CN1229367A - 新的吸附剂 - Google Patents
新的吸附剂 Download PDFInfo
- Publication number
- CN1229367A CN1229367A CN96180443A CN96180443A CN1229367A CN 1229367 A CN1229367 A CN 1229367A CN 96180443 A CN96180443 A CN 96180443A CN 96180443 A CN96180443 A CN 96180443A CN 1229367 A CN1229367 A CN 1229367A
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- adsorbent
- food
- absorption
- spawn
- digestive system
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Abstract
用高分子聚羧酸的二价金属盐、豆腐、冻胶、蒟蒻、琼脂、紫苏、凉粉或脱乙酰壳多糖草酸盐凝胶等凝胶状物质被覆活性炭等吸附体、然后冷冻处理,或者用含有防冻害物质的凝胶状物质被覆活性炭等吸附体、然后除去该防止冷冻物质而制成的吸附体。将其与食品等直接接触或直接对消化系统给药,可以以极高的效率吸附、除去在食品等中附着或含有的或者存在于消化系统内的食品添加剂、饮料添加剂、农药、引起食物中毒的物质、过敏原、重金属或毒性强的有机化合物、消化系统内存在的过剩营养素、酒类中含有的低聚物、添加剂等、摄入酒精后在消化系统内产生的酒精中间代谢物、油脂中的不饱和脂肪酸的氢过氧化物等有害物质以及鱼腥味等臭气成分。
Description
发明领域
本发明是关于用于吸附、除去有害物质的新的吸附剂,更具体地说,本发明是关于用凝胶状物质被覆吸附体构成的吸附剂。
发明背景
活性炭的比表面积大,具有高的吸附能力,作为一种有代表性的吸附剂被广泛用于各种用途。但是,为了吸附、除去引起自身中毒、药物中毒等的物质而将活性炭作为药用碳直接对消化系统内用药时,会产生便秘等问题。另外,如果将活性炭掺入食品中,在食用时会有异物感,并且将食物污染成黑色。此外,现已知道,动物细胞可以将微粒子活性炭吸附到细胞膜外层的蛋白或糖蛋白上,将微粒子活性炭作为有害物质的吸附、除去剂即直接对消化系统内用药时,其一部分被消化器官内的细胞所吸附而残留下来,很难将其从消化器官中完全排出去。
为了解决这些问题,有人提出了用蒟蒻等不溶于水的甘露聚糖或藻酸钙等交联聚合物被覆活性炭的吸附剂(特开昭55-95611、特开平4-210239)。但是,这些吸附剂由于在活性炭的粒子表面上形成被膜,导致表面积减小,不能充分发挥活性炭原有的吸附能力。
本发明是鉴于上述现有技术中存在的问题而完成的,本发明的目的是,提供一种不降低活性炭等吸附体原有的吸附能力,将其直接与食品等接触或者直接对消化系统内用药,可以以极高的效率吸附、除去食品等中附着或含有的或者消化器官内存在的有害物质的吸附剂。
发明概述
上述各项发明目的,可以通过使用本发明的用凝胶状物质被覆吸附体后进行冷冻处理而构成的吸附剂来实现。
另外,上述发明目的可以通过本发明的用含有防冻害物质的凝胶状物质被覆吸附体、然后将上述防冻害物质的一部分或全部除去而构成的吸附剂来实现。
此外,本发明是上述防冻害物质为甘油的上述吸附剂。
再有,本发明是上述吸附体为具有吸附能的碳素材料。
另外,本发明是上述具有吸附能的碳素材料为活性炭或木炭的上述吸附剂。
此外,本发明是上述凝胶状物质为高分子聚羧酸的二价金属盐的上述吸附剂。
另外,本发明是上述高分子聚羧酸的二价金属盐为藻酸钙的上述吸附剂。
此外,本发明是上述凝胶状物质为豆腐、冻胶、蒟蒻、琼脂、紫苏类(ェゴ)、凉粉或脱乙酰壳多糖草酸盐凝胶的上述吸附剂。
另外,本发明是将上述吸附剂干燥而得到的吸附剂。
此外,本发明是含有第一的凝胶状物质被覆吸附体的吸附剂部分和第二凝胶状物质部分的吸附剂。
另外,本发明是对上述吸附剂部分或上述第二凝胶状物质部分中的任一方进行调味而构成的上述吸附剂。
此外,本发明是上述吸附剂部分含有上述各吸附剂的上述吸附剂。
另外,本发明是含有上述吸附剂的有害物质吸附、除去剂。
此外,本发明是上述有害物质为食品或饲料中附着或含有的或者被摄入消化系统内的食品添加剂、饲料添加剂、农药、引起食物中毒的物质、过敏原、重金属或毒性强的有机化合物的上述有害物质吸附、除去剂。
另外,本发明是上述饲料添加剂为抗生素、合成抗生素或激素制剂的上述有害物质吸附、除去剂。
此外,本发明是上述引起食物中毒的物质为外来毒素、自然毒素或有害化学物质的上述有害物质吸附、除去剂。
另外,本发明是含有上述吸附剂的、将抗生素经口给药时的抗生素本身或抗生素作用于肠内细菌而产生的有害物质吸附、除去剂。
此外,本发明是含有上述吸附剂的、被摄入消化系统内的过剩营养素的吸附、除去剂。
另外,本发明是含有上述吸附剂的、摄入酒精后在消化系统内产生的酒精中间代谢物的吸附、除去剂。
此外,本发明是含有上述吸附剂的、油脂中的不饱和脂肪酸的氢过氧化物的吸附、除去剂。
另外,本发明是含有上述吸附剂的防臭剂。
此外,本发明是掺入0.01-60%(重量)上述吸附剂的加工食品或饲料。
另外,本发明是上述食品为乳制品、水产品熬炼凝固制品、鱼类和贝类加工食品、肉加工食品、豆制品、蔬菜加工食品、薯类加工品、粮食加工品、甜食类、油脂类或糕点类的上述加工食品。
本发明的吸附剂,通过用凝胶状物质被覆吸附体后进行冷冻处理,被覆的凝胶状物质中的水分凝结,在该被膜上形成孔径比单纯交联时形成的孔径大的微细孔,从而可以保持吸附体原有的吸附能力。
同样,用含有防冻害物质的凝胶状物质被覆吸附体后除去该防冻害物质,也可以在被膜的凝胶状物质中形成同样的微细孔,产生同样的效果。
另外,在使用粉末活性炭等微粒子作为吸附体时,本发明的吸附剂是由在凝胶状物质中均匀分散着吸附体的分散系构成的,由于活性炭高度分散,与单独使用活性炭相比,吸附剂整体的有效吸附面积增加,吸附能力增大,可以以极高的效率吸附、除去有害物质。
此外,本发明的吸附剂是用凝胶状物质被覆吸附体,可以对消化系统内直接用药,能够在消化系统内简便地吸附、除去掺入食品中被摄入消化系统内的有害物质。而且,对消化系统内直接给药也不会引起便秘,吸附、除去消化系统内的有害物质后的吸附剂可以非常迅速、容易地从消化系统中排除出去。
再有,本发明的吸附剂还可以吸附、除去与食品等混合、接触而包含在食品中的有害物质。在这种场合,与单独使用吸附体的情况相比,可以用较短时间、简便地将吸附、除去有害物质后的吸附剂从食品中分离也去。另外,即使由于失误而未分离吸附剂,致使吸附剂混入食品中被摄入消化系统内,也可以迅速将其排出到消化系统外,因而非常安全。
如上所述,本发明的吸附剂除了可以直接对消化系统内用药外,还可以混合到加工食品中加以利用。本发明的吸附剂混合到加工食品中食用时,没有异物感,食感很好,而且不会将食品污染成黑色。
本发明的吸附剂可以用于人,作为对人体有害物质的吸附、除去剂,此外也可以用于饲养的动物。即,可以用本发明的吸附剂处理饲料,或者将本发明的吸附剂直接给饲养动物喂食或掺混到饮料中给饲养动物喂食。
