SDS Composite Nanoparticles and Its

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Preparation of Lignin/SDS Composite Nanoparticles and Its Application in Pickering Emulsion Template based Microencapsulation Yuxia Pang, Shengwen Wang, Xueqing Qiu, Yanling Luo, Hongming Lou, and Jinhao Huang J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.7b03784 • Publication Date (Web): 20 Nov 2017 Downloaded from http://pubs.acs.org on November 20, 2017

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Journal of Agricultural and Food Chemistry

Preparation of Lignin/SDS Composite Nanoparticles and Its Application in Pickering Emulsion Template based Microencapsulation Yuxia Pang,† Shengwen Wang,† Xueqing Qiu,†, ‡, * Yanling Luo,† Hongming Lou,†, ‡, *

and Jinhao Huang.†

† School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, China. ‡ State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou, China. * Corresponding authors: Dr. Xueqing Qiu School of Chemistry and Chemical Engineering South China University of Technology Wu Shan Road, Guangzhou 510640, China E-mail: [email protected] Dr. Hongming Lou School of Chemistry and Chemical Engineering South China University of Technology Wu Shan Road, Guangzhou 510640, China E-mail: [email protected]

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ACS Paragon Plus Environment


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ABSTRACT

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Lignin is a vastly underutilized biomass resource. The preparation of water dispersed

3

lignin nanoparticles is an effective way to realize the high-value utilization of lignin.

4

However, the currently reported preparation methods of lignin nanoparticles still have

5

some drawbacks, such as the requirement for toxic organic solvent or chemical

6

modification, complicated operation process and poor dispersibility. Here, lignin/SDS

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composite nanoparticles (LSNPs) with outstanding water dispersibility and a size

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range of 70-200 nm were facilely prepared via acidifying the mixed basic solution of

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alkaline lignin and sodium dodecyl sulfate (SDS). No harsh chemical was needed.

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The formation mechanism was systematically studied. Results indicated that the

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LSNPs were obtained by acid precipitation of the mixed micelles formed by the

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self-assembly of lignin and SDS. In addition, based on the LSNPs-stabilized

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Pickering emulsions, lignin/polyurea composite microcapsules combining the

14

excellent chemical stability of synthetic polyurea shell with the fantastic

15

antiphotolysis and antioxidant properties of lignin were successfully prepared.

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Keywords: lignin, nanoparticle, Pickering emulsion, microcapsules

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INTRODUCTION

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Lignin is the most abundant aromatic natural polymer on the earth. Unfortunately, due

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to the complexity of the lignin structure with extremely broad molecular weight

20

distributions and poor water solubility,1 lignin finds very limited application in certain

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areas, such as surfactant, coloring agent, dyes, adhesives, polymer additives, and other

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uses.2-5 Lignin nanoparticles dispersed in the neutral or acidic water were found to be

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a multifunctional material which have many potential applications such as adsorbing

24

heavy metal ions in waste water,6 stabilizing Pickering emulsions,7-9 and

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strengthening phenolic foam.10 Thus the preparation of lignin nanoparticles is an

26

effective way to realize the high value utilization of lignin and has attracted

27

tremendous attention recently.7, 11, 12

28

In recent years, many researchers have introduced several lignin nanoparticle

29

preparation methods. Solvent-based processes are by far the most common methods

30

used to prepare lignin nanoparticles, which mainly include solvent exchange

31

precipitation11,

32

method for the preparation of colloidally stable lignin nanoparticles through dialysis.13

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Ago et al. prepared lignin particles via aerosol flow reactor.8 Bian et al. successfully

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prepared lignin nanoparticles by simply diluting the spent lignin p-toluenesulfonic

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acid liquor.18, 19 Meanwhile, researchers also prepared lignin particles by chemical

36

polymerization

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microemulsions.21 Besides, Gilca et al. obtained lignin nanoparticles by sonication.22

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Among those reported lignin nanoparticle preparation methods, toxic or harmful

13-19

and spray drying.8 For instance, Lievonen et al. proposed a

such

as

suspension

polymerization20 and cross-linking

3


in


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organic solvents, chemical modification on lignin or strict operation condition were

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needed. Meanwhile, due to the low surface charge, the lignin nanoparticles prepared

41

by some reported methods were prone to aggregate after long time standing. The

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research by Stewart et al. revealed that the addition of sodium dodecyl sulfate (SDS)

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or cetyltrimethylammonium bromide (CTAB) had a dramatic effect on improving the

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stability and reducing the size of lignin microparticles.23 However, the relatively high

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concentration of surfactants in the system may limits the further application of the

46

lignin microparticles.

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Alkaline lignin, recovered from the pulping black liquor, has a significant solubility in

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aqueous solutions at high pH (above pH 10), however, in acidic conditions, alkaline

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lignin becomes insoluble and micron aggregations are formed. Here, in this work,

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lignin/SDS composite nanoparticles (LSNPs) were facilely prepared via acidifying the

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mixed basic solution of alkaline lignin and sodium dodecyl sulfate (SDS) under the

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absence of any toxic or harmful organic solvents which was frequently used in other

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methods. The LSNPs dispersed stably in water by the electrostatic repulsion between

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sulfates. Pure LSNP dispersion could be obtained after removing the free SDS by

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dialysis. SDS is an anionic surfactant which is low toxic to humans and is commonly

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used in household detergents, personal care products and pharmaceuticals due to their

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ability to decrease the interfacial tension.24,

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remained in the LSNPs after dialysis. Therefore, this novel LSNPs possess the

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potential of being used in some high value-added field like cosmetic and food

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industry.

