CN109226181B - 一种电氧化降解玉米乙醇发酵工艺中呕吐霉素的新方法 - Google Patents
一种电氧化降解玉米乙醇发酵工艺中呕吐霉素的新方法 Download PDFInfo
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Abstract
本发明公开了一种电氧化降解乙醇发酵工艺玉米酒糟中的呕吐霉素(DON)的新方法,属于发酵工艺技术领域,其包括以下步骤:通过“三电极”系统对DON进行循环伏安(CV)扫描,确定DON的极化曲线;根据极化曲线确定的氧化还原峰位置,以恒电压模式对乙醇发酵工艺玉米酒糟中的呕吐霉素(DON)施一恒定电压进行电氧化降解处理,控制外加电压为0.6~0.8 V,采用钛电极或石墨、铂等惰性电极,添加廉价易得的氯盐作为电解介质,添加量为0.1~0.5 mol/L,处理60 min以上,即可将DON降解为其他物质从而降低其在玉米酒糟中的含量,该方法为乙醇发酵工业中DON的去除提供了一种新的技术,并且有望延伸至其他真菌毒素的降解以及实际应用到大规模工业化生产中。
Description
技术领域
本发明属于发酵工业技术领域,具体涉及玉米乙醇发酵工艺DDGS前体——玉米酒糟中呕吐霉素的电氧化降解新方法。
背景技术
真菌毒素是各种霉菌在适宜的温度、湿度及生长基质上产生的高毒性代谢产物,其中,镰刀菌、青霉、曲霉是产生霉菌毒素的主要霉菌,它们被认为是威胁人类食品安全的重要原因之一,引起了全世界的高度关注。脱氧雪腐镰刀菌烯醇(Deoxynivalenol,DON),俗称呕吐霉素,是最常见的真菌毒素之一,属于单端孢霉烯族毒素,主要由禾谷镰刀菌和粉红镰刀菌产生。DON普遍出现于被镰刀菌感染的谷物中,其感染不仅会加重作物赤霉病的发病程度,降低粮食的产量和品质;而且具有很强的细胞毒性,即使在DON浓度较低的情况下,长期摄入也会损害人类和动物的健康,如发生厌食、呕吐、腹泻、反应迟钝等多种临床症状,还与神经障碍、免疫抑制、致畸性等多种并发症相关,严重时还可能使造血系统受到损害从而造成死亡。由于DON对人体和动物健康长期或短期内的影响,中国政府设定了用于人类消费的小麦、大麦、玉米及其面粉的最高DON限值为1000 μg/kg,在动物饲料中最高DON含量为5000 μg/kg。
DON在全世界范围对粮食的污染却很普遍,特别是在中国、美国、日本、阿根廷等粮食生产区的污染情况更为突出。据粮食和农业组织(FAO)估计,全世界大约25-50%的粮食作物,包括许多基本食物,都受到了真菌毒素的影响,其中DON的存在更是其他霉菌毒素存在的良好指标,在所有受霉菌毒素污染的样本中,DON污染占90%以上。
据Frost & Sullivan报道,中国已经成为全世界第三大乙醇生产国,每年的乙醇产量超过900万吨,其中玉米是乙醇发酵工业的主要原料。然而,DON对玉米的污染将DON的危险蔓延至乙醇发酵工业。一方面,由于DON的热稳定性,已经存在于玉米原料上的DON毒素在发酵过程中不会被降解,它可以随着糖化、发酵和蒸馏转移至玉米酒糟中,另一方面,镰刀菌孢子可以在温暖的发酵条件下萌发,产生DON从而造成毒素的进一步累积。这就导致在乙醇发酵工业中,随着发酵工艺的进行,DON含量呈现出逐步增加状态,严重影响了后续产品酒糟饲料蛋白(Distillers Dried Grains with Solubles,DDGS)的品质,造成了经济上的巨大损失。目前一般采用添加蒙脱石、高岭土等活性吸附剂来吸附DDGS中的真菌毒素,但该方法仅仅是将毒素黏附在一起,未实现与饲料的真正分离,其仍然会随着动物的进食进入食物链,具有潜在的健康风险。也有研究提出了紫外光照射、微波处理、加压加热等物理方法,也有利用添加化学强氧化剂,例如臭氧、二氧化氯等,来实现对DON降解。但这些方法存在一些不可避免的局限性,如效果有限、安全问题、营养价值和适口性受损,以及难以与乙醇发酵工艺相结合等特点,这使得它们似乎不适合用于乙醇发酵工业的玉米酒糟处理。
相比起化学氧化降解方法,电氧化具有不需要或需要很少量化学药品的投放、不产生二次污染、反应条件温和、处理简单等优点,被称为环境友好技术,已被广泛应用到污水中有机氯农药、重金属污染物、偶氮染料、杀虫剂等污染物的降解处理。但就用电氧化的方法来处理谷物中的真菌毒素,目前的研究还很少。
发明内容
本发现主要是发现了一种电氧化降解玉米乙醇发酵工艺DDGS前体——玉米酒糟中呕吐霉素的新方法,旨在以廉价易得的氯盐为介质,通过恒电压电解模式对发酵后续的玉米酒糟进行电氧化处理,降低其中DON的含量,为玉米乙醇发酵工艺DON的去除提供一种新方法。
具体地,本发现通过以下技术方案实现,但不限于此。
1实验材料
实验用DON标准品,纯度99%,HPLC级;受DON污染的玉米酒糟样品,密封袋分装,室温下保存。
2 DON极化曲线的测定
使用典型的三电极系统对添加有适量DON的含氯盐电解液进行循环伏安(CV)扫描,扫描方向为正向扫描,工作电极为钛网电极,辅助电极为铂丝电极,参比电极为Ag/AgCl电极,以上三电极系统中的元件均可被同功效的其他元件所替代,电解缓冲液中 Cl- 浓度为0.2 mol/L,从而确定了DON在钛网阳极上的极化曲线,其在0.8 V左右有一明显的氧化峰,而无明显还原峰,说明DON可以在0.8 V的电压下发生氧化反应,并且该氧化反应是不可逆的,为后续实验确定外加电压强度的范围提供了指导意义。
3 电解
根据DON极化曲线确定的氧化峰位置,采用恒电位模式对乙醇发酵后续的玉米酒糟在分隔式电解槽中进行电解处理,阴阳电极均为钛电极或石墨棒等惰性电极,电解初期向玉米酒糟中添加适量氯盐,采用磁力搅拌保证电解过程中样品混合均匀,从而实现的玉米酒糟中DON的去除降解。
上述步骤3中采用的分隔式电解槽可为玻璃砂芯、隔膜式或盐桥式电解槽等同功效电解槽,电解时玉米酒糟样品置于阳极室中,阴极室为氯盐缓冲液。
上述步骤3中采用恒电位模式控制外加电压的强度为0.6~1.4 V。
上述步骤3中使用钛电极材料均为Ti/PbO2、Ti/RuO2、Ti/IrO2、Ti/RuO2-IrO2、Ti/RuO2-IrO2-SnO2,使用的惰性电极材料均为石墨、铂、金电极等,极间距为10~60 mm。
上述步骤3中添加的氯盐为氯化钠、氯化镁、氯化钾、氯化锌、氯化铝、氯化钙中的一种或几种混合,电解液中Cl- 浓度为0.1~0.5 mol/L。
上述步骤3中电解时电流密度为1~10 mA/cm3,电解处理时间为不少于60 min。
本发现的有益效果在于:
1) 真菌污染已经成为威胁人类食品安全的一大重要原因,引发了世界的广泛关注,乙醇发酵工业玉米酒糟中DON的大量累积,严重影响了后续DDGS副产品的品质,也给乙醇工业生产带来了很大的麻烦。本发明通过外加恒电压的方式对玉米酒糟进行电解处理,改变DON所处的氧化还原环境,利用电解过程中阳极产生的大量活性氯及活性氧等物质将DON氧化降解为其他物质从而达到降低其含量的目的;
2)经电解实验结果确定:随着外加电压的增大,DON降解率逐步提升,综合经济成本效益,确定最佳施加电压为1.2 V(见实施例1);
3)经电解实验结果确定:Cl- 盐的添加可以增强电氧化降解DON的效果,最佳添加量确定为0.2 mol/L(见实施例2);
4)经MS扫描图谱,电解处理后,出现的新的质量分数的降解产物,说明该方法能将DON氧化降解为其他物质;且电解处理前后,玉米酒糟中的粗蛋白以及脂质含量均未有明显变化,说明电解处理不会破坏玉米酒糟中的营养成分,不会对后续加工为DDGS副产品有品质上的影响(见实施例3);
5)电氧化降解法是以添加廉价易得的氯盐作为电解介质,很大程度上降低了成本需求,并且该方法具有不产生二次污染、反应条件温和、处理简单、易于与乙醇发酵工艺结合等优点,这是一个非常可观的方法,也是一个很有意义的发现,为乙醇发酵工业中DON的去除提供了一种新的技术,并且有望延伸至其他真菌毒素的降解以及实际应用到大规模工业化生产中。
附图说明
图1 DON在钛网阳极上的极化曲线: a) 添加有DON;b) 未添加DON;
图2 不同外加电压下电氧化降解处理对DON降解效果的影响;
图3 Cl- 盐添加浓度对DON降解效果的影响;
图4 电氧化降解处理对玉米酒糟粗蛋白和脂质含量的影响: A) 电氧化降解处理组;B) 添加有0.2 mol/L NaCl的电氧化降解处理组;
图5 玉米酒糟粗蛋白的SDS-PAGE图:泳道“1”为未处理组;泳道“2”为电氧化降解处理组;泳道“3”添加有0.2 mol/L NaCl的电氧化降解处理组;
图6 DON电氧化降解产物的MS图:a) 电氧化降解前;b) 电氧化降解后 。
具体实施方式
下文将通过实施例对本发明做进一步说明,但实施例不以任何方式限制本发明。
实施例1:
电解:采用钛网电极对玉米酒糟在0.6、0.8、1.0、1.2、1.4 V的电压下分别进行电氧化处理,添加的氯盐为NaCl,添加量为0.2 mol/L,处理时间为80 min,每隔10 min取样一次,每次取样量为2 mL,处理时间为80 min,每隔10 min取样一次,每次取样量为2 mL;
DON含量的检测:对取出样品进行HPLC检测预处理,预处理步骤为:向样品内加入8mL的提取液(乙腈:水=84:16,V/V),40 ℃恒温下超声提取30 min,8000 r/min离心10 min,取5 mL上清液于Oasis HLB小柱上样过滤(小柱提前用3 mL甲醇和3 mL去离子水预活化),过滤后用3 mL去离子水淋洗柱,空气抽干小柱,2 mL甲醇洗脱,45 ℃氮气吹干,用1 mL色谱甲醇复溶,经0.22 μm有机滤膜过滤后进样检测并计算DON的降解率,降解率%=(处理组DON含量-未处理组DON含量)/未处理组DON含量*100%;结果表明,与未处理组相比,电解处理后,玉米酒糟中的DON含量确实在一定程度上降低,当外加电压0.6 V~1.4 V时,DON降解率随电压的提高而提高,当电压为1.2 V时,80 min后玉米糟液中的DON从13 057 μg/kg降低至2 927 μg/kg,降解率达到79.58%。并且在处理60 min以后,降解率逐步趋于平稳。
实施例2:
电解:采用钛网电极对玉米酒糟在1.2 V的外加电压下进行电解处理,添加的氯盐为NaCl,添加量分别为0、0.1、0.2、0.3、0.4、0.5 mol/L,处理60 min后取样进行HPLC检测DON含量;
DON含量的检测:检测方法如实施例1中所述含量检测的步骤,结果显示,与未添加Cl- 盐的处理组相比,添加有Cl- 盐的处理组DON的降解率大大提升,且当Cl- 盐浓度为0.2mol/L时,降解率可达78.22%,降解效果最优。
实施例3:
电解:采用钛网电极对玉米酒糟在1.2 V的外加电压下进行电解处理,一组添加的氯盐为NaCl,添加量为0.2 mol/L,另一组不添加氯盐,两组均处理60 min后分别取样进行HPLC检测DON含量;
DON含量的检测:检测方法如实施例1中所述含量检测的步骤,结果显示,与未处理组相比,玉米酒糟中的DON含量明显明显降低,其中添加有氯盐的一组DON的降解效果更好;
电解对玉米酒糟品质的影响:为了评估电解处理对玉米发酵糟液引起的品质变化,我们对电解处理后的玉米发酵糟液和未处理的糟液相对比,检测粗蛋白、脂质的含量变化,粗蛋白使用0.1 mol/L的NaOH溶液进行碱法提取,料液比为1:5(V:V),50~80 ℃,以1000r/min的速度进行磁力搅拌,提取2 h,然后8000 r/min离心5 min,取上清液即为粗蛋白提取液;使用考马斯亮蓝G-250对粗蛋白的含量进行测定,并对粗蛋白提取液做SDS-PAGE实验;使用索式提取法对脂质进行测定;结果显示与未处理组相比,电解前后玉米酒糟的粗蛋白以及脂质含量变化不大,因此电解处理对玉米发酵糟液的营养品质没有显著影响;
MS全扫描:对电解处理前后的玉米酒糟样品进行DON提取纯化,提纯方法如实施例1中DON含量检测时所述的样品预处理步骤相同,对提取液进行MS负离子场全扫描,扫描范围为m/z 100~600,结果显示,电解处理后DON的相对丰度降低,并出现了两种质量分数为238.96和363.90的物质,为DON的降解产物,再次证明电解处理确实可以将乙醇发酵工业玉米酒糟中的DON降解为其他物质从而降低DON在玉米酒糟中的含量。
实施例4:
电解:采用石墨电极对玉米酒糟在1.2 V的外加电压下进行电解处理,添加的氯盐为NaCl,添加量为0.2 mol/L,电解处理60 min后分别取样进行HPLC检测DON含量;
DON含量的检测:检测方法如实施例1中所述含量检测的步骤,结果显示,与未处理组相比,玉米酒糟中的DON含量从13 943 μg/kg降低至2 411 μg/kg,降解率达82.71%。
本领域技术人员基于本发明的宗旨及核心思路所做的修改及变化属于本发明的保护范围。以上实施例对本发明做了详细说明,但实质未脱离本发明的宗旨,因此,基于以前实施例的变形例均包含在本发明保护范围之内。
Claims (6)
1.一种电氧化降解玉米酒糟中呕吐霉素(DON)的方法,其特征在于,包含以下步骤:
(1)DON极化曲线的测定:采用典型的“三电极”系统对添加有适量DON的含氯盐电解液进行循环伏安(CV)扫描,确定DON的极化曲线,为后续外加电压的施加范围提供理论依据;
(2)电解:根据DON极化曲线确定的氧化峰位置,采用恒电压模式对乙醇发酵后续的玉米酒糟在分隔式电解槽中施加恒定电压进行电解处理,所述恒定电压为0.6-1.4V,玉米酒糟置于阳极室中,氯盐缓冲液置于阴极室中,电解时采用磁力搅拌保证电解过程中样品的均匀混合,在电解初期向玉米酒糟中添加氯盐。
2.如权利要求1所述方法,其特征在于,所述玉米酒糟为玉米乙醇发酵工艺中发酵蒸馏后的玉米醪液。
3.如权利要求1或2所述方法,其特征在于,所述电解处理采用阴阳两个电极,电极材料选自钛、石墨或铂惰性电极。
4.如权利要求1或2所述方法,其特征在于,氯盐的添加浓度为0.1-0.5mol/L。
5.如权利要求1或2所述方法,其特征在于,电解时间不少于60min。
6.如权利要求1-5任一所述的电氧化降解玉米酒糟中呕吐霉素(DON)的方法在乙醇发酵领域中降解DON的应用。
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