近日，華中農(nóng)業(yè)大學(xué)生物質(zhì)與生物能源團(tuán)隊(duì)于國(guó)際綠色化學(xué)領(lǐng)域期刊Green Chemistry在線發(fā)表了題為Distinct cellulose nanofibrils generated for improved Pickering emulsions and lignocellulose-degradation enzymes secretion coupled with high bioethanol production in natural rice mutant的研究論文，于國(guó)際高分子化學(xué)領(lǐng)域期刊Carbohydrate Polymers刊發(fā)了題為Insights into pectin dominated enhancements for elimination of toxic Cd and dye coupled with ethanol production in desirable lignocelluloses的研究論文。這兩項(xiàng)研究利用優(yōu)質(zhì)水稻天然突變體，發(fā)現(xiàn)纖維素納米結(jié)構(gòu)缺陷增強(qiáng)功能材料特性的微觀機(jī)理，解析果膠糖醛酸去除重金屬和有機(jī)染料的作用機(jī)制，并構(gòu)建秸稈纖維乙醇聯(lián)產(chǎn)高值生物材料技術(shù)體系，從而開(kāi)辟基于遺傳背景的農(nóng)業(yè)廢棄物綠色高效利用的新路徑。

 

　　農(nóng)作物秸稈蘊(yùn)含豐富的生物質(zhì)資源，降解轉(zhuǎn)化為“零碳”生物能源和高值生物制品，可助力我國(guó)“雙碳”目標(biāo)實(shí)現(xiàn)，促進(jìn)農(nóng)業(yè)可持續(xù)發(fā)展和現(xiàn)代農(nóng)業(yè)產(chǎn)業(yè)鏈延長(zhǎng)。然而，植物細(xì)胞壁天然抗降解屏障制約了生物質(zhì)的全面綜合利用，遺傳改良細(xì)胞壁結(jié)構(gòu)，可從源頭解決農(nóng)作物秸稈高值利用效率低、成本高、易二次污染的瓶頸問(wèn)題。纖維素納米纖維（CNF）因其納米尺寸和界面效應(yīng)，具有比表面積大、穩(wěn)定性強(qiáng)、分散性好和反應(yīng)活性高等優(yōu)勢(shì)，但其制備工藝能耗高或存在化學(xué)污染，限制了CNF的大規(guī)模應(yīng)用。本研究發(fā)現(xiàn)，與普通水稻相比，天然水稻細(xì)胞壁突變體（Osfc16）秸稈的直接酶解效率顯著提高37%，纖維乙醇產(chǎn)率顯著提高19%，具有抗降解屏障降低的優(yōu)良特性。同時(shí)，在更少循環(huán)次數(shù)的高壓均質(zhì)工藝下，酶解殘?jiān)挟a(chǎn)生的CNF，其液滴粒徑更小、界面活性更高，改善了皮克林乳化劑的乳液性能和儲(chǔ)存穩(wěn)定性。此外，還發(fā)現(xiàn)低劑量的CNF可以作為里氏木霉分泌纖維素酶復(fù)合物的有效誘導(dǎo)劑，誘導(dǎo)酶的蛋白質(zhì)產(chǎn)量提高99%，內(nèi)切葡聚糖酶和木聚糖酶活性分別提高27%和51%。該研究揭示了由低抗性木質(zhì)纖維素產(chǎn)生新型CNF的多重作用，為充分利用生物質(zhì)生產(chǎn)具有成本效益的生物乙醇和高價(jià)值的生物產(chǎn)品提供了一種綠色新型技術(shù)（Green Chemistry, 2022, DOI:10.1039/D1GC04447H）。

 

　　果膠是一類富含半乳糖醛酸的細(xì)胞壁多糖，具有豐富的活性基團(tuán)，對(duì)重金屬和化學(xué)染料具有潛在的吸附性能。本研究發(fā)現(xiàn)，重金屬鎘（Cd）脅迫激活細(xì)胞壁網(wǎng)絡(luò)動(dòng)態(tài)調(diào)節(jié)，促進(jìn)果膠在細(xì)胞壁中的沉積，而天然水稻細(xì)胞壁突變體（Osfc16）表現(xiàn)出更強(qiáng)的去甲酯化半乳糖醛酸積累能力和微量Cd富集能力。同時(shí)，重金屬使細(xì)胞壁產(chǎn)生結(jié)構(gòu)缺陷，進(jìn)一步降低了細(xì)胞壁的抗降解性，顯著增強(qiáng)生物質(zhì)酶解糖化效率和生物乙醇產(chǎn)率，并且生物質(zhì)的預(yù)處理工藝能夠同步提取回收90%的Cd。利用果膠的特性，從富含果膠的柑橘皮中提取糖醛酸，與乙醇發(fā)酵殘?jiān)M(jìn)行化學(xué)交聯(lián)，生成一種同時(shí)吸附Cd和亞甲基藍(lán)（MB）的增強(qiáng)型生物吸附劑。該研究闡明了果膠在Cd和MB吸附以及生物質(zhì)酶促糖化中的多重作用機(jī)制，為農(nóng)田重金屬和化工染料的減污修復(fù)，植物修復(fù)收獲物的無(wú)害化處理，農(nóng)業(yè)廢棄物的增值利用和重金屬的回收處置，提供了新思路（Carbohydrate Polymers, 2022, 286:119298）。

 

　　華中農(nóng)業(yè)大學(xué)生物質(zhì)能團(tuán)隊(duì)王艷婷高級(jí)工程師為兩篇文章的通訊作者，博士生彭昊和趙雯悅碩士為Green Chemistry的共同第一作者，博士生余華為Carbohydrate Polymers第一作者，團(tuán)隊(duì)彭良才教授、夏濤副教授、食科院劉石林教授、理學(xué)院王運(yùn)教授、湖北文理學(xué)院余海忠教授等參與研究。

 

　　Green Chemistry摘要：

 

　　Although lignocellulose represents enormous and sustainable biomass resource convertible for biofuels and bioproducts, the green-like and cost-effective technology is increasingly considered to generate value-added bioproducts along with biofuel production. Herein, this study took advantage of the natural rice mutant （Osfc16） that is of recalcitrance-reduced lignocellulose, and performed a direct enzymatic hydrolysis of rice straw to achieve significantly raised bioethanol yield by 19% at p < 0.01, compared with wild type. Meanwhile, this work generated optimal cellulose nanofibrils （CNFs） from the remaining enzymatic residues under much less cycles of high-pressure homogenization. Notably, due to their characteristic surfaces, the CNFs at low dosage could not only act as the effective inducer for T. reesei secretion of cellulases complexes with significantly raised protein yields by 99% and enzymes （endoglucanases and xylanases） activities by 27% and 51% by using full rice straw as carbon source, but also play a more efficient stabilizer role for improving almost all major parameters of Pickering emulsions including emulsion index, droplet size, interfacial tension, zeta potential, water holding capacity and storage condition, compared to other chemical inducers and stabilizers （CNFs, proteins, starch） that have been applied in previous studies. Hence, this study has proposed a mechanism model to elucidate why the desirable rice mutant enables to generate the distinct CNFs that are favor for Pickering emulsions stabilization and mixed-cellulases induction coupled with relatively low-cost bioethanol production, providing multiple non-chemical processes as novel green-like technology for complete biomass utilization towards low-cost bioethanol production and high-value bioproducts.

 

　　原文鏈接：

 

　　https://pubs.rsc.org/en/content/articlepdf/2022/GC/D1GC04447H

 

　　Carbohydrate Polymers摘要：

 

　　Pectin is a minor wall polysaccharide with potential applications for bioproducts. Despite the application of specific plants and biomass-based sorbents for environmental remediation, little has been reported about characteristic roles of pectin. Using the natural rice mutant （Osfc16） treated with Cd, this study explored that pectin could predominately enhance Cd accumulation with lignocellulose, mainly due to remarkably raised uronic acids deposition. The Cd-treatment further reduced lignocellulose recalcitrance for significantly enhanced biomass saccharification and bioethanol production along with almost complete Cd release. Using all remaining fermentation rice residues that are of typical ribbon-structure and large surface, this study generated novel biosorbents by optimal chemical oxidation with the pectin extraction from citrus peels, and examined consistently raised Cd and methylene blue （MB） adsorption capacities. Therefore, this work has proposed a mechanism model about multiple pectin enrichment roles for Cd and MB removals in agricultural and industry locations with full lignocellulose utilization towards bioethanol production.

 

　　原文鏈接：

 

　　https://www.sciencedirect.com/science/article/pii/S0144861722002028