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Only a small amount of SDS was

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Thanks to the special performance of antiphotolysis and antioxidant devoted by the

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polyphenolic structure of lignin,26-28 successful utilization of lignin to embed

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avermectin has been reported in literatures and shown a good antiphotolysis

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performance.29, 30 Besides, it is worth noting that based on the concept of Pickering

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emulsion template, biopolymer based microcapsules has been successfully prepared

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through ionic cross-linking recently.31, 32 The polyanionic biopolymers can be gelled

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by ionic cross-linking with divalent cations (e.g., Ca2+) at room temperature to form

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an insoluble matrix, this provides an efficient method for microencapsulation.

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However, due to the permeability of the porous hydrogel-type microstructure, it

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remains very challenging for encapsulation of some volatile small molecules by

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biopolymer-based shell materials, in particular for aldehydes, ketones, and other

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phytochemicals used as fragrances, flavors, or insect repellents.33, 34 To protect the

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liquid core, capsules with polyurea or urea formaldehyde shell materials have

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previously been shown to provide good stability and mechanical characteristics.35, 36

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As an application of the novel LSNPs in this work, the LSNPs were successfully used

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to stabilize Pickering emulsions. Besides, based on the LSNPs-stabilized Pickering

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emulsions, we prepared lignin/polyurea

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combining a strong chemical shell formed by synthetic polyurea with the excellent

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antiphotolysis and antioxidant properties of lignin. The LSNPs adsorbed at the O/W

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interface of Pickering emulsion droplets were ionically cross-linked with the

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positively charged ethylenediamine hydrochloride (EH) ions to form the lignin shell

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and the polyurea shell was formed by interfacial polymerization reaction between

composite microcapsules (LPMCs)

5



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isophorone diisocyanate (IPDI) and ethylenediamine (EDA). The microcapsules were

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characterized using a particle size analyzer, optical microscopy, confocal laser

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scanning microscopy (CLSM), and field emission scanning electron microscopy.

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Taking the excellent chemical stability of synthetic polyurea shell with the fantastic

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antiphotolysis and antioxidant properties of lignin into account, these LPMCs are

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expected to be a good microcontainer for some photosensitive or oxygen sensitive

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small molecules.

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In a word, stable and nontoxic LSNPs were facilely prepared via acidifying the mixed

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basic solution of alkaline lignin and SDS. Finally, oil-in-water Pickering emulsion and

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LPMCs were successfully prepared with the prepared LSNPs.

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MATERIALS AND METHODS

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Materials

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Alkaline lignin was derived by first acidifying the black liquor provided by

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Xiangjiang Paper Industry Co., Ltd. (Hunan, China) and then purified by filtration

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with ultrapure water. The functional group and molecular weight data of alkaline

98

lignin according to non-aqueous potential titration and GPC respectively are given in

99

Table 1. Ethylenediamine (EDA), isophorone diisocyanate (IPDI), Sodium dodecyl

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sulfate (SDS) were purchased from energy chemical (China). Hydrochloric acid (HCl),

101

Sodium hydroxide (NaOH), and cyclohexane were bought from Guangzhou Chemical

102

Factory (China). All the reagents were analytic grade and used without further

103

purification. Ultrapure water was used throughout the study.

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Preparation of lignin/SDS composite nanoparticles (LSNPs) 6


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LSNPs were successfully prepared using a method based on acid precipitation, it can

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be briefly described as follows: Firstly, 1 g alkaline lignin was added into 100 ml

107

ultrapure water, and the pH of the lignin dispersion was adjusted to 11 using 4 M

108

NaOH under stirring. The resulting lignin solution (1wt%, pH 11) was stirred

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overnight to ensure complete dissolution of lignin and was filtered in order to remove

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the impurities before usage. Subsequently, SDS was added in amounts that lead to

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concentrations of SDS in the final solution of 0, 4, 6, 8, 10, and 12 mM to the 100 ml

112

lignin solution with a magnetic stirring for 30 min. Finally, the LSNPs were formed

113

by adjusting the pH of the mixed solution to 2.5 with 1 M HCl under stirring. After

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standing overnight, in order to remove the inorganic salts like sodium chloride and the

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free SDS, the prepared LSNP dispersion was introduced into a dialysis bag

116

(MWCO=10 kDa) which was then immersed in excess ultrapure water (periodically

117

replaced) for 5d. The mean particle size and zeta potential of LSNPs before and after

118

dialysis were determined and the sulfur content of LSNPs after dialysis were

119

analyzed.

120

Preparation of Lignin Particles (LPs)

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1 g alkaline lignin was added into 100 ml ultrapure water, and the pH of the lignin

122

dispersion was adjusted to 11 using 4 M NaOH under stirring. The resulting lignin

123

solution was stirred overnight to ensure complete dissolution of lignin and was

124

filtered in order to remove the impurities before usage. LPs were then prepared by

125

directly acidifying the lignin solution to a pH of 2.5 with 1 M HCl under stirring.

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Effects of SDS on LPs 7



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SDS was added in amounts that lead to concentrations of SDS in the final LP

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dispersion of 0, 4, 6, 8, 10, and 12 mM to the above LP dispersion with a magnetic

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stirring for 30 min to ensure the added SDS were completely dissolved. After standing

130

overnight, the resulting dispersion were subjected to the same dialysis process as the

131

LSNP dispersion. The mean particle size and zeta potential of LPs before and after

132

dialysis were determined and the sulfur content of LPs after dialysis were analyzed.