发明的优选实施方案
本发明的吸附剂可以通过用凝胶状物质被覆吸附体、然后冷冻处理而制备。
本发明的吸附剂中使用的吸附体可以举出:活性炭、木炭、氧化铝、硅胶、沸石、膨润土、磷酸钙、离子交换树脂、螯合树脂等,其中优先选用活性炭和木炭等具有吸附能的碳素材料,特别优先选用活性炭。
使用活性炭作为吸附剂时,可以采用粉状、粒状、纤维状等各种形状,特别优选的是粉状或粒状的活性炭。活性炭的粒径在5μm-10mm为宜。活性炭粒径小于5μm时,加工操作有困难,超过10mm时,每单位重量活性炭的吸附能力降低。另外,活性炭在凝胶状物质中的混合量以0.02-90%(重量)为宜,活性炭混合量低于0.02%(重量)时,吸附效果较低,反之,超过90%(重量)时,难以分散到凝胶状物质中。
在本发明的吸附剂中使用的凝胶状物质,可以举出对消化系统内给药时没有有害作用的凝胶状物质,例如高分子聚羧酸的二价金属盐。所述的高分子聚羧酸的二价金属盐可以举出:藻酸、果胶酸、羧甲基纤维素、羧甲基甲壳质、苯乙烯 马来酸共聚物、苯乙烯-马来酸半烷基脂共聚物、乙烯-丙烯酸共聚物、聚丙烯酸、聚甲基丙烯酸、丙烯酸-甲基丙烯酸共聚物、丙烯酸 马来酸共聚物、丙烯酸-马来酸半烷基脂共聚物等、侧链上具有羧基的高分子化合物的钙盐、镁盐、铁盐、铜盐等。
使用高分子聚羧酸的二价金属盐的吸附剂,可以通过在二价金属盐的水溶液中滴加高分子聚羧酸的碱金属盐或铵盐与活性炭粉末等吸附体的混悬液而制备。上述混悬液中的高分子聚羧酸的碱金属盐或铵盐的浓度在0.01-5摩尔为宜,低于下限值时,不能得到被覆或分散吸附体的牢固的凝胶,超过上限值时,包围吸附体的高分子聚羧酸盐过多,阻碍被吸附物进入吸附体内部,吸附能力显著降低。另外,二价金属盐水溶液的浓度在0.05-5摩尔为宜,低于下限值时,交联率低,吸附体的强度减弱,超过上限值时,交联率增大,吸附体的孔径变得很小,致使被吸附物难以进入吸附体内部。
另外,在本发明中,凝胶状物质还可以使用豆腐、冻胶、蒟蒻、琼脂、紫苏类或石花菜冻胶等凝胶状食品,或者脱乙酰壳多糖草酸盐凝胶等。使用这些凝胶状物质的吸附剂,可以通过在各凝胶状食品的制造过程中于凝胶形成之前适当添加并分散活性炭粉末等吸附体而制得。
在本发明的吸附剂中,可以单独使用上述各凝胶状物质,也可以多种上述各凝胶状物质混合使用。另外,还可以根据需要添加下列物质:扁桃树胶、气单胞菌属胶、维涅兰德固氮菌胶、ァマシ-ドガム、阿拉伯树胶、阿拉伯半乳聚糖、藻酸、芦芸提取物、韦兰(ゥェラン)树胶、密执安欧文氏菌(ェルゥィニァミッェンシス)胶、榄香脂、西马纳斯(シマナス)肠杆菌胶、肠杆菌胶、铁青树(ォラク)提取物、欧毒芹(カ-トラン)、海藻纤维素、苦木树胶、褐藻提取物、卡拉乙楠(カラギナン)、梧桐树胶、角豆树豆胶、卡奇胶(ガチィガム)、合成生物聚合胶、基塔奇芦芸(キタチァロェ)提取物、甲壳质、脱乙酰壳多糖、银菊胶、葡糖胺、酵母细胞膜、サィリゥムシ-ドガム、乔兰凤树胶、斯库莱洛树胶(スクレロガム)、噻斯莱洛树胶(セスレロガム)、噻斯巴尼阿树胶(セスバニァガム)、罗望子胶、刺云实(タラ)胶、达玛树胶、普崎司陶搔(プキストッソ)、西黄蓍胶、三刺魨胶、木槿根、发酵大豆杆菌胶、微小纤维状纤维素、那塞莱兰(ノァ-セレラン)、灶鲁兰(ゾルラン)、果胶、马库楼豪莫布西斯胶(マクロホモブシスガム)、拉姆散胶(ラムザンガム)、果聚糖等增稠稳定剂;榄香脂、螯利球蜡(ォゥリキュゥリロゥ)、奥扫开莱陶(ォゾケラィト)、奥泡巴那克司树脂(ォポバナックスガム)、贝壳杉树胶、巴西棕榈蜡、小烛树蜡、鲸蜡、冠胶(クラゥンガム)、古塔卡秋(グッタカチュゥ)胶、古塔汉砍(グッタハンカン)胶、古塔波胶(グッタベルカ)、愈创树脂、银菊胶、树脂、香脂、米糠蜡、橡胶、橡胶分解树脂、甘蔗蜡、山达脂、虫胶(精制虫胶、白虫胶)、紫胶蜡、菊路氽(ジュルトン)、香豆乳汁(ソルバ)、搔鲁宾巴(ソルビンバ)、滑石、达马树胶、崎库布录(チクブル)、糖胶树胶、奇路台(チルテ)、茨脉(ッメ-)、低分子橡胶、乳香、纽胳古塔(ニガ-グッタ)、纽斯百劳(ニスベロ)、巴拉塔树胶、石蜡、冷杉香脂、纸浆粉末、稻壳粉、委内瑞拉糖胶树胶、安息香胶、白利旧(ベリ-ジョ)、西蒙得木蜡(ホホパロゥ)、马萨兰道巴丘考莱陶(マッサランドバチョコレ-ト)、马萨兰道巴巴拉塔(マッサランドババラタ)、微晶蜡、乳香、蜂蜡、没药树脂、漆树蜡、褐煤蜡、油糠种子蜡、含水羊毛脂、莱邱布巴卡(レッチュブバカ)、楼机代因哈(ロジディンハ)、松脂等树胶基;螯利球蜡(ォゥリキュゥリロゥ)、巴西棕榈蜡、小烛树蜡、鲸蜡、胡荽子、藏红花、山椒、紫苏、夏洛特(シャロット)、刺柏子、生姜、桂皮、八角茴香、薄荷、鼠尾草、噻褒利(セポリ-)、芹菜籽、麝香草、蓼、洋葱、龙蒿、菊苣、细香葱、袷戊依鲁(チャ-ゥ″ィル)、提取粉末香辛料、番椒、草茴香、肉豆蔻、韭菜、大蒜、葱、罗勒、欧芹、薄荷、甜辣椒、开心果、发奴古利库(フェヌグリ-ク)、小茴香籽、辣根、马郁兰(マ-ジョラン)、鸭儿芹、姜、肉豆蔻、柚、酸橙、辣椒、柠檬、迷迭香、月桂、山俞菜等光泽剂;奶酪、生奶油、黄油、奶粉、乳清、炼乳等乳制品;柑桂酒、樱桃白兰地酒、雪利酒、清酒、啤酒、葡萄酒、白兰地、粉末酒、味美思、朗姆酒、利口酒等酒类;α化淀粉、α米、甜豆酱、乌龙茶、埃类哦物考茨库(ェロゥテロコック)、干菜、琼脂、麸质、小球藻、血球粉末、血浆粉末、曲子、红茶、咖啡、酵母、高丽人参、可可、米粉、米糠、小麦粉、小麦胚芽、骨胶原、蒟蒻粉、乙酸菌、酒糟、果酱、食盐、精制鱼肉蛋白质、精制小麦蛋白质、精制大豆蛋白质、明胶、荞麦粉、种曲子、巧克力、糊精、淀粉、玉米粉、发酵大豆杆菌、难消化性糊精、乳酸菌、乳糖、麦芽、麦芽提取物、火腿、双尾菌、麸子、部分α化淀粉、马铃薯粉、山药粉、红曲、半纤维素、末茶、柑桔浆、蛋黄粉、蛋黄油、蛋白、茶叶等。
本发明的吸附剂,可以通过用含有防冻害物质的凝胶状物质被覆吸附体、然后将该防冻害物质的一部分或全部除去而制得。
本发明的吸附剂中使用的防冻害物质可以举出:乙酰胺、L-丙氨酸、白蛋白、乙酸铵、氯仿、胆碱、葡聚糖、二甘醇、二甲基乙酰胺、二甲基甲酰胺、二甲砜、二甲亚砜、赤藓醇、乙醇、乙二醇、甲酰胺、葡萄糖、丙三醇、甘氨酸、羟乙基淀粉、肌醇、乳糖、氯化镁、磷酸镁、麦芽糖、甘露糖醇、甘露糖、甲醇、甲基乙酰胺、甲基甲酰胺、甲脲、一醋精、苯酚、聚乙二醇、聚环氧乙烷、聚氧乙烯、聚乙烯吡咯烷酮、L-脯氨酸、丙酰胺、丙二醇、吡啶、N-氧化物、间苯二酚、核糖醇、核糖、L-丝氨酸、溴化钠、氯化钠、碘化钠、硝酸钠、亚硝酸钠、硫酸钠、山梨糖醇、蔗糖、三乙二醇、尿素、L-吉草酮(バレン)、木糖等,其中特别优选的是丙三醇。
另外,在以消化器官内给药的形式使用本发明的吸附剂时,为了容易服用,也可以对吸附剂本身适当地进行调味。
本发明的吸附剂,可以用于吸附、除去在食品或饲料中附着或含有的或者被摄入消化系统内的食品添加剂、饲料添加剂、农药、引起食物中毒的物质、过敏原、重金属、毒性强的有机化合物等有害物质。
