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Structural Characterization of Lignin in Wild-Type Versus COMT Down

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Structural Characterization of Lignin in Wild-Type Versus COMT Down ORIGINAL RESEARCH ARTICLE published: 20 January 2014 ENERGY RESEARCH doi: 10.3389/fenrg.2013.00014 Structural characterization of lignin in wild-type versus COMT down-regulated switchgrass 1,2 2,3 1,2 4 2,4 1,2 Reichel Samuel ,Yunqiao Pu *, Nan Jiang , Chunxiang Fu , Zeng-YuWang and Arthur Ragauskas * 1 School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA, USA 2 BioEnergy Science Center, Oak Ridge, TN, USA 3 Institute of Paper Science and Technology, Georgia Institute of Technology, Atlanta, GA, USA 4 Forage Improvement Division, The Samuel Roberts Noble Foundation, Ardmore, OK, USA Edited by: This study examined the chemical structural characteristics of cellulolytic enzyme lignin Soo-Jeong Shin, Chungbuk National isolated from switchgrass focusing on comparisons between wild-type control and caf- University, South Korea feic acid 3-O-methyltransferase (COMT) down-regulated transgenic line. Nuclear magnetic Reviewed by: 13 31 13 1 JunYong Zhu, Forest Products resonance techniques including C, P,and two-dimensional C- H heteronuclear single Laboratory, USA quantum coherence as well as gel permeation chromatography were employed. Compared Luis Serrano, University of the to the wild-type, the COMT down-regulated transgenic switchgrass lignin demonstrated a Basque Country, Spain decrease in syringyl (S):guaiacyl (G) ratio and p-coumarate:ferulate ratio, an increase in rel- *Correspondence: ative abundance of phenylcoumaran unit, and a comparable content of total free phenolic Yunqiao Pu, Institute of Paper Science OH groups along with formation of benzodioxane unit. In addition, COMT down-regulation and Technology, Georgia Institute of Technology, 500 10th Street had no significant effects on the lignin molecular weights during its biosynthesis process. Northwest, Atlanta, GA 30332, USA Keywords: switchgrass, COMT transgenic, lignin, NMR, molecular weights e-mail: [email protected]; Arthur Ragauskas, School of Chemistry and Biochemistry, Georgia Institute of Technology, 500 10th Street Northwest, Atlanta, GA 30332, USA e-mail: arthur.ragauskas@chemistry. gatech.edu INTRODUCTION biomass to bioethanol production platform. Therefore, addressing There is a growing focus on innovative technologies that shift biomass recalcitrance through alternative approaches is a crucial bioethanol production to second generation cellulosic biofuels issue to the widespread, low-cost generation of cellulosic biofuels. due to the competition between food resources and first gener- One of the promising approaches for reducing biomass recalci- ation biofuels derived from agricultural resources such as corn trance is the development of genetically engineered plants involv- starch (Wyman, 1999; Wang et al., 2007; Rubin, 2008). Although ing down-regulation/overexpression of key enzymes involved in lignocellulosic resources, such as energy crops and agricultural lignin biosynthesis that can achieve an improved sugar release and forest residues, are readily becoming available for bioethanol performance with reduced pretreatment severities (Li et al., 2003; production, their processing requires a costly pretreatment step Chen and Dixon, 2007; Weng et al., 2008; Pu et al., 2011b; Shen to overcome their natural recalcitrance toward biological decon- et al., 2012; Tschaplinski et al., 2012). A recent report by Shen et al. struction to simple sugars (Sun and Cheng, 2002; Himmel et al., (2012) has demonstrated that overexpression of PvMYB4 genes 2007; Pu et al., 2008; Somerville et al., 2010). Lignocellulosic in switchgrass resulted in an approximately threefold increase biomass is a complex composite consisting primarily of three in sugar release efficiency from transgenic cell wall residues. biopolymers (i.e., cellulose, hemicelluloses, and lignin) and its Chen and Dixon (2007) reported that p-coumarate 3-hydroxylase recalcitrance has been attributed to several factors such as cel- (C3H) and hydroxycinnamoyl-CoA:shikimate/quinate hydrox- lulose accessibility to enzymes, lignin content/structure, lignin- ycinnamoyl transferase (HCT) down-regulated alfalfa lines carbohydrate complexes, as well as the presence and structure showed an improved fermentable sugar yield when compared of hemicelluloses (Wyman et al., 2005; Li et al., 2012; Leu and to wild-type plants. The engineering of these enzyme genes is Zhu, 2013; Pu et al., 2013). The goal of pretreatment is to reduce expected to generate a variation in lignin structures and thus the recalcitrance of biomass by disrupting/modifying the lignin- impact the recalcitrance of biomass; therefore, there has been con- polysaccharide matrix. In the past two decades, extensive research siderable interest