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The larger particle size fractions (rich in corn cob and stalk portions) were found to be more recalcitrant to hydrolysis compared to the smaller size fractions (rich in leaves and husk portion). Electron spectroscopy for chemical analysis (ESCA) and Fourier transform infrared spectroscopy (FTIR) were used for biomass surface and bulk compositional analysis, respectively. The ESCA results showed a 15\u201330% decrease in the O\/C (oxygen to carbon) ratio after the pretreatment indicating an increase in the hydrophobic nature of biomass surface. FTIR results confirmed cleavage of the lignin\u2013carbohydrate complex (LCC) for the AFEX\u2010treated fractions. The spectroscopic results indicate the extraction of cleaved lignin phenolic fragments and other cell wall extractives to the biomass surface upon AFEX. Water washing of AFEX\u2010treated fractions removed some of the hydrophobic extractives resulting in a 13% weight loss (dry weight basis). Phenolic content of wash stream was evaluated by the modified Prussian blue (MPB) method. Removal of ligno\u2010phenolic extractives from the AFEX\u2010treated biomass by water washing vastly improved the glucan conversion as compared to the unwashed samples. Reduction in substrate particle size was found to affect the AFEX process and rate of hydrolysis as well. Implications of the stover particle size, composition, and inhibitory role of the phenolic fragments on an integrated biorefinery are discussed. Biotechnol. Bioeng. 2007;96: 219\u2013231. \u00a9 2006 Wiley Periodicals, Inc.<\/jats:p>","DOI":"10.1002\/bit.21132","type":"journal-article","created":{"date-parts":[[2006,8,10]],"date-time":"2006-08-10T19:46:24Z","timestamp":1155239184000},"page":"219-231","source":"Crossref","is-referenced-by-count":330,"title":["Effect of particle size based separation of milled corn stover on AFEX pretreatment and enzymatic digestibility"],"prefix":"10.1002","volume":"96","author":[{"given":"Shishir P.S.","family":"Chundawat","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Balan","family":"Venkatesh","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bruce E.","family":"Dale","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2006,8,10]]},"reference":[{"key":"e_1_2_1_2_1","doi-asserted-by":"publisher","DOI":"10.2134\/agronj1982.00021962007400030006x"},{"key":"e_1_2_1_3_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0960-8524(97)00068-0"},{"key":"e_1_2_1_4_1","doi-asserted-by":"publisher","DOI":"10.1385\/ABAB:84-86:1-9:5"},{"key":"e_1_2_1_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/jsfa.2740320802"},{"key":"e_1_2_1_6_1","unstructured":"ChiangVLC TsaiC\u2010J HuW\u2010J.2005. Genetic engineering of plants through manipulation ofligninbiosynthesis. US Patent 6 969 784."},{"key":"e_1_2_1_7_1","first-page":"19","article-title":"Supercritical ammonia pretreatment of lignocellulosic materials","volume":"17","author":"Chou YCT","year":"1986","journal-title":"Biotechnol Bioeng Symp"},{"key":"e_1_2_1_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/bit.10905"},{"key":"e_1_2_1_9_1","unstructured":"DaleBE.1986. Method for increasing the reactivity and digestibility of cellulose with ammonia. US Patent 4 600 590."},{"key":"e_1_2_1_10_1","first-page":"721","article-title":"The surface analysis of paper and wood fibers by ESCA, II. Surface composition of mechanical pulps","volume":"12","author":"Dorris GM","year":"1978","journal-title":"Cellul Chem Technol"},{"key":"e_1_2_1_11_1","unstructured":"Dunn\u2010ColemanN LangdonT MorrisP.2006. 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