133

The Gelation of LSNPs

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10 ml of the dialysed LSNP dispersion prepared at an initial SDS concentration of

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12mM were transferred to a 30 ml sample bottle, and an excess of EH solution

136

(prepared by adding HCl to the 1M EDA solution to a pH of 2.5.) was added to the

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LSNP dispersion with a magnetic stirring. After standing for half an hour, the particle

138

size distribution of the LSNP aggregations was determined by dynamic light

139

scattering measurements.

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Preparation of LSNPs-stabilized Pickering Emulsions (LSNPEs)

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The lignin concentration of the dialysed LSNP dispersion (≈0.6 wt%, pH≈3.5)

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prepared at an initial SDS concentration of 12 mM was adjusted to 0.5% by adding

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water. The resulted LSNP dispersion was used as the aqueous phase, cyclohexane

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containing 10wt% IPDI as the oil phase was added to the aqueous phase and the

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system was emulsified at 11000 rpm for 3 min with a homogenizer (IKA Ultra Turrax

146

T25 basic instrument) to obtain a LSNPs stable Pickering emulsions. The volume

147

fraction of cyclohexane was fixed in 10% (v/v).

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Preparation of lignin/polyurea composite microcapsules (LPMCs) 8


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The above prepared emulsion was transferred into a two-necked flask, heated in a 35 ℃

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water bath and slowly stirred at 200 rpm with a stir bar, 15 ml of 1.5 M EDA solution

151

was added to the system drop by drop by using a peristaltic pump in 1 h. The reaction

152

was conducted for 6 h, and the LPMCs were efficiently formed.

153

Characterizations

154

The mean particle size of the LSNPs and LPs and the particle size distribution of the

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LSNP aggregations were determined by dynamic light scattering measurements at 25 ℃

156

using a particle size analyzer (Zetasizer Nano-ZS, Malvern Instruments, UK), whereas

157

the zeta potential of the LSNPs and LPs were measured at 25 ℃ using the same

158

instrument based on the laser Doppler microelectrophoresis technique. The pH of all

159

samples were adjusted to 2.5 by adding HCl before determination.

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LSNPs were observed by transmission electron microscopy (TEM, JEM-100CX.

161

Japan). The sample was prepared by dropping the LSNP dispersion to a carbon-coated

162

copper grid followed by dried at room temperature.

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The sulfur on the pure alkaline lignin, LSNPs and LPs after dialysis were analyzed by

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a high frequency infrared carbon−sulfur analyzer (QL-HW2000B, QILIN, China.).

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All the samples were freeze-dried before test.

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The size distributions of LSNPEs and LPMCs were studied using a particle size

167

analyzer (Mastersizer 2000, Malvern Instruments. UK) equipped with a Hydro EV

168

wet dispersion unit.

169

Optical microscopy images of the LSNPEs and microcapsules were recorded by a

170

Polarizing Microscope (BM-5000P, China.) equipped with a camera. 9



171

The morphological characteristics of microcapsules were observed by a confocal laser

172

scanning microscopy (Leica TCS-SP5) and field emission scanning electron

173

microscopy (SEM, LEO1530VP).

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RESULTS AND DISCUSSION

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Preparation and Formation Mechanism of lignin/SDS composite nanoparticles

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(LSNPs)

177

This work has developed a simple technology for the preparation of lignin/SDS

178

composite nanoparticle dispersion dispersion. To illustrate the formation mechanism

179

of LSNPs, LSNPs and LPs were prepared separately, and the effects of SDS and

180

dialysis process on their particle size and zeta potential were compared. LSNPs were

181

successfully prepared by adjusting the pH of the lignin/SDS mixed solution from 11

182

to a value of 2.5. Figure 1a showed the phenomenon of preparing LSNPs from

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lignin/SDS mixed basic solution with a SDS concentration of 12 mM, the dialysed

184

LSNP dispersion after a long-time standing was still similar to the homogeneous

185

lignin/SDS mixed basic solution. Similarly, LPs were successfully prepared by

186

adjusting the pH of the lignin solution from 11 to 2.5. Figure 1b showed that the LPs

187

aggregated and precipitated after 10 minutes of standing. Subsequently, the addition

188

of SDS with the amount equal to that in the Figure 1a leading particles to become

189

dispersed to some extent. However, after dialysis process, LPs aggregated and

190

precipitated again.

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The effect of the concentration of SDS added before acid precipitation on the mean

192

particle size and zeta potential of LSNPs are shown in Figure 2a and Figure 2b, 10


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respectively. For the pre-dialysis series, the sample with no SDS had a relatively large

194

mean particle size of 1.8 µm, the particle size was significantly decreased with the

195

increasing SDS concentration, and the minimum size was about 120 nm at a SDS

196

concentration of 12 mM. The absolute value of zeta potential of the dispersion at each

197

SDS concentration is significantly higher than that of the sample without SDS and

198

decreases with the increasing SDS concentration. Meanwhile, for the dialysed series,

199

the particle size of LSNPs at each SDS concentration was smaller than that of the

200

pre-dialysis samples and decreased with the increasing SDS concentration, the

201

minimum particle size of the dialysed LSNPs was about 70 nm at a SDS

202

concentration of 12 mM. The absolute value of zeta potential of the dialysed

203

dispersion at each SDS concentration was also higher than that of the pre-dialysis

204

samples and increases with the increasing SDS concentration.

205

The effect of the concentration of SDS added after acid precipitation on the mean

206

particle size and zeta potential of LPs are shown in Figure 2c and Figure 2d,

207

respectively. As can be seen, SDS added to the LP dispersion also has a significant

208

effect on reducing the mean size and increasing the zeta potential of the LPs, and the

209

LPs before dialysis possessed a relatively small particle size. Nevertheless, after

210

dialysis process, the particle size and zeta potential at each SDS concentration

211

dramatically changed to a value close to that of the sample without SDS. These results

212

indicate that the SDS added after acid precipitation could be removed by dialysis.

