, Volume 25, Issue 4, pp 2235–2247 | Cite as

Freeze-drying of oxidized corn starch: electrochemical synthesis and characterization

  • Xugang Dang
  • Hui Chen
  • Yajuan Wang
  • Zhihua Shan
Original Paper


Oxidized corn starch (OCS) was successfully synthesized by electrochemical oxidation in aqueous solution of sodium chloride, and freeze-drying technology was also used for the post-processing of the prepared OCS. The synthesized OCS solutions were analyzed by viscosity measurement and UV–vis spectroscopies. The OCS samples were characterized by the determination of amylose and amylopectin contents, carboxyl and carbonyl groups contents, FT-IR, XRD, SEM and 13C-NMR. The analyses revealed that the viscosity of OCS solutions decreased with increasing current. The determination and characterization results indicated that the amylopectin decreased gradually, while the carboxyl and carbonyl groups contents of OCS increased by electro-oxidation. The introduction of carboxyl and carbonyl groups promoted OCS hydration and swelling. After electro-oxidation, the crystallinity of the OCS decreased, and the surface formed a loose and porous structure. The electro-oxidation was able to selectively oxidize the hydroxyl groups of the C-2, C-3, and C-6 positions by adjusting the current.


Oxidized corn starch Electrochemical synthesis Freeze-drying 



The authors would like to acknowledge the National Natural Science Foundation of China (51703100). The authors are also grateful to the Key Laboratory of Leather Chemistry and Engineering (Sichuan University), Ministry of Education, for financial aid and machinery equipment to support the research work.


