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Spin Probe Multi-Frequency EPR Study of Unprocessed Cotton Fibers

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Abstract

Known since the ancient times, cotton continues to be one of the essential materials for the human civilization. Cotton fibers are almost pure cellulose and contain both crystalline and amorphous nanodomains with different physicochemical properties. While understanding of interactions between the individual cellulose chains within the crystalline phase is important from a perspective of mechanical properties, studies of the amorphous phase lead to characterization of the essential transport parameters, such as solvent diffusion, dyeing, drug release, and toxin absorption, as well as more complex processes of enzymatic degradation. Here, we describe the use of spin probe electron paramagnetic resonance methods to study local polarity and heterogeneous viscosity of two types of unprocessed cotton fibers, G. hirsutum and G. barbadense, harvested in the State of North Carolina, USA. These fibers were loaded with two small molecule nitroxide probes that differ in polarity—Tempo and its more hydrophilic derivative Tempol—using a series of polar and non-polar solvents. The electron paramagnetic resonance spectra of the nitroxide-loaded cotton fibers were analyzed both semi-empirically and by least-squares simulations using a rigorous stochastic theory of electron paramagnetic resonance spectra developed by Freed and coworkers. A software package and least-squares fitting protocols were developed to carry out automatic simulations of multi-component electron paramagnetic resonance spectra in both first-derivative and the absorption forms at multiple resonance frequencies such as X-band (9.5 GHz) and W-band (94.3 GHz). The results are compared with the preceding electron paramagnetic resonance spin probe studies of a commercial bleached cotton sheeting carried out by Batchelor and coworkers. One of the results of this study is a demonstration of a co-existence of cellulose nanodomains with different physicochemical properties such as polarity and microviscosity that are affected by solvents and temperature. Spin labeling studies also revealed a macroscopic heterogeneity in the domain distribution along the cotton fibers and a critical role the cuticular layer is playing as a barrier for spin probe penetration. Finally but not lastly, the simultaneous multi-component least-squares simulation method of electron paramagnetic resonance spectra acquired at different resonant frequencies and the display forms (e.g., absorption and first-derivative displays) and the strategy of spectral parameter sharing could be potentially applicable to other heterogeneous biological systems in addition to the cotton fibers studies here.

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Acknowledgements

The authors are thankful to Prof. C. Haigler (Department of Crop Science, NCSU) for a gift of cotton balls of G. hirsutum and G. barbadense. The authors are also grateful to Prof. David E. Budil (Northeastern University, Boston, MA) for providing a computer code for simulations of slow-motion nitroxide EPR spectra. The X-band EPR experiments on loading of cotton fibers were carried out as a part of The Center for Lignocellulose Structure and Formation, an Energy Frontier Research Center funded by the U.S. DOE, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001090. W-band EPR experiments and development of software for fitting multi-component EPR spectra and the final preparation of this manuscript was supported by U.S. DOE Contract DE-FG02-02ER15354 to AIS.

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  1. Department of Chemistry, North Carolina State University, 2620 Yarbrough Drive, Raleigh, NC, 27695-8204, USA

    Antonin Marek, Maxim A. Voinov & Alex I. Smirnov

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  1. Antonin Marek
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Correspondence to Alex I. Smirnov.

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Marek, A., Voinov, M.A. & Smirnov, A.I. Spin Probe Multi-Frequency EPR Study of Unprocessed Cotton Fibers. Cell Biochem Biophys 75, 211–226 (2017). https://doi.org/10.1007/s12013-017-0787-4

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