in lignin structural characteristics in genetically efforts have been directed at improving a diverse set of pretreat- engineered plants (Marita et al., 1999; Guo et al., 2001; Chen et al., ment technologies including: dilute acid, lime, hot water, steam 2004; Pu et al., 2009; Stewart et al., 2009; Lu et al., 2010; Tu et al., explosion, ammonia, and organosolv pretreatments. While these 2010; Vanholme et al., 2010; Ziebell et al., 2010). For example, pretreatments have achieved various level of success in overcom- Pu et al. (2009) and Ziebell et al. (2010) isolated ball-milled lignin ing the recalcitrance of lignocellulosic biomass, the pretreatment from C3H and HCT transgenic alfalfa lines and studied their struc- step still remains one of the most expensive steps in the current tural features. The results demonstrated that a substantial increase www.frontiersin.org January 2014 | Volume 1 | Article 14 | 1 Samuel et al. Lignin in COMT down-regulated switchgrass in p-hydroxyphenyl (H) units and a decrease in syringyl (S) and A transgenic line (T0–2) which had the greatest degree of guaiacyl (G) monolignol units were accompanied with a decrease COMT down-regulation was used to generate T1 progeny by cross- in the presence of b-O-4 aryl ether. ing with a wild-type Alamo plant. The T1-generation materials Recently, Fu et al. (2011) generated caffeic acid 3-O- were employed to study the structural differences in the COMT methyltransferase (COMT) down-regulated switchgrass and down-regulated transgenic and wild-type control plants. A null evaluated the impact of lignin pathway modification in these segregant (negative T1 plant identified from the progeny of the switchgrass lines on simultaneous saccharification and fermen- cross) was used as a control. The first internodes (hereafter referred tation (SSF) efficiency and their response to consolidated bio- as I1) from basal were collected for analysis when the plants had processing using Clostridium thermocellum. The fermentation of reached the E4 stage. the control and transgenic lines confirmed that transgenic lines produced more ethanol per gram than the control without pre- COMPOSITIONAL ANALYSIS treatment. Fermentation of select down-regulated switchgrass The compositional analysis was performed according to literature lines after a moderate dilute acid pretreatment resulted in a 38% procedure (Davis, 1998; Cao et al., 2012). The switchgrass samples increase in ethanol yield over the pretreated control sample under were sequentially extracted with water and dichloromethane 24 h SSF. The reduced recalcitrance in transgenic lines was further each before analysis. The extractive-free switchgrass (~0.175 g) demonstrated with a ~300–400% reduction in the required cel- was subjected to a two-step hydrolysis with sulfuric acid (72% lulase dosage with respect to the control for equivalent ethanol w/w, 1.5 mL) for 1 h at 30°C and then at 121°C for additional yield via SSF. In addition, the consolidated bioprocessing of mild 1 h after diluting with the addition of water (4% w/w sulfuric acid pretreated COMT transgenic switchgrass was observed to lead acid). The samples were filtered and the filtrates were quanti- to 18% more fermentation products than the control (Fu et al., fied for neutral monosaccharide contents using high performance 2011). The effects of COMT down-regulation on cellulose were anion exchange chromatography with pulsed amperometric detec- investigated and the results showed that the cellulose content in tion (Dionex ICS 3000, Dionex Corp., Sunnyvale, CA, USA). The the stems of COMT transgenic lines had small variations at −1 to filtrates were diluted 25 times before analysis. Nanopure deion- 3% relatively, whereas the cellulose crystallinity index and degree ized water was used as the eluent and sodium hydroxide solution of polymerization were essentially identical to the control, sug- (0.4 M NaOH) as post-column rinsing effluent. Fucose was used gesting that COMT down-regulation had negligible impact on as an internal standard. Flow rate was 1.0 mL/min. The residues cellulose in switchgrass. Therefore, the lignin structural character- were washed, dried, and weighed to give Klason lignin content. istics in the COMT transgenic switchgrass is of great interest as The measurements were carried out in duplicate and the results its alterations due to the COMT down-regulation could be related were reported as the average. to the reduced recalcitrance in the transgenic switchgrass. As a CELLULOLYTIC ENZYME LIGNIN ISOLATION continuation of this work, here we investigated and compared the Cellulolytic enzyme lignin was isolated from control and trans- structural features of lignin isolated from wild-type versus COMT genic switchgrass according to a slightly modified literature pro- down-regulated switchgrass in an attempt to explore the roles
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