This research was supported by the National Natural Science Foundation of China (51703100).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. Bidzinska E, Dyrek K, Fortuna T, Labanowska M, Pietrzyk S (2004) EPR studies of thermally treated oxidized corn starch. Starch-Starke 56(10):461–468CrossRefGoogle Scholar
  2. Bragd PL, van Besemer AC, Bekkum H (2000) Bromide-free TEMP-mediated oxidation of primary alcohol groups in starch and methyl alpha-D-glucopyranoside. Carbohydr Res 328:355–363CrossRefGoogle Scholar
  3. Chattopadhyay S, Singhal RS, Kulkarni PR (1997) Optimisation of conditions of synthesis of oxidised starch from corn and amaranth for use in film-forming applications. Carbohydr Polym 34(4):203–212CrossRefGoogle Scholar
  4. Chavez-Murillo CE, Wang YJ, Bello-Perez LA (2008) Morphological, physicochemical and structural characteristics of oxidized barley and corn starches. Starch-Starke 60(11):634–645CrossRefGoogle Scholar
  5. Chen H, Shan ZH, Woo MW, Chen XD (2017) Preparation and characteristic of gelatine/oxidized corn starch and gelatin/corn starch blend microspheres. Int J Biol Macromol 94:326–334CrossRefGoogle Scholar
  6. Chen L, Tian YQ, Sun BH, Cai CX, Ma RR, Jin ZY (2018) Measurement and characterization of external oil in the fried waxy maize starch granules using ATR-FTIR and XRD. Food Chem 242:131–138CrossRefGoogle Scholar
  7. Chong WT, Uthumporn U, Karim AA, Cheng LH (2013) The influence of ultrasound on the degree of oxidation of hypochlorite-oxidized corn starch. Food Sci Technol 50(2):439–443Google Scholar
  8. Colussi R, Kaur L, Zavareze ED, Dias ARG, Stewart RB, Singh J (2018) High pressure processing and retrogradation of potato starch: influence on functional properties and gastro-small intestinal digestion in vitro. Food Hydrocoll 75:131–137CrossRefGoogle Scholar
  9. Cozar O, Cioica N, Cota C, Nagy EM,k Fechete R (2017) Plasticizers effect on native biodegradable package materials. In: Tim15-16 physics conference, vol 1796Google Scholar
  10. Dai YY, Dong HZ, Hou HX, Qi XY, Zhang H (2012) Preparation of oxidized corn starch in a screw extruder under alkali-free conditions. Starch-Starke 64(5):374–381CrossRefGoogle Scholar
  11. Dai R, Woo MW, Chen H, Dang XG, Mansouri S, Shan ZH (2017) Hydrogel beads based on oxidized corn starch cross-linked with gelatin for tartrazine adsorption from aqueous environments. Polym J 49(7):549–555CrossRefGoogle Scholar
  12. Dang X, Shan Z, Chen H (2016) The Preparation and applications of one biodegradable liquid film mulching by oxidized corn starch-gelatin composite. Appl Biochem Biotechnol 180(5):917–929CrossRefGoogle Scholar
  13. Dang X, Shan Z, Chen H (2017a) Usability of oxidized corn starch-gelatin blends for suppression and prevention of dust. J Appl Polym Sci 134(6):1131–1139CrossRefGoogle Scholar
  14. Dang X, Yang M, Shan Z, Mansouri S, May BK, Chen X, Chen H, Woo MW (2017b) On spray drying of oxidized corn starch cross-linked gelatin microcapsules for drug release. Mater Sci Eng C 74:493–500CrossRefGoogle Scholar
  15. Degering EF (1998) Starch and its derivations. Wiley, New York, pp 306–353Google Scholar
  16. Farhadi S, Ajerloo B, Mohammadi A (2017) Low-cost and eco-friendly phyto-synthesis of silver nanoparticles by using grapes fruit extract and study of antibacterial and catalytic effects. Int J Nanodimens 8(1):49–60Google Scholar
  17. Ferfera-Harrar H, Dairi N (2013) Elaboration of cellulose acetate nanobiocomposites using acidified gelatin-montmorillonite as nanofiller: morphology, properties, and biodegradation studies. Polym Compos 34(9):1515–1524CrossRefGoogle Scholar
  18. Heine T, Talaba P, Heine U (2000) Starch Derivatives of High Degree of Functionalization. 1. Effective, homogeneous synthesis of ptoluenesulfonyl (tosyl) starch with a new functionalization pattern. Carbohydr Polym 42:41l–420Google Scholar
  19. Hornung PS, Avila S, Lazzarotto M, de Lazzarotto SRD, Siqueira GLD, Schnitzler E, Ribani RH (2017) Enhancement of the functional properties of dioscoreaceas native starches: mixture as a green modification process. Thermochim Acta 649:31–40CrossRefGoogle Scholar
  20. Jarvis CE, Walker JRL (1993) Simultaneous, rapid, spectrophotometric determination of total starch, amylose and amylopectin. J Sci Food Agric 63:89–92CrossRefGoogle Scholar
  21. Ji Y (2018) In vitro digestion and physicochemical characteristics of corn starch mixed with amino acid modified by low pressure treatment. Food Chem 242:421–426CrossRefGoogle Scholar
  22. Kato Y, Mastuo R, Isogal A (2004) Oxidation proess of watersoluble starch in TEMPO-mediated system. Carbohydr Polym 51:69–75CrossRefGoogle Scholar
  23. Kulshreshtha Y, Schlangen E, Jonkers HM, van Vardon PJ, Paassen LA (2017) Corncrete: a corn starch based building material. Constr Build Mater 154:411–423CrossRefGoogle Scholar
  24. Lian X, Wang C, Zhang K et al (2014) The retrogradation properties of glutinous rice and buckwheat starches as observed with FTIR, 13 C-NMR and DSC. Int J Biol Macromol 64:288–293CrossRefGoogle Scholar
  25. Lima TARM, Ilavsky J, Hammons J, Sarmento VHV, Rey JFQ, Valerio MEG (2017) Synthesis and synchrotron characterisation of novel dual-template of hydroxyapatite scaffolds with controlled size porous distribution. Mater Lett 190:107–110CrossRefGoogle Scholar
  26. Liu X, Zheng L, Zheng L, Ou C, Ye C, Wang A (2013) Determination of amylose and amylopectin in the commonly used starch materials by dual-wavelength spectrophotometry. Guangdong Agric Sci 40:97–100 (in Chinese) Google Scholar
  27. Marciello M, Rossi S, Caramella C, Remunan-Lopez C (2017) Freeze-dried cylinders carrying chitosan nanoparticles for vaginal peptide delivery. Carbohydr Polym 170:43–51CrossRefGoogle Scholar
