Skip to main content
SpringerLink
Log in

Buildup mechanism of carboxymethyl cellulose and chitosan self-assembled films

  • Original Paper
  • Published:
Cellulose Aims and scope Submit manuscript

Abstract

Films with different numbers of layers have been built by alternating the adsorption of carboxymethyl cellulose (CMC) and chitosan (CHI) at different pH levels. The adsorption process was recorded by quartz crystal microbalance (QCM). The results showed that under all pH conditions considered, the growth of the films is nonlinear. The film construction performed at pH 4.0 (preferred assembly pH) with different numbers of bilayers (CMC/CHI as one bilayer) was also observed step by step by atomic force microscopy (AFM). Comparing the growth process from QCM with the surface morphological changes from AFM shows the existence of an inhomogeneous structure for the first nine bilayers, and, after a coalescence of islands, an increase in the number of bilayers was demonstrated. The possible growth mechanism was also evaluated.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  • Bieker P, Schonhoff M (2010) Linear and exponential growth regimes of multilayers of weak polyelectrolytes in dependence on pH. Macromolecules 43:5052–5059

    Article  CAS  Google Scholar 

  • Dai J, Jensen AW, Mohanty DK, Erndt J, Bruening ML (2001) Controlling the permeability of multilayered polyelectrolyte films through derivatization, cross-linking, and hydrolysis. Langmuir 17:931–937

    Article  CAS  Google Scholar 

  • Decher G (1997) Fuzzy nanoassemblies: toward layered polymeric multicomposites. Science 277:1232–1237

    Article  CAS  Google Scholar 

  • Denuziere A, Ferriera D, Domard A (1996) Chitosan chondroitin sulfate and chitosan-hyaluronate polyelectrolyte complexes. Physico-chemical aspects. Carbohyd Polym 29:317–323

    Article  CAS  Google Scholar 

  • Elbert DL, Herbert CB, Hubbell JA (1999) Thin polymer layers formed by polyelectrolyte multilayer techniques on biological surfaces. Langmuir 15:5355–5362

    Article  CAS  Google Scholar 

  • Finkenstadt D, Johnson DD (2002) Model of ionization response of weak polyacids in a layered polyelectrolyte self-assembly. Langmuir 18:1433–1436

    Article  CAS  Google Scholar 

  • Fukao N, Kyu-Hong K, Fujimoto K, Shiratori S (2011) Automatic spray-LBL machine based on in situ QCM monitoring. Macromolecules 44:2964–2969

    Article  CAS  Google Scholar 

  • Gauczinski J, Liu Z, Zhang X, Schonhoff M (2010) Mechanism of surface molecular imprinting in polyelectrolyte multilayers. Langmuir 26:10122–10128

    Article  CAS  Google Scholar 

  • Guzman E, Ritacco H, Rubio JEF, Rubio RG, Ortega F (2009) Salt-induced changes in the growth of polyelectrolyte layers of poly(diallyl-dimethylammonium chloride) and poly(4-styrene sulfonate of sodium). Soft Mater 5:2130–2142

    Article  CAS  Google Scholar 

  • Guzman E, Miguel VS, Peinado C, Ortega F, Rubio RG (2010) Polyelectrolyte multilayers containing triblock copolymers of different charge ratio. Langmuir 26:11494–11502

    Article  CAS  Google Scholar 

  • Guzman E, Cavallo JA, Chulia-Jordan R (2011a) PH-Induced changes in the fabrication of multilayers of poly(acrylic acid) and chitosan: fabrication, properties, and tests as a drug storage and delivery system. Langmuir 27:6836–6845

    Article  CAS  Google Scholar 

  • Guzman E, Ortega F, Baghdadli N, Luengo GS, Rubio RG (2011b) Effect of the molecular structure on the adsorption of conditioning polyelectrolytes on solid substrates. Colloids Surf A 375:209–218

    Article  CAS  Google Scholar 

  • Guzman E, Ortega F, Baghdadli N, Cazeneuve C, Luengo GS, Rubio RG (2011c) Adsorption of conditioning polymers on solid substrates with different charge density. ACS Appl Mater Interfaces 3:3181–3188

    Article  CAS  Google Scholar 

  • Haynie DT, Cho E, Waduge P (2011) “In and out diffusion” hypothesis of exponential multilayer film buildup revisited. Langmuir 27:5700–5704

    Article  CAS  Google Scholar 

  • Heinze T (2005) Carboxymethyl ethers of cellulose and starch—a review. Chem Plant Raw Mater 3:13–29

    Google Scholar 

  • Hodak J, Etchenique R, Calvo EJ, Singhal K, Bartlett PN (1997) Layer-by-Layer self-assembly of glucose oxidase with a poly(allylamine)ferrocene redox mediator. Langumir 13:2708–2716

    Article  CAS  Google Scholar 

  • Kern W (1984) Purifying Si and SiO2 surfaces with hydrogen peroxide. Semicond Int 7:94–99

    Google Scholar 

  • Krasemann L, Tieke B (2000) Selective ion transport across self-assembled alternating multilayers of cationic and anionic polyelectrolytes. Langmuir 16:287–290

    Article  CAS  Google Scholar 

  • Lavalle P, Gergely C, Cuisinier FJG, Deched G, Schaaf P, Voegel JC, Picart C (2002) Comparison of the structure of polyelectrolyte multilayer films exhibiting a linear and an exponential growth regime: an in situ atomic force microscopy study. Macromolecules 35:4458–4465

    Google Scholar 

  • Lin YH, Chung CK, Chen CT, Liang HF, Chen SC, Sung HW (2005) Preparation of nanoparticles composed of chitosan/poly-gamma-glutamic acid and evaluation of their permeability through Caco-2 cells. Biomacromolecules 6:1104–1112

    Article  CAS  Google Scholar 

  • Liu GM, Hou Y, Xiao X, Zhang GZ (2010) Specific anion effects on the growth of a polyelectrolyte multilayer in single and mixed electrolyte solutions investigated with quartz crystal microbalance. J Phys Chem B 114:9987–9993

    Article  CAS  Google Scholar 

  • Lundin M, Solaqa F, Thormann E, Macakova L, Blomberg E (2011) Layer-by-layer assemblies of chitosan and heparin: effect of solution ionic strength and pH. Langmuir 27:7537–7548

    Article  CAS  Google Scholar 

  • McAloney RA, Sinyor M, Dudnik V, CynthiaGoh M (2001) Atomic force microscopy studies of salt effects on polyelectrolyte multilayer film morphology. Langmuir 17:6655–6663

    Article  CAS  Google Scholar 

  • Mendelsohn JD, Barrett CJ, Chan VV, Pal AJ, Mayes AM, Rubner MF (2000) Fabrication of microporous thin films from polyelectrolyte multilayers. Langmuir 16(11):5017–5023

    Article  CAS  Google Scholar 

  • Muller M, Rieser T, Lunkwitz K, Meie-Haack J (1999) Polyelectrolyte complex layers: a promising concept for anti-fouling coatings verified by in situ ATR-FTIR spectroscopy. Macromol Rapid Commun 20:607–611

    Article  CAS  Google Scholar 

  • Nuraje N, Asmatulu R, Cohen RE, Rubner MF (2011) Durable antifog films from layer-by-layer molecularly blended hydrophilic polysaccharides. Langmuir 27(2):782–791

    Article  CAS  Google Scholar 

  • Ott P, Trenkenschuh K, Gensel J, Fery A, Laschewsky A (2010) Free-standing membranes via covalent cross-linking of polyelectrolyte multilayers with complementary reactivity. Langmuir 26:18182–18188

    Article  CAS  Google Scholar 

  • Park SY, Rubner MF, Mayes AM (2002) Free energy model for layer-by-layer processing of polyelectrolyte multilayer films. Langmuir 18:9600–9604

    Article  CAS  Google Scholar 

  • Picart C, Lavalle P, Hubert P, Cuisinier FJG, Decher G, Schaaf P, Voegel JC (2001) Buildup mechanism for poly(l-lysine)/hyaluronic acid films onto a solid surface. Langmuir 17:7414–7424

    Article  CAS  Google Scholar 

  • Picart C, Mutterer J, Richert L, Luo Y, Prestwich GD, Schaaf P, Boulmedais F, Voegel J-C, Lavalle P (2002) Molecular basis for the explanation of the exponential growth of polyelectrolyte multilayers. Proc Natl Acad Sci USA 99:12531–12535

    Article  CAS  Google Scholar 

  • Porcel C, Lavalle P, Ball V, Decher G, Senger B, Voegel JC, Schaaf P (2006) From exponential to linear growth in polyelectrolyte multilayers. Langmuir 22:4376–4383

    Article  CAS  Google Scholar 

  • Richert L, Lavalle P, Payan E (2004) Layer by layer buildup of polysaccharide films: physical chemistry and cellular adhesion aspects. Langmuir 20:448–458

    Article  CAS  Google Scholar 

  • Sauerbrey GZ (1959) Verwendung von schwingquarzen zur wägung dünner schichten und zur mikrowägung. Z Phys 155:206–222

    Article  CAS  Google Scholar 

  • Schlenoff JB, Dubas S (2001) Mechanism of polyelectrolyte multilayer growth: charge overcompensation and distribution. Macromolecules 34:592–598

    Article  CAS  Google Scholar 

  • Schlenoff JB, Dubas ST, Farhat T (2000) Sprayed polyelectrolyte multilayers. Langmuir 16(26):9968–9969

    Google Scholar 

  • Shiratori SS, Rubner MF (2000) PH-dependent thickness behavior of sequentially adsorbed layers of weak polyelectrolytes. Macromolecules 33:4213–4219

    Article  CAS  Google Scholar 

  • Xie AF, Grannick S (2001) Weak versus strong: a weak polyacid embedded within a multilayer of strong polyelectrolytes. J Am Chem Soc 123:3175–3176

    Article  CAS  Google Scholar 

  • Zhou L, Yang J, Estavillo C, Stuart JD, Schenkman JB, Rusling JF (2003) Toxicity screening by electrochemical detection of DNA damage by metabolites generated in situ in ultrathin DNA-enzyme films. J Am Chem Soc 125:1431–1436

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors gratefully acknowledge the financial support of the Science Foundation of Henan Province (2011B430023) and the Scientific and Technological Projects of Henan Province (111100531717, 102101210100). The authors are particularly grateful to Margaret S. Cumberland for her help checking and amending the language.

Author information

Authors and Affiliations

  1. School of Materials Science and Engineering, Zhengzhou University, Zhengzhou, 450052, People’s Republic of China

    Shouwei Zhang, Wentao Liu, Jia Liang, Xiaoya Li, Wenna Liang, Suqin He, Chengshen Zhu & Luyuan Mao

Authors
  1. Shouwei Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Wentao Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jia Liang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xiaoya Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Wenna Liang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Suqin He
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Chengshen Zhu
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Luyuan Mao
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Wentao Liu.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 147 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Zhang, S., Liu, W., Liang, J. et al. Buildup mechanism of carboxymethyl cellulose and chitosan self-assembled films. Cellulose 20, 1135–1143 (2013). https://doi.org/10.1007/s10570-013-9895-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10570-013-9895-5

Keywords

Search

Navigation