即,本发明的吸附剂可以用于吸附、除去下列食品添加剂:糖精及其盐类、甘草酸二钾、甘草酸三钾、乙酰乙酸乙酯等甜味剂;三氧化二铁、食用红色素3号、40号、102号、104号、105号、106号、食用黄色素4号、5号、食用绿色素3号、食用青色素1号、2、二氧化钛等着色剂;苯甲酸、邻苯基苯酚、山梨酸、脱氢乙酸、丙酸及其盐类、联苯、噻苯哒唑、对羟基苯甲酸酯等防腐剂;丙二醇等品质保持剂;藻酸丙二醇、羧甲基纤维素钾、羧甲基纤维素钠、淀粉甘醇酸钠、淀粉磷酸酯钠、甲基纤维素、聚丙烯酸钠等增稠剂·稳定剂·胶凝剂·糊料;d1-α生育酚、山梨酸(ニリソルビン酸)及其钠盐、愈创木脂、柠檬酸异丙酯、二丁基羟基甲苯、去甲二氢愈创木酸、丁基羟基苯甲醚、没食子酸丙酯、乙二胺四乙酸钙二钠、乙二胺四乙酸二钠防氧化剂;亚硝酸钠、硝酸钾、硝酸钠、硫酸亚铁、磷酸盐等显色剂;过氧化氢、次氯酸、次氯酸钠等杀菌剂;亚硫酸及其盐类等漂白剂;邻苯基苯酚及其盐类、联苯、噻苄哒唑等防霉菌剂·杀真菌剂等。
另外,对于农药类可以适用于MEP、二嗪农(diazinon)、PAP、IBP、EDDP、DDVP、DEP、马拉硫磷、EPN等有机磷,百菌清(クロロサロニル)、氯化苦、D-D、杀草敏(ピラゾレ-ト)、PCNB、五氯硝基苯(Flacide)、DCIP、杀菌剂等有机氯;BPMC、MTMC、XMC、MCC、MIPC等氨基甲酸酯,甲基溴等有机溴,甲基托布津等苯丙咪唑,杀草丹等硫代氨基甲酸酯,CNP等二苯醚,氯酸盐等氯,克菌丹等苯邻二甲酰亚胺,代森锰等二硫代氨基甲酸酯,百草枯等联吡啶鎓,氯硝醚等二苯醚,DCPA等酰胺,无机酮等酮,塞陶基西基姆(セトキシジム)、富士一号、噻菌灵、香草隆、萘氧基苯基丙酰胺等杀菌剂、杀虫剂、除草剂等。此外,对于过敏原,可用于吸附、除去引起食物中毒而导致过敏反应的、由于肉等的腐败而产生的组胺,对于重金属,可以吸附、除去水银、铅、六价铬、镉、硒、砷、铜、铁、锌等,对于毒性强的有机化合物,可以用于吸附、除去磷化物、氯化物、苯等。
另外,本发明的吸附剂还可以用于吸附、除去外毒素、自然毒素、有毒化学物质等引起食物中毒的物质。上述外毒素可以举出:肉毒杆菌产生的毒素(A-F型),艰难梭菌产生的肠毒素和细胞毒素,产气荚膜梭菌产生的肠毒素,毒素原性大肠菌产生的易热性肠毒素和耐热性肠毒素,赤痢菌产生的志贺毒素,葡萄球菌产生的肠毒素(A-E型)、霍乱菌产生的霍乱毒素,副溶血弧菌产生的耐热性溶血毒和肠毒素,欧文氏菌(ェルシニァェンテロコリチカ)产生的肠毒素等引起肠道感染的病菌产生的毒素,别洛(ベロ)毒素等肠道出血性大肠菌产生的别洛毒素,蜡样芽胞菌产生的毒素;上述自然毒素可以举出:河豚毒素(河豚毒),Amatoxins、毒肽、腐鱼毒、毒蝇蕈啶、鹅膏蕈氨酸、蟾毒色胺、蝇蕈醇、裸头草碱、脱磷酸裸盖茹素、5-羟色胺(serotinin)、鹿花菌碱(helvellic acid)、陷杯伞素等真菌毒素,非蛋白质强毒素、新非蛋白质强毒素、旋沟藻毒素等麻痹性贝毒素,奥卡达(ォカダ)酸、鳍藻属毒素-1、-3、肛门毒素等腹泻性贝毒素,维生素A(石投鱼中毒)、贝毒素(蛤仔毒)、四胺(四胺中毒)、新骏河毒素及原骏河毒素(贝中毒)、派菲欧郝鲁派特(パィフェォホルパィト)a(光线过敏症)等鱼类和贝类的毒素,茄碱(茄属)、阿托品、莨菪胺、L-天仙子胺、乌头碱、氢氰酸(在梅子、桃、杏、苹果、梨中以无毒的氢氰酸配合体的形式存在,到人体内后产生氢氰酸)、4’-甲氧吡哆醇(银杏中毒)、黄曲酶素(霉毒)等;上述的有害化学物质,可以举出甲醇、砷、氰化物、谷氨酸钠、糖精钠、锡、铜、锌、镉、砷化合物、氟化钠等。
本发明的化合物还可以用于除去将抗菌素经口给药时的抗菌素本身或抗菌素作用于肠内细菌而产生的有害物质。
另外,近年来,为了促进家畜的生长以及治疗或预防传染病,往往将抗菌素或合成抗菌剂等添加到饲料中,或者为了改善公牛的肉质,往往使用雌性荷尔蒙等激素制剂,但这些药剂残留在乳制品和食用肉内,被人摄入,引起过敏反应症状和性发育异常,合成抗菌剂还可以引起癌症。本发明的吸附剂还可以用来吸附、除去残留在乳制品或食用肉中的青霉素等抗菌素、磺胺制剂等合成抗菌剂、黄体酮、雌二醇等激素制剂等饲料添加剂。
此外,本发明的吸附剂还可以用于吸附、除去被摄入消化系统内的过剩营养素。如下文中所述,本发明的吸附剂在细胞培养试验中吸附培养基中的营养源,具有抑制细胞增殖的作用,将其与食品等一起进食或者在饭前或饭后摄入,能抑制食物等的代谢,可以用作减肥药或用于食疗,将通常的食物量的20%左右置换成本发明的吸附剂摄入,本发明的吸附剂可进一步吸附、除去食品中20-25%的养分,因此吸收的养分量实际上只有60-64%。如果一面注意观察体重的减少量,一面按上面所述反复进行,就可以逐步减肥,使体重达到适宜的水平,而且由于摄入量与通常是相同的,没有空腹感,不会造成任何困难,可以长期进行食疗。
另外,本发明的吸附剂可吸附、除去酒类中含有的低聚物和添加剂等,可用于吸附、除去饮酒后消化系统内产生的酒精中间代谢物--乙醛等。即,哺乳动物的酒精(乙醇)代谢是分阶段进行的,作为中间代谢物先生成乙醛,随后乙醛被氧化成乙酸和乙酰基CoA。在上述酒精代谢过程中,如果乙醛的浓度升高,就会引起恶心、呕吐、脸红、心率加快、跳动性头痛、皮肤温度上升、低血压下降等症状(乙醛症状、即所谓宿醉)。另外,酒类中所含的低聚物和添加剂等也是引起上述症状的原因之一。因此,饮酒时或在饮酒前后摄入本发明的吸附剂,可以吸附、除去酒类中含有的低聚物和吸附剂等,同时还可以吸附、除去消化系统内产生的乙醛,从而预防或治疗上述乙醛症状。另外,误食甲醇而引起的中毒症状也是由于醇的中间代谢物而引起的,本发明的吸附剂也可以用于治疗这类酸中毒。
本发明的吸附剂还可以用于吸附、除去分子量100至数万的官能性低聚物,例如锯鹱等病原性蛋白质、脂肪酸、糖类或它们的组合物等。
本发明的吸附剂还可以在巴比妥酸系药剂、农药、安眠药、镇静剂、抗忧郁药、镇痛药、心血管药、抗菌素、抗癌药、兴奋剂等药物中毒时,用于吸附、除去上述药物。
另外,本发明的吸附剂可以用于吸附、除去引起食用油等油脂酸败的物质即不饱和脂肪酸的氢过氧化物。即,食用油等油脂的酸败主要是由于油脂中的不饱和脂肪酸被空气中的氧所氧化,生成氢过氧化物,氢过氧化物进一步分解,产生醛、酮、低级脂肪酸等,致使气味发臭或恶化。本发明的吸附剂能吸附油脂中因自动氧化而产生的不饱和脂肪酸的氢过氧化物,可以用来作为油脂的酸败防止剂。
此外,本发明的吸附剂还可用于吸附、除去鱼腥味等臭气成分。具体地说,本发明的吸附剂能吸附、除去下列鱼腥味的成分:氨、三甲胺等挥发性碱类,甲酸、乙酸等挥发性酸类,甲醛、乙醛等挥发性羰基化合物,硫化氢、甲硫醇等挥发性含硫化合物,乙醇、苯酚等非羰基中性化合物以及其它有代表性的臭气成分等,可以用来作为除臭剂。
另一方面,本发明是掺入0.01-60%(重量)上述吸附剂的加工食品或饲料。将本发明的吸附剂在加工食品等中的掺入量规定为0.01-60%(重量)是因为,不足0.01%(重量)时,不能得到足够的吸附能力,超过60%(重量)时,食品的风味和食感受到损害,异物感加重。