  28. Mittal A, Garg S, Kohli D, Maiti M, Jana AK, Bajpai S (2016) Effect of cross linking of pva/starch and reinforcement of modified barley husk on the properties of composite films. Carbohydr Polym 151:926–938CrossRefGoogle Scholar
  29. Nakthong N, Wongsagonsup R, Amornsakchai T (2017) Characteristics and potential utilizations of starch from pineapple stem waste. Ind Crops Prod 105:74–82CrossRefGoogle Scholar
  30. Nwe N, Furuike T, Tamura H (2010) Selection of a biopolymer based on attachment, morphology and proliferation of fibroblast Nih/3t3 cells for the development of a biodegradable tissue regeneration template: alginate, bacterial cellulose and gelatin. Process Biochem 45(4):457–466CrossRefGoogle Scholar
  31. Paramakrishnan N, Jha S, Kumar KJ (2016) Effect of carboxymethylation on physicochemical, micromeritics and release characteristics of kyllinga nemoralis starch. Int J Biol Macromol 92:543–549CrossRefGoogle Scholar
  32. Pietrzyk S, Fortuna T, Labanowska M, Juszczak L, Galkowska D, Baczkowicz M, Kurdziel M (2018) The effect of amylose content and level of oxidation on the structural changes of acetylated corn starch and generation of free radicals. Food Chem 240:259–267CrossRefGoogle Scholar
  33. Rodriguez-Castellanos W, Flores-Ruiz FJ, Martinez-Bustos F, Chinas-Castillo F, Espinoza-Beltran FJ (2015) Nanomechanical properties and thermal stability of recycled cellulose reinforced starch-gelatin polymer composite. J Appl Polym Sci 132(14):41787CrossRefGoogle Scholar
  34. Sangseethong K, Termvejsayanon N, Sriroth K (2010) Characterization of physicochemical properties of hypochlorite and peroxide-oxidized cassava starches. Carbohydr Poly. 82:446–453CrossRefGoogle Scholar
  35. Suh DS, Chang PS, Kim KO (2002) Physicochemical properties of corn starch selectively oxidized with 2,2,6,6-tetramethyl-1-piperidinyl oxoammonium ion. Cereal Chem 79(4):576–581CrossRefGoogle Scholar
  36. Suki FMM, Azahari NA, Othman N, Ismail H (2013) XRD analysis and tensile properties of attapulgite clay filled polyvinyl alcohol/corn starch blend films. In: Advanced X-ray characterization techniques, vol 620, pp 99–104Google Scholar
  37. Sun FS, Liu JN, Liu XY, Wang YS, Li KX, Chang JL, Yang GX, He GY (2017) Effect of the phytate and hydrogen peroxide chemical modifications on the physicochemical and functional properties of wheat starch. Food Res Int 100:180–192CrossRefGoogle Scholar
  38. Tabar IB, Zhang XM, Youngblood JP, Mosier NS (2017) Production of cellulose nanofibers using phenolic enhanced surface oxidation. Carbohydr Polym 174:120–127CrossRefGoogle Scholar
  39. Wang X, Chu D (2003) Study on preparation of starch adhesive with electrochemical oxidation method. China Adhesives. 12:52–54 (in Chinese) Google Scholar
  40. Wang Y, Wang L (2003) Physicochemical properties of common and waxy corn starches oxidized by different levels of sodium hypochloride. Carbohydr Polym 52:207–217CrossRefGoogle Scholar
  41. Wang J, Li Y, Tian Y et al (2010) A novel triple-wavelength colorimetric method for measuring amylase and amylopectin contents. Starch 62:508–516CrossRefGoogle Scholar
  42. Wang WH, Wang K, Xiao JD, Liu YW, Zhao YN, Liu AJ (2017) Performance of high amylose starch-composited gelatin films influenced by gelatinization and concentration. Int J Biol Macromol 94:258–265CrossRefGoogle Scholar
  43. Xiong B, Zhao P, Hu K (2014) Dissolution of cellulose in aqueous NaOH/urea solution: role of urea. Cellulose 21:1183–1192CrossRefGoogle Scholar
  44. Yang M, Zhen WJ, Chen H, Shan ZH (2016) Biomimetic design of oxidized bacterial cellulose-gelatin-hydroxyapatite nanocomposites. J Bionic Eng 13(4):631–640CrossRefGoogle Scholar
  45. Yu Y, Wang YN, Ding W, Zhou JF, Shi B (2017) Preparation of highly-oxidized starch using hydrogen peroxide and its application as a novel ligand for zirconium tanning of leather. Carbohydr Polym 174:823–829CrossRefGoogle Scholar
  46. Zhang L (1992) Denatured starch. Hunan Sicience and Technology University Press, GuangzhouGoogle Scholar
  47. Zhang Y, Zhong QX (2018) Freeze-dried capsules prepared from emulsions with encapsulated lactase as a potential delivery system to control lactose hydrolysis in milk. Food Chem 241:397–402CrossRefGoogle Scholar
  48. Zhang L, Yu L, Liu HS, Wang YF, Simon GP, Ji ZL, Qian JY (2017a) Effect of processing conditions on microstructures and properties of hydroxypropyl methylcellulose/hydroxypropyl starch blends. Food Hydrocoll 70:251–259CrossRefGoogle Scholar
  49. Zhang S, Zhou YB, Jin SS, Meng X, Yang LP, Wang HS (2017b) Preparation and structural characterization of corn starch-aroma compound inclusion complexes. J Sci Food Agric 97(1):182–190CrossRefGoogle Scholar
  50. Zhao DF, Liu HW, Fu HJ (2009) The development of an oxidized corn starch size. In: Proceedings of the fiber society 2009 spring conference, vols I and II, pp 1496–1498Google Scholar
  51. Zhuang C, Tao FR, Cui YZ (2015) Anti-degradation gelatin films crosslinked by active ester based on cellulose. RSC Adv 5(64):52183–52193CrossRefGoogle Scholar
  52. Zuo YF, Liu WJ, Xiao JH, Zhao X, Zhu Y, Wu YQ (2017) Preparation and characterization of dialdehyde starch by one-step acid hydrolysis and oxidation. Int J Biol Macromol 103:1257–1264CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V., part of Springer Nature 2018

Authors and Affiliations

  • Xugang Dang
    • 1
    • 2
  • Hui Chen
    • 1
    • 2
  • Yajuan Wang
    • 3
  • Zhihua Shan
    • 1
    • 2
  1. 1.The Key Laboratory of Leather Chemistry and EngineeringSichuan University, Ministry of EducationChengduChina
  2. 2.National Engineering Laboratory for Clean Technology of Leather ManufactureSichuan UniversityChengduChina
  3. 3.School of Materials and Chemical EngineeringNingbo University of TechnologyNingboChina

Personalised recommendations