Quantitative13C MultiCP solid-state NMR as a tool for evaluation of cellulose crystallinity index measured directly inside sugarcane biomass

Biotechnology for Biofuels

Eduardo Ribeiro deAzevedo²  Igor Polikarpov²  Camila Alves Rezende¹  Marisa Aparecida Lima²  Oigres Daniel Bernardinelli² 

[1]Instituto de Química, Universidade de Campinas-UNICAMP, Campinas 13084-971, SP, Brazil

[2]Instituto de Física de São Carlos, Universidade de São Paulo, São Carlos 13660-970, SP, Brazil

关键词: Cellulosic ethanol;    Pretreatments;    Solid-state NMR;    Crystallinity index;    Biomass;    Sugarcane bagasse;   

Others  :  1225777
DOI  :  10.1186/s13068-015-0292-1

 received in 2015-04-23, accepted in 2015-07-22,  发布年份 2015

【 摘 要 】

Background

The crystallinity index (CI) is often associated with changes in cellulose structure after biological and physicochemical pretreatments. While some results obtained with lignocellulosic biomass demonstrate a progressive increase in the CI as a function of pretreatments, it is also shown that the CI can significantly vary depending on the choice of the measurement method. Besides, the influence of the CI on the recalcitrance of biomass has been controversial for a long time, but the most recent results tend to point out that the efficiency of pretreatments in reducing the recalcitrance is not clearly correlated with the decrease of the CI. Much of this controversy is somewhat associated with the inability to distinguish between the CI of the cellulose inside the biomass and the CI of the full biomass, which contains other amorphous components such as lignin and hemicellulose.

Results

Cross polarization by multiple contact periods (Multi-CP) method was used to obtain quantitative¹³ C solid-state nuclear magnetic resonance (ssNMR) spectra of sugarcane bagasse biomass submitted to two-step pretreatments and/or enzymatic hydrolysis. By comparing the dipolar filtered Multi-CP¹³ C NMR spectra of untreated bagasse samples with those of samples submitted to acid pretreatment, we show that a 1% H ₂ SO ₄ -assisted pretreatment was very effective in removing practically all the hemicellulose signals. This led us to propose a spectral editing procedure based on the subtraction of MultiCP spectra of acid-treated biomass from that of the extracted lignin, to obtain a virtually pure cellulose spectrum. Based on this idea, we were able to evaluate the CI of the native cellulose inside the sugarcane bagasse biomass.

Conclusions

The results show the validity of the proposed method as a tool for evaluating the variations in the CI of the cellulose inside biomasses of similar kinds. Despite a clear increase in the CI of biomass as measured by X-ray diffraction, no significant variations were observed in the CI of the cellulose inside the biomass after a particular 1% H ₂ SO ₄ /0.25–4% NaOH chemical-assisted pretreatments. The CI of cellulose inside the biomass solid fraction that remained after the enzymatic hydrolysis was also evaluated. The results show a slight increase in crystallinity.

【 授权许可】

   
2015 Bernardinelli et al.

【 图 表 】

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