between di-amino-pyridine moieties of DAPHP and NPs. Preparation of silver-

164

heparin nanocomposites using chemical/thermal reduction method has been carried

165

out. Both of size and morphological shape of the manufactured nanocomposites is

166

affected by the concentration of heparin and metal salt, as increment in the

167

concentration of either heparin or silver salt resulted in enlarged nanoclusters.

168

Additionally, the surface plasmon resonance (SPR) band was red-shifted with

169

increasing concentrations of heparin and silver salt.

an

us

cr

ip t

158

Solutions of high-molecular-weight HA with its biological compatibility and

171

rheological properties are useful in different medical purposes (Doughty and Glavin,

172

2009). HA is incorporated in synthesis of NPs amining to increase their

173

biocompatibility. HA was used for synthesizing of AgNPs through chemical/thermal

174

procedure, and the manufactured nanocomposites exhibited size average of 5-30 nm,

175

where HA acted as both of reducing and stabilizing agent (Kemp et al., 2009b). These

176

Ag-HA nanocomposites showed higher size distribution than that of Ag-DAPHP

177

nanoparticles. Abdel-Mohsen et al illustrated that alkali treated HA fiber could be

178

successfully applied in green preparation of AgNPs, using wet-spinning technique

179

(Abdel-Mohsen et al., 2012b). As alkali treatment of HA fibers aid in solubilization,

180

formation of transparent solution of the so-called fiber, and increment of

181

reactivity/accessibility of functional groups for the solubilized units, which in turn,

182

played the dual role of reducer and chelating/capping agent. Abdel-Mohsen et al. also

183

offered a green method for AgNPs formation in alkaline medium by using triple

184

helical schizophyllan (SPG) which is found out to be a reducing and stabilizing agent

185

for NPs (Abdel-Mohsen et al., 2014).

Ac ce pt e

d

M

170

186 187

7

Page 7 of 24

188

Chitosan Carboxymethyl chitosan (CMCs) was evaluated as a template for synthesis of

190

Ag nanoparticles (Laudenslager et al., 2008). However, lacking of free amines in

191

CMCs led to poor crosslinking and a limited chelating ability, which makes CMCs a

192

poor choice as a reactor for synthesis of NPs. The same group studied the

193

enhancement of nanoparticles stability using chitosan, by binding to AgNPs through

194

the amino group (Wei et al., 2008).

195

structure of Ag-chitosan nanocomposites is influenced by the reaction temperature

196

(Potara et al., 2009). A dendritic Ag-chitosan film was prepared by mixing chitosan

197

with Ag salts under acidic conditions (Wei et al., 2009; Sathishkumar et al., 2009).

198

While Ag-chitosan film was synthesized by a photochemical reduction of silver ions

199

in acidic medium and chitosan was used as chelating agent for AgNPs (Thomas et al.,

200

2009).

ip t

189

an

us

cr

Controlling the size, shape and crystalline

Polymers which contain NH2-groups like chitosan is tightly coordinated with

202

metal ions, however, medium and high molecular weight chitosan is soluble in acidic

203

solutions, this property has been explored in some of difficulties in preparation of

204

narrow sized/ well dispersed AgNPs (Cheng et al., 2005; Long et al., 2007).

205

Therefore, it would be preferable to use a water-soluble derivative of chitosan for

206

preparing of stable AgNPs. Recently, sulfated derivatives of chitosan, with

207

anticoagulant activity as well as hemo-compatibility, have significant importance

208

regarding to the application and use of this polysaccharide in medical devices (Fasl et

209

al., 2010). Imparting of antimicrobial properties to anticoagulant materials has been

210

achieved by encapsulation of AgNPs in sulfated derivatives of chitosan (Kong et al.,

211

2010; Kulterer et al., 2012; Fasl et al., 2012). It was reported by Breitwieser et al.

212

that, AgNPs encapsulated by 6-O-chitosan sulfate is considered as anticoagulant and

213

hemo-compatible polysaccharide (Breitwieser et al., 2013a). S-Chi moiety with its

214

negative charge is resulting in particles stabilization through electrostatic interaction

215

or by covalent bonding.

Ac ce pt e

d

M

201

216

Breitwieser et al. also represented an environmentally friendly manufacturing of

217

silver-cellulose fibers nanocomposites using conventional and microwave assisted

218

heating (Breitwieser et al., 2013b). The Ag nanocomposites fibers are prepared by in

219

situ process where silver ions were reduced by the action of S-Chi, as S-Chi is in close

220

spatial proximity to the fiber where adsorption takes place. Controllable experimental 8

Page 8 of 24

conditions for both of microwave and conventional heating procedures induced no

222

size and structural changes in nano-silver when the two heating methods were

223

compared. Abdel-Mohsen et al was reported that, silver/chitosan-O-methoxy

224

polyethylene glycol (chitosan-O-MPEG) core shell nanoparticles with different

225

degree of substitution were successfully manufactured (Abdel-Mohsen et al., 2012a).

226

As N-phthaloyl chitosan was reacted with polyethylene glycol monomethyl ether

227

iodide in the presence of silver oxide (Kibeche et al., 2015; Ishihara et al., 2015).

228

Experimental results showed that the so-produced Ag core particles exhibited size of

229

18 ± 2 nm.

230

Cellulose and its Derivatives

us

cr

ip t

221

Cellulose with economic advantages of abundance, low cost, biodegradability,

232

and biocompatibility, is one of the most commonly polysaccharides employed in

233

preparation of NPs. So, using of cellulose (soluble or insoluble form) in synthesis of

234

AgNPs has received a considerable interest, where, reducing alcoholic and/or

235

aldehydic groups are acting in reduction and stabilization of silver ions

236

(Tummalapalli et al., 2015). Chemical modification and derivatization of cellulose

237

aims to improving its solubility, rendering them more applicable in synthesis of silver

238

nanocolloids (Table 1).