213

The sulfur content of the LSNPs and LPs after dialysis are given in Table 2. With the

214

increase in SDS concentration, the sulfur content of LSNPs increased from 1.42wt% 11



215

to 1.61wt%. While, the sulfur content of LPs varied little and were still close to the

216

pure lignin (1.13wt%, analyzed by the same carbon−sulfur analyzer.). The relatively

217

higher sulfur content of LSNPs indicated that a certain amount of SDS was retained in

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the LSNPs after dialysis and the weak change in sulfur content of LPs revealed that

219

the SDS added after acid precipitation has been removed during dialysis indeed.

220

Based on the sulfur content of pure lignin (1.13wt%) and the theoretical sulfur content

221

of SDS (11.1wt%), the composite ratio of SDS in LSNPs could be calculated by a

222

system of linear equations in two unknowns. Here, we use the molar amount of SDS

223

in 1 g of lignin to represent the composite ratio. The results are shown in Table 1. The

224

relatively low SDS composite ratio and pretty good stability of LSNPs is conducive to

225

its high value utilization.

226

The above results showed that the addition order of SDS has a significant effect on the

227

mean size of the particles after dialysis. The co-dissolving of SDS with lignin is a

228

necessary process for the preparation of LSNPs. Besides, lignin is known to possess

229

intriguing intrinsic π-stacking and aggregation properties, as well as to present various

230

hydrophobic interactions.37-39 Therefore, we suggest a hypothesis as shown in Figure

231

3 on the formation mechanism of LSNPs. In the lignin/SDS mixed basic solution, the

232

strong electrostatic repulsion caused by the ionized phenolic hydroxyl and carboxyl

233

makes the network structure of lignin macromolecules stretched and dissolved in

234

water. Under the drive of hydrophobic force, through self-assembly, the hydrophobic

235

long carbon chain in SDS molecule and the stretched network structure of lignin

236

macromolecules interweave together and form a mixed micelle. In this situation, when 12


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reducing the pH of the mixed solution by adding HCl, the ionized phenolic hydroxyl

238

and carboxyl groups are protonated which leading to a reduction in electrostatic

239

repulsion among the molecular skeleton. Subsequently, the hydrophobic interactions

240

and π-π interactions drive the lignin molecular skeleton to contract and clamp the

241

adsorbed SDS to form LSNPs. The intramolecular and intermolecular hydrogen

242

bonding further enhance the tightness of the formed LSNPs. The SDS is a strong

243

electrolyte whose sulfate radicals are still completely ionized even in a low pH

244

environment, thus providing the LSNPs a large number of surface charge which

245

prevent the formation of micron aggregations.

246

Since the electrostatic force between ions is related to the ionic strength in the

247

solution, with a high ionic strength caused by a large amount of free SDS and NaCl

248

produced during the acid precipitation process, the surface negative charge of the

249

LSNPs in the pre-dialysis sample is partially shielded and the absolute value of zeta

250

potential is lower than the dialysed sample, thus leading to the aggregation of

251

particles.

252

On the other hand, SDS added after acid precipitation will adsorb on the surface of the

253

formed lignin particles and result in more dispersive lignin particles, but these SDS

254

weakly adsorbed on the surface were different from the SDS added before acid

255

precipitation and will diffused to the outside of the dialysis bag during dialysis. After

256

dialysis, the lignin particles aggregate together to form larger particles, and the

257

absolute value of zeta potential of the dispersion decreases to a value close to that of

258

the sample without SDS. 13



259

The dialysed LSNPs prepared at an initial SDS concentration of 12 mM were studied

260

by TEM, the result indicated a number-average particle diameter of 40 nm (shown in

261

Figure 4). Nevertheless, dynamic light scattering (DLS) studies of highly dilute

262

aqueous dispersion (0.025wt %) of the same LSNP dispersion indicated their

263

intensity-average diameter was about 70 nm rather than 40 nm, the difference of the

264

results should be ascribed to the different testing conditions between TEM and DLS,

265

the nanoparticles were swollen in the aqueous media for DLS while the hydrophobic

266

chain of SDS tend to collapse onto the lignin core during the drying process of the

267

TEM sample. Besides, the difference can also be attributed to the nonspherical shape

268

of the particles, because DLS measures hydrodynamic particle size.

269

Because of the convenient operation, we purified the residual SDS and salt by dialysis

270

in this work. It is worth noting that dialysis is not practical for large scale production.

271

Fortunately, in industrial production, we can use ion exchange resin to remove

272

residual SDS and salt, the residual SDS and salt can be completely purified after the

273

LSNP dispersion was passed through the strong-acid cation exchange resin and

274

strong-basic anion exchange resin in turn. The particle size of gel type ion exchange

275

resin is 400-600 µm, the pore size of gel type ion exchange resin is 0.5～5 nm, and

276

the particle size of LSNP before purification is about 200 nm, thus the LSNP

277

dispersion can flow smoothly through the resin column. We have successfully purified

278

the SDS and salt by ion exchange resin, the resulting LSNPs has the same particle size

279

and sulfur content as the one purified by dialysis.

