l -histidine-functionalized carbon black pigment with zwitterionic property: Preparation, characterization and application

Journal Pre-proof l-histidine-functionalized

carbon black pigment with zwitterionic property: Preparation, characterization and application Tingting Ma, Xianghui Zhao, Yaxing Cao, Yajun Wu, Yingyu Zhou, Hongling Chen PII:

S0143-7208(19)31771-1

DOI:

https://doi.org/10.1016/j.dyepig.2019.107992

Reference:

DYPI 107992

To appear in:

Dyes and Pigments

Received Date: 26 July 2019 Revised Date:

15 October 2019

Accepted Date: 22 October 2019

Please cite this article as: Ma T, Zhao X, Cao Y, Wu Y, Zhou Y, Chen H, l-histidine-functionalized carbon black pigment with zwitterionic property: Preparation, characterization and application, Dyes and Pigments (2019), doi: https://doi.org/10.1016/j.dyepig.2019.107992. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. 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. © 2019 Published by Elsevier Ltd.

L-Histidine-functionalized carbon black pigment with zwitterionic property: Preparation, characterization and application Tingting Ma, Xianghui Zhao, Yaxing Cao, Yajun Wu, Yingyu Zhou, Hongling Chen* College of Chemical Engineering, Nanjing Tech University, Nanjing 211816, PR China

*Corresponding author. Fax: +86 25 83587206 E-mail address: [email protected]

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ABSTRACT In this paper, an L-histidine-functionalized carbon black (CB-HIS) with zwitterionic property was fabricated by covalently binding L-histidine to oxidized carbon black under the action of a crosslinker. The oxidized carbon black was prepared by two-step oxidation using ozone and hydrogen peroxide as oxidants respectively. Scanning electron microscopic techniques (SEM), Fourier transform infrared

spectroscopy

(FTIR),

X-ray

photoelectron

spectroscopy

(XPS),

Thermogravingmetric analysis (TGA) and Zeta potential were employed to characterize the composition, structure and properties of the CB-HIS as well as the intermediates. The results showed that the L-Histidine was successfully grafted on the pretreated CB through C-NH of the imidazole ring and remained the branched amino groups and carboxyl groups. The Zeta potential estimated that the isoelectric point of CB-HIS was about 3.78. The CB-HIS pigment was applied to dye wool fabrics through exhaust dyeing process. The K/S, L*a*b* values and the color appearance of dyed wool fabrics showed that the CB-HIS-dyed wool fabrics had darker black and better fastness properties than the pristine CB-dyed wool fabrics. This work provides a versatile route to prepare functionalized carbon blacks by autonomously selecting amino acids. Key words: Carbon black, Amino acid, Black pigment, Dyeing properties, Wool

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1. Introduction Black pigments and dyes, as a main kind of colorants, play an irreplaceable role in the printing, textile, cosmetics and other industries [1]. Since the advent of synthetic dyes in the 19th century, black azo dyes and metal complex dyes have been extensively investigated because of the simple synthetic procedures, acceptable dyeing properties as well as convenient application techniques. However, these dyes would release toxic aromatic amines and heavy metal ions in the dyeing and subsequent treatment process, causing genotoxicity, mutagenicity, carcinogenicity and other issues in the environmental and biological systems [2-4]. Nowadays, many azo dyes and metal complex colorants have been restricted or even banned to use in the European Union, the United States, Germany, Japan, Canada and other countries [5-9]. Therefore, developing eco-friendly black materials that can substitute synthetic dyes has attracted substantial attention from academia and industries. Carbon black (CB), a common black substance with excellent hiding power and coloring properties, high electrical conductivity and low cost [10-13], is a suitable alternative to toxic black dyes. Importantly, European Commission had authorized that nano-structural CB with a primary particle size of 20 nm or larger can be used as a colorant in cosmetics at a maximum concentration of 10% w/w [14]. With the development of nanotechnologies in coloration of textile fabrics, nano-sized CB pigment has been applied to cotton, wool, polyester, nylon and other fabrics, so that bestows them dark color appearance and special properties [15-17]. Fahad et al. [18] reported that a composite of carbon black and polyaniline could be coated on surface 3

