, Volume 19, Issue 1, pp 151–159 | Cite as

Employing perichromism for probing the properties of carboxymethyl cellulose films: an expedient, accurate method for the determination of the degree of substitution of the biopolymer derivative

  • Ludmila C. Fidale
  • Paulo M. LimaJr.
  • Lucas M. A. Hortêncio
  • Paulo A. R. Pires
  • Thomas Heinze
  • Omar A. El Seoud


The properties of films of carboxymethyl cellulose, CMC, of different degree of substitution, DS, have been examined by the use of perichromic indicators (probes). The film properties that have been determined are: empirical polarity, ET(33); “acidity”, α; “basicity”, β; and dipolarity/polarizability, π*. This has been achieved by employing the following perichromic probes: 4-nitroaniline, 4-nitroanisole, 4-nitro-N,N-dimethylaniline, and 2,6-dichloro-4-(2,4,6-triphenyl-pyridinium-1-yl)phenolate, WB. The correlations between both ET(33)- or π* and DS were found to be linear; that between β and DS is a second order polynomial; no obvious correlation was found between α and DS. The polarities of CMC films are in the range of those of butyl alcohols. As models for CMC, we have employed cellulose plus CMC of high DS; oxidized cellulose with degree of oxidation = 0.5; sodium glucuronate. The former model behaved akin to CMC, but the plots of the perichromic properties versus DS showed different slopes/intercepts. FTIR data and molecular dynamics simulations on the solvation of WB have shown that this difference can be traced to more efficient hydrogen bonding between the film of the model and the probe. This affects the intra-molecular charge-transfer energy of the latter, leading to different responses to the variation of DS. Based on the excellent linear correlation between ET(33) and DS, for CMC from different origins, we suggest that perichromism is a simple, accurate, and expedient alternative for the determination of DS of the biopolymer derivative.


Properties of carboxymethyl cellulose films Degree of substitution Perichromic indicators Molecular simulations 



O. A. El Seoud thanks the FAPESP (State of São Paulo Research Foundation) for financial support; the CNPq (National Council for Scientific and Technological Research) for a research productivity fellowship; Prof. C. Reichardt for helpful information about the term perichromism. P. M. Lima Jr. and L. M. A. Hortêncio thank the CNPq for PIBIC research fellowships. L. C. Fidale and T. Heinze thank the European Community Seventh Framework program [FP7/2007-2013] for funding through STEP – ITN, agreement no 214015. This work has been carried out within the frames of CAPES-DAAD project 325/09, and INCT-Catálise.

Supplementary material

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Supplementary material 1 (DOC 1007 kb)


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Copyright information

© Springer Science+Business Media B.V. 2011

Authors and Affiliations

  • Ludmila C. Fidale
    • 2
  • Paulo M. LimaJr.
    • 1
  • Lucas M. A. Hortêncio
    • 1
  • Paulo A. R. Pires
    • 1
  • Thomas Heinze
    • 2
  • Omar A. El Seoud
    • 1
  1. 1.Institute of ChemistryUniversity of São PauloSão PauloBrazil
  2. 2.Institute of Organic Chemistry and Macromolecular Chemistry, Center of Excellence for Polysaccharide ResearchFriedrich Schiller University of JenaJenaGermany

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