280

Characterization of LSNP Gel 14


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As shown in Figure 5a, an excess ethylenediamine hydrochloride (EH) solution

282

(prepared by adding HCl to the 1M EDA solution to a pH of 2.5, which would

283

undergo the reaction shown in Figure 5c) was added to the LSNP dispersion, and after

284

10 minutes of standing it was observed that the LSNP gel formed. The result of

285

dynamic light scattering measurements (Figure 5b) showed that the size of the LSNP

286

aggregations was around 5 µm which is evidently larger than that of the acid

287

precipitated lignin particles. This result indicated that by exploiting the electrostatic

288

attractions between the negatively charged sulfate on LSNPs and the positively

289

charged EH ions, the LSNPs could be gelled by ionic cross-linking with EH ions as

290

shown in Figure 5d.

291

Preparation of LSNPs-stabilized Pickering Emulsions (LSNPEs)

292

Unlike the traditional nonionic or ionic surfactant-based emulsions, Pickering

293

emulsions are stabilized by solid particles at the interface between the dispersed phase

294

and the continuous phase.40,

295

successfully prepared by emulsifying the mixture system of the oil phase

296

(cyclohexane containing 10wt% IPDI) and the aqueous phase (LSNP dispersion,

297

0.5wt%, pH=2.5) with a homogenizer at 11000 rpm for 3 min. Figure 6b is a typical

298

optical microscopy images of the emulsions. The emulsion droplets of

299

cyclohexane-in-water were spherical. Neither obvious droplet size change nor any

300

continuous oil layer was observed for the LSNPEs stored for more than 60 days

301

(Figure 6a,c) which means that the LSNPs with the hydrophobic lignin core and the

302

hydrophilic sulfate is a good emulsifier. Both the formation of a steric barrier by the

41

Here, LSNPEs at 10% (v/v) oil loading were

15



303

hydrophobic lignin core and an electrostatic repulsion provided by the composed SDS

304

contributed to the remarkable stability of the emulsion. Despite of great stability, the

305

emulsions exhibited relatively fast creaming over a period ranging from about 1 h due

306

to the great buoyant forces.

307

Characterization of lignin/polyurea composite microcapsules (LPMCs)

308

LPMCs, based on the LSNPEs template, were prepared by following the procedure

309

displayed in Figure 7. Pickering emulsions were prepared by the method described

310

above. The EDA added to the Pickering emulsion firstly reacted with HCl in the

311

aqueous phase as the way shown in Figure 5c to form ethylenediamine hydrochloride

312

(EH). And as a result, the LSNPs were cross-linked by EH ions at the O/W interface

313

as the way shown in Figure 5d thus forming the lignin microcapsules (LMCs).

314

Meanwhile, the decrease in the repulsion forces permitted the deposition of

315

un-adsorbed LSNPs on the outer wall of the lignin microcapsules. Once the HCl in the

316

aqueous phase was consumed, with the subsequent addition of EDA, the interfacial

317

reaction between EDA and IPDI was conducted to form a layer of polyurea. Finally,

318

LPMCs were generated. Since the isocyanate groups of IPDI at the oil–water interface

319

not only react with EDA but can also reacted with the hydroxyl group in lignin

320

molecules and be hydrolyzed by water to amine groups, also urethane linkages can be

321

found in the capsule shell.

322

The microcapsules were observed with optical microscope, confocal laser scanning

323

microscope (CLSM) and scanning electron microscopy (SEM), the results are shown

324

in Figure 8a-c. Based on the images of SEM and optical microscopy, the 16


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325

microcapsules were spherical in shape and possessed a double layer structure of rough

326

outer layer and relatively smooth inner layer. Taking advantage of the

327

autofluorescence of lignin, CLSM observation were conducted to confirm the

328

existence of lignin on these microcapsules, and the obvious fluorescence indicated

329

that the lignin aggregations were located at the outer surface of the microcapsules.

330

The SEM images showed the lignin layer of the microcapsules was severely cracked,

331

this may be caused by the drying process during the SEM sample preparation. Based

332

on the double-layer structure of the microcapsules and the fantastic antiphotolysis and

333

antioxidant properties of lignin, it is expected that the properties of the microcapsules

334

like

335

photodegradation and oxidative degradation will increase significantly compared to

336

the conventional polyurea microcapsules.

controlling

release

and

protecting

the

embedding

materials

against

337

In addition, the result of the size distribution (see Figure 9) indicated that the

338

volume-average diameter of the microcapsules was larger than the emulsion droplets

339

and showed a bimodal distribution. There are several reasons contributed to this

340

phenomenon. Firstly, the positively charged EH ions produced during the

341

microencapsulation process may have affected the stability of the emulsion stabilized

342

with the negatively charged LSNPs, causing the merging of the droplets thus forming

343

a larger droplets and further forming a larger microcapsules.42,

344

composite shell formed on the surface of the droplets increased the size of the droplets.

345

Thirdly, in the presence of EH ions, some formed LSNP aggregations with a smaller

346

size than microcapsules leading to the bimodal size distribution. 17


43

Secondly, the


347

In summary, a new kind of LSNPs were facilely prepared by acidifying the mixed

348

basic solution of alkaline lignin and SDS, LSNPs with different mean particle size can

349

be prepared by changing the initial concentration of SDS in the mixed solution. The

350

relatively smaller particle size, higher absolute value of zeta potential and sulfur

351

content of LSNPs after dialysis leaded to the conclusion that the co-dissolving of SDS

352

with lignin is a necessary process for the preparation of LSNPs. During the acidifying

353

process, the lignin molecular skeleton in the mixed micelle of lignin and SDS

354

contracted and clamped the adsorbed SDS to form LSNPs. This method can be termed

355

“the physical sulfation of alkaline lignin”. The LSNPs could be gelled by ionic

356

cross-linking with EH ions. To the best of our knowledge, this is the first report about

357

this novel LSNPs. As a proof of possible uses of the LSNPs, they were shown to be

358

effective in stabilizing O/W Pickering emulsions, and could be gelled by ionic

359

cross-linking with divalent cations. Spherical LPMCs covered with a large amount of

360

lignin on the surface were successfully prepared by interfacial polymerization. Thanks

361

to the excellent chemical stability of synthetic polyurea shell with the fantastic

362

antiphotolysis and antioxidant properties of lignin, these LPMCs possess the potential

363

of being a good microcontainer for some photosensitive or oxygen sensitive small

364

molecules.

