Electrochemical-assisted synthesis, spray granulation and

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Electrochemical-assisted synthesis, spray granulation and characterization of oxidized corn starch-gelatin Xugang DANG, Hui Chen, Rui Dai, Yajuan Wang, and Zhihua Shan Ind. Eng. Chem. Res., Just Accepted Manuscript • Publication Date (Web): 11 May 2018 Downloaded from http://pubs.acs.org on May 11, 2018

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Industrial & Engineering Chemistry Research

Electrochemical-assisted synthesis, spray granulation and characterization of oxidized corn starch-gelatin Xugang Dang 1,2, Hui Chen 1,2, Rui Dai 3, Yajuan Wang 4, Zhihua Shan 1,2* 1

The Key Laboratory of Leather Chemistry and Engineering (Sichuan University),

Ministry of Education, Chengdu 61006 5; 2

National Engineering Laboratory for Clean Technology of Leather Manufacture,

Sichuan University, Chengdu 610065 3

Sichuan University, Chengdu 610065

4

School of Materials and Chemical Engineering, Ningbo University of Technology,

Ningbo 315016

1

ACS Paragon Plus Environment

Industrial & Engineering Chemistry Research 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Abstract Oxidized corn starch-gelatin (OCS-Gel) was successfully synthesized by the electrochemical-assisted oxidation method. The introduction of spray-drying technology, as an advanced method for the post-processing of sample solution, also has greatly improved the application property of blend. The corn starch was gelatinized firstly, and then mixed with gelatin solution to prepare the blend solution in the electrolyzer with current (120 mA) and 0.5% sodium chloride. Finally, the prepared OCS-Gel solution was dehydrated and granulated using the spray drying process to obtain the powder particles of OCS-Gel. The spray-dried OCS-Gel was characterized by FT-IR, XRD, SEM. The introduction of active groups (amino, carboxyl, carbonyl) promoted OCS-Gel hydration and swelling. In addition, compared with CS the crystallinity of spray-dried OCS-Gel decreased obviously. The OCS-Gel formed a hollow or deflated spherical structure. The electrochemical-assisted oxidation and spray-drying technology were masterfully combined to prepare the OCS-Gel, which can dramatically improve the application performance of biomaterials. Keywords: Oxidized corn starch; gelatin; electrochemical synthesis;

2


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1. Introduction In recent year, with the rapid development of modern science and technology and people’s living quality increase 1, people attached more and more importance to the safety and environmental performance issues of used materials in daily life 2. Especially on the polymer materials research and development, creation of pollution-free is in great demand

3, 4

. The natural polymers are the most promising

candidate among the wide-ranging applications and many kinds, and providing polymeric materials which degrades to green components after accomplishment of the period of their utilization 5, 6. Oxidized corn starch (OCS) and gelatin, as abundant and environmentally friendly materials, have been widely applied in the food (food packing materials materials

9, 10

7, 8

), pharmaceutical (microencapsules, medicine slow release

), agriculture (Biodegradable liquid film mulching 11) and environment

(dust suppressors

12

) based on the advantages and good performances, such as:

bio-degradability, high-quality bio-compatibility, wide-ranging applications, non-toxic and non-flammable nature, high reactivity, high molecular weight, low cost, easy availability and so on, therefore they have been counted as superb raw chemical substances for conserving petroleum resources and shielding the environment 3. According to the previous researches, based on the inherent weakness of OCS or Gel itself

6, 13

, such as: the limited hydrophilic character, brittleness and limited chemical

reactivity of OCS; the hot sticking and cold brittleness, rapid water solubility and limited corrosion-resistance of Gel, they usually needs to be processed by copolymerization and modified composite

14

cross-linking in achieving the effective

3



influence in different fields

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15, 16

. In addition, the OCS-Gel blend can be synthesized

when the OCS was cross-linked with Gel. And the preparation of OCS-Gel blend depends chiefly on the chemical crosslink reactions between the carbonyl groups in the OCS molecules and amine groups in the Gel molecules to form the stable schiff base structure

16

, which can improve the blend properties (hygroscopicity and

retention characteristic, thermal stability) to a great extent. Although the properties of the OCS-Gel blend have been improved by the chemical cross-linking and intermolecular forces between OCS and Gel

17

, the synthesis of blend has complex

operations and high production cost. In addition, the synthesized OCS-Gel blend solution has poor storage stability due to the presence of unreacted OCS. Thus, development of the new synthetic methods and post-processing strategies with green, advanced technology, simple fabrication, safe and high efficiency operation is important to prepare the OCS-Gel blend and retain the good performance 18. Electrochemical synthesis, as a synthetic method with green, simple, safe and high efficiency, has been introduced into the synthesis of polymer materials

19

. The

synthetic method not only is a quick and effective sample preparing method, but also can achieve the requested performances of blend. In this research, the electrochemical synthesis method has been used to prepare the OCS-Gel blend. At the same time, in the blend molecules the unreacted OCS can induce the phase separation of blend solution due to the special features (retrogradation) of gelatinized OCS at low temperature, which will seriously impact the storage stability of blend solution and then influence the width and depth of its usage

20

. In this research, the spray

4


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granulation has also been used for post-processing of the blend sample solution

21

.

Namely, the OCS-Gel blend was synthesized by electrochemical method firstly, after that the sample solution was immediately dried by spray-drying method to obtain the powder blend sample, which will be one of the most effective ways to improve the application performance. The spray-drying technology was shown in Figure 1.

Figure 1. Schematic of spray-drying technology 2. Experimental 2.1 Materials Corn Starch (CS, CAS Number: S5296) and gelatin (Gel, type A, CAS Number: G2500) used for the experimental work were purchased from Sigma Aldrich (Shanghai) Tarding Company Ltd, China. Sodium chloride and other general chemicals were purchased from Chengdu Kelong Company, which was of analytical grade. 2.2 Preparation of OCS-Gel 2.2.1 The preparation of OCS-Gel samples 5



The CS was dissolved in distilled water at 80 oC and stirred continuously for 45 min until completely dissolved (CS gelatinization process). The Gel was dissolved in distilled water and heated with magnetic stirring at 50 oC for 30 min until a clear solution was obtained. Then, the gelatinized CS and Gel solution were mixed and transferred to an electrolyzer containing a graphite sheet and a steel sheet as anode and cathode materials respectively. The electrolytic oxidation of the system was performed in 1% aqueous solution of sodium chloride, the current was adjusted to 120 mA, heated to 50 oC for 25 min under continuous stirring. After the electrolysis was competed, the mixture was continued to whisk for a further 30 min. Finally, the OCS-Gel precursor solution was obtained. Among the blending ratio of CS/Gel was 1/1 (by weight) in the preparation process. 2.2.2 spray drying Spray drying process was performed in a JOYN-8000Y laboratory spray dryer (Hangzhou Jutong Instrument Co., China) with a 0.75 diameter nozzle in the Sichuan University. The prepared precursor solutions were obtained with a 0.75Ø pressure nozzle assisted with a vibration generated by the piezoceramic material surrounding the nozzle

22

. From preliminary trials, we found that free flowing powders were

obtained with a feed flow rate (15 mL/min), an air flow rate (140 m3/h) and an atomization pressure of 0.06 MPa. The dryer inlet temperatures were adjusted at 140 o

C and 180 oC, and the corresponding outlet temperature were adjusted at 60 oC and

80 oC, respectively. The obtained dried powders were collected and kept in sealed reagent bottle. The flow chart of the whole synthesis of OCS-Gel was shown in 6


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Figure 2.

Figure 2. The flow chart of the whole synthesis of OCS-Gel particles 2.3 Determination and characterization of samples 2.3.4 FT-IR analysis After the gelatinized CS was mixed with G solution in the current function, the changes of functional groups were analyzed by Fourier transform infrared spectrometer (FT-IR, PE, USA). The CS and spray-dried OCS-Gel samples were granulated by a blender, and then a quantitative of powder specimens diluted with KBr powder of spectroscopic grade was tested in a selected wavenumber region (4000 cm-1 to 500 cm-1). 2.3.5 XRD (X-ray diffraction) analysis XRD of the CS and spray-dried OCS-Gel samples was conducted using a Rigaku Mini Flex 600 diffractometer (Rigaku,Japan) with Ni-filtered Cu Kα(alpha) radiation (40 kV, 15 mA). The scanning range (2θ) was 10˚ to 60˚ with a step size of 2˚, and the

7



scanning rate was 2˚ min-1. 2.3.6 SEM analysis The surface morphologies of the CS and spray-dried OCS-Gel samples were investigated using a Hitachi S-4800 scanning electron microscope (SEM, Hitachi Co., Japan). Before the specimens were imaged they were fixed onto metallic sample holders and then sputtered with a layer of gold, and subsequently observed in the SEM at an accelerating voltage of 2.00 kV. 2.3.7 Swelling behavior of OCS-Gel samples The swelling behavior of spray-dried OCS-Gel samples was investigated by testing the increase in the weight of OCS samples at increasing time intervals of 1, 2, 3, and 4 h, etc. The spray-dried samples were weighed and then fully immersed in water, the temperature was hold at 25 oC. At every time interval, the swollen sample particles were filtered through a 200 mesh sieve and wiped away the surface water with a filter paper, weighed and then put back into same bath. The weight of the samples was measured continuously until a constant-weight particle was formed. Three readings of viscosity were recorded for each solution, and average values were reported. Tests were run in triplicate. The water absorption capacity of spray-dried samples was expressed by testing the water absorption ratio of samples. The computation formula for the water absorption ratio was showed in the following equation: Q = (m1 − m0 ) / m0 Where, Q was used to represent the water absorption ratio of samples; m0 (g) 8


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represented the weight of the samples before water absorption; m1 (g) represented the weight of the samples before water absorption. 3. Results and discussions 3.1 FT-IR analysis Figure 3 shows the FT-IR spectra of native CS, Gel and OCS-Gel. The CS (curve a) had an intense band at about 3278 cm-1 for the hydroxyl groups (O–H) of CS. In the Gel (curve b), the bands at 1694 cm-1, 1531 cm-1 and 1247 cm-1 were assigned to absorption peaks of Amide I, Amide II and Amide III, respectively 23, and the bands at 3373 cm-1 and 3305 cm-1 were assigned to absorption peak of the amide group (N–H). After the OCS was cross-linked with Gel, the characteristic bands for the carbonyl groups (C=O) and amide groups (N–H) became weaker

24

, and the bands

appeared at 1650 cm-1 and 1356 cm-1 for characteristic vibration peak of C=N and C–N, respectively, in the OCS-Gel (curve c). The results showed that the aldehyde groups of OCS had reacted with the amino groups of Gel and formed stable Schiff's base structures

25

. Meanwhile, compared with the characteristic vibration peak of

OCS-Gel molecule in the curve c, the characteristic vibration peak of Gel became weaker, especially the band at 1694 cm-1 disappeared, which was also attributed to the cross-linking between OCS and Gel. In addition, the introduction of spray-drying technology, as an advanced method for the post-processing of sample solution, also does not affect the chemical structures of OCS-Gel molecules.

9



1650

2968

1356

c

b

3000

1736

1247

1694

1531

3500

2920 2850

3373 3305 3278

Transmittance (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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a 2500

2000

1500

1000

Wavenumbers (cm-1)

Figure 3. Fourier transform infrared spectroscopy of the samples (a: native CS; b: Gel; c: OCS-Gel) 3.2 XRD analysis According to previous research, the hydroxyl groups of CS is oxidized to carboxyl and carbonyl functional groups by electrochemical oxidation, breaking the hydrogen bond between CS molecules and loosening the CS molecules so that the crystalline structure of CS molecules was destroyed 26. XRD was used to analyze the crystalline structure changes of CS and OCS-Gel samples, as shown in Figure 4. The CS granules were composed of amorphous and crystalline regions, as showed by the XRD patterns. In Figure 4 (a), the peak positions at around 15°, 17°, 18° and 22°of 2θ indicated the characteristics peaks of CS, which described the degree of crystallinity of CS

27

. After cross-linking with Gel, in Figure 4 (b, c), the XRD diffraction peak 10


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positions of spray-dried OCS-Gel samples obviously disappeared. It can illustrate that crystallization of CS was greatly destroyed 26. At the same time, the peak positions at 2θ of 17°, 18° and 22° disappeared 28, indicating the formation of amorphous region 29. Moreover, as shown in Figure 4 (b, c), the crystalline phases of OCS-Gel samples remained almost unchanged under spray-drying temperatures. The results indicated that the electrochemical oxidation of the samples caused the crystalline peaks to disappear, different spray-drying temperatures does not affect the crystal structure of OCS-Gel molecules.

Figure 4. XRD patterns of the prepared samples (a: native CS; b: OCS-Gel produced at spray-drying with inlet temperature 140 oC and outlet temperature 60 oC; c: OCS-Gel produced at spray-drying with inlet temperature 180 oC and outlet temperature 80 oC) 11



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3.3 Micro-structures analysis Figure 5 showed the scanning electron microscopes of CS and OCS-Gel samples. It was noted that there were some differences in surface and internal structure morphology of various samples. As showed in Figure 5, when the magnification was 2000, it can be seen that the micro-structures of obtained samples gradually changed from initially solid spherical with small holes into a hollow or deflated spherical structure during the electrochemical synthesis and spray-drying process of OCS-Gel, which indicated that the electrochemical oxidation and spray-drying can really change the micro-structures of CS and OCS-Gel samples. At the same time, by the electrochemical oxidation

30

, in the OCS-Gel molecules the introduction of active

groups (amino, carboxyl and carbonyl functional groups)

31

can increase the

intermolecular forces, which can achieve the continuous structures of OCS-Gel molecules very well. In addition, when the magnification was adjusted to 1000, it can be seen that the micro-structures of obtained samples showed an obviously hollow structure by spray-drying with inlet temperature 180 oC and outlet temperature 80 oC, and a deflated spherical structure by spray-drying with inlet temperature 140 oC and outlet temperature 60 oC. The formed structures can improve the application properties of blend, such as: materials with deflated spherical structure can be used for biomass absorbents, materials with hollow structure can be used for drug delivery materials

32

. In addition, in the surfaces of CS, the porous structures almost

disappeared when the CS was reacted with Gel under electrochemical oxidation; the surfaces of blend formed a continuous phase structures, and the Gel stretched as 12


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covering on grain surface of CS.

Figure 5. SEM images of the prepared samples (a: native CS; b: OCS-Gel produced at spray-drying with inlet temperature 140 oC and outlet temperature 60 oC; c: OCS-Gel produced at spray-drying with inlet temperature 180 oC and outlet temperature 80 oC) 13



3.4 The swelling behaviour of samples The swelling behavior 33 of CS and OCS-Gel samples has been introduced in Figure 6. It can be seen that the water adsorption ratio of the samples increased noticeably after the CS reacted with Gel under electrochemical oxidation. Compared with the native CS, the water adsorption ratio of OCS-Gel samples was markedly increased over prolonged time. Meanwhile, as shown in Figure 6, the water adsorption ratio of the samples held steady when the swelling time was about 13 hours. According to the results, it can be concluded that the CS was oxidized and then cross-linked with Gel, which will cause the increase of active groups (-CHO, -NH2, -COOH) in the blend samples, and then lead to the increase of swelling capacity

27,34

. In addition, in the

Figure 6, the water adsorption ratio of obtained sample that had been post-treated by spray-drying with inlet temperature 180 oC and outlet temperature 80 oC clearly higher than it was post-treated by spray-drying with inlet temperature 140 oC and outlet temperature 60 oC, which was attributed to the special structure of samples. Namely, the OCS-Gel with the hollow structure had excellent water absorbing and swelling abilities 35. 10

c 8

Water absorption ratio

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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b a

6

4

2

0 0

1

2

3

4

5

6

7

814 9 10 11 12 13 14 15 16 17

Time (h)


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Figure 6. The swelling behavior of the prepared samples (a: native CS; b: OCS-Gel produced at spray-drying with inlet temperature 140 oC and outlet temperature 60 oC; c: OCS-Gel produced at spray-drying with inlet temperature 180 oC and outlet temperature 80 oC) 4.

Conclusions

In the research oxidized corn starch-gelatin (OCS-Gel) has been successfully prepared by the combination of electrochemical synthetic and spray-drying technology. After the OCS reacted with Gel, the introduction of active groups (amino, carboxyl, carbonyl) promoted OCS-Gel hydration and swelling. The OCS-Gel can form a hollow or deflated spherical structure under different spray-drying conditions (inlet temperature, outlet temperature), and the blends are made of the Gel stretched as covering on grain surface of CS after spray-drying process. In addition, compared with CS the crystallinity of spray-dried OCS-Gel decreased obviously. The electrochemical-assisted oxidation and spray-drying technology were masterfully combined to prepare the OCS-Gel, which can dramatically improve the potential application of CS and Gel as bio-materials. Author information Corresponding author E-mail: [email protected] (Z. Shan) ; Tel: +86 028 8540 7289. Notes The authors declare that they have no conflict of interest. Acknowledgments 15



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micro/nano-porous

superabsorbent hydrogel: Synthesis, optimization and investigation on swelling 20


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behavior. Sci Iran 2015, 22, (3), 883-893. (35) Padrao, J.; Silva, J. P.; Rodrigues, L. R.; Dourado, F.; Lanceros-Mendez, S.; Sencadas, V., Modifying Fish Gelatin Electrospun Membranes for Biomedical Applications: Cross-Linking and Swelling Behavior. Soft Mater 2014, 12, (3), 247-252.

Graphical Abstract

21


Electrochemical-assisted synthesis, spray granulation and

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