Cellulose swelling by protic solvents: which properties of the biopolymer and the solvent matter?

The question posed in the title has been addressed by studying the swelling of celluloses at 20 C by twenty protic solvents, including water; linear- and branched-chain aliphatic alcohols; unsaturated aliphatic alcohols, and alkoxyalcohols. The biopolymers investigated included microcrystalline cellulose, MC, native and never-dried mercerized cotton cellulose, cotton and M-cotton, and native and never-dried mercerized eucalyptus cellulose, eucalyptus and M-eucalyptus, respectively. In most cases, better correlations with the physico-chemical properties of the solvents were obtained when the swelling was expressed as number of moles of solvent/anhydroglucose unit, nSw, rather than as % increase in sample weight. The descriptors employed in these correlations included, where available, Hildebrand`s solubility parameters, Gutmann`s acceptor and donor numbers, solvent molar volume, V(S), as well as solvatochromic parameters. The latter, employed for the first time for correlating the swelling of biopolymers, included empirical solvent polarity, E(T)(30), solvent ""acidity"", alpha(S), ""basicity"", beta(S), and dipolarity/polarizability, pi(S)*, respectively. Small regression coefficients and large sums of the squares of the residues were obtained when values of nSw were correlated with two solvent parameters. Much better correlations were obtained with three solvent parameters. The most statistically significant descriptor in the correlation equation depends on the cellulose, being pi(S)* for MC, cotton, and eucalyptus, and V(S) for M-cotton and M-eucalyptus. The best correlations were obtained with the same set of four parameters for all celluloses, namely, solvent pKa (or alpha(S)) beta(S), pi(S)*, and V(S), respectively. These results indicate that the supra-molecular structure of the biopolymer, in particular the average sizes of crystallites and micro-pores, and the presence of its chains in parallel (cellulose I) or anti-parallel (cellulose II) arrangements control its swelling. At least for the present biopolymer/solvent systems, use of solvatochromic parameters is a superior alternative to Hildebrand`s solubility parameters and/or Gutmann`s acceptor and donor numbers. The relevance of these results to the accessibility of the hydroxyl groups of cellulose, hence to its reactivity, is briefly discussed.

Acetylation of cellulose in LiCl-N,N-dimethylacetamide: first report on the correlation between the reaction efficiency and the aggregation number of dissolved cellulose

The acylation of three cellulose samples by acetic anhydride, Ac(2)O, in the solvent system LiCl/N,N-dimethylacetamide, DMAc (4 h, 110 A degrees C), has been revisited in order to investigate the dependence of the reaction efficiency on the structural characteristics of cellulose, and its aggregation in solution. The cellulose samples employed included microcrystalline, MCC; mercerized cotton linters, M-cotton, and mercerized sisal, M-sisal. The reaction efficiency expresses the relationship between the degree of substitution, DS, of the ester obtained, and the molar ratio Ac(2)O/AGU (anhydroglucose unit of the biopolymer); 100% efficiency means obtaining DS = 3 at Ac(2)O/AGU = 3. For all celluloses, the dependence of DS on Ac(2)O/AGU is described by an exponential decay equation: DS = DS(o) - Ae(-[(Ac2O/AGU)/B]); (A) and (B) are regression coefficients, and DS(o) is the calculated maximum degree of substitution, achieved under the conditions of each experiment. Values of (B) are clearly dependent on the cellulose employed: B((M-cotton)) > B((M-sisal)) > B((MCC)); they correlate qualitatively with the degree of polymerization of cellulose, and linearly with the aggregation number, N(agg), of the dissolved biopolymer, as calculated from static light scattering measurements: (B) = 1.709 + 0.034 N(agg). To our knowledge, this is the first report on the latter correlation; it shows the importance of the physical state of dissolved cellulose, and serves to explain, in part, the need to use distinct reaction conditions for MCC and fibrous celluloses, in particular Ac(2)O/AGU, time, temperature.

(1)H NMR spectroscopy as a tool to determine accurate photoisomerization quantum yields of stilbene-like ligands coordinated to rhenium(I) polypyridyl complexes

In this work, the use of proton nuclear magnetic resonance, (1)H NMR, was fully described as a powerful tool to follow a photoreaction and to determine accurate quantum yields, so called true quantum yields (Phi(true)), when a reactant and photoproduct absorption overlap. For this, Phi(true) for the trans-cis photoisomerization process were determined for rhenium(I) polypyridyl complexes, fac-[Re(CO)(3)(NN)(trans-L)](+) (NN = 1,10-phenanthroline, phen, or 4,7-diphenyl-1,10-phenanthroline, ph(2)phen, and L = 1,2-bis(4-pyridyl) ethylene, bpe, or 4-styrylpyridine, stpy). The true values determined at 365 nm irradiation (e. g. Phi(NMR) = 0.80 for fac-[Re(CO)(3)(phen)(trans-bpe)](+)) were much higher than those determined by absorption spectral changes (Phi(UV-Vis) = 0.39 for fac-[Re(CO)(3)(phen)(trans-bpe)](+)). Phi(NMR) are more accurate in these cases due to the distinct proton signals of trans and cis-isomers, which allow the actual determination of each component concentration under given irradiation time. Nevertheless when the photoproduct or reactant contribution at the probe wavelength is negligible, one can determine Phi(true) by regular absorption spectral changes. For instance, Phi(313) nm for free ligand photoisomerization determined both by absorption and (1)H NMR variation are equal within the experimental error (bpe: Phi(UV-Vis) = 0.27, Phi(NMR) = 0.26; stpy: Phi(UV-Vis) = 0.49, Phi(NMR) = 0.49). Moreover, (1)H NMR data combined with electronic spectra allowed molar absorptivity determination of difficult to isolate cis-complexes. (C) 2009 Elsevier B. V. All rights reserved.