365

Acknowledgment

366

The authors acknowledge the financial supports of the National Natural Science

367

Foundation of China (21436004, 21676109) and Fundamental Research Funds for the

368

Central Universities (2015ZZ120).

369

18


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370

References

371

(1) King, A. W.; Kilpeläinen, I.; Heikkinen, S.; Järvi, P.; Argyropoulos, D. S.

372

Hydrophobic interactions determining functionalized lignocellulose solubility in

373

dialkylimidazolium chlorides, as probed by 31P NMR. Biomacromolecules. 2009, 10,

374

458.

375

(2) Calvoflores, F. G.; Dobado, J. A. Lignin as renewable raw material. Chemsuschem.

376

2010, 3, 1227.

377

(3) Norgren, M.; Edlund, H. Lignin: Recent advances and emerging applications. Curr.

378

Opin. Colloid Interface Sci. 2014, 19, 409-416.

379

(4) Sahoo, S.; Seydibeyoğlu, M. Ö.; Mohanty, A. K.; Misra, M. Characterization of

380

industrial lignins for their utilization in future value added applications. Biomass

381

Bioenergy. 2011, 35, 4230-4237.

382

(5) Li, Y.; Zhu, H.; Yang, C.; Zhang, Y.; Xu, J.; Lu, M. Synthesis and super retarding

383

performance in cement production of diethanolamine modified lignin surfactant.

384

Constr. Build. Mater. 2014, 52, 116-121.

385

(6) Z, L.; Y, G.; Wan, L. Fabrication of a green porous lignin-based sphere for the

386

removal of lead ions from aqueous media. J. Hazard. Mater. 2015, 285, 77-83.

387

(7) Silmore, K. S.; Gupta, C.; Washburn, N. R. Tunable Pickering emulsions with

388

polymer-grafted lignin nanoparticles (PGLNs). J. Colloid Interface Sci. 2016, 466, 91.

389

(8) Ago, M.; Huan, S.; Borghei, M.; Raula, J.; Kauppinen, E. I.; Rojas, O. J.

390

High-Throughput Synthesis of Lignin Particles (∼30 nm to ∼2 µm) via Aerosol Flow

391

Reactor: Size Fractionation and Utilization in Pickering Emulsions. ACS Appl. Mater.

392

Interfaces. 2016, 8, 23302. 19



393

(9) Yang, Y.; Wei, Z.; Wang, C.; Tong, Z. Lignin-based Pickering HIPEs for

394

macroporous foams and their enhanced adsorption of copper (II) ions. Chem.

395

Commun. 2013, 49, 7144.

396

(10) Saz-Orozco, B. D.; Oliet, M.; Alonso, M. V.; Rojo, E.; Rodríguez, F. Formulation

397

optimization of unreinforced and lignin nanoparticle-reinforced phenolic foams using

398

an analysis of variance approach. Compos. Sci. Technol. 2012, 72, 667-674.

399

(11) Qian, Y.; Deng, Y.; Qiu, X.; Li, H.; Yang, D. Formation of uniform colloidal

400

spheres from lignin, a renewable resource recovered from pulping spent liquor. Green

401

Chem. 2014, 16, 2156-2163.

402

(12) Wurm, F. R.; Weiss, C. K. Nanoparticles from renewable polymers. Front. Chem.

403

2014, 2, 49.

404

(13) Lievonen, M.; Valle-Delgado, J. J.; Mattinen, M. L.; Hult, E. L.; Lintinen, K.;

405

Kostiainen, M. A.; Paananen, A.; Szilvay, G. R.; Setälä, H.; Österberg, M. Simple

406

process for lignin nanoparticle preparation. Green Chem. 2016, 18, 1416-1422.

407

(14) Frangville, C.; Rutkevičius, M.; Richter, A. P.; Velev, O. D.; Stoyanov, S. D.;

408

Paunov, V. N. Fabrication of environmentally biodegradable lignin nanoparticles.

409

Chemphyschem. 2012, 13, 4235–4243.

410

(15) Li, H.; Deng, Y.; Liu, B.; Ren, Y.; Liang, J.; Qian, Y.; Qiu, X.; Li, C.; Zheng, D.

411

Preparation of Nanocapsules via the Self-Assembly of Kraft Lignin: A Totally Green

412

Process with Renewable Resources. ACS Sustainable Chem. Eng. 2016, 4.

413

(16) Stewart, H.; Golding, M.; Matiamerino, L.; Archer, R.; Davies, C. Manufacture

414

of lignin microparticles by anti-solvent precipitation: effect of preparation temperature 20


Page 20 of 37

Page 21 of 37


415

and presence of sodium dodecyl sulfate. Food Res. Int. 2014, 66, 93-99.

416

(17) Richter, A. P.; Bharti, B.; Armstrong, H. B.; Brown, J. S.; Plemmons, D.; Paunov,

417

V. N.; Stoyanov, S. D.; Velev, O. D. Synthesis and Characterization of Biodegradable

418

Lignin Nanoparticles with Tunable Surface Properties. Langmuir. 2016, 32, 6468.