M

d

Cai et al. used an aqueous alkali hydroxide-urea system to obtain transparent

Ac ce pt e

239

an

231

240

nano-porous cellulose gels, followed by immersing in AgNO3 solution as precursor

241

salt for generating AgNPs (Cai et al., 2009). Francis et al., used hydroxy-propyl

242

cellulose (HPC) as capping agent for AgNPs and ethylene glycol was used as solvent

243

(Francis et al., 2010). Recently, HPC was investigated to be a reducer and stabilizer

244

for AgNPs concurrently by Abdel-Halim et al. and Hussain et al. (Abdel-Halim et al.,

245

2011; Hussain et al., 2015), as enlarged AgNPs was obtained, compared to that of

246

Francis et al. Carboxymethyl cellulose (CMC) prepared by Hebeish et al. using slurry

247

method, was used as reducer and stabilizer for AgNPs. Size and structural features of

248

the so-prepared AgNPs was strongly dependant on the degree of polymerization and

249

degree of substitution for CMC. Higher concentration of well dispersed AgNPs (1000

250

ppm) with average size of 10–25 nm was obtained (Hebeish et al., 2010). More

251

recent, hydroxyethyl cellulose (HEC) and hydroxypropyl carboxymethyl cellulose

252

(HPCMC) was prepared for manufacturing of AgNPs by El-Sheikh et al. and Abdel-

253

Halim et al., respectively. HEC produced stable AgNPs, which was exposed to be 9

Page 9 of 24

254

stored for six months at room temperature (El-Sheikh et al., 2013). HPCMC afforded

255

AgNPs similar in size to that obtained by CMC. Enlarged AgNPs (11-60 nm) was

256

produced by HEC compared to that produced by CMC and HPCMC. According to the studies of Emam et al., insoluble cellulose was used for

258

preparation of AgNPs by immersion of different cellulosic fibers in the silver salt

259

solution (Emam et al., 2013; Emam et al., 2014; Emam and El-Bisi 2014; Emam et

260

al., 2015a). AgNPs with very high size distribution (25-300 nm) were formed on the

261

surface of Lyocell and Viscose fibers in an acidic medium at 30 °C (Emam et al.,

262

2013). As an alkaline medium acted in swelling, catalyzing, increasing reducibility

263

and activating the functional groups on the cellulose building units, resulting in

264

smaller sized spherical AgNPs (Emam et al., 2014; Emam and El-Bisi 2014; Emam et

265

al., 2015a). In situ deposition of AgNPs into different cellulosic fibers was performed

266

at 70 °C for producing new functional fibers (Emam et al., 2014, Emam et al., 2015a),

267

as AgNPs with size distribution of 0-160 nm was deposited on cotton fibers.

268

However, smaller sized nanoparticles (0-50 nm) were directly incorporated on viscose

269

fibers, due to its higher chemical reactivity comparing to cotton fibers (Emam et al.,

270

2014, Emam et al., 2015a).

M

an

us

cr

ip t

257

The most recent researches was interested in preparation of AgNPs using

272

different cellulosic fibers (Emam and El-Bisi, 2014) as a removable reducing agent to

273

produce merely AgNPs colloidal solution. The reduction of Ag+ to Ag0 was confirmed

274

by measuring carboxylic content, as the redox reaction between Ag+ and cellulose

275

leads to oxidation of alcoholic and aldehydic groups in cellulose to carboxylic groups

276

(Emam and El-Bisi, 2014). For different cellulose fibers, spherical AgNPs with 0-50

277

nm size distribution was produced. The smaller sized AgNPs was obtained in case of

278

using viscose fibers and the storage showed that it was stable at room temperature up

279

to two months.

Ac ce pt e

280

d

271

Cellulose nanocrystals can be isolated through mechanical treatment, acid

281

hydrolysis and enzymatic hydrolysis methods; however, the acid hydrolysis method is

282

described as the most commonly used one (Klemm et al., 2011). Cellulose

283

nanowiskers were prepared from purified cotton fibers by acid hydrolysis and then

284

copolymerized with polyacrylamide by Hebeish et al. Spherical and hyperbranched

285

AgNPs were produced by the so-prepared copolymer under alkaline conditions, with

286

size range of 100-150 nm (Hebeish et al., 2014). 10

Page 10 of 24

287

Table 1: Comparison between different cellulosic materials for production of AgNPs.

288 State

Cellulosic material

Role / medium

Hydroxypropyl cellulose

Stabilizer / Ethylene

Size (nm) / shape of AgNPs

Reference

3 – 18 / Sherical

Francis et al., 2010

5 – 50 / Sherical

Abdel-Halim et al.,

Hydroxypropyl cellulose

Reducer & Stabilizer /

ip t

glycol

Hydroxypropyl cellulose

2011

Reducer & Stabilizer /

25 – 55 / Sherical

cr

Soluble cellulose (grafted)