of the cotton fabrics via a simple ‘dip and dry’ method and the conductivity was improved. Luo et al. [19] reported that CB water-based dispersion could dye human hair to form continuous coatings with brown shades by spraying and combing. Fu et al. [20] used CB nanoparticles to print cotton/nylon fabrics, and found that the added CB particles could enhance NIR absorption of printed fabrics and improve the light and washing fastness. However, the dyeing-used CB in the previous investigations was weakly compatible and affinitive to fabrics due to the lack of functional groups on the surface, which limited its application in the textile. Amino acids are the common and natural organic compounds with carboxyl groups, amino groups and a side chain specific to each amino acid. And these small molecules have unique catalytic properties, chirality and biocompatibility [21-22]. In recent years, with the successful application of amino acids as zwitterionic surface modification materials, amino acid functionalized inorganic or organic materials have been highly sought after by researchers [23-24]. The presence of amino acids may not only impart optical properties, pH responsiveness, biocompatibility, structure and self-assembly properties to the material, but also alleviate the problems of agglomeration, cytotoxicity and instability of inorganic particles in certain biological environments [21, 25]. Hadi et al. [26] reported that the multi-walled carbon nanotubes functionalized by arginine and lysine on the surface enhanced the antibacterial activity. Tanmoy et al. [27] investigated the solution properties of serine-based zwitterionic polymer, and found that the polymer exhibited dual responsiveness toward pH and temperature in aqueous solution. Fujii et al. [28] also 4

reported the synergistic interaction between the positive and negative charges of a glutamic acid-grafted dodecyl polymer. This work highlighted the versatility and biocompatibility of amino acids as functional building blocks. Obviously, the unique advantages and diverse structures of amino acids provide many convenient and effective choices for the functional modification of substrates. However, to the best of our knowledge, using amino acid to modify CB for improving the dyeing properties and compatibility in substrates, especially wool fabrics, has not yet been reported. Ball milling, a green and efficient mechanochemical synthesis method, has attracted great interest in the last decade. In general, ball milling, as a method in organic synthesis, can not only effectively avoid the need for a large amount of solvent, but also achieve selectivity and reduce the generation of waste [29-31]. Up to date, ball milling can be used for many different types of organic synthesis including condensation reactions, nucleophilic additions, Diels–Alder reactions and so on [32-37]. In this paper, the ball milling method was taken to modify carbon black. Herein, we designed and synthesized an L-histidine-functionalized carbon black (CB-HIS) via ball milling method using L-Histidine (side chain was imidazole ring) as a modifier and diethylene glycol bis-chloroformate as a crosslinker. In order to enhance the chemical reactivity of CB, the CB was oxidized by ozone and hydrogen peroxide respectively before modification to form oxidized CB with abundant hydroxyl groups. Furthermore, the dyeing properties of CB-HIS for wool fabrics were further investigated in brief. 2. Experimental 5

