Effect of nanocellulose polymorphism on electrochemical analytical performance in hybrid nanocomposites with non-oxidized single-walled carbon nanotubes

Silvia Dortez,Miguel Á Álvarez-Sánchez,Agustín G Crevillen,Alberto Escarpa,José M González-Domínguez,Tania Sierra,Ana M Benito,Wolfgang K Maser

doi:10.1007/s00604-021-05161-w

Silvia Dortez, Miguel Á Álvarez-Sánchez + Show 6 more

Open Access

https://doi.org/10.1007/s00604-021-05161-w

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Abstract

Two cellulose nanocrystals/single-walled carbon nanotube (CNC/SW) hybrids, using two cellulose polymorphs, were evaluated as electrochemical transducers: CNC type I (CNC-I/SW) and CNC type II (CNC-II/SW). They were synthesized and fully characterized, and their analytical performance as electrochemical sensors was carefully studied. In comparison with SWCNT-based and screen-printed carbon electrodes, CNC/SW sensors showed superior electroanalytical performance in terms of sensitivity and selectivity, not only in the detection of small metabolites (uric acid, dopamine, and tyrosine) but also in the detection of complex glycoproteins (alpha-1-acid glycoprotein (AGP)). More importantly, CNC-II/SW exhibited 20 times higher sensitivity than CNC-I/SW for AGP determination, yielding a LOD of 7 mg L−1.These results demonstrate the critical role played by nanocellulose polymorphism in the electrochemical performance of CNC/SW hybrid materials, opening new directions in the electrochemical sensing of these complex molecules. In general, these high-active-surface hybrids smartly exploited the preserved non-oxidized SW conductivity with the high aqueous dispersibility of the CNC, avoiding the use of organic solvents or the incorporation of toxic surfactants during their processing, making the CNC/SW hybrids promising nanomaterials for electrochemical detection following greener approaches.Graphical abstract

Highlights

The need for sustainable alternatives to conventional materials has led to a growth in demand for bio-based materials directed to applications in different areas of the industry
As a matter of example, we recently demonstrated that dispersions of SWCNT with cellulose nanocrystals (CNC) type II exhibited selective cytotoxicity on human colon cancer (Caco-2) cells, with no harm on equivalent normal cells, while the SWCNT hybrids with CNC type I were generally innocuous [6]
We explored the potential of cellulose nanocrystals/single-walled carbon nanotube (CNC/SW) hybrids for the quantification of glycoproteins, which are biomacromolecules with high clinical relevance because some of them are used as disease biomarkers

Summary

Introduction

The need for sustainable alternatives to conventional materials has led to a growth in demand for bio-based materials directed to applications in different areas of the industry. Type I is dominant in natural cellulose sources and exhibits a parallel arrangement of chains with sharp and straight needle-like morphology, while type II is obtained by dissolution and recrystallization of type I, displaying an antiparallel arrangement with shorter and twisted rod-like nanocrystals [5]. These differences between types I and II in their structures and morphologies provide them with different properties and behavior. CNC type II is more enzymatically degradable than type I [7], and these nanostructures may exert very different properties to their hybrids with other nanostructures. As a matter of example, we recently demonstrated that dispersions of SWCNT with CNC type II exhibited selective cytotoxicity on human colon cancer (Caco-2) cells, with no harm on equivalent normal (healthy) cells, while the SWCNT hybrids with CNC type I were generally innocuous [6]

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