Perichromism: A powerful tool for probing the properties of cellulose and its derivatives

doi:10.1016/j.carbpol.2012.06.061

Carbohydrate Polymers

Volume 93, Issue 1, 1 March 2013, Pages 129-134

https://doi.org/10.1016/j.carbpol.2012.06.061 Get rights and content

Abstract

This overview is concerned with the use of certain dyes (perichromic indicators, hereafter designated as “probes”) in order to determine the properties of cellulose, its solutions and solid derivatives. It is arranged as follows: (i) the properties of cellulose and its derivatives that are relevant to their applications are listed; (ii) a general discussion is presented on how perichromism can be employed in order to gain information on the medium where the probe is present; (iii) the results of perichromism, as applied to cellulose, cellulose solutions, and derivative films are discussed.

Highlights

► Using perichromic indicators for investigating cellulose and its derivatives. ► Perichromism is a simple and powerful tool to gain information on the medium. ► Provides information on polarity, acidity, basicity, dipolarity/polarizability. ► Perichromic properties correlate well with DS of cellulose derivatives.

Section snippets

Relevant properties of cellulose and its derivatives

The semi-crystalline nature of cellulose fibers bears on their useful mechanical properties and determines their accessibility; hence reactivity in any intended application, dyeing, derivatization, etc. In general terms, the accessibility of cellulose depends on its origin, processing condition, and composition, i.e., index of crystallinity (I_c), degree of polymerization (DP), and contents of α-cellulose, hemicellulose, and lignin.

Derivatization of cellulose leads to modifications of several

Perichromism: fundamentals and applications

A brief description of the origin of the phenomenon and the terms employed is presented. In principle, the spectrum of any substance, absorption or emission, is expected to be affected by the (surrounding) medium. What distinguishes perichromic probes from other substances, e.g., aliphatic alcohols, chlorinated hydrocarbons, simple aromatics, etc., is that the (ground state → excited state) transition energy is highly medium-sensitive. The perichromic probes usually show medium-dependent colors;

Application of perichromism to cellulose and its derivatives

Using perichromic probes in order to investigate the surface properties of cellulose derivatives offers several advantages. The method is simple, fast, reproducible, and requires easily accessible apparatus such as a spectrophotometer with a reflectance attachment. Care should be taken, however, because the method is sensitive to the presence of impurities, whose perichromic parameters are different from those of cellulose, or cellulose derivative. Potentially, these include residual impurities

Cellulose and its solutions in non-derivatizing solvents

The properties of native and regenerated celluloses have been investigated. Values of E_T(30) can be calculated either directly or (where RB does not adsorb properly on the sample) using the perichromic parameters (α) and (π*) (Marcus, 1993): E_T(30) = 31.2 + 15.2 α + 11.5 π* (n = 155, linear correlation coefficient, r = 0.98) (Bigos, 2000, Spange et al., 1998). The experimentally determined E_T(30) values (51.4–53.0 kcal/mol), were found to be lower than those calculated from other perichromic parameters,

Cellulose solutions in non-derivatizing solvents

Derivatization of cellulose under homogeneous solution conditions has several advantages, in particular, control of the average DS, and the distribution pattern among the AGUs, and along the polymer chain (El Seoud and Heinze, 2005, Hudson and Cuculo, 1980). Solvatochromic parameters can be used as a tool in order to investigate the relative importance to dissolution of solute–solvent interaction mechanisms (Spange et al., 1992b, Spange et al., 1998). Spange et al. have employed probes number

Cellulose derivatives

The surface properties of some cellulose derivatives have been studied by perichromic probes, including: cellulose acetates (CAs), Spange, Heinze, and Klemm (1992) butyrates (CBs) and hexanoates (CHs); carboxymethyl celluloses (CMCs); cellulose tosylates (CTs), and others derivatives (Casarano et al., 2011, Fidale et al., 2010, Fischer et al., 2003, Spange et al., 2003).

The perichromism properties of cellulose tosylates (CTs), DS from 0.38 to 1.68 were investigated (Fischer et al., 2003). The

Applications of dye perichromism: an expedient and accurate method for the determination of DS of cellulose derivatives

As discussed in the preceding section, there are excellent correlations between the perichromic properties and DS. Consequently, we have suggested that this method can be fruitfully employed for the determination of DS of cellulose derivatives, including cellulose esters, CAs, CBs, and CHs and cellulose ether, CMCs (Casarano et al., 2011). The excellent linear correlations shown in Fig. 3 for CAs is satisfying for several reasons: the high correlation coefficient observed; the results are

Conclusions

There is a need to understand, on the molecular level, the properties of different celluloses, their derivatives, and solutions in non-derivatizing solvents. Perichromism is a simple and powerful tool to do the job; it offers information on the overall polarity, as well as the acidity, basicity, and dipolarity/polarizability. This approach is attractive because of the availability of a large number of probes; the simplicity of the equipment; and the relatively straightforward correlation

Acknowledgments

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 discussion of the term perichromism. 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

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Perichromism: A powerful tool for probing the properties of cellulose and its derivatives

Abstract

Highlights

Section snippets

Relevant properties of cellulose and its derivatives

Perichromism: fundamentals and applications

Application of perichromism to cellulose and its derivatives

Cellulose and its solutions in non-derivatizing solvents

Cellulose solutions in non-derivatizing solvents

Cellulose derivatives

Applications of dye perichromism: an expedient and accurate method for the determination of DS of cellulose derivatives

Conclusions

Acknowledgments

Carbohydrate Polymers

Journal of Membrane Science

Biomaterials

Solvent effects in organic chemistry—Recent developments

Canadian Journal of Chemistry

Cellulose acetates: Properties and applications

Toward a generalized treatment of the solvent effect based on four empirical scales: Dipolarity (SdP, a new scale), polarizability (SP), acidity (SA), and basicity (SB) of the medium

Journal of Physical Chemistry B

Cellulose esters as membrane materials for hemodialysis

International Journal of Artificial Organs

Cellulose carbamates and derivatives as hemocompatible membrane materials for hemodialysis

Journal of Artificial Organs

Cellulose esters in drug delivery

Cellulose

Investigation of the cellulose/lithium chloride/dimethylacetamide and cellulose/lithium chloride/N-methyl-2-pyrrolidinone solutions by 13C NMR spectroscopy

Journal of Applied Polymer Science

Solvation in pure and mixed solvents: Some recent developments

Pure and Applied Chemistry

Understanding solvation

Pure and Applied Chemistry

Polysaccharides I structure, characterization and use advances in polymer science

Applications of ionic liquids in carbohydrate chemistry: A window of opportunities

Biomacromolecules

Surface properties of calcinated titanium dioxide probed by solvatochromic indicators: Relevance to catalytic applications

Journal of Physical Chemistry C

Probing the dependence of the properties of cellulose acetates and their films on the degree of biopolymer substitution: Use of solvatochromic indicators and thermal analysis

Cellulose

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

Cellulose

Probing the polarity of various cellulose derivatives with genuine solvatochromic indicators

Macromolecular Chemistry and Physics

Empirical surface polarity parameters for native polysaccharides

Macromolecular Chemistry and Physics

Probing the polarity of native celluloses by genuine solvatochromic dyes

Cellulose

Steam exploded biomass for the preparation of conventional and advanced biopolymer-based materials

Biomass Bioenergy

Tailored media for homogeneous cellulose chemistry: Ionic liquid/co-solvent mixtures

Macromolecular Material and Engineering

Synthesis and opto-electronic properties of cholesteric cellulose esters

Cellulose

Carboxymethyl ethers of cellulose and starch – A review

Macromolecular Symposium

The solubility of unmodified cellulose: A critique of the literature

Journal of Macromolecular Science, Reviews in Macromolecular Chemistry

Investigation of the cellulose/lithium chloride/dimethylacetamide and cellulose/lithium chloride/N-methyl-2-pyrrolidinone solutions by ¹³C NMR spectroscopy