NaOH

NaOH Reducer & Stabilizer / NaOH Hydroxyethyl cellulose

Reducer & Stabilizer /

Cellulose nanowiskerspolyacrylamide coploymer Viscose fibers

NaOH

M

carboxymethyl cellulose

Reducer & Stabilizer /

Reducer &Stabilizer / NaOH

d

Hydroxypropyl

11 – 60 / Sherical

an

NaOH

10 – 25 / Spherical

us

Carboxymethyl cellulose

Reducer & Stabilizer /

7 – 24 / Spherical

100-150 / Spherical &

Hussain et al., 2015

Hebeish et al., 2010

El-Sheikh et al., 2013

Abdel-Halim et al., 2015 Hebeish et al., 2014

Hyperbranched 25 – 300 / --------

Emam et al., 2013

0 – 50 / Spherical

Emam et al., 2014

0 – 30 / Spherical

Emam and El-Bisi,

Ac ce pt e

Acidic

Viscose fibers

Reducer & Stabilizer / NaOH

Viscose fibers

Reducer & Stabilizer /

(fibers/fabrics)

Insoluble cellulose

NaOH

Lyocell fibers

2014

Reducer & Stabilizer /

25 – 300 / --------

Emam et al., 2013

0 – 30 / Spherical

Emam and El-Bisi,

Acidic

Lyocell fibers

Reducer & Stabilizer / NaOH

Cotton fibers

2014

Reducer & Stabilizer /

0 – 160 / ---------

Emam et al., 2015

0 – 35 / Spherical

Emam and El-Bisi,

NaOH Cotton fibers, DP = 960

Reducer & Stabilizer / NaOH

Cotton fibers, DP = 1850

2014

Reducer & Stabilizer /

0 – 50 / Spherical

NaOH Cotton fabrics

Emam and El-Bisi, 2014

Stabilizer / Citrate

11

20 – 90 / ----------

Rehan et al., 2015

Page 11 of 24

Direct deposition of AgNPs into cotton fabrics was successfully attained by

289

Rehan et al for multi-functionalization of fabrics (Rehan et al., 2015). In this

290

technique, tri-sodium citrate acted in reducing of Ag+ to Ag0 on the surface of cotton

291

fabrics at 90 °C, and cellulosic chains of fabric stabilized the so-produced AgNPs.

292

XPS analysis confirmed that AgNPs acted as cross-linkers between citrate and

293

cellulose building blocks. Size distribution of the so-produced AgNPs (20-90 nm), but

294

enlarged NPs were produced by using viscose fabrics. Table 1 summarizes recent

295

studies considered with AgNPs produced by using different cellulosic materials.

296

Starch and its derivatives

cr

ip t

288

According to Vigneshwaran et al. AgNPs was synthesized using glucose as a

298

reducing agent and starch as a capping agent. Ag salt was incubated with starch and

299

glucose at 40 °C for 20 h to give AgNPs with a mean size of 5.3 nm. This AgNPs

300

solution was stable without significant aggregation even after 2 months of storage.

301

Another thermal method, an autoclaving method (15 psi, 121 °C, 5 min), was studied

302

for manufacturing of stable AgNPs in size range of 10–34 nm where soluble starch

303

acted as both a reducing and stabilizing agent (Vigneshwaran et al., 2006). AgNPs

304

were stabilized by entrapping inside the helical amylose structure of starch, as

305

confirmed by iodometric titration.

an

M

d

Ac ce pt e

306

us

297

Carboxymethyl starch was prepared using 4-(Tri-methyl ammonium methyl)

307

benzo-phenone chloride as photo-initiator for synthesis of AgNPs (El-Sheikh, 2014).

308

The reduction of Ag+ to Ag0 was achieved via the generation of active CMS free

309

radicals. Spherical AgNPs with size range of 1-21 nm was obtained and were stable in

310

aqueous solution for three weeks at room temperature. However, using of

311

hydroxypropyl starch gave better results for reduction and stabilization of AgNPs, as

312

AgNPs with smaller size of 2-16 nm was produced (El-Rafie et al., 2011).

313

Recent studies were considered with starch solubilization in alkaline for

314

manufacturing of form small sized spherical AgNPs (El-Rafie et al., 2014).

315

Gelatinization of starch by strong alkali was carried out for :(i) increasing the water

316

affinity of starch building blocks; and subsequently resulted in swelling and

317

significant size increment for starch granules; (ii) increasing starch reducibility by

318

degradation of starch macromolecules to give sugars with lower molecular weights

319

and higher reduction power; and (iii) increasing the affinity of the free hydroxyl

12

Page 12 of 24

groups of the so-obtained sugars by removing the protons which in turns acted in

321

reduction of silver ions and generating of nano-silver. Compared to starch derivatives,

322

alkalized starch was more effective as a reductant for Ag ions and stabilizer for

323

AgNPs. As Ag0 with size average of 0-10 nm were produced and high

324

concentrated/well dispersed/stable AgNPs (1000 ppm in 100 ml) was obtained using

325

0.1 g starch (El-Rafie et al., 2014).

326

Sodium alginate and Pectin

ip t

320

AgNPs were recently prepared in alginate hydrocolloids using gamma

328

irradiation (Liu et al., 2009), and on the surfaces of alginate microbeads using

329

photochemical reduction (Saha et al., 2009; Saha et al., 2010). Zahran et al.

330

investigated a simple, safe, one-step and cost effective approach for preparation of

331

AgNPs, using sodium alginate which is solubilized in water as a non toxic and

332

ecofriendly solvent for stable/well dispersed AgNPs. Alkali hydrolysis of sodium

333

alginate was carried out to improve its water solubility, and provide more fragments

334

with higher reducibility. Alkali hydrolyzed alginate played the dual role of a reducer

335

for silver ions and stabilizing agent for the synthesized AgNPs. Highly dispersed

336

small spherical AgNPs with narrow size distribution of 1-4 nm was synthesized from

337

the first minute at 70 °C (Zahran et al., 2014a).

us

an

M

d

Alkali hydrolysis of pectin leads to polymeric destruction, and produced more

Ac ce pt e

338

cr

327

339

soluble/accessible/reducible fragments (galacturonic acid, arabinose, galactose,

340

rhamnose, glucose, mannose, and xylose), a property that is recently being explored

341

for preparation of silver nanocolloids (Zahran et al., 2014b). These fragments were

342

supposed to interact with silver salt in a redox reaction, which in turn, generates

343

AgNPs with particle size of 5-10 nm (Zahran et al., 2014b). The efficiency of alginate

344

in manufacturing of AgNPs is considered to be higher than that of pectin, as smaller

345

sized AgNPs was produced once Ag salt added to hot alkalized alginate solution.

346

Cyclodexrins

347

β-cyclodextrin grafted poly acrylic acid [β-CD-g-PAA] was prepared by

348

Hebeish et al and this copolymer was used as a reductant and a protecting agent

349

concurrently for nano-silver colloidal solutions (Hebeish et al., 2011). The size of

350

nanoparticles was intensively dependent on the type and concentration of alkali, the

351

graft yield of the copolymer, the concentrations of both silver nitrate and copolymer

13

Page 13 of 24

and the method of heating (thermal, ultrasonic or microwave). As size average of 3–6

353

nm, 7–30 nm and 9–42 nm were obtained using ultrasonic, microwave and thermal

354

radiation respectively. Unmodified β-cyclodextrin which was exposed to alkali

355

hydrolysis, acted as both of nano-silver generator and capping agent for the so-

356

prepared nano-structured silver (Premkumar & Geckeler, 2014). Furthermore, the

357

authors studied the preparation of AgNPs with different sizes and many shapes

358

(spherical, polygonal, rod, wire, flower-like and ant-like) by varying the experimental

359

conditions such as the reactant concentrations and temperature.

360

Xanthan and Acacia gums (Gums)

cr

ip t

352

During autoclaving at 121°C, gum ghatti (Anogeissus latifolia) and gum

362

kondagogu was concurrently used as a reducer and stabilizing agent of AgNPs (Kora

363

et al., 2012; Rastogi et al., 2015). Small controllable size of AgNPs (4.8 – 6.4 nm)

364

was obtained by using 0.1 % gum ghatti after autoclaving for 30 minute. While higher

365

amounts of gum kondagogu (0.5 %) was used to produce enlarged particles with mean

366

size of 2 – 9 nm (Rastogi et al., 2015). More recent, Emam et al was studied the usage

367

of alkali soluble xanthan and acacia in production of well dispersed spherical AgNPs

368

(Emam & Zahran, 2015; Emam & El-Rafie et al., 2015). The high alkalinity acted in

369

activation and increment of the reduction power for the considered gums, by

370

generation of soluble and higher reducible fragments. AgNPs with size ranged

371

between 0 and 25 nm was obtained at 70 °C by using alkalized xanthan. Reducing

372

sugar content measured in colloidal solution was significantly high in case of using

373

xanthan, however, similar sized AgNPs with the same concentration was produced by

374

using the same concentration of acacia gum. The unique advantage of using alkali

375

hydrolyzed acacia gum is that, it could be described as energy saving method, where,

376

AgNPs manufacturing was carried out at room temperature after 30 minutes from

377

mixing alkali hydrolyzed acacia gum with silver salt.

378

III. Conclusion

Ac ce pt e

d

M

an

us

361

379

Using of polysaccharides as templates for preparation of AgNPs has shown to

380

be quite effective, since they are ecofriendly, cost effective, biocompatible,

381

biodegradable and easily processed into different hydrogel shapes. From the

382

represented review, it could be summarized that, polysaccharides were firstly applied

383

as stabilizers for preparation of silver nanoparticles; however, recent researches were

14

Page 14 of 24

interested in application of polysaccharide macromolecule as a reducer and stabilizer

385

concurrently by making some of chemical modifications, in order to increase the

386

solubility, reducibility and accessibility of polysaccharide building units. The most

387

recent researches were focused in preparation of merely silver nanoparticles using

388

removable polysaccharide blocks such like cellulosic fibers. Application of AgNPs

389

based on these findings may lead to valuable discoveries in various fields such as

390

medical devices and antimicrobial agents.

391

IV. References

392

1.

cr

ip t

384

Abdel-Halim E. S., Alanazi H. H, Al-Deyab S. S. (2015). Utilization of hydroxypropyl carboxymethyl cellulose in synthesis of silver nanoparticles.

394

International Journal of Biological Macromolecules, 75, 467–473. 2.

Abdel-Halim E. S., Al-Deyab S. S. (2011). Utilization of hydroxypropyl cellulose

an

395

us

393

for green and efficient synthesis of silver nanoparticles. Carbohydrate Polymers,

397

86, 1615–1622.

398

3.

M

396

Abdel-Mohsen A. M., Abdel-Rahman R. M., Fouda M. M. G., Vojtova L., Uhrova L., Hassan A.F., Al-Deyab S. S., El-Shamy I. E., Jancar J. (2014).

400

Preparation, characterization and cytotoxicity of schizophyllan/silvernanoparticle

401

composite. Carbohydrate Polymers, 102, 238– 245. 4.

403

core shell nanoparticles. Journal of Polymer Environment, 20:459–468.

5.

406

Abdel-Mohsen A. M., Radim H., Ladislav B., Gabriela K., Rasha M. A., Anna K., Milos S., Ludvik B. (2012b). Green synthesis of hyaluronan fibers with silver

407 408

Abdel-Mohsen A. M., Aly A. S., Hrdina R., El-Aref A. T. (2012a). A novel

method for the preparation of silver/chitosan-O-methoxy polyethylene glycol

404 405

Ac ce pt e

402

d

399

nanoparticles. Carbohydrate Polymers, 89, 411– 422.