2.1 Materials Pristine carbon black nanoparticles (CB) with average diameter of 25 nm and diethylene glycol bis-chloroformate were obtained from Nanjing Jayful novel Material Co., Ltd., China. L-Histidine monohydrochloride monohydrate, hydrochloric acid (36-38 wt.%), N,N-Dimethylformamide (DMF), triethylamine and sodium sulfate anhydrous were purchased from Sinopharm Chemical Reagent Co., Ltd. Hydrogen peroxide (30 wt.%) and acetic acid were purchased from Shanghai Ling Feng Chemical Reagent Co., Ltd., China. Dichloromethane was supplied by Wuxi Yasheng Chemical Co., Ltd., China. Sodium hydroxide was provided by Xilong Chemical Co., Ltd. Peregal O was provided by Jiangsu Jiafeng Chemical Co. Ltd. All the chemicals were used without any further purification. Pure wool fabrics were purchased from Heng Yuanxiang Group, China. 2.2 Pretreatment of carbon black Pristine CB was pretreated by oxidation of ozone and hydrogen peroxide respectively. First step: oxidation by ozone. 2 g pristine carbon black, 5 g mixed zirconia balls with the diameter of 2-5 mm and 100 g de-ionized water were mixed in a 250 mL flask by stirring at 15 °C for 15 min. Then ozone generated by an ozone generator was introduced to the mixture with a flow rate of 150 L/h. After 1 h, 0.4 g sodium hydroxide was added into the reaction system; next the system continuously reacted for 7 h. After that, the system was acidified with 1 mL hydrochloric acid (36-38 wt.%) for 30 min. Finally, the resultant sample was centrifuged, washed, dried to obtain oxidized-CB. Second step: oxidation by hydrogen peroxide. 1.5 g OCB was 6

mixed with 50 g H2O2 (30 wt.%) and 0.2 mL hydrochloric acid (36-38 wt.%) under stirring at room temperature for 15 min. Then the mixture reacted at 90 °C for 24 h. After that, the sample was centrifuged, washed and dried to obtain a secondary oxidized CB, which was designated as HOCB. 2.3 Preparation of L-histidine-functionalized carbon black L-histidine-functionalized CB was prepared by ball milling method. The schematic drawing for the preparation process is shown in Fig. 1. 1.5 g HOCB, 30 g dichloromethane, 0.04g DMF and 1 g diethylene glycol bis-chloroformate were added into a milling jar with some zirconia balls (2-5 mm in diameter). At the same time, 0.5 g triethylamine as an acid binding agent was also added. Then the mill jar was placed into a planetary ball milling (QM-3SP04, Nanjing University instrument plant) and ball-milled

at

500

rpm

for

4

h,

getting

the

diethylene

glycol

bis-chloroformate-modified HOCB (designated as CB-Cl). Next, 0.5 g L-Histidine and 0.5 g triethylamine were added into the milling jar; the system continuously reacted for 4 h. Finally, the modified CB dispersion was centrifuged at 8000 rpm for 5 min and washed with ethanol and water for several times respectively until the modified CB could be uniformly dispersed in the de-ionized water without precipitation. The final product was dried at 70°C to obtain the L-histidine -functionalized CB power, which was designated as CB-HIS.

7

Fig.1 Synthetic strategy and preparation process of L-histidine-functionalized carbon black.

2.4 Dyeing of wool fabrics with L-Histidine functionalized CB pigment L-Histidine functionalized CB pigment (CB-HIS) was used for exhaust dyeing of wool fabrics. The concentration of CB-HIS was 5% owf. The pH of dye bath was adjusted to 4 using acetic acid, and the liquor ratio was 40:1. Peregal O (4% owf) as a leveling agent and sodium sulfate anhydrous (5% owf) as an accelerating agent were both added to assist exhaustion. The dyeing process was carried out at 45 °C for 30 min; then the dyeing temperature was raised to 85 °C with the velocity of 2 °C/min and held on 30 min. Finally, the dyed wool fabrics were washed with tap water and dried at 40 °C, and this process repeated three times. And its color change was recorded by a camera (Canon 760D). As comparison, wool fabrics were also dyed with pristine CB under the same conditions above. 2.5 Materials Characterization The morphology and size of pristine CB and modified CB (HOCB, CB-HIS) were observed through a scanning electron microscope (SEM, Hitachi S4800). The functional groups on the samples’ surface were characterized through a Fourier transform infrared spectroscopy (FT-IR, WQF-510A) in the range of 4400-400 cm-1 8

