谷物及制品中修饰型真菌毒素的风险与防控

doi:10.3864/j.issn.0578-1752.2022.06.013

摘要/Abstract

摘要：

修饰型真菌毒素是重要的食品安全危害因子。通过综述修饰型真菌毒素的形成机制、种类、污染水平、毒理研究、代谢规律、分析检测、脱毒方法等方面的进展,识别已知风险、潜在风险以及分析风险防控措施。已知风险包括：谷物及制品中修饰型真菌毒素的阳性检出率高,浓度跨度大,其存在会增加人群真菌毒素膳食暴露的风险。毒理学研究表明,有的修饰型真菌毒素在体内代谢转化为原型而产生与原型同等毒性,有的本身则具有毒性。潜在风险包括：代谢转化而成的多种修饰型真菌毒素共存时会引起毒性机制和毒性作用不明。在农作物代谢或食品加工中也可产生结构、性质、毒性均未知的修饰型真菌毒素。受分析技术和质量控制手段的制约,难以获得其准确可靠的定性定量结果,使毒理学数据十分匮乏,导致毒理学性质引起争议。风险防控措施包括：从源头抓起,培育抗病品种,规范标准体系和检测体系,严把农产品收购、储藏、生产及产品加工关。另外,在生产加工环节中,要加强产后脱毒技术的研究。

关键词: 修饰型真菌毒素, 原型, 谷物及制品, 风险, 防控措施

Abstract:

Modified mycotoxins are a principal group of food safety hazards. In this study, based on reviews of the formation mechanism, classification, pollution status, toxicological research, metabolic rule, and analytical and detoxification methods of modified mycotoxins, the known and potential risks were identified, and risk prevention and control measures were analysed. The known risks were: in grain and its products, there was a high positive detection rate of modified mycotoxins, with a wide range of concentrations, which increased the risk of exposure to mycotoxins. Toxicological research on modified mycotoxins demonstrated that some modified mycotoxins transform back into their parent form during the process of metabolism and produced toxic effects equal to their parent form. Additionally, some other modified mycotoxins were toxic in themselves. The potential risks were: the coexistence of a diversity of metabolized toxins might lead to obscure toxicological mechanisms and effects. Some new modified mycotoxins with unknown structures, properties, or toxicities could be produced in the process of crop metabolism or food processing. Because it was restricted by a lack of analytical technology and quality control methods, it was difficult to obtain accurate and reliable qualitative and quantitative results for modified mycotoxins. Thus, the toxicological data for modified mycotoxins were extremely scarce, resulting in disputes over toxicological properties. The risk prevention and control measures were: starting from the source, the new varieties should be bred that were resistant to mycotoxin infection, normalize standards and testing systems should be built, and the purchase, storage, and production of agriculture products should be strictly controlled. In the food processing stage, more detailed research into detoxification technology after mycotoxin infection needs was required.

Key words: modified mycotoxins, parent mycotoxins, grain and its products, risk, prevention and control measures

杨虹,曹文明,陈何妍,卫学青,束莉丹,李彤. 谷物及制品中修饰型真菌毒素的风险与防控[J]. 中国农业科学, 2022, 55(6): 1213-1226.

YANG Hong,CAO WenMing,CHEN HeYan,WEI XueQing,SHU LiDan,LI Tong. Risks and Their Prevention and Control of Modified Mycotoxins in Grain and Its Products[J]. Scientia Agricultura Sinica, 2022, 55(6): 1213-1226.

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图/表 5

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表1

表2

谷物及制品中常见真菌毒素的毒性及欧洲人群的慢性膳食暴露量"

真菌毒素 Mycotoxin	IARC分类 IARC classification	每日耐受摄入量TDI Tolerable daily intake (ng·kg^-1 body weight·day^-1)	毒性与危害 Toxicity and hazard	慢性膳食暴露平均消费者 Chronic dietary exposure at the mean percentile (ng·kg^-1 body weight·day^-1)		慢性膳食暴露高消费者（P95） Chronic dietary exposure at the 95th percentile (ng·kg^-1 body weight·day^-1)		参考文献 Reference
真菌毒素 Mycotoxin	IARC分类 IARC classification		毒性与危害 Toxicity and hazard	幼儿 Toddlers	成人 Adults	幼儿 Toddles	成人 Adults	参考文献 Reference
DON 3-AcDON 15-AcDON DON-3-Glc	Group 3	DON+3-AcDON+15- AcDON+DON-3-Glc= 1000	引发呕吐、腹痛、腹泻、发烧以及内毒素血症等极性中毒症状;引起食欲减退、消化不良等慢性中毒症状,高剂量摄入会导致休克甚至死亡。具有细胞毒性、基因毒性、免疫毒性和致癌性,与人类大骨节病、克山病的发生有关 It triggers some polar poisoning symptoms such as vomiting, bellyache, diarrhea, fever and indotoxemia; It can cause some chronic poisoning symptoms such as decreasing appetite, indigestion and so on. High intake of it can lead to shock or even death. It has cytotoxin, genotoxin, immunotoxicity and carcinogenicity, relating to the occurrence of Kaschin-Beck disease and Keshan disease	600—1700	300—700	1100—2700	500—1400	[1,49-50]
T-2 HT-2	Group 3	T-2+HT-2=100	危害造血组织和免疫器官,引发出血性综合征,白细胞减少,贫血,胃肠道功能受损等 Endanger hemopoietic system and immune organs, causing hemorrhagic bowel syndrome, leukopenia, anemia, impaired the function of gastrointestinal tract, etc.	12—43	3.4—18	23—91	7.2—39
NIV	Group 3	NIV=1200	急性毒性较脱氧雪腐镰刀菌烯醇强,具有较强的细胞毒性,抑制免疫系统,造成血清总蛋白下降,碱性磷酸酶、谷草转氨酶活性升高等,并具有胚胎毒性作用 Acute toxicity of it is stronger than that of DON. It has quite strong cytotoxin to suppress immune system, causing decreasing of total serum protein and increasing of the enzyme activity of alkaline phosphatase and glutamic oxalacetic transaminase. It also has embryotoxicity	4.3—202	0.4—75	12—484	1.1—224
ZEN	Group 3	ZEN=250	生殖毒性、肾脏毒性、免疫毒性、肝脏毒性和诱发肿瘤的形成 It has reproduction toxicity, nephrotoxicity, immunotoxicity, liver toxicity. It induces the formation of tumor	93—100	2.4—29	24—277	4.7—54
FB1 FB2 FB3	Group 2B	FB1+FB2+FB3=2000	可致大脑白质软化症,神经性中毒而表现意识障碍、失明和运动失调等症状,严重者甚至造成死亡。对猪造成肺水肿综合征,并能造成肝脏和食道损伤。引起灵长类动物的动脉粥样硬化样改变,诱发大鼠肝癌,与人类食道癌的发生密切相关 It causes leukomalacia and neurotoxicity to exhibit some symptoms including disturbance of consciousness, blindness and ataxia, and even death. For pig, it can give rise to edema syndrome and impair liver and esophagus. It triggers the change of atherosclerosis of quadrumane, inducing rat hepatocarcinoma, having a close relation to the occurrence of human esophageal cancer	180—1650	50—650	580—3260	90—1250

表2

表3

脱氧雪腐镰刀烯醇修饰型、玉米赤霉烯酮修饰型和伏马毒素修饰型的数量、潜在毒性及涉及反应类型"

类型 Type	数量（个）Number	分析方法(个) Analytical method	举例 Example	毒性情况 Toxicity	反应类型 Reaction type	文献 References
Modified DON	44	3	DON-3-Glc	毒性与DON相当 Equivalent toxicity of DON	糖苷化 Glycosylation	[54]
			DON-diGlc	未报道, 因结合寡糖,极性增强,更易排出体外 Unreported. The combination with oligose increased DON-diGlc polarity, made it more easier being eliminated from body	糖苷化 Glycosylation	-
			DON-3-GlcA	可能低毒,随尿液排毒 Maybe low toxicity, excreted in urine	糖酸化Glucuronidation	[32]
			DON-15-sulfate	低毒,植物核糖体活性中度抑制剂 Low toxicity, DON-15-sulfate is considered as a moderate inhibitor of plant ribosome activity	磺化 Sulfonation	[32]
			DON-glutathione	可能低毒。谷胱甘肽本身能帮助保持正常的免疫系统功能,并具有抗氧化和整合解毒的作用 Maybe low toxicity. Glutathione is beneficial to retain the immune system functioning normally and has effect of anti-oxidation and integrated detoxification	硫化 Sulfuration	[32]
			3-AcDON	毒性与DON相当 Equivalent toxicity of DON	乙酰化 Acetylation	[32]
			norDON A	无毒 Nontoxicity	热降解 Thermal degradation	[6]
			DOMs	可能低毒,C12-C13 位环氧键被破坏,随尿液排毒 Maybe low toxicity, the epoxy bond of C12-C13 of mother nucleus is damaged, excreted from body in urine	去环氧化 De-epoxidation	[32,57]
			3-epimer-DON	可能低毒,体内和体外实验研究表明毒性比DON低 Maybe low toxicity, the results of vivo- and vitro- experiments demonstrated 3-epimer-DON toxicity is lower than DON	异构化 Isomerization	[57-59]
Modified ZEN	43	2	α-ZEL	可能有毒,其与雌激素受体结合能力比ZEN强9—2200多倍 Likely to be toxic, its capacity of combining with oestrogen receptors are 9-2200 times stronger than ZEN	还原化 Reduction	[27]
			ZEN-14-Glc	可能有毒。猪口服方式给药时,主要转化为ZEN和α-ZEL Likely to be toxic. After oral administration in pig, ZEN-14-Glc mainly transforms into ZEN and α-ZEL	糖苷化 Glycosylation	[22,32]
			ZEN-14-GlcA	可能低毒,随尿液排毒 Maybe low toxicity, excreted in urine	糖酸化 Glucuronidation	[22]
			ZEN-14-sulfate	可能有毒。猪口服给药时,转化为ZEN、ZEN-14-GlcA和其他代谢物 Likely to be toxic. After oral administration in pig, ZEN-14-sulfate mainly transforms into ZEN, ZEN-14-GlcA and other metabolites	磺化 Sulfonation	[22,32]
Modified FB	15	0	HFB1	可能低毒,老鼠喂养试验中,有肝、肾毒性,抑制神经酰胺合成酶 Maybe low toxicity. In rat trials, HFB1 exhibits liver toxicity, nephrotoxicity, and suppression of ceramide synthetase	水解 Hydrolyzation	[11]
			N-fatty-acyl-FB1	可能有毒,通过细胞实验,毒性比HFB1强,约是FB1的10倍 Maybe low toxicity. Through cell experiment, N-fatty-acyl-FB1 toxicity is stronger than HFB1, and is almost ten times stronger than FB1	酰化 Acylation	[28,32]
			EFB1 palmitic acid	未明确,极性比FBs更弱,毒性不同于FBs Undetermined. EFB1 palmitic acid polarity is much weaker than FBs, and its toxicity is different from FBs	酯化 Esterification	[14,32]

表3

表4

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类别 Type	种类¹⁾ Classification	检出率 Positive rate (the range of mean, %）	浓度Concentration (the range of mean, μg∙kg^-1)	修饰型/原型（均值） Modified/free ratio (mean)	样本量 Sample size	基质²⁾ Matrix	国家³⁾ Country	文献 Reference
单端孢霉烯族Trichothecene	DON-3-Glc	6.3—100	5.5—1080	0.01—16	2151	1—7,8	1—12	[29-31,33-38,40-45]
	3-AcDON	3.3—100	2.1—341	0.01—4.7	1642	1—4,8	1—3,7—9	[29-31,37-38,41-42]
	15-AcDON	4.2—100	2.4—334	0—2.8	1547	1—3,8	1—3,7—8	[29,31,37-38,42]
	NIV-3-Glc	0.08—100	13—1042	0.18—0.41	200	1,3—7,8	4,9,12	[30,33,43]
	HT2-3-Glc	41—58	5.4—41	0.26—3.3	95	1,3—4	9	[30]
	小计 Sub-total	11—92	5.7—568	0.1—5.4	2151	7种谷物11种制品 7 grain and 11 grain products	12
玉米赤霉烯酮类 Zearalenone	α-ZEL	2.9—100	0.6—97	0—4.4	299	1—4,8	7,9	[30,37,42]
	β-ZEL	2.9—83	2—49	0—3.5				[30,37,42]
	α-ZEL-14-Glc	0.03—24	3.1—283	0—2.7				[30,37,42]
	β-ZEL-14-Glc	0.01—50	0.1—152	0—1.8				[30,37,42]
	ZEN-14-Glc	3.2—50	0.15—174	0—4.6	323			[30,37,39,42]
	ZEN-14-sulfate	8.8—53	4.9—51	0—0.86	383		1,7,9,11	[30,37,41-42]
	ZEN-16-Glc	6.7—58	0.45—4.2	0.03—0.06	95	1,3—4	9	[30]
	小计 Sub-total	3.5—60	1.6—116	0—2.6	407	4种谷物9种制品 4 grain and 9 grain proproducts	4

类型 Type	基质 Matrix	修饰型真菌毒素 Modified mycotoxin	数量 Number (positive)	与原型的含量百分比 Modified/Free ratio	文献 Reference
谷物原料 Grain raw material	玉米 Corn	ZEN-14-sulfate	41	高达30% UP to 30%	[1]
	小麦 Wheat	ZEN-14-Glc	10	高达30% UP to 30%
	玉米Corn	Physical emtrapped fumonisins	31	高达100% UP to 100%
		Physical emtrapped fumonisins	97	高达60% UP to 60%
		Physical emtrapped fumonisins	120	高达60% UP to 60%
谷物食品 Grain products	高纤维面包 Fiber enriched bread	ZEL, ZEN-14-Glc, ZEN-14-sulfate,	52	总和,高达100% As the sum, up to 100%
	高纤维面包 Fiber enriched bread	α-ZEL-14Glc, β-ZEL-14-Glc	52	总和,高达100% As the sum, up to 100%
	谷物早餐 Breakfast cereals	ZEL, ZEN-14-Glc, ZEN-14-sulfate,	62	总和,高达110% As the sum, up to 110%
	谷物早餐 Breakfast cereals	α-ZEL-14-Glc, β-ZEL-14-Glc	62	总和,高达110% As the sum, up to 110%
	燕麦片 Oatmeal	ZEL, ZEN-14-Glc, ZEN-14-Sulfate,	13	总和,高达100% As the sum, up to 100%
	燕麦片 Oatmeal	α-ZEL14Glc, β-ZEL-14-Glc	13	总和,高达100% As the sum, up to 100%
	玉米片 Corn flakes	Physical emtrapped fumonisins	4	高达100% UP to 100%
	无麸质产品 Gluten-free products	Physical emtrapped fumonisins	21	高达100% UP to 100%