Fabrication of Microcapsules by the Combination of Biomass Porous

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Agricultural and Environmental Chemistry

Fabrication of Microcapsules by the Combination of Biomass Porous Carbon and Polydopamine for Dual Self-Healing Hydrogels Shumin Liu, Zhilu Rao, Ruiyue Wu, Zhixiang Sun, Zhiru Yuan, Liangjiu Bai, Wenxiang Wang, Huawei Yang, and Hou Chen J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.8b06241 • Publication Date (Web): 07 Jan 2019 Downloaded from http://pubs.acs.org on January 11, 2019

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Journal of Agricultural and Food Chemistry

Fabrication of Microcapsules by the Combination of Biomass Porous Carbon and Polydopamine for Dual Self-Healing Hydrogels

Shumin Liu, Zhilu Rao, Ruiyue Wu, Zhixiang Sun, Zhiru Yuan, Liangjiu Bai*, Wenxiang Wang*, Huawei Yang, Hou Chen School of Chemistry and Materials Science, Ludong University, Yantai 264025, China; Key Laboratory of High Performance and Functional Polymer in the Universities of Shandong Province; Collaborative Innovation Center of Shandong Province for High Performance Fibers and Their Composites. Abstract: Artificial development of smart materials from agricultural waste or food residues are particularly desirable for green chemistry. In this paper, dual network self-healing hydrogels were successfully fabricated by using functional microcapsule. This microcapsule was established by biomass porous carbon after recycling of apple residues. And glutaraldehyde (GA) as the healing agent was embedded in the porous carbon and the outer was coated with polydopamine (PDA). After adding the microcapsules, modifying guar gum-type hydrogels were successfully obtained with dual self-healing performance by combination of healing agent and metal-ligand coordination. The self-healing efficiency was about 89.9% from tension test and fracture strength displayed as 7.68 MPa. These results not only highlight a new idea for the utilization of apple residues, but also provide a new method for the preparation of excellent self-healing hydrogels. Key Words: Self-Healing Hydrogels; Apple Residue; Porous Carbon; Microcapsules; Polydopamine

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INTRODUCTION As a kind of hydrophilic polymer network, hydrogels have important application prospects in biomedicine1, tissue engineering2, chemical industry3 and other fields, due to their special properties such as high water content and good biocompatibility4. However, the application of traditional hydrogels is usually limited by their own mechanical properties, such as low strength, vulnerable structure and low recoverability. In recent years, the synthesis of hydrogels with highly mechanical and self-healing properties has drawn lots of attention by researchers5. Self-healing hydrogels6 is a new type of bionic material that is inspired by nature to imitate the healing of living body damage. The micro-damage of the hydrogels can be automatically healed through the material replenishment or energy replenishment mechanism. According to the different forms of self-healing7, self-healing process can also be classified as extrinsic self-healing8 and intrinsic self-healing9. The former occurs with the aid of an embedded healing agent, whereas the latter is achieved spontaneously or under certain external stimuli using the reversible and dynamic physicochemical action in the molecular network. At present, the discussion on the self-healing methods of extrinsic and intrinsic has gradually become clear. However, the single healing process can no longer meet the double requirements of the enhancement of self-healing and mechanical performance. In order to solve the defects of single healing and optimize the dual performance of self-healing and strength of materials at the same time, constructing self-healing system under the dual self-healing


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mechanisms has become the hotspot of current research1a, 10. For example, Cao et al.11 designed the supramolecular noncovalent dual network consist of interpenetrated metal–ligand coordination and hydrogen bonding interaction. The enhanced mechanical strength and high stretchability made it promising for further applications. As well, An et al.12, Zhao et al.13, Dohler et al.14 and Li et al.15 prepared a series of dual self-healing materials with various non-covalent bonding. However, dual self-healing is mostly limited to the interaction between different dynamic chemical bonds. The dual self-healing research between extrinsic and intrinsic have not attracted enough attention. As an important healing method, microencapsulated self-healing16 can repair the crack without changing the structure of the substrate. In addition, the microcapsules have important industrial application values with the advantage of abundant types and simple and easy preparation process. While the surface of the microcapsule was modified to reversible non-covalent bonding polymer, microcapsule can combine extrinsic and intrinsic self-healing performance to improve the self-healing efficiency and mechanical strength. Moreover, functionalized microcapsules can improve the compatibility of the substrate. For example, Ma et al.17 successfully prepared double-responsive microcapsule by surface initiated polymerization of polydopamine (PDA) coated silica and then removing the SiO2 core. Cheng et al.18 successfully prepared a novel and efficient drug carrier by functionalizing on the surface of PDA microcapsules. Recently, with the emphasis on environmental issues, the development of green and