6.

Ahmadi T. S., Wang Z. L., Green T. C., Henglein A., El-Sayed M. (1996). Shape

409

Controlled Synthesis of Colloidal Platinum Nanoparticles. Science, 272, 1924–

410

1926.

411

7.

Breitwieser D., Moghaddam M., Spirk S., Baghbanzadeh M., Pivec T., Fasl H.,

412

Ribitsch V., Kappe C.(2013b). In situ preparation of silver nanocomposites on

413

cellulosic fibers – Microwave vs. conventional heating. Carbohydrate Polymers,

414

94, 677– 686

15

Page 15 of 24

415

8.

Breitwieser D., Spirk S., Fasl H., Ehmann H., Chemelli A., Reichel V., Gspan

416

C., Stana-Kleinschek K., Ribitsch V. (2013a). Design of simultaneous

417

antimicrobial

418

polysaccharides. Journal of Materials Chemistry B, 1, 2022.

420

9.

anticoagulant

surfaces

based

on

nanoparticles

and

Cai J., Kimura S., Wada M., Kuga S. (2009). Nanoporous Cellulose as Metal Nanoparticles Support. Biomacromolecules, 10, 87–94.

ip t

419

and

10. Castonguay A., Kakkar A. K. (2010). Dendrimer Templated Construction of

422

Silver Nanoparticles. Advances in Colloid and Interface Science, 160, 76–87.

423

11. Cheng D., Zhou X., Xia H., Chan H. S. O. (2005). Encapsulating Pd

424

Nanoparticles in Double-Shelled Graphene @ Carbon Hollow Spheres for

425

Excellent Chemical Catalytic Property. Chemical Materials, 17, 3578–3581.

426

12. Chou K. S., Ren C. Y. (2000). Synthesis of nanosized silver particles by chemical

us

an

427

cr

421

reduction method. Materials Chemistry and Physics, 64, 241–246. 13. Doughty M. J., Glavin S. (2009). Efficacy of Different Dry Eye Treatments with

429

Artificial Tears or Ocular Lubricants: A Systematic Review, Ophthalmic and

430

Physiological Optics, 29, 573–583.

d

M

428

14. El-Rafie M. H., Ahmed H. B., Zahran M. K. (2014). Facile precursor for

432

synthesis of silver nanoparticles using alkali treated maize starch, International

433

Ac ce pt e

431

Scholarly Research Notices, ID 702396, 12.

434

15. El-Rafie M. H., El-Naggar M. E., Ramadan M. A., Fouda M. M.G., Al-Deyab S.

435

S., Hebeish A. (2011). Environmental synthesis of silver nanoparticles using

436 437 438 439

hydroxypropyl starch and their characterization. Carbohydrate Polymers, 86,

630–635.

16. El-Sheikh M. A. (2014). A Novel Photosynthesis of Carboxymethyl StarchStabilized Silver Nanoparticles. Scientific World Journal, ID 514563, 11.

440

17. El-Sheikh M. A., El-Rafie S. M., Abdel-Halim E. S., El-Rafie M. H. (2013).

441

Green Synthesis of Hydroxyethyl Cellulose-Stabilized Silver Nanoparticles.

442

Journal of Polymers, ID 650837, 11.

443 444

18. Emam H. E., El-Bisi M. K. (2014). Merely Ag nanoparticles using different cellulose fibers as removable reductant, Cellulose, 21, 4219–4230.

16

Page 16 of 24

445

19. Emam H. E., El-Rafie M. H., Ahmed H. B., Zahran M. K. (2015). Room

446

Temperature Synthesis of Metallic Nanosilver Using Acacia to Impart Durable

447

Biocidal Effect on Cotton Fabrics. Fibers and Polymers, 16(8), 1676–1687. 20. Emam H. E., Manian A. P., Široká B., Duelli H., Redl B., Pipal A., Bechtold T.

449

(2013). Treatments to Impart Antimicrobial Activity to Clothing and Household

450

Cellulosic-Textiles – Why “Nano”-silver?. Journal of Cleaner Production, 39, 17-

451

23

ip t

448

21. Emam H. E., Mowafi S., Mashaly H. M., Rehan M. (2014). Production of

453

antibacterial colored viscose fibers using in situ prepared spherical Ag

454

nanoparticles. Carbohydrate Polymers, 110, 148–155.

us

cr

452

22. Emam H. E., Saleh, N. H., Khaled S. Nagy, Zahran M. K. (2015a).

456

Functionalization of Medical Cotton by Direct Incorporation of Silver

457

nanoparticles. International Journal of Biological Macromolecules, 78, 249–256.

an

455

23. Emam H. E., Zahran M. K. (2015b). Ag0 nanoparticles containing cotton fabric:

459

Synthesis, characterization, color data and antibacterial action, International

460

Journal of Biological Macromolecules, 75, 106–114.

d

462

24. Ershov B. G., Abkhalimov E. V. (2007). Nano-size precursors as building blocks for monodispersed colloids. Colloid Journal, 69, 29-38.

Ac ce pt e

461

M

458

463

25. Evanoff D. Jr., Chumanov G. J. (2004). Size-Controlled Synthesis of

464

Nanoparticles: II. Measurement of Extinction, Scattering, and Absorption Cross

465

Sections. Journal of Physical Chemistry: B, 108(37), 13948–13957.

466

26. Fasl H., Stana J., Stropnik D., Strnad S., Stana-Kleinschek K. Ribitsch, V. (2010).

467

Improvement of the Hemocompatibility of PET Surfaces Using Different

468 469

Sulphated Polysaccharides as Coating Materials. Bio-macromolecules, 11, 377–

381.