419

(18) Bian, H.; Chen, L.; Gleisner, R.; Dai, H.; Zhu, J. Y. Producing wood-based

420

nanomaterials by rapid fractionation of wood at 80 °C using a recyclable acid

421

hydrotrope. Green Chem. 2017, 19.

422

(19) Chen, L.; Dou, J.; Ma, Q.; Li, N.; Wu, R.; Bian, H.; Yelle, D. J.; Vuorinen, T.; Fu,

423

S.; Pan, X. Rapid and near-complete dissolution of wood lignin at ≤80°C by a

424

recyclable acid hydrotrope. Sci. Adv. 2017, 3, e1701735.

425

(20) Saidane, D.; Barbe, J. C.; Birot, M.; Deleuze, H. Preparation of functionalized

426

lignin beads from oak wood alkaline lignin. J. Appl. Polym. Sci. 2013, 128, 424-429.

427

(21) Nypelö, T. E.; Carrillo, C. A.; Rojas, O. J. Lignin supracolloids synthesized from

428

(W/O) microemulsions: use in the interfacial stabilization of Pickering systems and

429

organic carriers for silver metal. Soft Matter. 2015, 11, 2046.

430

(22) Gilca, I. A.; Popa, V. I.; Crestini, C. Obtaining lignin nanoparticles by sonication.

431

Ultrason. Sonochem. 2015, 23, 369.

432

(23) Stewart, H.; Golding, M.; Matia-Merino, L.; Archer, R.; Davies, C. Surfactant

433

stabilisation of colloidal lignin microparticulates produced through a solvent attrition

434

process. Colloids Surf., A. 2016, 498, 194-205.

435

(24) Gunstone,

436

preparations used in everyday life. (Book Review). Chem. Ind. 2003.

F. Chemical formulation--an overview of surfactant-based

21



437

(25) Myers, D. Surfactant Sci. Technol., Third Edition. 2005.

438

(26) Qian, Y.; Qiu, X.; Zhu, S. Sunscreen Performance of Lignin from Different

439

Technical Resources and Their General Synergistic Effect with Synthetic Sunscreens.

440

ACS Sustainable Chem. Eng. 2016, 4.

441

(27) Qian, Y.; Qiu, X.; Zhu, S. Lignin: A nature-inspired sun blocker for

442

broad-spectrum sunscreens. Green Chem. 2014, 17, 320-324.

443

(28) Chang, H. T.; Su, Y. C.; Chang, S. T. Studies on photostability of butyrylated,

444

milled wood lignin using spectroscopic analyses. Polym. Degrad. Stab. 2006, 91,

445

816-822.

446

(29) Deng, Y.; Zhao, H.; Qian, Y.; Lei, L.; Wang, B.; Qiu, X. Hollow lignin azo

447

colloids encapsulated avermectin with high anti-photolysis and controlled release

448

performance. Ind. Crops Prod. 2016, 87, 191-197.

449

(30) Zhou, B.; Zhao, J. Microencapsulation and Release Kinetics of Abamectin by

450

Layer-by-layer Polyelectrolyte Self-assembly. Fine Chem. 2008.

451

(31) Leong, J. Y.; Tey, B. T.; Tan, C. P.; Chan, E. S. Nozzleless Fabrication of

452

Oil-Core Biopolymeric Microcapsules by the Interfacial Gelation of Pickering

453

Emulsion Templates. ACS Appl. Mater. Interfaces. 2015, 7, 16169.

454

(32) Mwangi, W. W.; Ho, K. W.; Ooi, C. W.; Tey, B. T.; Chan, E. S. Facile method for

455

forming ionically cross-linked chitosan microcapsules from Pickering emulsion

456

templates. Food Hydrocolloids. 2016, 55, 26-33.

457

(33) Jerri, H. A.; Jacquemond, M.; Hansen, C.; Ouali, L.; Erni, P. “Suction Caps”:

458

Designing Anisotropic Core/Shell Microcapsules with Controlled Membrane 22


Page 22 of 37

Page 23 of 37


459

Mechanics and Substrate Affinity. Adv. Funct. Mater. 2016, 26, 6224-6237.

460

(34) Yeo, Y.; Bellas, E.; Firestone, W.; Langer, R.; Kohane, D. S. Complex

461

Coacervates for Thermally Sensitive Controlled Release of Flavor Compounds. J.

462

Agric. Food Chem. 2005, 53, 7518-25.

463

(35) Polenz, I.; Datta, S. S.; Weitz, D. A. Controlling the morphology of polyurea

464

microcapsules using microfluidics. Langmuir. 2014, 30, 13405-10.

465

(36) Dailey, M. M. C.; Silvia, A. W.; Mcintire, P. J.; Wilson, G. O.; Moore, J. S.;

466

White, S. R. A self℃healing biomaterial based on free℃radical polymerization. J.

467

Biomed. Mater. Res., Part A. 2014, 102, 3024-3032.

468

(37) Contreras, S.; Gaspar, A. R.; Guerra, A.; Lucia, L. A.; Argyropoulos, D. S.

469

Propensity of lignin to associate: light scattering photometry study with native lignins.

470

Biomacromolecules. 2008, 9, 3362-3369.

471

(38) Guerra, A.; Gaspar, A. R.; Contreras, S.; Lucia, L. A.; Crestini, C.; Argyropoulos,

472

D. S. On the propensity of lignin to associate: a size exclusion chromatography study

473

with lignin derivatives isolated from different plant species. Phytochemistry. 2007, 68,

474

2570-2583.

475

(39) Deng, Y.; Feng, X.; Zhou, M.; Qian, Y.; Yu, H.; Qiu, X. Investigation of

476

aggregation and assembly of alkali lignin using iodine as a probe. Biomacromolecules.

477

2011, 12, 1116-25.

478

(40) Zhang, Y.; Zheng, X.; Wang, H.; Du, Q. Encapsulated phase change materials

479

stabilized by modified graphene oxide. J. Mater. Chem. A. 2014, 2, 5304-5314.

480

(41) Yin, G.; Zheng, Z.; Wang, H.; Du, Q.; Zhang, H. Preparation of graphene oxide 23



481

coated polystyrene microspheres by Pickering emulsion polymerization. J. Colloid

482

Interface Sci. 2013, 394, 192-198.

483

(42) Williams, J. M.; Gray, A. J. Wilkerson, M. H. Emulsion stability and rigid foams

484

from styrene or divinylbenzene water-in-oil emulsions. Langmuir. 1990, 6, 437-444.

485

(43) Paunov, V. N.; Cayre, O. J.; Noble, P. F.; Stoyanov, S. D.; Velikov, K. P.; Golding,

486

M. Emulsions stabilised by food colloid particles: Role of particle adsorption and

487

wettability at the liquid interface. J. Colloid Interface Sci. 2007, 312, 381-389.

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FIGURE CAPTIONS Figure 1 (a) Illustration of the preparation of LSNPs from lignin/SDS mixed basic solution; (b) Illustration of the preparation of LPs from lignin basic solution and the effect of SDS and dialysis on LPs. Figure 2 Effect of the concentration of SDS added before acid precipitation on (a) the mean particle sizes and (b) zeta potential of LSNPs; Effect of the concentration of SDS added after acid precipitation on (c) the mean particle sizes and (d) zeta potential of LPs. Figure 3 Illustration of the formation mechanism of LSNPs. Figure 4 Typical TEM images of LSNPs prepared at an initial SDS concentration of 12mM. Figure 5 (a) Illustration of the gelation of LSNPs; (b) Size distribution of the LSNP aggregations; (c) Reaction between EDA and HCl; (d) Reaction between LSNPs and EH ions. Figure 6 (a) Digital camera photo of the LSNPEs after a 60-day storage period; (b) Optical microscopy images of the LSNPEs at day 0; (c) Size distribution of the LSNPEs at day 0 and after a storage period of 60 days. Figure 7 Illustration of the preparation of LPMCs. Figure 8 (a1-a2) Optical microscopy images of the LPMCs; (b1-b2) Confocal micrograph of the LPMCs; (c1-c2) SEM images of the LPMCs. Figure 9 Size distribution of the LPMCs and LSNPEs.

25



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Table 1 Functional group and molecular weight data of alkaline lignin according to non-aqueous potential titration and GPC respectively. Phenolic OH (mM/g) 2.18

Carboxylic (mM/g) 2.00

Mw (Da) 4500

26


Mn (Da) 2470

Mw/Mn (PDI) 1.82

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Table 2 The sulfur content on the LSNPs and LPs after dialysis and the composite ratio of SDS on LSNPs SDS concentration （mM） 8 10 12

Sulfur content Sulfur content of LPs (wt%) of LSNPs (wt%) 1.12 1.42 1.15 1.50 1.17 1.61

27


Composite ratio of LSNPs (mM/g) 0.104 0.129 0.167


Figure 1 (a) Illustration of the preparation of LSNPs from lignin/SDS mixed basic solution; (b) Illustration of the preparation of LPs from lignin basic solution and the effect of SDS and dialysis on LPs. (This figure should be published in color.) 254x118mm (300 x 300 DPI)


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Figure 2 Effect of the concentration of SDS added before acid precipitation on (a) the mean particle sizes and (b) zeta potential of LSNPs; Effect of the concentration of SDS added after acid precipitation on (c) the mean particle sizes and (d) zeta potential of LPs. (This figure should be published in color.) 44x31mm (600 x 600 DPI)



Figure 3 Illustration of the formation mechanism of LSNPs. (This figure should be published in color.) 254x91mm (300 x 300 DPI)


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Figure 4 Typical TEM images of LSNPs prepared at an initial SDS concentration of 12mM. 63x31mm (300 x 300 DPI)



Figure 5 (a) Illustration of the gelation of LSNPs; (b) Size distribution of the LSNP aggregations; (c) Reaction between EDA and HCl; (d) Reaction between LSNPs and EH ions. (This figure should be published in color.) 254x220mm (300 x 300 DPI)


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Figure 6 (a) Digital camera photo of the LSNPEs after a 60-day storage period; (b) Optical microscopy images of the LSNPEs at day 0; (c) Size distribution of the LSNPEs at day 0 and after a storage period of 60 days. (This figure should be published in color.) 254x95mm (300 x 300 DPI)



Figure 7 Illustration of the preparation of LPMCs. (This figure should be published in color.) 254x89mm (300 x 300 DPI)


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Figure 8 (a1-a2) Optical microscopy images of the LPMCs; (b1-b2) Confocal micrograph of the LPMCs; (c1c2) SEM images of the LPMCs. (This figure should be published in color.) 254x287mm (300 x 300 DPI)



Figure 9 Size distribution of the LPMCs and LSNPEs. (This figure should be published in color.) 44x31mm (600 x 600 DPI)


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Graphic for table of contents (This figure should be published in color.) 254x129mm (300 x 300 DPI)


SDS Composite Nanoparticles and Its

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