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- Li, Zhenglun, et al.
(author)
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Catalysis with Cuii(bpy) improves alkaline hydrogen peroxide pretreatment
- 2013
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In: Biotechnology and Bioengineering. - : Wiley. - 0006-3592 .- 1097-0290. ; 110:4, s. 1078-1086
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Journal article (peer-reviewed)abstract
- Copper(II) 2,2′-bipyridine (CuII(bpy))-catalyzed alkaline hydrogen peroxide (AHP) pretreatment was performed on three biomass feedstocks including alkali pre-extracted switchgrass, silver birch, and a hybrid poplar cultivar. This catalytic approach was found to improve the subsequent enzymatic hydrolysis of plant cell wall polysaccharides to monosaccharides for all biomass types at alkaline pH relative to uncatalyzed pretreatment. The hybrid poplar exhibited the most significant improvement in enzymatic hydrolysis with monomeric sugar release and conversions more than doubling from 30% to 61% glucan conversion, while lignin solubilization was increased from 36.6% to 50.2% and hemicellulose solubilization was increased from 14.9% to 32.7%. It was found that CuII(bpy)-catalyzed AHP pretreatment of cellulose resulted in significantly more depolymerization than uncatalyzed AHP pretreatment (78.4% vs. 49.4% decrease in estimated degree of polymerization) and that carboxyl content the cellulose was significantly increased as well (fivefold increase vs. twofold increase). Together, these results indicate that CuII(bpy)-catalyzed AHP pretreatment represents a promising route to biomass deconstruction for bioenergy applications
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| 2. |
- Li, Zhenglun, et al.
(author)
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Chemical and structural changes associated with Cu-catalyzed alkaline-oxidative delignification of hybrid poplar
- 2015
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In: Biotechnology for Biofuels. - : Springer Science and Business Media LLC. - 1754-6834. ; 8:1
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Journal article (peer-reviewed)abstract
- Background: Alkaline hydrogen peroxide pretreatment catalyzed by Cu(II) 2,2′-bipyridine complexes has previously been determined to substantially improve the enzymatic hydrolysis of woody plants including hybrid poplar as a consequence of moderate delignification. In the present work, cell wall morphological and lignin structural changes were characterized for this pretreatment approach to gain insights into pretreatment outcomes and, specifically, to identify the extent and nature of lignin modification. Results: Through TEM imaging, this catalytic oxidation process was shown to disrupt cell wall layers in hybrid poplar. Cu-containing nanoparticles, primarily in the Cu(I) oxidation state, co-localized with the disrupted regions, providing indirect evidence of catalytic activity whereby soluble Cu(II) complexes are reduced and precipitated during pretreatment. The concentration of alkali-soluble polymeric and oligomeric lignin was substantially higher for the Cu-catalyzed oxidative pretreatment. This alkali-soluble lignin content increased with time during the catalytic oxidation process, although the molecular weight distributions were unaltered. Yields of aromatic monomers (including phenolic acids and aldehydes) were found to be less than 0.2 % (wt/wt) on lignin. Oxidation of the benzylic alcohol in the lignin side-chain was evident in NMR spectra of the solubilized lignin, whereas minimal changes were observed for the pretreatment-insoluble lignin. Conclusions: These results provide indirect evidence for catalytic activity within the cell wall. The low yields of lignin-derived aromatic monomers, together with the detailed characterization of the pretreatment-soluble and pretreatment-insoluble lignins, indicate that the majority of both lignin pools remained relatively unmodified. As such, the lignins resulting from this process retain features closely resembling native lignins and may, therefore, be amenable to subsequent valorization.
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| 3. |
- Li, Zhenglun, et al.
(author)
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Rapid and effective oxidative pretreatment of woody biomass at mild reaction conditions and low oxidant loadings
- 2013
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In: Biotechnology for Biofuels. - : Springer Science and Business Media LLC. - 1754-6834. ; 6:1
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Journal article (peer-reviewed)abstract
- Background: One route for producing cellulosic biofuels is by the fermentation of lignocellulose-derived sugars generated from a pretreatment that can be effectively coupled with an enzymatic hydrolysis of the plant cell wall. While woody biomass exhibits a number of positive agronomic and logistical attributes, these feedstocks are significantly more recalcitrant to chemical pretreatments than herbaceous feedstocks, requiring higher chemical and energy inputs to achieve high sugar yields from enzymatic hydrolysis. We previously discovered that alkaline hydrogen peroxide (AHP) pretreatment catalyzed by copper(II) 2,2-bipyridine complexes significantly improves subsequent enzymatic glucose and xylose release from hybrid poplar heartwood and sapwood relative to uncatalyzed AHP pretreatment at modest reaction conditions (room temperature and atmospheric pressure). In the present work, the reaction conditions for this catalyzed AHP pretreatment were investigated in more detail with the aim of better characterizing the relationship between pretreatment conditions and subsequent enzymatic sugar release.Results: We found that for a wide range of pretreatment conditions, the catalyzed pretreatment resulted in significantly higher glucose and xylose enzymatic hydrolysis yields (as high as 80% for both glucose and xylose) relative to uncatalyzed pretreatment (up to 40% for glucose and 50% for xylose). We identified that the extent of improvement in glucan and xylan yield using this catalyzed pretreatment approach was a function of pretreatment conditions that included H2O2 loading on biomass, catalyst concentration, solids concentration, and pretreatment duration. Based on these results, several important improvements in pretreatment and hydrolysis conditions were identified that may have a positive economic impact for a process employing a catalyzed oxidative pretreatment. These improvements include identifying that: (1) substantially lower H 2O2 loadings can be used that may result in up to a 50-65% decrease in H2O2 application (from 100 mg H 2O2/g biomass to 35-50 mg/g) with only minor losses in glucose and xylose yield, (2) a 60% decrease in the catalyst concentration from 5.0 mM to 2.0 mM (corresponding to a catalyst loading of 25 μmol/g biomass to 10 μmol/g biomass) can be achieved without a subsequent loss in glucose yield, (3) an order of magnitude improvement in the time required for pretreatment (minutes versus hours or days) can be realized using the catalyzed pretreatment approach, and (4) enzyme dosage can be reduced to less than 30 mg protein/g glucan and potentially further with only minor losses in glucose and xylose yields. In addition, we established that the reaction rate is improved in both catalyzed and uncatalyzed AHP pretreatment by increased solids concentrations.Conclusions: This work explored the relationship between reaction conditions impacting a catalyzed oxidative pretreatment of woody biomass and identified that significant decreases in the H2O 2, catalyst, and enzyme loading on the biomass as well as decreases in the pretreatment time could be realized with only minor losses in the subsequent sugar released enzymatically. Together these changes would have positive implications for the economics of a process based on this pretreatment approach.
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