by KBr pellets. The chemical structure and composition of samples were analyzed by an X-ray photoelectron spectroscopy (XPS, ThermoFisher, ESCALAB250Xi) with Al Kα radiation (hv = 1486.6 eV). The content of carbon, hydrogen, nitrogen and sulfur in samples were evaluated using an element analyzer (EA, Elementar Vario ELcube). The thermal gravimetric analysis of the samples was assessed using a thermogravimetric analyzer (TGA, Shimadze DYG 60H) from 25 °C to 800 °C at the heating rate of 10 °C/min in nitrogen atmosphere. The zeta potential and mean particle size of CB-HIS at different pH were analyzed by a Nanotrac wave particle analyzer (zeta potential, Microtra MN401-ZS) at room temperature using Britton-Robinson buffer solution to adjust the pH value from 2 to 11 respectively. 2.6 Color and fastness measurement The color strength value (K/S) of the dyed wool fabrics was measured on a DataColor SF600 spectrophotometer (Datacolor, USA) under D65 illuminant using the 10° observer. The color coordinate values (L*, a* and b*) of dyed wool fabrics were measured on an automatic whiteness meter (WSD-3, Beijing Kangguang Optical Instruments Co., Ltd.) using D65 illuminant and 10° observer field of view. The dry and wet rubbing fastness of dyed wool fabrics was tested using a rubbing tester (Y571B) according to ISO 105-X12: 2001. The surface morphology of wool samples were characterized by the scanning electron microscopy. And the color appearance of dyed wool fabrics was recorded by a camera (Cannon 760D). 3. Results and discussion 3.1 Chemical structure and composition analysis 9

The FT-IR spectra of pristine CB, HOCB, CB-Cl, CB-HIS and L-Histidine were shown in Fig. 2. In the curve a, the stretching vibration of C=C at 1565 cm-1 and the bending and stretching vibration of -CH2- at 2840 cm-1 and 2917 cm-1 were observed, all of which originated from the carbon skeleton and the incompletely-cleaved hydrocarbons remaining on the surface of CB. In the curve b, some new bands appeared at 1717 cm-1 and 1280 cm-1 corresponding to the stretching vibration of the C=O in carboxyl groups and the stretching vibration of C-O in aromatic hydroxyl groups respectively [38], which indicated the existence of phenolic hydroxyl groups and carboxyl groups on the HOCB surface. Compared with the curve b, the FTIR spectrum of CB-Cl had additional bands at 790 cm-1, 1005 cm-1, 1250 cm-1, 1135 cm-1, 1175 cm-1and 1740 cm-1, which were attributed to the stretching vibration of the C-O-C (1005 cm-1, 1250 cm-1) formed by the substitution reaction of hydroxyl groups on the HOCB surface and the absorption peaks of C-Cl (790 cm-1), C-O-C (1135 cm-1, 1175 cm-1) and C=O (1740 cm-1) in the diethylene glycol bis-chloroformate that grafted on the HOCB. After the modification by L-Histidine, new bands corresponding to tertiary amide (stretching vibration of C=O) and primary amines (stretching vibration of N-H) were observed at 1630 cm-1 and 1334 cm-1 respectively in curve d, while the N-H of secondary amine in the imidazole groups did not appeared at 1500 cm-1 compared with the curve e of L-Histidine [39]. It could be deduced that L-Histidine had been linked to the CB-Cl successfully via the amidation reaction between the N-H of imidazole groups and the –Cl of CB-Cl.

10

Fig. 2. FTIR spectra of (a) pristine CB, (b) HOCB, (c) CB-Cl, (d) CB-HIS and (e) L-Histidine.

