Perichromism: A powerful tool for probing the properties of cellulose and its derivatives
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 (Ic), 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 ET(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): ET(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 ET(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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