sustainable chemistry has received widespread attention from researchers19. Therefore bio-derived activated carbon materials have been widely investigated because of their biocompatibility and economy20. As a renewable biomass energy, fruit residues can be also used to prepare porous carbon materials for reducing manufacturing costs and improving the utilization rate of agricultural waste. For example, Ma et al.21 reported that porous carbon microspheres were successfully prepared by using waste Camellia oleifera shells. If mimicking the porous material loading the drug, embedding the self-healing agent into the porous carbon and coating the surface will greatly simplify the microcapsule preparation process. Importantly, mussel-inspired chemistry22 has received wide attention from researchers in the field of materials and surface science due to its mild reaction conditions, wide application range and diverse functionalities. Under mildly alkaline conditions, PDA and its derivatives can be polymerized and adhered to almost any materials surface from dopamine (DA).23 Using PDA as a favorable tool, a great deal of previous research by Zhang et al have focused on the development of mussel inspired chemistry for surface modification in the applications of biological imaging24 and adsorption materials25. Therefore, PDA and its derivatives are coated on the surface of porous materials to form a PDA coating to obtain microcapsules, and a large amount of amino groups on the surface can exert self-healing effects. Herein, a self-healing hydrogel composed of porous carbon-based microcapsules was designed from the basis of fruit residues. Firstly, the apple residue was used to prepare porous carbon through conventional carbonization, activation and other steps.


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Then, glutaraldehyde (GA) as the healing agent was embedded and the outer layer was coated with PDA to obtain microcapsules. Finally, the microcapsules and Fe(III) were added to acrylic acid (AA) and acrylate-guar gum (AGG), which a dual self-healing hydrogel was obtained by combined healing agent and metal-ligand coordination interaction. The effects of the different proportions of AA and AGG, the content of microcapsules, Fe(III) on the mechanical and self-healing properties were studied.

MATERIALS AND METHODS Materials. Apple residues were obtained from Yantai North Andry Juice Co., Ltd. Glutaraldehyde (GA, 50% solution, Tianjin Bodi Chemical Industry Co., Ltd，China), potassium hydroxide (KOH, ≥ 85%, Tianjin Reagent chemical co. Ltd, China ), triethylamine (TEA, ≥ 99.0%, Tianjin Reagent Chemical Co. Ltd, China ), acrylylchloride (≥ 99.9%, Tianjin Hengxing Chemical Reagent Manufacturing Co., Ltd., China), guar gum (GG, Shandong dongda biochemical co. Ltd, China), 3-hydroxytyramine hydroohloride (≥ 98%, Zhengzhou Alfa Chemical Co., Ltd, China), tris (hydroxymethyl) aminomethane (≥ 99.9%, Shanghai Macklin biochemical Co., Ltd, China), ferric chloride hexahydrate (FeCl3•6H2O, ≥ 99.0%, Sinopharm Chemical Co., Ltd, China), dopamine (DA, ≥ 99.0%, Sinopharm Chemical Co., Ltd, China), acrylic acid (AA, ≥ 98.0%, Tianjin Hengxing Chemical Reagent Manufacturing Co., Ltd., China), potassium persulfate (KPS, ≥ 99.5%,Tianjin Da Mao Chemical Co., Ltd, China), ethanol (≥ 99.0%, Tianjin Fu Yu Fine Chemical Co., Ltd, China), toluene (≥ 99%,Yantai Yuandong Fine Chemical Co. Ltd, China),