To further investigate the atomic composition and the chemical structure of HOCB and CB-HIS, XPS analysis was performed and the corresponding results were presented in Fig. 3. As shown in the XPS wide-scan spectra of HOCB and CB-HIS (Fig. 3a), the C1s (284.9 eV) and O1s (532.7 eV) signals were observed on the surface of HOCB and CB-HIS. In addition, the CB-HIS samples also exhibited one new peak of N1s at 400.8 eV, resulting from the nitrogen atoms in the grafted L-Histidine. The C1s core-level XPS spectrum of HOCB was presented in Fig. 3b, which could be curve-fitted with four peak components at the binding energy of 284.8 eV, 286.0 eV, 287.2 eV, 288.5 eV, corresponding to the C=C species, C-O species, C=O species and O-C=O species respectively [40]. While the C1s core-level XPS spectrum of CB-HIS in Fig. 3c was primarily fitted as five components at the binding energy of 284.8 eV, 286.0 eV, 287.1 eV, 288.5 eV and 289.9 eV, assigned to C=C species, C-N/C-O species, C=O species, O=C-N species and O-C=O species respectively. The existence of O=C-N bonds confirmed that L-Histidine had been 11

covalently grafted on the CB-Cl. However, considering that both the C-NH of the imidazole ring and the –NH2 outside the ring in L-Histidine could react with the CB-Cl to form the O=C-N bonds, the N1s core-level XPS spectrum of CB-HIS was used to explore the specific binding mode between L-Histidine and CB-Cl. In Fig. 3d, the N1s spectrum was fitted with three peaks at the binding energy of 399.8 eV, 400.8 eV and 401.6 eV respectively. It can be seen from the N1s spectrum that the binding energy at 399.8 eV and 401.6 eV corresponding to the unprotonated N atom (C=N-C) in imidazole ring and the zwitterionic protonated α-amine nitrogen (-NH3+) respectively [41, 42]. In Figure. 3c, a C1s peak at 288.5eV of bind energy was associated to the carbon of the amide groups. Moreover, literatures indicated that the N1s peak in the amide group (NHC=O) is between 400.2-400.7 eV [42, 43], which did not appear in Figure 3d. Combined with the FTIR analysis, we guessed that the bind energy at 400.8 eV in the N1s spectrum could be ascribed to the N atom in the amide groups (N-C=O) of imidazole ring formed during the grafting of L-Histidine on HOCB through diethylene glycol bis-chloroformate. Therefore, we conclude that the amidation reaction probably mainly occurred on the -NH- of the imidazole ring, retaining the branched amino and carboxyl amphoteric structure.

12

Fig. 3. (a) XPS wide-scan spectra of HOCB and CB-HIS, (b) C1s core-level XPS spectrum of HOCB, (c) C1s and (d) N1s core-level XPS spectra of CB-HIS.

Besides, the C, H, O and N contents of pristine CB, HOCB and CB-HIS samples were shown in Table 1. After oxidation, the C content decreased from 89.41% for pristine CB to 79.76% for HOCB, while the O content increased from the 6.793% for pristine CB to 16.642% for HOCB. The change of contents indicated that there were large amounts of oxygen-containing functional groups generated on the surface of CB. Compared with HOCB, the nitrogen content of CB-HIS increased to 5.50%, coming from the L-Histidine which bonded to the HOCB. In addition, it could be calculated that the CB-HIS contained about 20.3% of L-Histidine according to the relative molecular mass. Table 1 Composition of pristine CB, HOCB and CB-HIS nanoparticles. 13

Samples

C/%

N/%

O/%

H/%

S/%

Pristine CB

89.41

0.18

6.793

2.911

0.706

HOCB

79.96

0.23

16.642

2.67

0.698

CB-HIS

70.44

5.50

21.646

1.805

0.609

3.2 Morphology observation The SEM micrographs of the pristine CB, HOCB and CB-HIS were shown in Fig. 4. It could be seen that the single CB particle with the average diameter of ca. 25 nm had the spherical-like morphology and formed lots of irregular agglomerates (Fig. 4a). After treated by oxidation, the particle size of HOCB somewhat deceased and the agglomeration behavior between the nanoparticles was weakened (Fig. 4b). This phenomenon was caused by the oxidative destruction of the carbon skeleton which did not have a high degree of graphitization on the surface of CB. In Fig. 4c, the morphology and particle diameter of CB-HIS did not change significantly, indicating that the grafted organic component had little effect on the morphology of particles.