470

27. Fasl H., Zemljic L. F., Goessler W., Stana-Kleinschek K., Ribitsch V. (2012).

471

Investigations into Amphiphilic Chitosan: Properties and Availability of Original

472

and Newly Introduced Functional Groups. Macromolecules Chemistry and

473

Physics, 213, 1582– 1589.

17

Page 17 of 24

474

28. Francis L., Balakrishnan A., Sanosh K. P., Marsano E. (2010). Hydroxy propyl

475

cellulose capped silver nanoparticles produced by simple dialysis process.

476

Materials Research Bulletin, 45, 989–992. 29. Guoping L., Wenting L., Yunjun L., Min X., Chunpeng C., Xiaoqing W. Chin.

478

(2012). Synthesis and Characterization of Dendrimer-Encapsulated Bimetallic

479

Core-Shell Pd Pt Nanoparticles. Journal of Chemistry, 30, 541-546.

ip t

477

30. Harriman, A., Thomas J. M., Millward G. R. (1987). Catalytic and Structural

481

Properties of Iridium Iridium Dioxide Colloids. New Journal of Chemistry, 11,

482

757-762.

cr

480

31. Hebeish A. A., El-Rafie M. H., Abdel-Mohdy F. A., Abdel-Halim E. S., Emam

484

H. E. (2010). Carboxymethyl cellulose for green synthesis and stabilization of

485

silver nanoparticles. Carbohydrate Polymers, 82, 933-941.

an

us

483

32. Hebeish A., El-Shafei A., Sharaf S., Zaghloul S. (2011). Novel precursors for

487

green synthesis and application of silver nanoparticles in the realm of cotton

488

finishing. Carbohydrate Polymers, 84, 605–613.

M

486

33. Hebeish A., Farag S., Sharaf S., Shaheen Th. I. (2014). Development of cellulose

490

nanowhisker-polyacrylamide copolymer as a highly functional precursor in the

491

synthesis of nanometal particles for conductive textiles. Cellulose, 21, 3055–3071

Ac ce pt e

d

489

492

34. Heilmann A. (2003). Polymer Films with Embedded Metal Nanoparticles.

493

Springer series In Materials Science, 52, Berlin, New York: Springer, X, 216.

494

35. Huang L., Liao W., Ling H., Wen T. (2009). Simultaneous Synthesis of

495

Polyaniline Nanofibers and Metal (Ag and Pt) Nanoparticles. Materials

496

Chemistry and Physics, 116, 474–478.

497

36. Hussain M. A., Shah A., Jantan I., Shah M. R., Tahir M. N., Ahmad R., Bukhari

498

S. N. A. (2015). Hydroxypropylcellulose as a novel green reservoir for the

499

synthesis, stabilization, and storage of silver nanoparticles. International Journal

500

of Nanomedicine, 10, 2079–2088.

501

37. Hutchinson J. E. (2008). Greener Nanoscience: A Proactive Approach to

502

Advancing Applications and Reducing Implications of Nanotechnology". ACS

503

Nano, 2, 395–402.

18

Page 18 of 24

504

38. Ishihara M., Nguyen V.Q., Mori Y., Nakamura S., Hattori H.(2015).Adsorption

505

of Silver Nanoparticles onto Different Surface Structures of Chitin/Chitosan and

506

Correlations with Antimicrobial Activities. International Journal of Molecular

507

Science, doi: 10.3390/ijms160613973. 39. Jin R., Cao Y. W., Mirkin C. A., Kelly K. L., Schatz G. C., Zheng J. G. (2001).

509

Photoinduced Conversion of Silver Nano-spheres to Nano-prisms. Science, 294,

510

1901-1903.

514 515

cr

513

Metal Nanoparticles. Journal of Physics Chemistry B, 106, 7729–7744.

41. Kamel S. (2007). Nanotechnology and its applications in lignocellulosic

us

512

40. Kamat P. V. (2002). Photophysical, Photochemical and Photocatalytic Aspects of

composites, a mini review, Express Polymer Letters, 1, 546–575.

42. Kemp M. M., Kumar A., Clement D., Ajayan P., Mousa S., Linhardt R. J.

516

(2009b).

and

Heparin-Reduced

Silver

Nanoparticles

517

Antimicrobial Properties. Nanomedicine (London), 4, 421-429.

with

M

Hyaluronan

an

511

ip t

508

43. Kemp M.M., Kumar A., Mousa S. (2009a). Gold and Silver Nanoparticles

519

Conjugated with Heparin Derivative Possess Antiangiogenesis Properties.

520

Nanotechnology, 20, 455104 - 455111.

d

518

44. Kibeche A., Dionne A., Brion-Roby R., Gagnon C., Gagnon J.(2015).Simple and

522

green technique for sequestration and concentration of silver nanoparticles by

527

46. Kong M., Chen X. G., Xing K., Park H. J. (2010). Antimicrobial properties of

528

Ac ce pt e

521

chitosan and its mode of action: state of the art review. International Journal of

529

Food Microbiology, 144, 51–63.

523 524 525 526

polysaccharides immobilized on glass beads in aqueous media. Chemical Center Journal, doi: 10.1186/s13065-015-0110-7.

45. Knoll B., Keilmann F. (1999). Near-Field Probing of Vibrational Absorption for Chemical Microscopy. Nature, 399, 134–137.

