2D Assignment and quantitative analysis of cellulose and oxidized celluloses using solution-state NMR spectroscopy

The limited access to fast and facile general analytical methods for cellulosic and/or biocomposite materials currently stands as one of the main barriers for the progress of these disciplines. To that end, a diverse set of narrow analytical techniques are typically employed that often are time-consuming, costly, and/or not necessarily available on a daily basis for practitioners. Herein, we rigorously demonstrate a general quantitative NMR spectroscopic method for structural determination of crystalline cellulose samples. Our method relies on the use of a readily accessible ionic liquid electrolyte, tetrabutylphosphonium acetate ([P-4444][OAc]):DMSO-d(6), for the direct dissolution of biopolymeric samples. We utilize a series of model compounds and apply now classical (nitroxyl-radical and periodate) oxidation reactions to cellulose samples, to allow for accurate resonance assignment, using 2D NMR. Quantitative heteronuclear single quantum correlation (HSQC) was applied in the analysis of key samples to assess its applicability as a high-resolution technique for following cellulose surface modification. Quantitation using HSQC was possible, but only after applying T(2)correction to integral values. The comprehensive signal assignment of the diverse set of cellulosic species in this study constitutes a blueprint for the direct quantitative structural elucidation of crystalline lignocellulosic, in general, readily available solution-state NMR spectroscopy. [GRAPHICS] .Peer reviewe

Biofilms from micro/nanocellulose of NaBH4-modified kraft pulp

WOS: 000407842800009Industrial applications of microfibrillated cellulose (MFC) and nanofibrillated cellulose (NFC) have been in use for some time; however, there is a need to improve the production steps and at the same time to obtain better quality products. NFC and MFC were generated from -modified kraft pulp, produced from a red gum tree plant (Eucalyptus camaldulensis). The generated NFC and MFC were characterized by high-performance liquid chromatography, Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA) and -nuclear magnetic resonance (NMR). Morphological and viscoelastic properties were investigated by scanning electron microscopy and rheometry, respectively. The storage moduli of biofilms produced from NFC and MFC were investigated by dynamic mechanical thermal analysis (DMTA). Both exhibited mostly identical FTIR spectra. When the spectra were compared with those of -modified kraft pulp, minor shifts were observed due to crystallinity. In NMR spectra, disordered cellulose structures were observed for both NFC and MFC, and these findings were also confirmed by differential scanning calorimetry. Rheology studies revealed that the lowest viscosity was observed with MFC. TGA results showed that NFC degraded earlier compared with -modified kraft pulp. DMTA exhibited that NFC films had about six times higher storage modulus compared with MFC.TUBITAKTurkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK) [COST 114O022]; Istanbul University Research FundIstanbul University [4806, 19515]We thank TUBITAK (Project Number: COST 114O022) for supporting this research. We also acknowledge Istanbul University Research Fund for financially supporting this study (Project Numbers 4806 and 19515)