dichloromethane (DCM, ≥ 99.0%, Tianjin Fu Yu Fine Chemical Co., Ltd, China), N,N-dimethylformamide (DMF, ≥ 99.0%, Tianjin Fu Yu Fine Chemical Co., Ltd, China) were used as received. Synthesis of Biomass Porous Carbon (PC) from Apple Residues. As reported in literature26, porous carbon was prepared by using abandoned apple residues as carbon source, KOH as activator, respectively. Typical carbonization and activation processes are as follows. The apple residues collected from the farm of Yantai North Andry Juice Co., Ltd. were washed, dried, and ground into a powder, respectively. The powdery apple residue was extracted by Soxhlet extractor method with a mixture of toluene and ethanol (Vtoluene:Vethanol = 2:1) for 8 h, then washed with ethanol, and dried under vacuum. Finally, apple residues were carbonized under argon atmosphere at 500 °C for 2 h with heating rate of 5 °C/min. The carbonized apple residues were chemical activated. Apple residues (1.0 g) and KOH (2.0 g) were added into ethanol (50 wt%, 10 mL), impregnated for 4 h and dried in an oven at 60 °C for 12 h. The dried mixture was activated under argon atmosphere at 600 °C for 2 h. After activation, the obtained carbon materials were washed with aqueous HCl solution (2 M) to remove any inorganic salts, then rinsed with deionized water and ethanol for several times until pH = 7.0. Then, biomass PC were further dispersed in ethanol (500 mL) under ultrasound and mechanical stirring for about 24 h and dried in vacuum oven. Synthesis of Microcapsules (PC-GA@PDA). The obtained PC (50.0 mg) and GA (150.0 mg) were added in a small amount of ethanol under mechanical stirring (3,000


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rpm) for 24 h. After added Tris-HCl buffer (pH=8.5, 50 mL) in 30 min, DA (100.0 mg) were added slowly. Under rapid mechanical agitation, PDA were coating on the surface of biomass carbon, and microcapsules can be successfully prepared. Subsequently, the PDA-type microcapsules after reacting about 36 h, were isolated by centrifugation and washed three times with ethanol and deionized water, respectively. After freeze-drying, microcapsules (PC-GA@PDA) could be easily obtained. Synthesis of Acrylate-Guar Gum (AGG). After dispersed in DCM (40.0 mL), guar gum (GG, 12.0 g) and TEA (28.0 mL) were added and in situ polymerized at room temperature under nitrogen for 30 min. Then, acryloyl chloride (10.0 mL) was added dropwise with stirring at 0 °C under a nitrogen atmosphere. After reacted of 24 h, AGG was further obtained by washing three times with ethanol and drying under vacuum oven. Preparation of Dual Self-Healing Hydrogels. A typical amount of AA (200.0 mg), AGG (40.0 mg), FeCl3•6H2O (4.0 mg), H2O (25.0 mL), microcapsules (6.0 mg), KPS solution (1.0 mL, 6.6 mg/mL) were sequentially added to the bottle, and reacted at 50 °C for 1 h. Different amount of monomer ratio (mAGG:mAA = 1:1, 2:1, 3:1), microcapsules (3.0 mg, 6.0 mg, 9.0 mg), and self-healing time were investigated, respectively. Characterization. The FT-IR spectra measurements were performed on a Nicolet is 50 (Thermo Fisher Nicolet, United States) Fourier transform infrared spectrometer equipped

with

Thermo

Nicolet

corporation

OMINIC

32

software.

The

thermogravimetric analysis (TGA) was performed on a Netzsch STA 409PC



instrument under the nitrogen atmosphere. The images of healing process were performed on a DMM-300C metallurgical microscope (Shanghai Caikon Optical Instrument Co., Ltd.). Scanning electron microscope (SEM) was measured on SU-8010 (Hitachi, Japan). Tensile testing was measured via LDW-5 Microcomputer control electronic universal material testing machine from Shanghai Songdun Machine Equipment Co., Ltd. X-ray photoelectron spectroscopy (XPS) analysis was performed on an ESCALAB Xi+ from Thermo Scientific. Raman spectra of samples were measured using a Laser Confocal Micro Raman Spectrometer with an Focal length of 700 mm.

RESULTS AND DISCUSSION The Synthesis Procedure of Microcapsules from Biomass Porous Carbon. The overall preparation process of self-healing hydrogels and the self-healing mechanism are shown in Scheme 1. Scheme 1 (a) described the general preparation procedure of microcapsules from apple residues. After typical pretreatment, the biomass porous carbon (PC) can be obtained by carbonizing and activating the collected apple residue at high temperature. As the healing agent, GA can be loaded in the porous carbon in ethanol. Inspired by the composition of adhesive proteins in mussels, surface-coating strategy based on the oxidative self-polymerization of DA has been employed to construct PDA microcapsules. Recently, much functional materials, ie. carbon nanomaterials27, silica28, polymers29 and magnetite nanoparticles30, have been coated by PDA for fabricating of functional microcapsules in a weak alkaline solution. Likely reported carbon materials, biomass carbon from apple residues can also be


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used as template particles in the formation of PDA microcapsules. Under ultrasound and mechanical stirring, biomass PC from apple residues were firstly dispersed in aqueous solution for period of time. PDA-typical microcapsules were coating on the surface of biomass carbon with loading GA under Tris-HCl buffer solution (pH = 8.5) and rapid mechanical agitation. After reacting about 36 h, PDA-type microcapsules can be achieved by washed three times with ethanol and deionized water, respectively. After added functional microcapsules, self-healing hydrogels were successfully obtained in situ polymerization by using AGG and AA as monomer, KPS as initiator, H2O as solvent and FeCl3.6H2O as additive, respectively (Scheme 1b).31 The extrinsic-type and intrinsic-type healing mechanism was achieved by using this microcapsule and showed in Scheme 1c. As the intrinsic self-healing mechanism, PDA in the surface of microcapsules can continually heal the hydrogels with coordination interaction, which the compatibility of microcapsule in the hydrogels can also be enhanced. As the extrinsic self-healing mechanism, GA as crosslinking agent can release from microcapsule and react with modified guar gum to heal the microcracks in hydrogels.32 Therefore, this dual-healing process can be achieved with added the biomass microcapsule with coordination in the surface and healing agent from the interior.



Scheme 1. (a) Synthesis process of PC and PC-GA@PDA microcapsules. (b) The typical fabricated process of self-healing hydrogels with microcapsules. (c) The self-healing process and mechanism of obtained hydrogels by the coordination interaction and the crosslinking interaction. In order to visually observe the morphology, the PC and PC-GA@PDA were characterized by SEM as shown in Figure 1. Figure 1(a) and (b) are the surface morphology of PC at different magnifications. Figure 1(c) and (d) are the surface morphology of PC-GA@PDA. It can be clearly seen from the results that the PC prepared from the apple residues has a sheet-like structure, and the pore distribution


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on the sheet layer can be clearly observed. The surface morphology of microcapsules can be significantly observed by coating PDA on the surface of PC after self-polymerizing of DA under mechanical force. The coarse spherical shape accumulated together was obtained, which had a relatively uniform size distribution and average value. It indicates that DA has been successfully self-polymerized on the surface of porous carbon after 36 h. In order to investigate the specific surface areas, the BET data of PC and PC-GA@PDA were further provided in Figure S1. According to IUPAC classification33, the nitrogen adsorption isotherm of biomass porous carbon showed an intermediate between type I and II, which often represented by microporous solids with well-developed mesoporous structures34. The BET surface area of biomass porous carbon is 373.7 m2/g. As reported most of renewable biomass carbon35, the porosity of biomass porous carbon is generated due to a series physical and chemical reaction or structural ordering process in the carbonizing process of apple residues. For the PC-GA@PDA microcapsules in Figure S1, the N2 adsorption/desorption isotherm have less pore structure and specific BET surface area. The difference of adsorption isotherms also illustrates the successful preparation of microcapsules.



Figure 1. The SEM image of (a) (b) PC (the working distance was 8.6 mm and the accelerating voltage was 10.0 KV) and (c) (d) GA-PC@PDA (the working distance was 7.3 mm and the accelerating voltage was 2.0 KV). The main chemical composition and bonding configuration were further analyzed by X-ray photoelectron spectroscopy (XPS) (Figure 2). As shown in Figure 2, wide region spectroscopy of pure PC, PC-GA and PC-GA@PDA can detect the elements of carbon (C), nitrogen (N) and oxygen (O) from XPS curves, respectively. All three samples, two peaks at 283.4 eV and 529.7 eV can be attributed to C 1s and O 1s, respectively. The new peak of N 1s at 399.8 eV was observed by diazotization. The C 1s high resolution spectrum of pure PC, PC-GA and PC-GA@PDA are further depicted in Figure. 2(b, c, d). The deconvoluted C 1s spectra of the pure PC (Figure. 2b) exhibit four Lorentzian peaks with different binding energies. The C 1s spectrum of nonoxygenated carbon, i.e., the graphitic carbon (C-C) appear at 284.7 eV. In


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addition, the low intensity peaks of C-O bonds and C=O bonds observed at 286.1 eV and 288.8 eV were caused by KOH when porous carbon was prepared by biological method. However, substantial increment in peak intensity of the oxygen functionalities have been observed in the C 1s de-convoluted spectra of PC-GA composites (Figure 2 (c)) and the new peak "C=O" function was observed at 287.8eV, which confirmed that GA has been successfully loaded in PC. The C 1s high resolution spectrum of PC-GA@PDA (Figure 2 (d)) show several peaks at 284.7, 284.9, 285.8, 286.9 and 287.6 eV originating from C-C, C=C, C=N, C-O and C=O groups, respectively. In comparison to PC-GA, the relative intensity of the C-C peak decreased slightly after coated with DA, but the intensity of the C-N peak increased significantly, and it became one of the main peaks, which was mainly caused by -NH2 in PDA. In addition, the benzene ring in the PDA showed C=C peak at 287.6 eV. thus it can be seen that PDA has been successfully coated on the PC-GA surface. (a) O 1s

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Figure 2. (a) Wide-scan spectra of PC, PC-GA and PC-GA@PDA, respectively. (b) XPS high resolution spectra of C 1s of PC (b), C 1s of PC-GA (c) and C 1s of PC-GA@PDA (d), respectively. Table 1 Chemical composition of PC, PC-GA, PC-GA@PDA form XPS. Samples

XPS (atom %) C

N

O

PC

76.58

3.01

17.89

PC-GA

74.35

1.73

22.45

PC-GA@PDA

69.91

7.39

19.98

Table 1 shows their relative percentage on chemical composition. Compared with PC, the percentage of O in PC-GA increased from 17.89% to 22.45%, while the percentage of C decreased slightly. Combined with Figure 2 (c) and table 1, it can be inferred that these changes are caused by the aldehyde groups on the GA loaded in the PC. Compared with PC-GA, PC-GA@PDA significantly increased the content of N from 1.73% to 7.39%. It is speculated that the N element is provided by -NH2 on PDA. The percentage content of C and O elements has decreased to some extent, which is presumably due to the coating of PC-GA surface by PDA, so that some of the C and O elements are not detected. TGA analysis is used to further demonstrate the successful synthesis of


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PC-GA@PDA microcapsules. As shown in Figure S2, the obvious weight loss of pristine PCs is occurred at the temperature between 200 and 800 °C. When the temperature was heated to 800 °C, the weight loss of pristine PCs is about 20.5%. After loaded with GA, the weight loss of PC-GA at 800 °C is about 24.5%, suggesting that GA was successfully loaded into PCs pore space. Therefore, the weight percentage of GA loaded into PCs pore space could calculate to be 4% based on the TGA results. After further coat on the PC-GA surface with PDA, much more weight loss was observed in PC-GA@PDA as compared with PC-GA. It can be seen that weight loss of PC-GA@PDA was increased to 30.8%. It is therefore the mass percentage of PDA coated on the PC-GA was calculated to be 6.3%. All of these above

results

demonstrated

that

successful

preparation

of

PC-GA@PDA

microcapsules. Raman spectroscopy was utilized to further illuminate PCs, PC-GA, and PC-GA@PDA structures, and results are shown in Figure S3. Two distinctive peaks can be observed in all specimens, and they correspond to D (1337 cm -1) and G (1580 cm -1) band. The intensity of the D band to the G band (ID/IG) was used to provide information of structural defects present in the materials. It can be seen from Figure S3 that ID/IG (intensity of the D band to the G band) was slightly increased from 0.93 to 0.98 and 1.01after loading GA into PC pores and the PC-GA surface was coated with PDA. Generally speaking, the increase of ID/IG values indicated the introduction of sp3 C onto carbon-based materials (PC). Therefore, Raman spectra further demonstrated the successful introduction of GA and PDA layer onto PC. Swelling Ratio of Self-Healing Hydrogels. In order to investigate swelling



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performance with different pH, the swelling ratio kinetics of the self-healing hydrogel was showed in Figure 3. As shown the swelling kinetics of Figure 3(a), the swelling rate remained basically constant after 50 min. The swelling ratio of the self-healing hydrogel can retain stable with the increase of time36. Therefore, the effect of pH on the swelling ratio of this hydrogel were gave after 60 min in Figure 3(b). It can be seen that at low pH conditions, the swelling ratio of the hydrogel were slow growth. With the increasing pH from 1.0 to 7.0, the ratio increased from 103.6% to 422.6%. This is because carboxyl groups are difficult to dissociate at low pH, and the hydrogen bond of hydrogels makes the network shrink tightly. After pH reached to 13.0, the swelling ratio of hydrogel increases rapidly, which caused by the electrostatic repulsion between the molecular chains and rapid ionization.37 (b) 450

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Figure 3. (a) The swelling kinetics curve of the self-healing hydrogels (microcapsules 6 mg, AA:AGG=1:2); (b) The effect of pH on the swelling ratio of the self-healing hydrogels (microcapsules 6 mg, AA:AGG=1:2). Rheological Studies of Self-Healing Hydrogels. For the viscoelastic materials like hydrogel, the storage modulus G′ (correspond to elastic portion) demonstrates the energy storage of material after straining, while loss modulus G″ (correspond to


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viscous portion) denotes energy loss of material during the generation of deformation. The two parameters are vital to characterize the mechanical property of hydrogel. Therefore, oscillatory measurements were performed on hydrogels and the results were shown in Figure 4(a-c). Strain sweep measurement of (hydrogel prepared with 3 mg PC-GA@PDA microcapsules) hydrogel was performed at 25 °C (Figure 4(a)), it was clear that G" remained constant and G' is slightly decreased under the strain from 0.1–100%, suggesting the prepared hydrogel could withstand relatively large deformations from damage. In addition, the value of G′ was larger than that of G″ under this strain range, indicating the hydrogel was stiff and kept at gel state. With the crossover of G′ and G″ curves at around strain γ = 900%, a gel–sol transition began to appear, which implied that polymer chains started to dislocate severely when the strain was beyond this point. When continue to increase the strain over 900%, the value of G″ exceeded G′, indicating the complete collapse of cross-linked networks. After large strain deformation (γ = 1000%), a 1% of strain was immediately applied for a period of time and it was found that the mechanical property of hydrogel could recover fully without any loss (Figure 4(b)). To amply research the self-healing property of prepared hydrogel, repeated dynamic strain step tests (γ = 1% or 400%) were carried out on hydrogel prepared with 3mg PC-GA@PDA microcapsules for ten cycles. As presented in Figure 4(c), when a lower strain (γ = 1%) was applied to the hydrogel, the value of G′ and G″ kept constant while G′ was larger than G″. But when subjected to a large strain (γ = 400%), G′ dropped dramatically within a few seconds and became lower than G″ in value. This phenomenon indicated that the fabricated



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hydrogel could rapidly achieve the transformation from gel state to sol state under relatively large deformation. Surprisingly, once the large strain was removed and a lower strain was applied, both G′ and G″ were able to return to its initial value instantaneously. After ten cycles test, the G′ and G″ could still recover to initial value without significant decrease. This excellent behavior was totally reversible and endowed the hydrogel outstanding self-healing property. (a)

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Figure 4. Rheological characterization of prepared hydrogels with 3mg PC-GA@PDA microcapsules: (a) strain sweep measurements, (b) an immediate recovery after the 1000% strain deformation, (c) dynamic strain amplitude cyclic test (γ = 1% or 400%). Study on Self-Healing Performance. The stretchability of the hydrogels of different ratio (AA:AGG=1:1, 1:2 and 1:3), are characterized with the same gauge length and stretching speed. The stretch process is shown in Figure 5. The mechanical


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performance of tensile strength can be increased by the appropriately increasing percent of the incorporation of AGG . From the results, by increasing the ratio from 1:1, 1:2 to 1:3, tensile strength is remarkably increased from 1.68 MPa to 5.76 MPa, then reduced to 2.48 MPa, respectively. In our self-healing experiment, hydrogels are typically cut into two pieces and then put together to heal itself. The self-healing efficiency of hydrogels, which is closed to the ratio of the original to self-healing tensile strength, are also illustrated in Figure 5(a). Without any external stimuli, the tensile modulus can reach the original levels after about 10 hours at ambient temperature. The self-healing efficiency of 1:1, 1:2 and 1:3, is about 85.1%, 89.1% and 53.5%, respectively. These results showed that the hydrogels with a mass ratio of AA:AGG=1:2 had excellent mechanical strength and self-healing properties. Repeated experiments of self-healing efficiency with different hydrogels or different amount of microcapsule were conducted in Figure 5(d) and (e). From Figure 5(d), the average healing efficiency of hydrogels with different ratio of 1:1, 1:2 and 1:3 (AA:AGG) is 84.9 %, 89.9% and 53.2%, respectively. From Figure 5(e), the hydrogels with more microcapsules (PC-GA@PDA) have a relatively maximum healing efficiency of 89.9%. All these repeated results demonstrate that the hydrogels with microcapsules (PC-GA@PDA) have excellent self-healing properties.