530

47. Kora A. J., Beedu S. R., Jayaraman A. (2012). Size-controlled green synthesis of

531

silver nanoparticles mediated by gum ghatti (Anogeissus latifolia) and its

532

biological activity. Organic and Medicinal Chemistry Letters, 2, 17–27

19

Page 19 of 24

533

48. Kozan M., Thangala J., Bogale R., Mengüç M. P., Sunkara, M. K. (2008). In-Situ

534

characterization of Dispersion Stability of WO3 Nanoparticles and Nanowires.

535

Journal of Nanoparticle Research, 10, 599-612. 49. Kulterer M. R., Reichel V. E., Kargl R., Ostler S. K., Sarbova V., Heinze T.,

537

Stana-Kleinschek K., Ribitsch, V. (2012). Functional Polysaccharide Composite

538

Nanoparticles from Cellulose Acetate and Potential Applications. Advanced

539

Functional Materials, 8, 1749–1758.

ip t

536

50. Laudenslager M. J., Schiffman J. D., Schauer C. L. (2008). Carboxymethyl

541

Chitosan as A Matrix Materials for Platinum, Gold and Silver Nanoparticles.

542

Biomacromolecules, 9, 2682-2685.

us

cr

540

51. Li Y., Liu J., Wang Y., Wang Z. L. (2001). Preparation of Mono-dispersed

544

Fe−Mo Nanoparticles as the Catalyst for CVD Synthesis of Carbon Nanotubes".

545

Chemistry of Materials, 13, 1008-1014.

an

543

52. Long D., Wu G., Chen S. (2007). Preparation of oligochitosan stabilized silver

547

nanoparticles by gamma irradiation. Radiation Physics Chemistry, 76, 1126–

548

1131.

M

546

53. Ma Y., Li N., Yang C., Yang X. (2005). One-Step Synthesis of Aminodextran-

550

Protected Gold and Silver Nanoparticles and Its Application in Biosensors.

Ac ce pt e

551

d

549

Analysis and Bio-analysis Chemistry, 382, 1044–1048.

552

54. Malinsky M. D., Kelly K. L., Schatz G. C., Van D. R.P. (2001). Nano-sphere

553

lithography: Effect of Substrate on the Localized Surface Plasmon Resonance

554 555

spectrum of Silver Nanoparticles. Journal of Physical Chemistry B, 105, 2343-

2350.

556

55. Mata Y. N., Torres E., Blazquez M. L., Ballester A., Gonzalez F., Munoz J. A.

557

(2009). Gold (III) Biosorption and Bioreduction with The Brown Alga Fucus

558

Vesiculosus. Journal of Hazard Materials, 166, 612–618.

559

56. Merga G., Wilson R., Lynn G., Milosavljevic B. H., Meisel D. (2007). Redox

560

catalysis on “naked” silver nanoparticles. Journal of Physical Chemistry, 111,

561

12220–12226.

562 563

57. Nadkarni V. D., Pervin A., Linhardt R. J. (1994). Directional Immobilization of Heparin onto Beaded Supports. Analysis and Biochemistry, 222, 59–67.

20

Page 20 of 24

564

58. Nickel U., Castell A. Z., Poppl K., Schneider S. A. (2000). Silver colloid

565

produced by reduction with hydrazine as support for highly sensitive surface-

566

enhanced Raman spectroscopy. Langmuir, 16, 9087–9091. 59. Pal S., Tak Y. K., Joardar J., Kim W., Lee J. E., Han M. S., Song J. M. (2009).

568

Nanocrystalline Silver Supported on Activated Carbon Matrix from Hydrosol:

569

Antibacterial Mechanism under Prolonged Incubation Conditions. Journal of

570

Nanosciences and Nanotechnology, 9, 2092–2103.

ip t

567

60. Panyala N. R., Pena M. E. M., Havel J. (2008). Silver or Silver Nanoparticles: A

572

Hazardous Threat to The Environment and Human Health?. Journal of Applied

573

Biomedicines, 6, 117–129.

us

575

61. Petit C., Lixon P., Pileni M. (1993). In situ synthesis of silver nanocluster in AOT reverses micelles. Journal of Physical Chemistry B, 97, 12974–12983.

an

574

cr

571

62. Potara M., Maniu D., Astilean S. (2009). The Synthesis of Biocompatible and

577

SERS-Active Gold Nanoparticles Using Chitosan. Nanotechnology, 20, 315602-

578

315607.

M

576

63. Premkumar T., Geckeler K. E. (2014). Facile Synthesis of Silver Nanoparticles

580

Using Unmodified Cyclodextrin and Their Surface-Enhanced Raman Scattering

581

Activity. New Journal of Chemistry, 38, 2847-2855.

Ac ce pt e

d

579

582

64. Rastogi L., Arunachalam J. (2011). Sunlight Based Irradiation Strategy for Rapid

583

Green Synthesis of Highly Stable Silver Nanoparticles Using Aqueous Garlic

584 585

(Allium Sativum) Extract and Their Antibacterial Potential. Materials Chemistry and Physics, 129, 558–563.

586

65. Rastogi L., Kora A. J., Sashidhar R. B. (2015). Antibacterial effects of gum

587

kondagogu reduced/stabilized silver nanoparticles in combination with various

588

antibiotics: a mechanistic approach. Applied Nanoscience, 5, 535–543.

589

66. Rehan M., Mashaly H. M., Mowafi S., Abou El-Kheir A., Emam H. E. (2015).

590

Multi-Functional Textile Design using in-situ Ag NPs Incorporation into Natural

591

Fabric Matrix. Dyes and Pigments, 118, 9-17.

592

67. Richter T. V., Schüler F., Thomann R., Mülhaupt R., Ludwigs S. (2009).

593

Nanocomposites of Size-Tunable ZnO-Nanoparticles and Amphiphilic Hyper

594

Branched Polymers. Macromolecular Rapid Communications, 30, 579–583.

21

Page 21 of 24

595

68. Saha S, Pal A, Pande S, Sarkar S, Panigrahi S, Pal T. (2009). Alginate Gel-

596

Mediated Photochemical Growth of Mono- and Bimetallic Gold and Silver

597

Nanoclusters and Their Application to Surface-Enhanced Raman Scattering.

598

Journal of Physical Chemistry C, 113, 7553–7560. 69. Saha S., Pal A., Kundu S., Basu S., Pal T. (2010). Photochemical Green

600

Synthesis of Calcium-Alginate-Stabilized Ag and Au Nanoparticles and Their

601

Catalytic Application to 4-Nitrophenol Reduction. Langmuir, 26, 2885–2893.

602

70. Scott R. W. J., Wilson O. M., Crooks R. M. (2005). Synthesis, Characterization,

603

and Applications of Dendrimer-Encapsulated Nanoparticles. Journal of Physical

604

Chemistry B, 109, 692–704.

us

cr

ip t

599

71. Sengupta S., Eavarone D., Capila I., Zhao G. L., Watson N., Kiziltepe T.,

606

Sasisekharan R. (2005). Temporal Targeting of Tumour Cells and Neovasculature

607

with A Nanoscale Delivery System. Nature, 436, 568–572.

an

605

72. Shirtcliffe N., Nickel U., Schneider S. (1999). Reproducible preparation of silver

609

sols with small particle size using borohydride reduction: for use as nuclei for

610

preparation of larger particles. Journal of Colloid Interface Science, 211(1), 122–

611

129.

d

M

608

73. Sondi I., Goia D. V. Matijevic E. (2003). Preparation of Highly Concentrated

613

Stable Dispersions of Monodispersed Silver Nanoparticles. Journal of Colloid

614 615 616

Ac ce pt e

612

Interface Science, 260, 75–81.

74. Sun Y., Xia Y. (2002). Shape-Controlled Synthesis of Gold and Silver Nanoparticles. Science, 298, 2176–2179.

617

75. Thomas V., Yallapu M. M., Sreedhar B., Bajpai S. K. (2009). Fabrication,

618

Characterization of Chitosan/Nanosilver Film and Its Potential Antibacterial

619

Application. Journal of Biomaterial Science Polymer, 20, 2129–2144.

620

76. Tummalapalli M., Deopura B. L., Alam M.S., Gupta B. (2015). Facile and green

621

synthesis of silver nanoparticles using oxidized pectin. Material Science and

622

Engneering C: Material Biology Application. doi: 10.1016/j.msec.2015.01.055.

623 624

77. Ullman A. (1996). Formation and Structure of Self-Assembled Monolayers. Chemical Reviewer, 96, 1533–1554.

22

Page 22 of 24

625

78. Vigneshwaran N., Ashtaputre N., Varadarajan P., Nachane R., Paralikar K.,

626

Balasubramanya R . (2007). Biological Synthesis of Silver Nanoparticles Using

627

The Fungus Aspergillus Flavus. Material Letters, 61, 1413–1418.

628 629

79. Warrier R., Burrell R. (2005). Infection and The Chronic Wound: A Focus On Silver. Advances in Skin and Wound Care, 18, 2–12. 80. Wei D., Qian W. (2008). Facile Synthesis of Ag and Au Nanoparticles Utilizing

631

Chitosan as a Mediator Agent. Colloids and Surfaces: B Biointerfaces, 62, 136–

632

142.

cr

ip t

630

81. Wei D., Qian W., Wu D., Xia Y., Liu X. (2009). Synthesis, Properties, And

634

Surface Enhanced Raman Scattering of Gold and Silver Nanoparticles In

635

Chitosan Matrix. Journal of Nanosciences and Nanotechnology, 9, 2566–2573.

636

82. White W. C., Bellfield R., Ellis J., Vandendaele, I. P. (2010). Controlling the

637

Spread of Infections in Hospital Wards by the Use of Antimicrobials on Medical

638

Textiles and Surfaces. In: Medical And Healthcare Textiles, Wood head

639

Publishing Limited.

641

an

M

83. Wiley B., Sun Y., Xia Y. (2007). Synthesis of Silver Nanostructures with Controlled Shapes and Properties. Accounts Chemical Research, 40, 1067–1076.

d

640

us

633

84. Yoksan R., Chirachanchai S. (2009). Silver Nanoparticles Dispersing In Chitosan

643

Solution: Preparation by Gamma-Ray Irradiation and Their Antimicrobial

644 645 646

Ac ce pt e

642

Activities. Material Chemistry and Physics, 115, 296–302.

85. Zahran M. K., Ahmed H. B., El-Rafie M. H. (2014a). Alginate Mediate for Synthesis Controllable Sized AgNPs. Carbohydrate Polymers, 111, 10–17.

647

86. Zahran M. K., Ahmed H. B., El-Rafie M. H. (2014b). Facile Size-Regulated

648

Synthesis of Silver Nanoparticles Using Pectin. Carbohydrate Polymers, 111,

649

971–978.

650 651

Highlights

652

The review focuses on recent synthesis protocols for AgNPs using polysaccharides

653

Polysaccharides were firstly applied as capping agents for metal nanoparticles

23

Page 23 of 24

654

Recently polysaccharides were used as both of reducer and stabilizer for AgNPs

655

Pure AgNPs colloidal solutions are recently prepared by removable polysaccharides

656 657

Ac ce pt e

d

M

an

us

cr

ip t

658

24

Page 24 of 24