Fig. 4. SEM micrographs of (a) pristine CB, (b) HOCB and (c) CB-HIS

3.3 Zeta potential and particle size analysis

14

Fig. 5. Zeta potential of CB-HIS dispersion at different pH

The zeta potential of CB-HIS dispersion at different pH was presented in Fig. 5. When the pH of dispersion was 2, the CB-HIS particles carried the positive charges on the surface. With the increase of pH, the zeta potential grew up gradually at first and then declined quickly until it reached the zero at the pH of 3.78. While the pH continued to increase, the zeta potential changed to negative. At the same time, the absolute value of zeta potential also increased continuously, and then decreased due to the compression of double-layer compression. The phenomenon above was mainly attributed to the amphoteric property of L-Histidine grafted on the CB. The amino groups could be protonated to form the cationic structure of –NH3+-R-COOH at the lower pH, in contrast, the carboxyl groups underwent the dissociation of proton at the higher pH, forming the anionic structure of –NH2-R-COO-. The isoelectric point (pI) of CB-HIS, defined as the pH where the net charge was zero, was about 3.78 15

estimated by the curve of zeta potential in Fig. 5, which was less than the isoelectric point of L-Histidine (7.59) [44]. This result indicated that the basic group of L-Histidine (-NH- and part -NH2) was consumed during the process of modification. On the other hand, a certain extra negative charges on surface of CB was produced during the oxidation, which also made the isoelectric point of CB-HIS decrease. 3.4 Thermal behavior

Fig. 6. TGA thermograms of pristine CB, CB-HIS nanoparticles and L-Histidine.

TGA thermograms of pristine CB, CB-HIS nanoparticles and L-Histidine were presented in Fig. 6. For the pristine CB, the weight loss from 120°C to 530°C was about 2.56%, resulting from the decomposition of residual hydrocarbons on the CB surface. After 530 °C, the carbon skeleton of CB with a low degree of graphitization started to decompose. In the TGA curve of CB-HIS, it was obvious that the weight loss before 800°C was higher than that of the pristine CB and contained two major 16

degradation processes. The first region ranging from 120 °C to 247 °C was the weight loss of the partial components of L-Histidine grafted on the CB surface, and the second one ranging from 247 °C to 800 °C was the decomposition of the remaining L-Histidine pieces as well as other organic components. Compared with the TGA curve of L-Histidine, there was an increase about 16°C for the initial weight loss temperature in the second degradation step. This behavior indicated that the covalent modification could improve the stability of the modified substance slightly. In addition, the weight of the residue carbon was 71.6 wt%, in accordance with the results of elemental analysis in Section 3.1. 3.4 Dyeing properties of L-Histidine-functional carbon black pigment

Fig. 7. Selection of the pH on the dyebath

The dyeing mechanism of CB-HIS pigment for the wool fabrics mainly includes two aspects: electrostatic adsorption and diffusion deposition. On the one hand, as shown in Fig. 7, the optimum pH of the dyebath is between 3.78 and 4.80 according to the isoelectric point of wool fabrics (pI=4.80) and CB-HIS (pI=3.78) [45]. In this case, the CB-HIS particles carried negative charges can be adsorbed on the surface of cationic wool fabrics by electrostatic interactions [46]. On the other hand, the long 17

chain of polydiethylene glycol attached with an imidazole ring has flexibility and a certain chain length, which facilitates the free diffusion of the imidazole ring into the scales, further enhancing the dye uptake and color fastness [47, 48]. K/S and L*a*b* values of wool fabrics dyed with pristine CB and CB-HIS pigment were shown in Table 2. Compared with the pristine CB-dyed wool fabrics, the CB-HIS-dyed wool fabrics had a higher K/S value and the lower L* value, that was to say, the CB-HIS pigment produced a deeper shade on wool fabrics than pristine CB. The graft of amino acid improved the substantivity and fastness properties of pigments, resulting in the better color strength and color appearance in dyed wool fabrics. Table 2 K/S and L*a*b* values of wool fabrics dyed with pristine CB and CB-HIS pigment