掺入吸附剂的加工食品可以举出:酸乳、奶酪等乳制品,鱼糕、烤鱼卷、鱼肉山芋方形蒸饼、油炸鱼丸、海带鱼肉卷、蒸鱼丸子等水产熬炼制品,鱼松等鱼类和贝类加工制品,香肠、牛肉香肠、牛肝酱等肉食加工品,豆腐、烤豆腐、过油豆腐、油炸豆腐、油豆腐、豆腐渣、冻豆腐、豆腐皮等豆制品,菜泥等蔬菜加工品,土豆泥、淀粉、粉条、蒟蒻粉、粉丝等薯加工食品,年糕、糯米粉团、白米饭、麸、米粉、通心粉、细面条、挂面、荞麦面条、面条、中国面条、主食面包、面包干、带馅面包等粮食加工品,果酱等甜味食品,黄油、人造黄油、蛋黄酱、调味汁等油脂类,麦芽糖、点心、薄脆饼干、糯米点心、蛋糕、羊羹、糯米豆馅点心、豆包、豆馅年糕、米面丸子、米粉糕、巧克力、饼干、小甜饼、油炸饼、蛋糕、馅饼、冰激凌、布丁、巴伐利亚乳脂等糕点类,豆腐、果冻、蒟蒻粉、琼脂、紫苏或凉粉等凝胶状食品,海带、裙带菜、紫菜、石花菜等海草类。
另外,将吸附剂混入加工食品中时,为了防止吸附剂吸附加工食品中的味成分,以果冻为例,可以采取下述方法:设置未调味的部分(层)和经过调味的部分(层),在未调味的部分(层)中混入吸附剂,或者将如前所述的预先经过调味的吸附剂混入未调味的果冻中。
下面通过实施例进一步说明本发明,但本发明不受这些实施例的限制。
实施例1
吸附剂(经过冷冻处理、含有活性炭的蒟蒻粉)的制造
将16g精粉与4g平均粒径15μm的活性炭充分混合,一点一点地添加到750ml、30℃的温水中,注意使其不结疙瘩,一面搅拌一面用急火加热约5分钟。待咕嘟咕嘟地冒气泡后,换成中火,继续搅拌7-8分钟,然后冷却至40℃。用研钵充分磨碎0.64g CaO,溶解在50ml 40℃的热水中,然后添加到上述食料中,迅速揉和,将其放入型葙中,用手指按压,排除内部的空气,使其达到均质,然后连同型葙一起放入热水中,加热约5分钟,从型葙中取出后,再在热水中继续加热25分钟,使其完全凝固,得到640g含有活性炭的蒟蒻粉。
将500g上述制得的含有活性炭的蒟蒻粉放入1l水中,在-30℃下冷冻,5分钟后取出,在80℃的热水中解冻1分钟。使其暴露于流水中,去除色味,细切成约1mm3,得到本发明的吸附剂(经过冷冻处理、含有活性炭的蒟蒻粉)。
实施例2
吸附剂(经过冷冻、干燥处理、含有活性炭的蒟蒻粉)的制造
将200g实施例1中制备的吸附剂在干燥器中充分干燥,得到本发明的吸附剂(经过冷冻、干燥处理、含有活性炭的蒟蒻粉)。
实施例3
将16g精粉与16g平均粒径30μm的活性炭充分混合,一点一点地添加到750ml 30℃的5%(重量)丙三醇水溶液中,注意使其不结疙瘩,一面搅拌一面用急火加热约5分钟。待咕嘟咕嘟地冒气泡后,换成中火,继续搅拌7-8分钟,然后冷却至40℃。用研钵充分磨碎0.64gCaO,溶解在50ml 40℃的热水中,然后添加到上述食料中,迅速揉和,将其放入型葙中,用手指按压,排除内部的空气,使其达到均质,然后连同型葙一起放入热水中,加热约5分钟,从型葙中取出后,再在1000ml5%(重量)丙三醇水溶液中继续加热25分钟,使其完全凝固,得到650g添加丙三醇、含有活性炭的蒟蒻粉。使其暴露于流水中,除去丙三醇并去除色味,细切成约1mm3,得到本发明的吸附剂(添加丙三醇、含有活性炭的蒟蒻粉)。
实施例4
吸附剂(添加丙三醇、经过冷冻处理、含有活性炭的蒟蒻粉)的
制造
将500g与实施例3同样制造的添加丙三醇、含有活性炭的蒟蒻粉在液氮(-196℃)中冷冻,然后在40℃的温水中解冻。将其暴露于流水中,除去丙三醇并去除色味,细切成约1mm3,得到本发明的吸附剂(添加丙三醇、经过冷冻处理、含有活性炭的蒟蒻粉)。
实施例5
吸附剂(添加丙三醇、经过干燥处理、含有活性炭的蒟蒻粉)的
制造
将200g实施例3中制备的吸附剂放入干燥器中进一步充分干燥,得到本发明的吸附剂(添加丙三醇、经过干燥处理、含有活性炭的蒟蒻粉)。
实施例6
吸附剂(添加丙三醇、经过冷冻干燥处理、含有活性炭的蒟蒻粉)
的制造
将200g实施例4中制备的吸附剂放入干燥器中进一步充分干燥,得到本发明的吸附剂(添加丙三醇、经过冷冻干燥处理、含有活性炭的蒟蒻粉)。
比较例1
吸附剂(含有活性炭的蒟蒻粉)的制造
除了不进行冷冻、解冻处理之外,与实施例1同样进行操作,得到比较例的吸附剂(含有活性炭的蒟蒻粉)。
比较例2
吸附剂(经过干燥处理、含有活性炭的蒟蒻粉)的制造
将200g比较例1中制备的吸附剂放入干燥器中进一步充分干燥,得到比较例的吸附剂(经过干燥处理、含有活性炭的蒟蒻粉)。
实施例7
吸附剂(经过冷冻处理、含有活性炭的藻酸钙凝胶球)的制造
将2g藻酸钠与3g平均粒径15μm的活性炭充分混合,在搅拌下将其一点一点地添加到800ml水中,进一步添加水使总量达到1000ml,搅拌24小时,得到含有0.3%(重量)活性炭的藻酸钠溶液。另外,将11.1g氯化钙溶解在800ml蒸馏水中,进一步添加蒸馏水使总量达到1000ml,得到1.11%(重量)氯化钙溶液。
随后,将上述藻酸钠溶液注入50ml的滴定管中,一滴一滴地滴入500ml上述氯化钙溶液中,得到10g含有活性炭的藻酸钙凝胶球的粗制品。将其放入5l的容器内,一面流过离子交换水、一面处理10小时,除去未反应物和副产物,得到含有活性炭的藻酸钙凝胶球。
将10g上述制备的含有活性炭的藻酸钙凝胶球在-85℃下冷冻,然后在40℃的温水中解冻。将其暴露于流水中,除去未反应物和副产物,得到本发明的吸附剂(经过冷冻处理、含有活性炭的藻酸钙凝胶球)。
实施例8
吸附剂(经过冷冻干燥处理、含有活性炭的藻酸钙凝胶球)的制
造
将10g实施例7中制备的吸附剂放入干燥器中进一步充分干燥,得到本发明的吸附剂(经过冷冻干燥处理、含有活性炭的藻酸钙凝胶球)。
实施例9
吸附剂(添加丙三醇、含有活性炭的藻酸钙凝胶球)的制造
将2g藻酸钠与3g平均粒径15μm的活性炭充分混合,在搅拌下将其一点一点地添加到800ml 5%(重量)的丙三醇水溶液中,进一步添加水使总量达到1000ml,搅拌24小时,得到含有0.3%(重量)活性炭的藻酸钠-丙三醇溶液。另外,将11.1g氯化钙溶解在800ml蒸馏水中,进一步添加蒸馏水使总量达到1000ml,得到1.11%(重量)氯化钙溶液。
随后,将上述藻酸钠-丙三醇溶液注入50ml的滴定管中,一滴一滴地滴入500ml上述氯化钙溶液中,得到10g添加丙三醇并含有活性炭的藻酸钙凝胶球的粗制品。将其放入5l的容器内,一面流过离子交换水、一面处理10小时,除去未反应物和副产物,得到本发明的吸附剂(添加丙三醇、含有活性炭的藻酸钙凝胶球)。
实施例10
吸附剂(添加丙三醇、经过冷冻处理、含有活性炭的藻酸钙凝胶
球)的制造
将10g实施例9中制备的吸附剂在-85℃中冷冻,然后在40℃的温水中解冻。使其暴露于流水中,除去未反应物和副产物,得到本发明的吸附剂(添加丙三醇、经过冷冻处理、含有活性炭的藻酸钙凝胶球)。
实施例11
吸附剂(添加丙三醇、经过干燥处理、含有活性炭的藻酸钙凝胶
球)的制造
将10g实施例9中制备的吸附剂放入干燥器中进一步充分干燥,得到本发明的吸附剂(添加丙三醇、经过干燥处理、含有活性炭的藻酸钙凝胶球)。
实施例12
吸附剂(添加丙三醇、经过冷冻干燥处理、含有活性炭的藻酸钙
凝胶球)的制造
将10g实施例10中制备的吸附剂放入干燥器中进一步充分干燥,得到本发明的吸附剂(添加丙三醇、经过冷冻干燥处理、含有活性炭的藻酸钙凝胶球)。
比较例3
吸附剂(含有活性炭的藻酸钙凝胶球)的制造
除了不进行冷冻、解冻处理之外,与实施例7同样进行操作,得到比较例的吸附剂(含有活性炭的藻酸钙凝胶球)。
比较例4
吸附剂(经过干燥处理、含有活性炭的藻酸钙凝胶球)的制造
将10g比较例3中制备的吸附剂放入干燥器中进一步充分干燥,得到比较例的吸附剂(经过干燥处理、含有活性炭的藻酸钙凝胶球)。
实施例13
吸附速度评价试验
用吸附速度来评价实施例1-12和比较例1-4中制备的各吸附剂的吸附能力。
每一种吸附剂各量取1g,分别放入300ml的烧杯中,一点一点地添加50ml青色墨水稀释液(吸光度0.112)。在搅拌下测定墨水稀释液的波长475nm的吸光度随时间的变化,以添加墨水后至上述吸光度达到0.01以下的时间作为吸附速度。结果示于表1中。表1中还一并示出各吸附剂的处理条件。
表1
吸附剂 | 凝胶状物质 | 冷冻处理 | 干燥处理 | 添加丙三醇 | 吸附速度 |
实施例1 | 蒟蒻 | 有 | 无 | 无 | 7分 |
实施例2 | 蒟蒻 | 有 | 有 | 无 | 15分 |
实施例3 | 蒟蒻 | 无 | 无 | 有 | 1分 |
实施例4 | 蒟蒻 | 有 | 无 | 有 | 3分 |
实施例5 | 蒟蒻 | 无 | 有 | 有 | 10分 |
实施例6 | 蒟蒻 | 有 | 有 | 有 | 5分 |
实施例7 | 藻酸钙 | 有 | 无 | 无 | 15分 |
实施例8 | 藻酸钙 | 有 | 有 | 无 | 20分 |
实施例9 | 藻酸钙 | 无 | 无 | 有 | 10分 |
实施例10 | 藻酸钙 | 有 | 无 | 有 | 15分 |
实施例11 | 藻酸钙 | 无 | 有 | 有 | 15分 |
实施例12 | 藻酸钙 | 有 | 有 | 有 | 20分 |
比较例1 | 蒟蒻 | 无 | 无 | 无 | 200分 |
比较例2 | 蒟蒻 | 无 | 有 | 无 | 150分 |
比较例3 | 藻酸钙 | 无 | 无 | 无 | 70分 |
比较例4 | 藻酸钙 | 无 | 有 | 无 | 140分 |
活性炭单体 | 无 | 无 | 无 | 无 | 5分 |
实施例14
着色剂(食用红色色素104号(焰红染料))的吸附、除去试
验
食品着色剂是为了美化食品或模仿天然色的色彩而使用的,在合成焦油系色素中目前得到认可而使用的只有红色104号等水溶性酸性色素,其使用也受到限制。
使用实施例3和比较例1中制备的吸附剂,进行香肠中的含用红色素104号的吸附、除去试验。将20g腊肠细细切碎,添加0.5g吸附剂和100ml水,在搅拌下每隔一定时间采集10ml液层,向该液层中添加5倍容量的热水,溶解后进行离心分离,以上清液作为试验溶液。按“目て见る食品卫生检查法”、春田三佐夫等编集、中央法规出版、第146-149页中记载的方法处理该溶液,用滤纸色谱法进行判定。
到检测不出食用红色素104号为止的时间,比较例1的吸附剂是10分钟,而实施例3的吸附剂是1分钟。
实施例15
防腐剂(邻苯基苯酚(OPP))的吸附、除去试验
现以发现,邻苯基苯酚与硫化苯甲酸锌(TBZ)一样,具有致癌性和致畸形性。这种防腐剂对于霉菌类、各种嗜氧菌和厌氧菌具有阻止发育的作用,因而广泛用于各种加工食品中。
使用实施例10和比较例3中制备的吸附剂,进行桔子中的邻苯基苯酚吸附、除去试验。将桔子细切,取50g试料放入烧杯中,加水至约100ml,再加1g吸附剂,在搅拌下每隔一定时间采集10ml液层作为试验溶液。按“目て见る食品卫生检查法”、春田三佐夫等编集、中央法规出版、第142-143页中记载的方法处理该试验溶液,用气相色谱法测定邻苯基苯酚的浓度。
邻苯基苯酚浓度达到检测极限(0.01ppm)以下的时间,比较例3的吸附剂是10分钟,而实施例10的吸附剂是3分钟。
实施例16
防氧化剂(二丁基羟基甲苯(BHT))的吸附、除去试验
防氧化剂可以防止油脂酸败,此外还具有防止食品风味的损失,保持食品营养价值不因氧化而劣化,防止水产加工品干涸,以及防止色素变成褐色等作用,被广泛地用于多种食品中。
使用实施例10和比较例3中制备的吸附剂,进行口香糖中的二丁基羟基甲苯的吸附、除去试验。将5g口香糖、150g NaC、0.2g焦培粉、200ml水、沸石和1g吸附剂放入500ml的茄型烧瓶中,连接到带有回流冷冻器的连续提取器上,连续进行提取,每隔一定时间采集10ml提取液作为试验溶液。按“目て见る食品卫生检查法”、春田三佐夫等编集、中央法规出版、第158-159页中记载的方法对其进行处理,用气相色谱法测定二丁基甲苯酚的浓度。
二丁基羟基甲苯浓度达到检测极限(0.01g/kg)以下的时间,比较例3的吸附剂是10分钟,而实施例10的吸附剂是4分钟。
实施例17
杀菌剂(过氧化氢)的吸附、除去试验
过氧化氢的氧化作用很强,具有杀菌力,但对小鼠经口给药发现,其十二指肠上产生微弱的癌细胞,因此其使用受到限制,目前仅用于干青鱼卵。
使用实施例3和比较例1中制备的吸附剂,进行干青鱼卵中的过氧化氢的吸附、除去试验。取细切的干青鱼卵约5g放入磨碎用的杯子中,添加40ml浸出液,一面从外侧冰冷却,一面强烈搅拌3分钟,然后添加0.3g吸附剂,在搅拌下每隔一定时间采集10ml液层,向其中添加0.1ml聚硅氧烷,除去生成的气泡,加水至50ml后,充分搅拌、过滤。将最初的5ml滤液倒掉,其余作为试验溶液。按“目て见る食品卫生检查法”、春田三佐夫等编集、中央法规出版、第144-145页中记载的方法对其进行处理,用氧电位测定法测定过氧化氢的浓度。
过氧化氢浓度达到检测极限(0.01ppm)以下的时间,比较例1的吸附剂是5分钟,而实施例3的吸附剂是1分钟。
实施例18
漂白剂(亚硫酸)的吸附、除去试验
亚硫酸及其盐类具有漂白作用,此外还具有防腐和防氧化等效果,因而在多种食品中被用来作为添加剂,对于不同的食品根据二氧化硫的残存量加以限制。
使用实施例1和比较例1中制备的吸附剂,进行葫芦干中的亚硫酸的吸附、除去试验,取0.2g细切的葫芦干,添加0.2g吸附剂和20ml蒸馏水,在搅拌下每隔一定时间采集10ml液层作为试验溶液。按“目て见る食品卫生检查法”、春田三佐夫等编集、中央法规出版、第150-151页中记载的方法对其进行处理,用改进的兰金法测定亚硫酸浓度。
亚硫酸浓度达到检测极限(160ppm)以下的时间,比较例1的吸附剂是10分钟,而实施例1的吸附剂是5分钟。
实施例19
牛肉中的雌性荷尔蒙(雌二醇)的吸附、除去试验
使用实施例3和比较例1中制备的吸附剂,进行牛肉中的雌二醇的吸附、除去试验。将雌二醇与食物混合给公牛喂食,取25g该公牛肉,加水至总量达到50g,向其中添加7g吸附剂,在搅拌下每隔一定时间采集10ml液层,以5000rpm离心分离,用上清液作为试验溶液。按照RIA(Radioimmunoassay)放射免疫测定法(“临床检查法提要”改定第30版金井正光编著金原出版株式会社第818页),使用雌二醇测定试剂盒(雌二醇=抗体试剂盒;日本DPC制造)测定雌二醇浓度。
雌二醇浓度达到测量极限(5pg/ml)以下的时间,比较例1的吸附剂为10分钟,而实施例3的吸附剂是1.5分钟。
实施例20
牛奶中的雌性荷尔蒙(雌二醇)的吸附、除去试验
使用实施例3和比较例1中制备的吸附剂,进行牛奶中的雌二醇的吸附、除去试验。在厚3mm、内径6cm、长100cm的不锈钢制柱中填充吸附剂(5mm×3mm×1.5mm)的粒块,制成吸附、除去用的柱。使含有雌二醇300pg/ml的原奶(脂肪率3.0%)5l以2.8l/分的流速流入该柱中。每隔一定时间采集溶出的处理奶30g,添加150gH2O,搅拌30分钟后,以10000rpm的转速进行离心分离,用上清液作为试样。与实施例19同样对其测定雌二醇浓度,雌二醇浓度达到测量极限(5pg/ml)以下的时间,比较例1的吸附剂为30分钟,而实施例3的吸附剂是3分钟。
实施例21
有机磷(二嗪农)的吸附、除去试验
有机磷制剂是目前使用的杀虫剂,共有35种,作为杀菌剂注册的有3种,作为除草剂注册的有8种,由于低残留性和低毒性而被广泛使用。
使用实施例9和比较例3中制备的吸附剂,进行苹果中的二嗪农吸附、除去试验。将20g薄的苹果片放入100ml丙酮中,用高速均化器混合5分钟。添加1g吸附剂,在搅拌下每隔一定时间采集10ml液层,用桐山制漏斗(过滤助剂5mm)过滤,再用100ml30%含水丙酮同样萃取过滤,用滤液作为试验溶液。按“目て见る食品卫生检查法”、春田三佐夫等编集、中央法规出版、第94-95页中记载的方法对其进行处理,用气相色谱法测定二嗪农的浓度。
二嗪农的浓度达到测量极限(10ppb)以下的时间,比较例3的吸附剂为5分钟,而实施例9的吸附剂是3分钟。
实施例22
有机氯制剂(百菌清(TPN))的吸附、除去试验
有机氯制剂因毒性和残留性等问题现在已基本上禁止使用,只有百菌清(TPN)、PCNB、邻苯二甲酰亚胺系、乙酯杀螨醇类等目前仍作为杀菌剂、杀螨剂使用。
使用实施例10和比较例3中制备的吸附剂,进行黄瓜中的百菌清吸附、除去试验。将20g薄的黄瓜片放入100ml丙酮中,用高速均化器混合5分钟。添加1g吸附剂,在搅拌下每隔一定时间采集10ml液层,用该提取液作为试验溶液。按“目て见る食品卫生检查法”、春田三佐夫等编集、中央法规出版、第96-99页中记载的方法对其进行处理,用气相色谱法测定百菌清的浓度。
百菌清的浓度达到测量极限(0.001ppm)以下的时间,比较例3的吸附剂为10分钟,而实施例10的吸附剂是3分钟。
实施例23
氨基甲酸酯制剂的吸附、除去试验
有氨基甲酸酯制剂作为杀虫剂注册的有11种,作为除草剂注册的有8种,由于其具有低残留性和低毒性,因而与有机磷制剂一起广泛地用来作为杀虫剂。
使用实施例3和比较例1中制备的吸附剂,进行西红柿中的氨基甲酸酯制剂的吸附、除去试验。将20g薄的西红柿片加到100ml丙酮中,用高速均化器混合5分钟。然后添加1g吸附剂,在搅拌下每隔一定时间采集10ml液层,用该提取液作为试验溶液。按“目て见る食品卫生检查法”、春田三佐夫等编集、中央法规出版、第102-103页中记载的方法对其进行处理,用气相色谱法测定氨基甲酸酯制剂的浓度。
氨基甲酸酯制剂的浓度达到测量极限(0.001ppm)以下的时间,比较例1的吸附剂为10分钟,而实施例3的吸附剂是1分钟。
实施例24
自然毒素(茄碱)的吸附、除去试验
茄碱是马铃薯的新芽部分中存在的生物碱糖甙。对兔子经口给药时,LD50为0.45g/kg,对于人来说,0.2-0.4g即可引起中毒。
使用实施例9和比较例3中制备的吸附剂,进行马铃薯中的茄碱的吸附、除去试验。将5g薄的马铃薯片放入30ml甲醇中,经过5分钟高速均化后,添加0.5g吸附剂,在搅拌下每隔一定时间采集10ml液层,用该提取液作为试验溶液。按“目て见る食品卫生检查法”、春田三佐夫等编集、中央法规出版、第82-83页中记载的方法对其进行处理,用液相色谱法测定茄碱浓度。
茄碱浓度达到测量极限(0.001ppm)以下的时间,比较例3的吸附剂为5分钟,而实施例9的吸附剂是1分钟。
实施例25
组胺的吸附、除去试验
容易引起过敏反应状食物中毒的鲐鱼、竹荚鱼、秋刀鱼等赤身鱼类,其肌肉中的游离组胺含量较高。这些鱼肉如果被组氨酸脱羧酶活性强、组胺酶活性弱的细菌污染,组胺就会蓄积起来。
使用实施例1和比较例1中制备的吸附剂,进行鲐鱼中的组胺吸附、除去试验。在10g鲐鱼的肌肉中添加15ml水,均化5分钟,再添加1g吸附剂,在搅拌下每隔一定时间采集10ml液层,作为试验溶液。按“目て见る食品卫生检查法”、春田三佐夫等编集、中央法规出版、第134-135页中记载的方法对其进行处理,用液相色谱法测定组胺浓度。
组胺浓度达到测量极限(2.5mg/100g)以下的时间,比较例1的吸附剂为10分钟,而实施例1的吸附剂是7分钟。
实施例26
镉的吸附、除去试验
镉在自然界中分布很广,被大量地用于工业生产中,随之而带来环境污染以及通过食品而引起人体内的镉污染等问题。经口大量摄入镉时,会产生急性肠胃病,微量摄入时引起慢性中毒,产生肾病。日本人每天的镉摄入量大约是30-60μg,据推测,其中的30-40%来源于大米。
使用实施例4和比较例1中制备的吸附剂,进行糙米中的镉的吸附、除去试验。取10g细粉糙米和3g吸附剂放入反应器中,添加40ml蒸馏水,再添加硫酸,然后缓慢加热。待分解液变成浅黄色透明状后将其冷却,再添加蒸馏水使总量达到100ml,用来作为试验溶液。按“目て见る食品卫生检查法”、春田三佐夫等编集、中央法规出版、第126-127页中记载的方法对其进行处理,用原子吸光光度法测定镉的浓度。
镉的浓度达到测量极限(0.02ppm)以下的时间,比较例1的吸附剂为10分钟,而实施例4的吸附剂是3分钟。
实施例27
二甘醇(DEG)的吸附、除去试验
二甘醇(DEG)被用来作为汽车用防冻液、制动油配合剂、玻璃纸柔软剂、橡胶·油脂等的溶剂,对人而言,经口给药时其毒性为LD50 1000mg/kg。昭和60年规定,不允许使用二甘醇作为食品添加剂,但国外为了增加葡萄酒的味道和甜度而将其混入葡萄酒中,我国也进口了这样的葡萄酒。
使用实施例4和比较例1中制备的吸附剂,进行二甘醇的吸附、除去试验。将二甘醇溶解在甲醇中,使其浓度达到100μg/ml,制成100g溶液。采集40g该溶液,添加3g吸附剂,在搅拌下每隔一定时间采集10ml液层,在45℃下浓缩该提取液,然后加水至10ml,用来作为试验溶液。按“目て见る食品卫生检查法”、春田三佐夫等编集、中央法规出版、第114-115页中记载的方法对其进行处理,用气相色谱法测定二甘醇浓度。
二甘醇浓度达到测量极限(10ppm)以下的时间,比较例1的吸附剂为10分钟,而实施例4的吸附剂是3分钟。
实施例28
防止宿醉(乙醛的吸附、除去)试验
使用实施例3和比较例1中制备的吸附剂,进行防止宿醉试验。由20名成年男性进行试验,在饮酒之前,让其中10人分别食用10g实施例3的吸附剂,其它10人分别食用比较例1的吸附剂,2小时内平均每人摄入500ml的酒精饮料(日本酒、酒精含量16%)。
饮酒12小时后观察每个人的身体情况,在饮酒前摄入比较例1的吸附剂的10人中,恶心或不舒服的人数是0人,反胃的人数是6人,而饮酒前摄入实施例3的吸附剂的10人中,恶心或不舒服的人数是0人,反胃的人数是0人。
实施例29
防止油脂劣化(氢过氧化物的吸附、除去)的试验
使用实施例6和比较例1中制备的吸附剂,进行防止油脂劣化的试验,将500ml芝麻加热至145-150℃,油炸50g鲤鱼10分钟。使油温冷却至28±1℃,再次加热至145-150℃。使用该油反复进行同样操作,油炸鲤鱼10次。在不锈钢制的筐中放入10g吸附剂,盖上盖子,放入用过的油中,对于恶臭、颜色、起泡性、粘度、油雾和油烟(230-240℃)各评价项目与未使用过的油进行比较,评价油的劣化情况。
与未使用过的油相比,回复到一点也没有发生劣化状态的时间,比较例1的吸附剂是30分钟,而实施例6的吸附剂是10分钟。
实施例30
陈米的脱臭(羰基化合物的吸附、除去)试验
用陈米做的米饭,在高温、多湿的环境下存放时脂肪酸分解,生成正茂醛、正己醛等羰基化合物,产生陈米臭味。
与实施例3和比较例1同样操作,制成球状吸附剂(直径约2cm),使用该吸附剂进行陈米脱臭试验。将540g陈米水洗后放入电饭煲中,再放入吸附剂,加入浸渍水,做成米饭。
陈米臭味完全被除去所需要的吸附剂个数,比较例1的吸附剂是3个,而实施例3的吸附剂是1个。
实施例31
大肠杆菌别洛毒素的吸附、除去试验
使用实施例4中制备的吸附剂,进行病原性大肠杆菌○157株产生的毒素(别洛毒素1型·2型)的吸附、除去试验。使用的试剂、培养基和大肠杆菌如下:
·试剂
大肠杆菌别洛毒素检测用试剂盒(电卡(デンカ)生研株式会社制造)
·CA-YE培养基(カザシノ酸)
酪蛋白氨基酸 20g
酵母提取物 6g
NaCl 2.5g
K2HPO4 8.71g
盐类溶液 1ml
蒸馏水 1000ml
pH8.5(使用1N NaOH)
*盐类溶液的组成
MgSO4 5%
MnCl2 0.5%
FeCl3 0.5%
将上述试剂溶解在0.001N H2SO4中。
·LB培养基
细菌(バクト)胰胨 10g
酵母提取物 5g
NaCl 5g
蒸馏水 100ml
pH7.2(使用1N NaOH)
·大肠杆菌
TT-11(国立小儿医疗中心提供的菌种)
在每个经过灭菌的试管中分别放入10mlCA-YE培养基,用铂丝接种被试验的细菌,在37℃下激烈摇瓶培养(120次/分)18小时。在4℃下、以3500rpm的转速离心分离该培养液20分钟,然后用阿库罗底斯科(Acrodisc)0.45μm过滤灭菌。将滤液放入试管中,每个试管内2ml,分别加入一定量的吸附剂,混合10分钟后在4℃下静置24小时。在4℃下、以3000rpm的转速将该混合液离心20分钟,然后用阿库罗底斯科0.45μm过滤,得到试样。
对每一个试验样品,在微板(U型)3系列上使用滴管在8个小井中分别滴入25μl稀释液。作为对照别洛毒素用,在2系列上使用滴管,在8个小井中分别滴入25μl稀释液。除了最后的小井外,将试验样品依次以2次幂稀释(最后的小井作为胶乳对照物)。同样,对照别洛毒素1型和2型每1系列分别依次以2次幂稀释。在试验样品的稀释系列的第1列、第2列和第3列中分别滴入25μl致敏胶乳VT1、致敏胶乳VT2和对照胶乳。在对照别洛毒素1型的稀释系列和对照别洛毒素2型中分别滴入25μl致敏胶乳VT1和致敏胶乳VT2。充分摇动微板,使样品与胶乳试剂混合。为了防止反应液蒸发,用盖子盖住微板,在室温下静置20小时以上,然后在明亮、平坦的地方铺上黑纸,将微板放在黑纸上,用肉眼从上方观察各小井的胶乳沉降像。表2和表3中分别示出别洛毒素1型和2型的吸附、除去结果。
表2
小井胶乳沉降像肉眼观察
(VT1) 1:(CA-YE培养基) 2 4 8 16 32 64 128 对照 |
吸附剂(0.2g) - - - - - - - -吸附剂(0.1g) - - - - - - - -TT-11(对照) + + + + + ± - - |
表3
小井胶乳沉降像肉眼观察
(VT1) 1:(CA-YE培养基) 2 4 8 16 32 64 128 256 512 对照 |
吸附剂(0.2g) - - - - - - - - - -吸附剂(0.1g) - - - - - - - - -TT-11(对照) + + + + + + + ± - - |
实施例32
防止因抗生素(红霉素)经口给药引起腹泻的试验
使用一组6只体重3.0-3.2kg的免子,将红霉素掺入食物中经口给药,每6小时一次40mg,一共给药12次。每次将红霉素给药前30分钟,将实施例6制造的吸附剂经口给药,每次3g。
出现腹泻症状的数量,非吸附剂给药组是100%,而吸附剂给药组是0%。此时,无论是吸附剂给药组还是非吸附剂给药组,经口给药1.5小时后测定的血中红霉素浓度都是0.12-0.13μg/ml。
实施例33
防止因抗生素(红霉素)经口给药引起腹泻的试验
让男性(60岁、体重78kg)每6小时吃一次饭,饭后5分钟经口给药300mg红霉素,第18次给药时出现腹泻症状,终止给药。
对同一另性,在腹泻症状消失后1个月内使之正常饮食,然后与上述同样将红霉素经口给药,同时在饭前30分钟经口给药实施例2制造的吸附剂10g,第20次给药时仍未出现腹泻症状。
实施例34
含有吸附剂的琼脂的制造
将比较例1中制造的吸附剂100g放入1升沸腾的鲣鱼汤中沸煮3分钟。将10g该试料放入30cm3的铝制容器中,再添加15g琼脂溶液,充分搅拌。将其脱气后,用铝片盖住并热封,放入高压釜内在121℃下灭菌20分钟,得到含有吸附剂的琼脂。
实施例35
含有吸附剂的琼脂的制造
除了使用比较例3中制造的吸附剂之外,与实施例31同样操作,得到含有吸附剂的琼脂。
实施例36
含有吸附剂的琼脂的制造
在约50cm3的铝制容器中放入10g与实施例31同样制造的含有吸附剂的琼脂,向其中添加20g琼脂溶液。在其上面叠放用中国风味色拉油调味的海带,在其上面进一步添加10g琼脂溶液。将其脱气后,用铝片盖住并热封,放入高压釜内在121℃下灭菌20分钟,得到含有吸附剂的琼脂。
实施例37
含有吸附剂的藻酸钙凝胶的制造
使用实施例3中制造的吸附剂并用同样数量的藻酸钙凝胶代替琼脂溶液,除此之外与实施例31同样操作,得到含有吸附剂的藻酸钙凝胶。
实施例38
含有吸附剂的藻酸钙凝胶的制造
除了使用实施例9中制造的吸附剂之外,与实施例34同样操作,得到含有吸附剂的藻酸钙凝胶。
实施例39
含有吸附剂的藻酸钙凝胶的制造
使用实施例4中制造的吸附剂并用同样数量的藻酸钙凝胶代替琼脂溶液,除此之外与实施例33同样操作,得到含有吸附剂的藻酸钙凝胶。
产业上的应用
本发明的吸附剂是用凝胶状物质被覆吸附体后经冷冻处理制成,是由吸附体均匀分散于凝胶状物质中形成的分散系构成,不会降低吸附体原有的吸附能力,可以以极高的效率吸附、除去有害物质。
另外,本发明的吸附剂是用含的防冻害物质的凝胶状物质被覆吸附体、然后除去该防冻害物质而制成的,可以发挥与上述同样的效果。
此外,本发明的吸附剂在使用粉末活性炭等微粒子作为吸附体时,是同吸附体均匀分散于凝胶状物质中的分散系构成,由于活性炭高度分散,与单独使用活性炭相比,吸附剂整体的有效吸附面积增加,吸附能力增大,可以以极高的效率吸附、除去有害物质。
再有,本发明的吸附剂是用凝胶状物质被覆吸附体,因此可以对消化系统内直接给药,可以在消化系统内简便地吸附、除去混入食品中而被摄入消化器官内的有害物质。而且,对消化系统内直接给药也不会产生便秘,吸附、除去消化系统内的有害物质后的吸附剂可以极迅速而容易地排出到消化系统外。
另外,本发明的吸附剂还可以吸附、除去与食品等混合接触而包含在食品中的有害物质。与单独使用吸附体的场合相比,可以在短时间内简便地将吸附、除去有害物质后的吸附剂从食品中分离出去。即使由于失误未将吸附剂分离,混入食品中被摄入消化系统内,也可以迅速排出到消化系统外,因此十分安全。
如上所述,本发明的吸附剂除了直接对消化系统内给药外,还可以混合到加工食品中使用。本发明的吸附剂,即使混入到加工食品中食用时也没有异物感,食感很好,而且不会将食品污染成黑色。
本发明的吸附剂具有上述优异的效果,特别适合用于吸附、除去在食品等中附着或含有的或者存在于消化系统内的食品添加剂、饮料添加剂、农药、引起食物中毒的物质、过敏原、重金属或毒性强的有机化合物、将抗菌素经口给药时的抗菌素本身或抗菌素作用于肠内细菌而产生的有害物质、消化系统内存在的过剩营养素、酒类中含有的低聚物、添加剂等、摄入酒精后在消化系统内产生的酒精中间代谢物、油脂中的不饱和脂肪酸的氢过氧化物等有害物质以及鱼腥味等臭气成分。
Claims (23)
1.吸附剂,其特征是,该吸附剂是用凝胶状物质被覆吸附体后进行冷冻处理而形成的。
2.吸附剂,其特征是,该吸附剂是用含有防冻害物质的凝胶状物质被覆吸附体、然后将上述防冻害物质的一部分或全部除去而形成的。
3.权利要求2所述的吸附剂,其特征是,所述的防冻害物质是丙三醇。
4.权利要求1-3所述的吸附剂,其特征是,所述的吸附体是具有吸附能的碳素材料。
5.权利要求4所述的吸附剂,其特征是,所述的具有吸附能的碳素材料是活性炭或木炭。
6.权利要求1-5所述的吸附剂,其特征是,所述的凝胶状物质是高分子聚羧酸的二价金属盐。
7.权利要求6所述的吸附剂,其特征是,所述的高分子聚羧酸的二价金属盐是藻酸钙。
8.权利要求1-5所述的吸附剂,其特征是,所述的凝胶状物质是豆腐、冻胶、蒟蒻、琼脂、紫苏、凉粉或脱乙酰壳多糖草酸盐凝胶。
9.将权利要求1-8所述的吸附剂干燥而得到的吸附剂。
10.吸附剂,其特征是,该吸附剂含有用第一凝胶状物质被覆吸附体而形成的吸附剂部分和第二凝胶状物质部分。
11.权利要求10所述的吸附剂,其特征是,该吸附剂是对所述的吸附剂部分和第二凝胶状物质部分中任一方进行调味而构成的。
12.权利要求10或11所述的吸附剂,其特征是,所述的吸附剂部分含有权利要求1-9所述的吸附剂。
13.有害物质吸附、去除剂,含有权利要求1-12所述的吸附剂。
14.权利要求13所述的有害物质吸附、去除剂,其特征是,所述的有害物质是食品或饲料中附着或含有的或者被摄入消化系统内的食品添加剂、饲料添加剂、农药、引起食物中毒的物质、过敏原、重金属或毒性强的有机化合物。
15.权利要求14所述的有害物质吸附、去除剂,其特征是,所述的饲料添加剂是抗生素、合成抗生素或激素制剂。
16.权利要求14所述的有害物质吸附、去除剂,其特征是,所述的引起食物中毒的物质是外毒素、自然毒素或有害化学物质。
17.权利要求13所述的有害物质吸附、去除剂,其特征是,所述的有害物质是将抗生素经口给药时的抗生素本身或抗生素作用于肠内细菌而产生的有害物质。
18.摄入消化系统内的过剩营养素的吸附、去除剂,含有权利要求1-12所述的吸附剂。
19.摄入酒精后在消化系统内产生的酒精中间代谢物的吸附、除去剂,含有权利要求1-12所述的吸附剂、。
20.油脂中的不饱和脂肪酸的氢过氧化物的吸附、除去剂,含有权利要求1-12所述的吸附剂。
21.防臭剂,含有权利要求1-12所述吸附剂。
22.加工食品或饲料,掺入0.01-60%(重量)的权利要求1-12所述吸附剂。
23.权利要求22所述的加工食品,其特征是,所述食品是乳制品、水产品熬炼凝固制品、鱼类和贝类加工食品、肉类加工食品、豆制品、蔬菜加工食品、薯类加工品、粮食加工品、甜食类、油脂类或糕点类。
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- 1996-07-22 AU AU64716/96A patent/AU6471696A/en not_active Withdrawn
- 1996-12-27 KR KR10-1999-7000513A patent/KR100442474B1/ko not_active IP Right Cessation
- 1996-12-27 AU AU12104/97A patent/AU1210497A/en not_active Abandoned
- 1996-12-27 CN CNB961804432A patent/CN100345625C/zh not_active Expired - Fee Related
- 1996-12-27 AT AT96943349T patent/ATE372826T1/de not_active IP Right Cessation
- 1996-12-27 JP JP50677598A patent/JP3914265B2/ja not_active Expired - Lifetime
- 1996-12-27 DE DE69637247T patent/DE69637247T2/de not_active Expired - Lifetime
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- 1996-12-27 WO PCT/JP1996/003891 patent/WO1998003259A1/ja active IP Right Grant
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Also Published As
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ATE372826T1 (de) | 2007-09-15 |
AU1210497A (en) | 1998-02-10 |
EP0914862A4 (en) | 2000-04-19 |
US6299867B1 (en) | 2001-10-09 |
WO1998003259A1 (fr) | 1998-01-29 |
KR20000029491A (ko) | 2000-05-25 |
EP0914862A1 (en) | 1999-05-12 |
EP0914862B1 (en) | 2007-09-12 |
WO1998003260A1 (fr) | 1998-01-29 |
US20020025911A1 (en) | 2002-02-28 |
AU6471696A (en) | 1998-02-10 |
JP3914265B2 (ja) | 2007-05-16 |
KR100442474B1 (ko) | 2004-07-30 |
DE69637247D1 (de) | 2007-10-25 |
CA2261310A1 (en) | 1998-01-29 |
CA2261310C (en) | 2007-04-17 |
DE69637247T2 (de) | 2008-06-19 |
CN100345625C (zh) | 2007-10-31 |
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