(a) 7

5

PC-GA@PDA = 3mg PC-GA@PDA = 3mg (healed) PC-GA@PDA = 6mg PC-GA@PDA = 6mg (healed) PC-GA@PDA = 9mg PC-GA@PDA = 9mg (healed) PC@PDA = 3mg PC@PDA = 3mg (healed)

8

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(b) AA:AGG = 1:1 AA:AGG = 1:1 (healing) AA:AGG = 1:2 AA:AGG = 1:2 (healing) AA:AGG = 1:3 AA:AGG = 1:2 (healing)

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9mg 6 mg PC-GA@PDA

Blank

Figure 5. (a) Tensile stress-strain curves of original and self-healing hydrogels (microcapsules 6 mg) with various mass ratios of AA and AGG. (b) Stress-Strain curves of original and self-healing hydrogels (AA:AGG = 1:2) with various mass of microcapsules. (d) Stress-Strain curves of original and self-healing hydrogels (microcapsules 3 mg, AA:AGG = 1:2) at various healing time. (d) The self-healing efficiency of the self-healing hydrogels (microcapsules 6 mg) with different ratio of mAA:mAGG (mAA = 200 mg); (e) the self-healing efficiency of hydrogels (mAA:mAGG =


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1:2, mAA = 200 mg) with different amounts of microcapsules (3 mg, 6 mg, 9 mg and blank). In addition, by increasing the amount of PC-GA@PDA microcapsules incorporated, the self-healing properties and mechanical strength of the hydrogel can be significantly improved. For example, by increasing the amount of PC-GA@PDA microcapsules incorporated from 3 mg, 6 mg to 9 mg, the tensile strength is increased from 3.35 MPa, 5.76 MPa to 7.68 MPa, respectively. In the absence of any external stimuli, the hydrogel was cut into two pieces and placed together for healing a period of time. The self-healing efficiency of 3 mg, 6 mg and 9 mg as shown in Figure 5(b) were about 72.7%, 87.8% and 90.0%, respectively. When the hollow microcapsules, the PC@PDA microspheres not loaded with GA, were incorporated into the hydrogels, respectively, the self-healing efficiency and the tensile strength are remarkably lower. The results showed that GA as a healing agent played a significant role in the self-healing process. PDA also has a certain degree of promoting effect on the tensile strength and self-healing efficiency of hydrogel through the coordination with Fe(III). Figure 5(c) shows the effect of healing time on the healing efficiency of this hydrogels. and the modulus, tensile strength and elongation at break can be observed with healing time increased by the extension. The healing efficiency at 3 h, 6 h, 9 h, and 12 h were compared with 43.5%, 54.0%, 76.2%, and 86.1%, respectively. In order to clearly demonstrate the self-healing ability of hydrogels, the healing experiments were carried out by two different colored strips (add respectively Prussian blue and Rhodamine B). Figure 6(a) shows that the two strips have different



colors. Afterwards, the two strips were cut from the middle, and the different colored strips were intertwined and healed at ambient temperature for 4 h, as shown in Figure 6(b). Figure 6(c) shows that the two color strips have been healed together. The stretched strip was subjected to a tensile test in Figure 6(d). The results show that MPs exhibits excellent self-healing properties at ambient temperature.

Figure 6. (a) The stretch strips added with different dyes (Prussian blue and Rhodamine B); (b) cut two different colors of the stretch strips and contact them together; (c) Self-healing hydrogels were healed at room temperature for about 4 h; (d) tensile testing were measured via Microcomputer control electronic universal material testing machine. Conclusion and Potential Applications. In this paper, a self-healing hydrogel composed of porous carbon-type microcapsules from fruit residues was introduced. The dual self-healing hydrogels were obtained from microcapsule by using GA as the healing agent and PDA as coating. Compared with traditional hydrogels, this hydrogel combines intrinsic and extrinsic self-healing functionality, which greatly improves the mechanical strength and self-healing efficiency of the hydrogels. The stress and the self-healing efficiency of this dual self-healing hydrogel can reach 7.68 MPa and 89.9 %, respectively. Importantly, this methods not only introduces a new type of


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highly efficient self-healing hydrogel, but also provides ideas for the preparation of biomass in hydrogels. As reported in literature, biomass hydrogels from GG can be widely used in environmental adsorption or controlled molecule release. For example, hydrogels with mussel-inspired chemistry38 or GG39 matrix can have strong adsorption capacity for heavy metal ion40 or organic dyes41. The obtained self-healing hydrogels from modified GG and PDA, can also have a potential applications in the adsorption of heavy metal ion or organic dyes. Additionally, GG-type hydrogels as a natural polymer can be widely used in controlled drug release42. The obtained microcapsules from biomass porous carbon and PDA have also extremely potential applications as controlled release carrier for verify drug delivery. These self-healing hydrogels of environmental adsorption and drug controlled release will be explored in the future work. ASSOCIATED CONTENT

Supporting Information The BET nitrogen adsorption/desorption isotherm shows the specific surface area of PC and PC-GA@PDA (Figure S1). The TGA curves (Figure S2) and Raman spectra (Figure S3) of PC, PC-GA and PC-GA@PDA are used to characterize the successful preparation of microcapsules. AUTHOR INFORMATION

Corresponding Author *L.B. Phone: +86 535 6669070. E-mail: [email protected]. *W.W. Phone: +86 535 6669070. E-mail: [email protected].



Funding The research was financial supported by the National Natural Science Foundation of China (Nos. 51773086 and 51573075), the Key Program for Basic Research of Natural Science Foundation of Shandong Province (No. ZR2018ZC0946), the Natural Science Foundation of Shandong Province (No. ZR2018BB027) and the Project of Shandong Province Higher Educational Science (Nos. J16LC20 and J18KA080). Notes The authors declare no competing financial interest. ACKNOWLEDGMENTS The authors sincerely thank Dr. Yi Liu, Dr. Yuming Cui and Dr. Xunyong Liu for the supporting of characterization.

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Acid-co-Acrylamide-co-3-Acrylamido Propanoic Acid) IPN via in Situ Attachment of Acrylamido Propanoic Acid for Analyzing Superadsorption Mechanism of Pb(II)/Cd(II)/Cu(II)/MB/MV. Polym. Chem. 2017, 8, 6750-6777. (b) Zong, G. X.; Chen, H.; Qu, R. J.; Wang, C. H.; Ji, N. Y., Synthesis of polyacrylonitrile-grafted cross-linked N-chlorosulfonamidated polystyrene via surface-initiated ARGET ATRP, and use of the resin in mercury removal after modification. J. Hazard. Mater. 2011, 186, 614-621. (c)

Zhang, S. X.; Zhang, Y. Y.; Bi, G. M.; Liu, J. S.; Wang, Z.

G.; Xu, Q.; Xu, H.; Li, X. Y., Mussel-inspired polydopamine biopolymer decorated with magnetic nanoparticles for multiple pollutants removal. J. Hazard. Mater. 2014, 270, 27-34. 41. (a) Gupta, V. K.; Pathania, D.; Singh, P.; Kumar, A.; Rathore, B. S. Adsorptional Removal of Methylene Blue by Guar Gum-Cerium (IV) Tungstate Hybrid Cationic


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Exchanger. Carbohydr. Polym. 2014, 101, 684-691. (b) Yang, H. W.; Bai, L. J.; Wei, D. L.; Yang, L. X.; Wang, W. X.; Chen, H.; Niu, Y. Z.; Xue, Z. X., Ionic self-assembly of poly(ionic liquid)-polyoxometalate hybrids for selective adsorption of anionic dyes. Chem. Eng. J. 2019, 358, 850-859. 42. Zeng, G. J.; Chen, T. T.; Huang, L.; Liu, M. Y.; Jiang, R. M.; Wang, Q.; Dai, Y. F.; Wen, Y. Q.; Zhang, X. Y.; Wei, Y. Surface Modification and Drug Delivery Applications of MoS2 Nanosheets with Polymers Through the Combination of Mussel Inspired Chemistry and SET-LRP. J. Taiwan Inst. Chem. Eng. 2018, 82, 205-213.



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Fabrication of Microcapsules by the Combination of Biomass Porous

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