Dyestuff

K/S value

L*

a*

b*

Pristine CB (5% owf)

19.2

40.35

1.96

3.04

CB-HIS (5% owf)

34.7

27.37

0.52

-1.51

The color appearance of wool fabrics dyed with pristine CB and CB-HIS pigment were presented in Fig. 8. It could be observed that the color of CB-HIS-dyed wool fabrics was deeper than that of pristine CB-dyed wool fabrics, which was consistent with the result of K/S and L* values analysis mentioned above. In particular, the CB-HIS-dyed wool fabrics still maintained a darker black after rinsing with water for three times, while the pristine CB-dyed wool fabrics faded obviously at the same condition. And the rating of dry and wet rubbing fastness of CB-HIS-dyed 18

wool fabrics was 3~4 and 4 respectively. The good washing and rubbing fastness were attributed to the electrostatic interaction between the CB-HIS pigment and wool fabrics. The surface morphology of untreated wool fabrics, pristine CB-dyed wool fabrics and CB-HIS-dyed wool fabrics was further observed by SEM, as shown in Fig. 9. Compared with the untreated wool fabrics (Fig. 9a), the treated wool fabrics whether dyed by pristine CB or CB-HIS pigment still had the clear scales in Fig. 9(b-c), indicating that the thickness of pigment coating was very thin. Besides, the surface of the wool fabrics coated with CB-HIS was denser than that coated with pristine CB because of the great compatibility and adhesion on the wool fabrics.

Fig.8. Color appearance of (a) untreated wool fabrics and (b-d) dyed wool fabrics rinsed with water for one, two and three times respectively: (A) pristine CB pristine CB-dyed wool fabrics and (B) CB-HIS-dyed wool fabrics

Fig. 9. SEM micrographs of (a) untreated wool fabrics, (b) pristine CB-dyed wool fabrics and (c) CB-HIS-dyed wool fabrics

4. Conclusions 19

In summary, the L-histidine-functionalized CB pigment with zwitterionic property was successfully synthesized via grafting L-Histidine on the surface of oxidized CB under the action of crosslinker. Oxidative pretreatment of CB was intended to introduce hydroxyl groups, thereby increasing the surface chemical reactivity and further decreasing the size of CB. L-Histidine modified CB covalently through C-NH of the imidazole ring and remained the branched amino groups and carboxyl groups, which imparted the amphoteric property to CB-HIS particles. The Zeta potential estimated that the isoelectric point of CB-HIS was about 3.78. The CB-HIS pigment was applied to the coloration of wool fabrics at the dye-bath pH of 4. After dyeing, the CB-HIS-dyed wool fabrics covered with a thin pigment coating showed darker black than the pristine CB-dyed wool fabrics and had good washing and rubbing fastness properties. This work provides a facile, controllable, and versatile method for surface modification and functionalization of CB, which can impart specific functions to carbon black based on the autonomous selection of amino acids. References [1]. R. Jafari, S.H. Amirshahi, S.A.H. Ravandi, Spectral analysis of blacks, Color Research & Application. 37 (2012) 176-185. [2]. K.T. Chung, Azo Dyes and Human Health: A Review, Journal of Environmental Science & Health Part C Environmental Carcinogenesis Reviews. 34 (2016) 233-261. [3]. M. Işik, D.T. Sponza, Fate and toxicity of azo dye metabolites under batch 20

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Highlights We grafted the L-Histidine to the surface of HOCB through diethylene glycol bis-chloroformate by ball milling method. The CB was oxidized by ozone and hydrogen peroxide respectively. The amino acid modified carbon black for wool dyeing was developed. The dyeing properties of CB-HIS for wool fabrics were further investigated.

Declaration of interests ☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. ☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: