Please wait a minute...
Frontiers of Materials Science

ISSN 2095-025X

ISSN 2095-0268(Online)

CN 11-5985/TB

Postal Subscription Code 80-974

2018 Impact Factor: 1.701

Front. Mater. Sci.    2021, Vol. 15 Issue (2) : 266-279    https://doi.org/10.1007/s11706-021-0555-7
RESEARCH ARTICLE
New starch capsules with antistatic, anti-wear and superlubricity properties
Nannan WANG1,2, Youbin ZHENG1,3, Yange FENG1,3(), Liqiang ZHANG1,2, Min FENG1,2, Xiaojuan LI1,2, Daoai WANG1,3()
1. State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China
2. Center of Materials Sciences and Opto-Electronic Technology, University of Chinese Academy of Sciences, Beijing 100049, China
3. Qingdao Center of Resource Chemistry and New Materials, Qingdao 266100, China
 Download: PDF(3893 KB)   HTML
 Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks
Abstract

Adsorption of drug powder is caused by triboelectrification on the surface of starch capsule during filling process. Furthermore, high wear rate and poor water lubricity also hinder the further practical applications of traditional starch capsule. To solve these problems, a glycerol-modified starch capsule with perfect anti-triboelectrification and enhanced lubrication performance was fabricated. Hydrogen bond between glycerol and starch molecules could reduce the bound water content on the capsule surface and thus realizes anti-triboelectrification. By adding glycerol, a three-tier structure composed of starch-glycerol-water is formed through hydrogen bonding on the surface of the starch film, which has been proven to be favorable for lubrication performance. When 5% glycerol is added, the short-circuit current (Isc) of starch-based triboelectric nanogenerator (TENG) is reduced by 86%, and the wear volume of the starch film is reduced by 89%. Under water lubrication condition, the lubrication performance of the starch-glycerol film can reach the super lubricated level with a friction coefficient of about 0.005. This work provides a new route to obtain modified starch capsules with improved anti-triboelectrification property, reduced wear rate and superlubricity property.

Keywords starch capsules      hydrogen bonds      anti-triboelectrification      anti-wear      superlubricity     
Corresponding Author(s): Yange FENG,Daoai WANG   
Online First Date: 14 May 2021    Issue Date: 08 June 2021
 Cite this article:   
Nannan WANG,Youbin ZHENG,Yange FENG, et al. New starch capsules with antistatic, anti-wear and superlubricity properties[J]. Front. Mater. Sci., 2021, 15(2): 266-279.
 URL:  
https://academic.hep.com.cn/foms/EN/10.1007/s11706-021-0555-7
https://academic.hep.com.cn/foms/EN/Y2021/V15/I2/266
Fig.1  (a) The preparation process of the starch-glycerol (GC) film. (b) Schematic of the formation of hydrogen bond between starch molecule and glycerol molecule. (c) Comparison of infrared spectra of the blank starch film and the one with 5% glycerol.
Fig.2  (a) Comparison of infrared spectra between the blank starch film and the one with 5% glycerol before and after completely drying at 90 °C. (b)(c) UV-absorption spectra and mechanical properties of the blank starch film and the ones with 1% and 5% glycerol. (d) Friability test of the blank starch capsule shell and the one with 5% glycerol. (e)(f)(g) Compression–recovery experiment of the blank starch capsule and the one with 5% glycerol.
Fig.3  (a) Triboelectric sequence of starch films with different glycerol contents. (b) Short-circuit current (Isc), (c) output voltage (Uo), (d) integrated charge density, and (e) changes in current with voltage of blank starch-based TENG and the ones with 1% and 5% glycerol. (f) Stability test of blank starch-based TENG and the one with 5% glycerol at 35% RH.
Fig.4  Changes of (a) Isc and (b) Uo for the blank starch-based TENG and the one with 5% glycerol with humidity. Real-time changes of Isc for (c) the blank starch-based TENG and (d) the one with 5% glycerol with humidity. Schematics of (e) hydrogen bonds between glycerol inside the starch film and water molecules, (f) hydroxyl sites on the surface of the starch film occupied by glycerol, and (g) glycerol molecules on the surface of the starch film forming hydrogen bonds with water molecules in the environment. (h)(i)(j) Comparison of powder adsorption of starch capsules with different glycerol contents.
Fig.5  Comparison of (a) friction coefficient, (b) wear volume, and (c) friction coefficient under water lubrication. (d)(e)(f) 3D topographies of wear scars on the starch film with different glycerol contents. Applied load: 2 N; frequency: 5 Hz.
  Fig. S1 (a)(b)(c) Transparency photos of starch films with different glycerol contents. SEM images of (d) the blank starch film and (e) the one with 5% glycerol content.
  Fig. S2 Disintegration experiment of capsules with different glycerol contents: (a) schematic diagram of capsule administration process; (b) disintegration demonstration experiment of blank starch capsule and glycerol-starch capsule; comparison of residue on baffle between (c) blank starch capsule and (d) glycerol-starch capsule after disaggregation.
  Fig. S3 Dissolution curves of gelatin and starch capsules filled with drugs.
  Fig. S4 Surface resistivities of starch films with different glycerol contents.
  Fig. S5 Resistance values of (a) glycerol and (b) blank starch film.
  Fig. S6 (a) Comparison of water absorptions of starch film and glycerol at 95% RH. (b) Comparison of friction coefficients between the starch film coated with glycerol and the one without glycerol.
SP CT DOT FB LOD/% DT/min
Gelatin capsule Pale yellow transparency, elastic 0/10 0/50 12.82 8–10
Starch capsule Colorless and transparent, elastic 0/10 0/50 10.13 3–5
  Table S1 Performances comparison of gelatin and starch capsules
SP Day 0 Day 5 Day 10
CT DOT FB LOD/% DT/min CT DOT FB LOD/% DT/min CT DOT FB LOD/% DT/min
A1 0/10 0/50 12.82 8–10 0/10 0/50 8.79 12–15 0/10 0/50 7.11 11–14
A2 0/10 0/50 12.82 8–10 0/10 0/50 11.57 9–13 0/10 0/50 7.80 10–12
B1 0/10 0/50 10.13 3–5 0/10 0/50 7.51 4–7 0/10 0/50 6.39 5–7
B2 0/10 0/50 10.13 3–5 0/10 0/50 8.95 5–8 0/10 0/50 6.86 6–8
  Table S2 Effect of high temperature on properties of gelatin and starch capsules
SP Day 0 Day 5 Day 10
CT DOT FB LOD/% DT/min CT DOT FB LOD/% DT/min CT DOT FB LOD/% DT/min
A1 0/10 0/50 12.82 8–10 0/10 0/50 22.36 6–10 0/10 0/50 21.57 8–12
A2 0/10 0/50 12.82 8–10 0/10 0/50 19.65 8–12 0/10 0/50 19.62 9–11
B1 0/10 0/50 10.13 3–5 0/10 0/50 15.03 3–6 0/10 0/50 15.48 3–5
B2 0/10 0/50 10.13 3–5 0/10 0/50 11.13 2–5 0/10 0/50 12.05 4–6
  Table S3 Effect of high humidity on properties of gelatin and starch capsules
SP Day 0 Day 5 Day 10
CT DOT FB LOD/% DT/min CT DOT FB LOD/% DT/min CT DOT FB LOD/% DT/min
A1 0/10 0/50 12.82 8–10 0/10 0/50 9.96 12–14 0/10 0/50 11.71 12–15
A2 0/10 0/50 12.82 8–10 0/10 0/50 11.10 10–13 0/10 0/50 12.08 11–13
B1 0/10 0/50 10.13 3–5 0/10 0/50 6.43 4–6 0/10 0/50 6.02 3–5
B2 0/10 0/50 10.13 3–5 0/10 0/50 7.27 5–7 0/10 0/50 7.30 4–6
  Table S4 Effect of strong light on properties of gelatin and starch capsules
1 N Oladzadabbasabadi, S Ebadi, A Mohammadi Nafchi, et al.. Functional properties of dually modified sago starch/κ-carrageenan films: An alternative to gelatin in pharmaceutical capsules. Carbohydrate Polymers, 2017, 160: 43–51
https://doi.org/10.1016/j.carbpol.2016.12.042 pmid: 28115099
2 Z Misic, K Muffler, G Sydow, et al.. Novel starch-based PVA thermoplastic capsules for hydrophilic lipid-based formulations. Journal of Pharmaceutical Sciences, 2012, 101(12): 4516–4528
https://doi.org/10.1002/jps.23315 pmid: 22949383
3 P Watts, A Smith. TARGITTM technology: Coated starch capsules for site-specific drug delivery into the lower gastrointestinal tract. Expert Opinion on Drug Delivery, 2005, 2(1): 159–167
https://doi.org/10.1517/17425247.2.1.159
4 V D Vilivalam, L Illum, K Iqbal. Starch capsules: An alternative system for oral drug delivery. Pharmaceutical Science & Technology Today, 2003, 3(2): 64–69
https://doi.org/10.1016/S1461-5347(99)00238-2
5 T Jankowski, M Zielinska, A Wysakowska. Encapsulation of lactic acid bacteria with alginate/starch capsules. Biotechnology Techniques, 1997, 11(1): 31–34
https://doi.org/10.1007/BF02764447
6 M H Fakharian, N Tamimi, H Abbaspour, et al.. Effects of κ-carrageenan on rheological properties of dually modified sago starch: Towards finding gelatin alternative for hard capsules. Carbohydrate Polymers, 2015, 132: 156–163
https://doi.org/10.1016/j.carbpol.2015.06.033 pmid: 26256336
7 H J Bae, D S Cha, W S Whiteside, et al.. Film and pharmaceutical hard capsule formation properties of mungbean, waterchestnut, and sweet potato starches. Food Chemistry, 2008, 106(1): 96–105
https://doi.org/10.1016/j.foodchem.2007.05.070
8 N Zhang, H Liu, L Yu, et al.. Developing gelatin-starch blends for use as capsule materials. Carbohydrate Polymers, 2013, 92(1): 455–461
https://doi.org/10.1016/j.carbpol.2012.09.048 pmid: 23218320
9 R P Gullapalli, C L Mazzitelli. Gelatin and non-gelatin capsule dosage forms. Journal of Pharmaceutical Sciences, 2017, 106(6): 1453–1465
https://doi.org/10.1016/j.xphs.2017.02.006 pmid: 28209365
10 X X Liu, Y F Wang, N Z Zhang, et al.. Morphology and phase composition of gelatin-starch blends. Chinese Journal of Polymer Science, 2014, 32(1): 108–114
https://doi.org/10.1007/s10118-014-1377-1
11 C J Kenyon, E T Cole, I R Wilding. The effect of food on the in-vivo behavior of enteric-coated starch capsules. International Journal of Pharmaceutics, 1994, 122(3): 207–213
https://doi.org/10.1016/0378-5173(94)90356-5
12 G Baier, A Musyanovych, M Dass, et al.. Cross-linked starch capsules containing dsDNA prepared in inverse miniemulsion as “nanoreactors” for polymerase chain reaction. Biomacromolecules, 2010, 11(4): 960–968
https://doi.org/10.1021/bm901414k pmid: 20329746
13 L Zhang, Y Wang, H Liu, et al.. Developing hydroxypropyl methylcellulose/hydroxypropyl starch blends for use as capsule materials. Carbohydrate Polymers, 2013, 98(1): 73–79
https://doi.org/10.1016/j.carbpol.2013.05.070 pmid: 23987318
14 U C Gohil, F Podczeck, N Turnbull. Investigations into the use of pregelatinised starch to develop powder-filled hard capsules. International Journal of Pharmaceutics, 2004, 285(1–2): 51–63
https://doi.org/10.1016/j.ijpharm.2004.07.008 pmid: 15488679
15 M F Shukur, F M Ibrahim, N A Majid, et al.. Electrical analysis of amorphous corn starch-based polymer electrolyte membranes doped with LiI. Physica Scripta, 2013, 88(2): 025601
https://doi.org/10.1088/0031-8949/88/02/025601
16 O A Bin-Dahman, M Rahaman, D Khastgir, et al.. Electrical and dielectric properties of poly(vinyl alcohol)/starch/graphene nanocomposites. Canadian Journal of Chemical Engineering, 2018, 96(4): 903–911
https://doi.org/10.1002/cjce.22999
17 M F Shukur, M F Z Kadir. Electrical and transport properties of NH4Br-doped cornstarch-based solid biopolymer electrolyte. Ionics, 2015, 21(1): 111–124
https://doi.org/10.1007/s11581-014-1157-5
18 M F Shukur, R Ithnin, M F Z Kadir. Electrical characterization of corn starch-LiOAc electrolytes and application in electrochemical double layer capacitor. Electrochimica Acta, 2014, 136: 204–216
https://doi.org/10.1016/j.electacta.2014.05.075
19 M D Hazrol, S M Sapuan, R A Ilyas, et al.. Electrical properties of sugar palm nanocrystalline cellulose reinforced sugar palm starch nanocomposites. Polimery, 2020, 65(5): 363–370
https://doi.org/10.14314/polimery.2020.5.4
20 M Wu, Y Wang, M Wang, et al.. Effect of SiO2 nanoparticles on the wear resistance of starch films. Fibres & Textiles in Eastern Europe, 2008, 16(4): 96–99
21 G Biresaw, J A Kenar, T L Kurth, et al.. Investigation of the mechanism of lubrication in starch-oil composite dry film lubricants. Lubrication Science, 2007, 19(1): 41–55
https://doi.org/10.1002/ls.29
22 A B Dias, C M O Müller, F D S Larotonda, et al.. Biodegradable films based on rice starch and rice flour. Journal of Cereal Science, 2010, 51(2): 213–219
https://doi.org/10.1016/j.jcs.2009.11.014
23 V M A Calado, A Ramos. Applications of starch nanocrystal-based blends, composites and nanocomposites. In: P M Visakh, L Yu, eds. Starch-based Blends, Composites and Nanocomposites. RSC Green Chemistry Series, 2016, 37: 143–216
24 W Wang, H Yang, M Cui. Effects of additives on the properties of starch. In: P M Visakh, L Yu, eds. Starch-based Blends, Composites and Nanocomposites. RSC Green Chemistry Series, 2016, 37: 403–432
25 A Donnadio, M Pica, M Taddei, et al.. Design and synthesis of plasticizing fillers based on zirconium phosphonates for glycerol-free composite starch films. Journal of Materials Chemistry, 2012, 22(11): 5098–5106
https://doi.org/10.1039/c2jm15201k
26 N Wang, Y Zheng, Y Feng, et al.. Biofilm material based triboelectric nanogenerator with high output performance in 95% humidity environment. Nano Energy, 2020, 77: 105088
https://doi.org/10.1016/j.nanoen.2020.105088
27 C Ma, S Zhao, G Huang. Anti-static charge character of the plasma treated polyester filter fabric. Journal of Electrostatics, 2010, 68(2): 111–115
https://doi.org/10.1016/j.elstat.2009.11.005
28 H T Baytekin, B Baytekin, T M Hermans, et al.. Control of surface charges by radicals as a principle of antistatic polymers protecting electronic circuitry. Science, 2013, 341(6152): 1368–1371
https://doi.org/10.1126/science.1241326
29 Y Kugimoto, A Wakabayashi, T Dobashi, et al.. Preparation and characterization of composite coatings containing a quaternary ammonium salt as an anti-static agent. Progress in Organic Coatings, 2016, 92: 80–84
https://doi.org/10.1016/j.porgcoat.2015.11.013
30 F R Fan, Z Q Tian, Z L Wang. Flexible triboelectric generator. Nano Energy, 2012, 1(2): 328–334
https://doi.org/10.1016/j.nanoen.2012.01.004
31 Y Jin, W Xu, H Zhang, et al.. Complete prevention of contact electrification by molecular engineering. Matter, 2021, 4(1): 290–301
https://doi.org/10.1016/j.matt.2020.10.019
32 X Li, L Zhang, Y Feng, et al.. Solid–liquid triboelectrification control and antistatic materials design based on interface wettability control. Advanced Functional Materials, 2019, 29(35): 1903587
https://doi.org/10.1002/adfm.201903587
33 J Joseph, E D Jemmis. Red-, blue-, or no-shift in hydrogen bonds: A unified explanation. Journal of the American Chemical Society, 2007, 129(15): 4620–4632
https://doi.org/10.1021/ja067545z pmid: 17375920
34 P P Kannan, N K Karthick, A Mahendraprabu, et al.. Red/blue shifting hydrogen bonds in acetonitrile-dimethyl sulphoxide solutions: FTIR and theoretical studies. Journal of Molecular Structure, 2017, 1139: 196–201
https://doi.org/10.1016/j.molstruc.2017.03.036
35 I S Ryu, X Liu, Y Jin, et al.. Stoichiometric analysis of competing intermolecular hydrogen bonds using infrared spectroscopy. RSC Advances, 2018, 8(42): 23481–23488
https://doi.org/10.1039/C8RA02919A pmid: 30386590
[1] FMS-21555-OF-Wnn_suppl_1 Video  
[2] FMS-21555-OF-Wnn_suppl_2 Video  
[3] FMS-21555-OF-Wnn_suppl_3 Video  
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed