CN1787748A - 铁和钙强化的谷粒 - Google Patents
铁和钙强化的谷粒 Download PDFInfo
- Publication number
- CN1787748A CN1787748A CNA200480012832XA CN200480012832A CN1787748A CN 1787748 A CN1787748 A CN 1787748A CN A200480012832X A CNA200480012832X A CN A200480012832XA CN 200480012832 A CN200480012832 A CN 200480012832A CN 1787748 A CN1787748 A CN 1787748A
- Authority
- CN
- China
- Prior art keywords
- calcium
- iron
- grain
- ferrous
- malate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 104
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000011575 calcium Substances 0.000 title claims abstract description 80
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 80
- 239000004464 cereal grain Substances 0.000 title abstract 4
- 239000000203 mixture Substances 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 47
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 86
- 235000013339 cereals Nutrition 0.000 claims description 80
- 235000007164 Oryza sativa Nutrition 0.000 claims description 52
- 235000009566 rice Nutrition 0.000 claims description 52
- 229940092124 calcium citrate malate Drugs 0.000 claims description 47
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 41
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 37
- 150000001413 amino acids Chemical class 0.000 claims description 28
- 235000015165 citric acid Nutrition 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 27
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 24
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 21
- 238000005728 strengthening Methods 0.000 claims description 21
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- 159000000007 calcium salts Chemical group 0.000 claims description 13
- 230000002787 reinforcement Effects 0.000 claims description 13
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 10
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 7
- 239000004471 Glycine Substances 0.000 claims description 4
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 claims description 4
- 239000001354 calcium citrate Substances 0.000 claims description 4
- OLOZVPHKXALCRI-UHFFFAOYSA-L calcium malate Chemical compound [Ca+2].[O-]C(=O)C(O)CC([O-])=O OLOZVPHKXALCRI-UHFFFAOYSA-L 0.000 claims description 4
- 239000001362 calcium malate Substances 0.000 claims description 4
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 235000013337 tricalcium citrate Nutrition 0.000 claims description 4
- 241000209094 Oryza Species 0.000 claims 6
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- 235000001465 calcium Nutrition 0.000 description 63
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- MPCMQXRREZMSPJ-UHFFFAOYSA-L calcium;2-hydroxybutanedioate;2-hydroxypropane-1,2,3-tricarboxylic acid;pentahydrate Chemical compound O.O.O.O.O.[Ca+2].[O-]C(=O)C(O)CC([O-])=O.OC(=O)CC(O)(C(O)=O)CC(O)=O MPCMQXRREZMSPJ-UHFFFAOYSA-L 0.000 description 43
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- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 21
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
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- 125000003118 aryl group Chemical group 0.000 description 4
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
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- 244000215068 Acacia senegal Species 0.000 description 3
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- 229920000084 Gum arabic Polymers 0.000 description 3
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- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
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Abstract
本文描述了铁和钙强化的谷粒。还描述了制备铁和钙强化谷粒的方法,该方法包括提供谷粒并将所述谷粒与包含铁源和钙源的组合物混合。
Description
技术领域
本发明涉及用高生物利用率的铁源和高度易溶且高生物利用率的钙源来强化谷粒。更具体地讲,本发明涉及用铁源和柠檬酸和苹果酸的钙盐强化的谷粒。
发明背景
在许多国家,平均饮食中并不包含足量的铁,铁缺乏已有充分记载。尽管在美国缺铁只是少数营养缺乏中的一种,但它在大多数发展中国家较为普遍。铁是血红蛋白分子的一种基本组分:没有铁骨髓就不能制造血色素。红细胞数目下降,那些并不参与进循环的红细胞变得小于正常形态(小红细胞),并且由于缺乏血色素,它们呈苍白色(低血色素)。贫血有许多症状。但个体患者不会体验到所有的症状,并且如果贫血比较轻微的话,这些症状可能不会引起人们的注意。其中的一些症状是:肤色苍白、疲劳感、易怒、晕眩、体虚、呼吸短促、舌痛、指甲易脆、食欲降低(尤其是儿童)、前额疼痛。缺铁性贫血严重损害婴儿和儿童的心智发展。
一般成年男性体内的平均铁含量是4mg,而一般成年女性的平均铁含量是2.5gm。每天的标准北美饮食中含有约15mg至20mg的铁。大多数铁存在于肉类和绿色蔬菜中;每天人体吸收约1.0mg的铁而同时在粪便和汗液中损失了大约等量的铁。结果造成成年人的平均铁摄入量处于一种脆弱的平衡中,但由于铁的吸收略多于其损失且铁的存储逐渐积累,该脆弱平衡不会有太大后果。假如因为某些原因铁的损失率增加,人体储存的铁会被耗尽而出现一种绝对的铁缺乏状态。这种缺乏需要大剂量的铁进行补充以再次供给体内存储,同时应对补充情况充分监视以防止铁的过量摄入。在发展中国家,大约一半的妇女和儿童患有缺铁性贫血。在美国,7%的1至2岁的幼儿和9%至16%的青少年以及年龄在12至49岁的成年妇女缺铁。据估计铁缺乏在非西班牙裔黑人和墨西哥裔美国妇女人群的发生率(19%至22%)两倍于在非西班牙裔白人妇女人群中的发生率(10%)(参见WWW.cdc.gov/mmwr/preview/mmwrhtml/mm5140a1。)铁可以添加到食品和饮料中以补充饮食来源。不溶性的铁化合物需要以悬浮液的形式加入到产品中。
钙是一生所需的基本营养物质,以用于多种生理功能。据报道,人体百分之九十九的钙存在于牙齿和骨骼中。因此,钙对骨骼和牙齿的形成和维持都是必需的。剩余百分之一的钙位于身体各处的血液和软组织中,部分以离子的形式存在。离子形式存在的钙对血液凝结,心脏、神经和肌肉的正常机能以及膜的渗透性来说都非常重要。科学研究证实钙有防止高血压和结肠癌的作用。如果从饮食中得不到足够的钙,骨钙会转移以满足软组织的代谢需要。因而,当饮食中得不到足够的钙,骨骼代谢会受到损害。在这种情况下,发育过程中的骨骼积累较少,成人骨骼中的钙会发生流失并伴随骨骼强度的降低。
世界许多地区的钙摄入量远低于推荐摄入量。虽然营养学家强调饮食中的钙达到日常营养需求的重要性,但通过规律的饮食很难获得所需数量的钙。钙还可以通过多种饮食来源获得,但是从食品和饮料中补钙得一个主要问题是钙的溶解度。不溶性的钙盐需要以悬浮液的形式加入到产品中,但是这经常会导致产品味道和结构的不利变化以及悬浮液的沉降。此外,不溶性的钙源与可溶形式相比通常吸收较少。当服用钙含量较高时会赋予口腔以刺痛或烧灼感,并依钙源的不同在口腔中留下令人难受的余味。
铁和钙的缺乏可以通过增加天然包含这些矿物质的食物的摄入或者服用补充物来克服。关于前一种方法,增加高铁高钙食物的摄入有明显的困难,尤其是在发展中国家。关于后一种方法,在许多人们遭受这些缺乏的国家,其经济状况使得提供矿物质作为补充物这一选择非常昂贵,并存在明显的销售物流问题。此外,是否能够做到,即要求人们每日摄入矿物质补充物是一个严重的问题。因此,以具有高生物利用率并同时具有不令人讨厌的味道和外观的形式,并且以被高比例的危险人群消费的形式来递送铁和钙是需要的。
谷粒已经被许多不同的维生素和包括铁和钙在内的矿物质强化了。例如,2000年12月12日公布的Christiansen等人的美国专利6,159,530描述了金属氨基酸螫合物强化的加工谷物,金属可选自包括铁和钙在内的多个部分。2001年3月27日公布的Christensen等人的美国专利6,207,204描述了金属氨基酸螫合物强化的谷粒,其中金属仍可选自例如铁或钙。然而,上述文献中所述的钙形式的可溶性低于本文所述的钙形式。在这点上,申请人已令人惊讶地发现本文所述的钙形式显示具有增加的溶解度,从而能获得更高水平的谷粒强化效果。
根据上文所述,提供被铁和钙强化的改良谷粒是有用的。更具体地讲,提供这样的强化谷粒是有用的,其中掺入铁和钙以提供增加的生物利用率,从而使用较少量的这些物质即可强化谷粒,因此减少不需要的副作用和不适口性。
发明概述
一方面,本发明涉及用铁和钙强化的谷粒,其中钙为柠檬酸和苹果酸的钙盐形式。
另一方面,本发明涉及制造强化谷粒的方法,该方法包括提供谷粒,并混合所述谷粒与组合物,所述组合物包括铁源以及柠檬酸和苹果酸的钙盐混合物。
发明详述
I.
定义:
除非内容中有明确的另外规定,单数形式“一个”和“所述”包括涉及的复数对象。
术语“可生物利用的”是指矿物源处于一种能够经主动运输完整地跨肠壁传送到血液循环中去的形式。至于食物中的铁,其生物利用率,或更具体地讲相对生物利用率(RBV),被测量为在标准饮食或测试食物中该铁增加的吸收。一种测定哺乳动物生物利用率地方法是大鼠耗竭/充满法。Forbes,A.L.等人,1989,Am.J.Clin.Nutr.49:225-238。该方法可对铁化合物的相对生物利用率进行精确地比较。使用这种方法,刚断奶的大鼠被喂以不含铁的食物,直到它们变得贫血。在基线血色素测量之后,大鼠被喂以包含一种待测试铁化合物的食物。对照组喂以包含硫酸亚铁的标准饮食。两个星期后,测量最后的血色素含量并与基线测量做比较。使用这种方法,大鼠体内的铁平均相对生物利用率得到测量。硫酸亚铁作为参考物,其RBV为100%,其它铁化合物与它做比较。生物利用率是超出化合物溶解度的结果。环境因素,如pH值或铁的浓度、粒径以及抑制剂的存在也会影响生物利用率。已显示二甘氨酸螯合亚铁(氨基酸螯合铁)有比硫酸亚铁更大的RBV。婴儿中二甘氨酸亚铁的RBV值为90.9%,相比之下硫酸亚铁的RBV值为26.7%,(Pineda,O.和Ashmead H.D.,2001,Nutr.17381至17384页)成年大学生的二甘氨酸亚铁吸收率是硫酸亚铁的4.7倍。(Bovell-Benjamin,A.等人1999,Am.J.Clin.Nutr.71卷:1563至1569页)。
术语“柠檬酸苹果酸钙”(CCM)是指柠檬酸和苹果酸的钙盐组合物。柠檬酸苹果酸钙可由柠檬酸钙和苹果酸钙的混合物,包含柠檬酸和苹果酸配体的钙络合物,钙盐与柠檬酸和苹果酸的混合物以及它们的任何组合组成。对于本公开内容而言,以及如下文更详细描述的,CCM可根据“当量比”进行描述,也可根据柠檬酸根与苹果酸根的摩尔比。当量比是柠檬酸根和苹果酸根的当量(3X摩尔柠檬酸根+2X摩尔苹果酸根)除以钙的当量(2X摩尔钙)。柠檬酸根与苹果酸根的摩尔比只是这两种组分的摩尔比。对柠檬酸根与苹果酸根的摩尔比和当量比,柠檬酸根和苹果酸根包括其酸形式(柠檬酸和苹果酸)与其阴离子盐形式(柠檬酸盐和苹果酸盐)。此外,用以计算当量比和柠檬酸根与苹果酸根的摩尔比的柠檬酸根和苹果酸根的量也包括通过除CCM外的来源引入的柠檬酸或苹果酸。
II.
强化谷粒
本发明的强化谷粒可用包含所需矿物质的液体混合物(例如,溶液、浆液、悬浮液)涂敷谷粒并在包装前干燥涂敷谷粒来制备。强化过程可通过喷洒或滴注矿物质溶液于有一层或连续多层大米的旋转床上进行。柠檬酸苹果酸钙和铁源的溶解性度使得矿物质均匀施用于大米,覆盖所有的谷粒,同时保持预混物(强化大米)的正常外观。煮预混强化大米,不管是否与未涂矿物质的大米混合,都会导致整釜的大米被钙和铁均匀强化。据信煮的过程中矿物质更易被谷粒吸附。
A.
铁组分
通常,高生物利用率的铁源可优选用于本文。一种优选的高生物利用率的铁源是二甘氨酸螯合亚铁,因为其RBV大于硫酸亚铁。游离水溶性的含铁化合物或可溶于稀酸的那些与不溶性的铁源相比有更好的生物利用率,因而也可优选用于本文。取决于环境条件,水不溶性的含铁化合物或很难溶于稀酸的那些通常具有低生物利用率至中等生物利用率,因而不太优选,尽管仍可潜在用于本文。一方面,用于本文的优选含铁化合物具有至少约50%的RBV。在该方面,更优选的含铁化合物具有至少约70%,还更优选至少约80%的RBV。一些化合物,如维生素C或其它有机酸,已知为铁吸收增强剂,可提高铁生物利用率。增强剂内含物可使较低生物利用率的铁源更易被生物所利用。
不管所用的铁源如何,包括的铁含量按强化谷粒的总重量计典型为至少约0.001%。包括的铁含量按强化谷粒的总重量计典型为约0.001%至约0.1%,更典型地为约0.0015%至约0.007%,还更典型地为约0.002%至约0.005%。
优选的铁组分选自铁盐、亚铁盐、氨基酸螯合亚铁、铁-糖-羧酸盐络合物,以及它们的混合物。
至于铁盐,可用于本发明的食品级亚铁盐包括,例如,硫酸亚铁、延胡索酸亚铁、琥珀酸亚铁、葡糖酸亚铁、乳酸亚铁、酒石酸亚铁、柠檬酸亚铁,以及这些亚铁盐的混合物。如所提及的,虽然二价铁典型地比三价铁具有更高的生物利用率,但三价铁盐也可提供可生物利用的铁源。可用于本发明的食品级三价铁盐包括,例如,乙二胺四乙酸(EDTA)钠铁、糖酸铁、柠檬酸铁铵、硫酸铁铵、血色素、白蛋白铁、柠檬酸铁胆碱、甘油磷酸铁、柠檬酸铁、焦磷酸铁、硫酸铁、氯化铁,以及这些铁盐的混合物。
可用于本文的优选铁化合物是氨基酸螯合铁。氨基酸螯合铁最优选的实施方案是二甘氨酸亚铁。术语“氨基酸螯合铁”和“氨基酸螯合亚铁”是指存在于铁(亚铁)原子和氨基酸的羧基氧、羰基碳、α-碳和α-氨基氮之间的配位共价键。同样地,螯合物中会形成铁作为闭环成分的杂环。然而,当pH值下降时,羧基氧和铁闭环成分间的共价结合降低,离子化程度增强,但仍以环结构形式存在。因而,对本公开内容而言,氨基酸螯合铁包括由氨基酸和形成环结构的铁构成的任何螯合物或络合物。其实际结构取决于配体对铁的摩尔比。在任何情况下,配体对铁的摩尔比为至少约1∶1,优选至少约2∶1。在某些实施例中,配体对铁的摩尔比可为约3∶1或甚至约4∶1。
尤其适于作为高生物利用率的氨基酸螯合铁用于本发明的氨基酸螯合亚铁是配体对金属的比率为至少约2∶1的那些。例如,配体与金属的摩尔比为2的合适的亚铁氨基酸螯合物是具有下式的那些:
Fe(L)2
其中L是α-氨基酸、二肽、三肽或四肽反应配体。因此,L可为选自下列天然存在的α-氨基酸的任何反应配体:丙氨酸、精氨酸、天冬酰胺、天冬氨酸、半胱氨酸、胱氨酸、谷氨酰胺、谷氨酸、甘氨酸、组氨酸、羟脯氨酸、异亮氨酸、亮氨酸、赖氨酸、甲硫氨酸、鸟氨酸、苯基丙氨酸、脯氨酸、丝氨酸、苏氨酸、色氨酸、酪氨酸和缬氨酸;或由这些α-氨基酸的任何组合形成的二肽、三肽或四肽。参见公布于1976年7月13日的美国专利3,969,540(Jensen)和公布于1977年4月26日的美国专利4,020,158(Ashmead);公布于1989年9月5日的美国专利4,863,898(Ashmead等人);公布于1989年5月16日的美国专利4,830,716(Ashmead);和公布于1986年7月8日的美国专利4,599,152(Ashmead),所有这些均引入以供参考。尤其优选的氨基酸螯合亚铁是反应配体为甘氨酸、赖氨酸和亮氨酸的那些。最优选的为由Albion Laboratories(Clearfield,Utah)以商品名FERROCHEL出售的氨基酸螯合亚铁,其中反应配体是甘氨酸。
氨基酸螯合物的结构、化学性质和生物利用率在文献中已有充分记载录,例如:Ashmead等人的Chelated Mineral Nutrition,(1982),Chas.C.Thomas Publishers,Springfield,Ill.;Ashmead等人的Intestinal Absorption of Metal Ions,(1985),Chas.C.ThomasPublishers,Springfield,Ill.;Ashmead等人的Foliar Feedingof Plants with Amino Acid Chelates,(1986),Noyes Publications,Park Ridge,N.J.;Ashmead,S.(2001)Arch.Lat.Amer.Nutr.,Supp.51:7-12;Ashmead,H.D.(2001)Arch.Lat.Amer.Nutr.,Supp.51:12-21;美国专利4,020,158、4,167,564、4,216,143、4,216,144、4,599,152、4,774,089、4,830,716、4,863,898及其它。
氨基酸螯合物在矿物质营养学领域的一个优点可归因于这些螯合物在肠和粘膜细胞中易于通过主动运输吸收的事实,好象它们为二肽。换句话讲,矿物质利用氨基酸作为载体分子,作为一个单独单元与氨基酸一起被吸收。因此,能够避免离子彼此竞争活性位点和具体的营养矿物成分被其它成分抑制的问题。对诸如硫酸铁的化合物尤其如此,因其必须相对大量地递送以使身体吸收适当的量,并因此导致可能的恶心、痢疾和其它不适。因为铁对许多生理机能是如此重要的矿物质,并且因为一个典型的人摄入的未强化的食物缺少足够量的铁,强化方法一直是提供人们日常所需最少量铁的最好方法之一。
适用于本文的另一种铁源包括铁-糖-羧酸盐络合物。在这些铁-糖-羧酸盐络合物中,羧酸盐为亚铁(优选的)或三价铁提供抗衡离子。这些铁-糖-羧酸盐络合物的全部合成包括在含水介质中钙-糖部分的形成(例如,通过氢氧化钙与糖反应);在含水介质中铁源(如硫酸亚铁铵)与钙-糖部分反应,以提供铁-糖部分;和用羧酸(“羧酸盐抗衡离子”)中和反应体系,以提供所需的铁-糖-羧酸盐络合物。可用于制备钙-糖部分的糖包含任何可吸收的糖类物质以及它们的混合物,如葡萄糖、蔗糖和果糖、甘露糖、半乳糖、乳糖、麦芽糖等,其中更优选蔗糖和果糖。提供“羧酸盐抗衡离子”的羧酸可为任何可吸收的羧酸,如柠檬酸、苹果酸、酒石酸、乳酸、琥珀酸、丙酸等,以及这些酸的混合物。
这些铁-糖-羧酸盐络合物可通过公布于1988年11月22日的美国专利4,786,510和4,786,518(Nakel等人)中描述的方式制备。这些物质被称作“络合物”,但它们实际上在溶液中作为复杂、高度水化的、被保护的胶体存在;出于简化的目的而使用术语“络合物”。
B.
钙组分
钙的营养补充量按强化谷粒的总重量计通常应包括在约0.03%至约2%的含量内。包括的钙典型含量按强化谷粒的总重量计为约0.08%至约1.5%,更典型为约0.1%至约1%。
申请者已经发现了使用高度溶解的柠檬酸苹果酸钙有利于以理想的钙量强化谷粒,但对所得谷粒的感官特征没有负面影响。与以前的铁和钙强化谷粒相比,这种溶解度结合相对高的钙生物利用率,提供了更理想的钙形式。
如上所讨论的,柠檬酸苹果酸钙可由柠檬酸钙和苹果酸钙的混合物,包含柠檬酸和苹果酸配体的钙络合物,钙盐与柠檬酸和苹果酸的混合物或它们的任何组合组成。
一方面,利用的CCM的柠檬酸根与苹果酸根的摩尔比为约10∶90至约80∶20,和当量比为约0.5至约2。另一方面,利用的CCM的柠檬酸根与苹果酸根的摩尔比为约20∶80至约70∶30,和当量比为约0.6至约1.4。另一方面,利用的CCM的柠檬酸根与苹果酸根的摩尔比为约35∶65至约55∶45,和当量比为约0.8至约1.2。除了柠檬酸根和苹果酸根之外,柠檬酸苹果酸钙还可非必需地包含其它阴离子。此类阴离子包括,例如碳酸根、氢氧根、磷酸根,以及它们的混合物。
一方面,柠檬酸苹果酸钙优选是中性的,完全由柠檬酸和苹果酸阴离子组成。因而,在这个实施方案中,钙的当量(2x摩尔钙)近似等于柠檬酸根(3x摩尔柠檬酸根)加苹果酸根(2x摩尔苹果酸根)的总当量数。优选的柠檬酸苹果酸钙具有的柠檬酸根与苹果酸根的摩尔比为约35∶65至约55∶45,和当量比为约1至约1.2。
钙盐与柠檬酸和苹果酸的混合物可用于就地形成柠檬酸苹果酸钙,所得的液体混合物随后用作强化谷粒的来源。可供选择地,可以使用柠檬酸苹果酸钙盐并添加该物质制备CCM液体混合物,其可以随后用于强化谷粒。例如,柠檬酸苹果酸钙可通过首先将所需摩尔比的柠檬酸和苹果酸溶解在水中来制备。钙源随后加入到溶液中,加入的钙量使钙和柠檬酸、苹果酸的摩尔比达到所需的比率。多种钙源可用于本发明。例如,可使用氯化钙、磷酸钙和硫酸钙,但是它们都不是优选的,因为其中的阴离子可能会形成酸溶液,即分别形成盐酸、硫酸和磷酸,这些酸溶液会对包含柠檬酸苹果酸钙的食品的味道产生不利影响。优选的钙源包括碳酸钙、氧化钙和氢氧化钙。
在氧化钙或氢氧化钙与柠檬酸和苹果酸混合期间可能会形成固体。当使用这些物质时,人们期望一直混合溶液直到所有的钙溶解。柠檬酸苹果酸钙量超出其溶解度时会形成沉淀。
优选的制备方法是制备柠檬酸苹果酸钙的高浓度溶液,其迅速有效地促使亚稳态的柠檬酸苹果酸钙析出溶液。优选的浓度为20%至75%。优选地,浓度为40%至65%。反应温度可以是环境温度(20℃)或更高。反应温度优选在约30℃至约80℃,更优选在约40℃至约60℃的范围内。如果需要,混合物可被过滤和/或用低于100℃的干燥温度干燥。
C.
非必需组分
着色剂,如二氧化钛,可非必需地在适当时候被包括。例如当用二甘氨酸亚铁涂敷白米时,可使用二氧化钛作为增白剂以减少变色。
食用酸及它们的盐可用作络合剂或还原剂,或用以改善强化产品的感观可接受性,或用以添加别的矿物质。合适的还原剂包括抗坏血酸、抗坏血酸棕榈酸酯、亚硫酸氢钠、异抗坏血酸,以及这些还原剂的混合物。合适的络合剂包括:羟基多羧酸,如柠檬酸、酒石酸和苹果酸;磷酸、聚磷酸及它们各自的盐,如六偏磷酸钠、三偏磷酸钠和三聚磷酸钠;氨基多羧酸及它们各自的部分盐,如乙二胺四乙酸、乙二胺四乙酸二钠盐和二亚乙基三胺五醋酸;某些短链羧酸,如乳酸、富马酸和乙酸;以及这些络合剂的混合物。优选的络合剂是柠檬酸。(不包括经由柠檬酸苹果酸钙来源递送的柠檬酸。)
谷粒上的涂层还包括食品级抗氧化剂,其用量足以抑制谷粒表面上的物质尤其是类脂的氧化。过度氧化可导致变味或走味。已知的或常规的抗氧化剂包括,但不限于:丁基化羟基苯甲醚(BHA),丁基化羟基甲苯(BHT),叔丁基对苯二酚(TBHQ),迷迭香提取物,以及它们的混合物。
为进一步提高氧化稳定性,产品应该包装在水分不能透过的容器内。此类容器包括例如内衬箔的包装袋、金属罐和塑料或层压封装袋。产品包装内可充以氮气、二氧化碳或其它惰性非氧化气体,以进一步提高产品的氧化稳定性和储藏期限。这些包装方法是本领域所熟知的。
调味剂或芳香剂也可以加入涂层混合物中。谷粒可以用任何天然的或合成的果类或植物类调味剂、芳香化合物或它们的混合物进行调味或增味。合适的天然或人造调味剂或芳香剂包括大米、茉莉、竹子、芭蕉叶或其它相容的调味剂或芳香剂。
D.
强化谷粒的制备
任何核完整的谷粒可用于本发明,包括去胚芽和/或去壳的谷粒。大麦、玉米、小米、燕麦、奎奴亚藜、大米、野稻、黑麦、高梁、黑小麦和小麦是优选的谷物。尤其优选大米。
在本发明中,将包含铁和钙的涂层涂敷于谷粒(或使用液体混合物涂敷谷粒)。铁和钙可以由一种液体混合物添加于谷粒上,也可以作为两种单独的液体混合物。涂层混合物可非必需地包括稳定剂。这种稳定剂优选为亲水的或中性的水胶体,如羟丙基纤维素、羟丙基甲基纤维素、阿拉伯树胶、淀粉或改性淀粉和乙基纤维素,但是也可以包括疏水性或醇溶性聚合物,如紫胶或玉米蛋白。
包含铁和钙源的涂层的施用可通过几种方法完成。例如,假如想要用二甘氨酸亚铁和柠檬酸苹果酸钙强化大米,可通过用包含铁螯合物和钙源、稳定剂载体及非必需着色剂的液体混合物喷洒或浸泡谷粒来制备涂层并涂敷。如此制备的涂层其实从纹理上无法觉察且味道鲜美。
一种常用的用氨基酸鳌合铁和柠檬酸苹果酸钙强化谷物的方法如下所述。首先,提供一种谷物和一种包含氨基酸鳌合铁、柠檬酸苹果酸钙和载体稳定剂的液体混合物。接下来,为了获得所需的每个谷粒矿物质浓度,将包含氨基酸鳌合铁和钙的已知量的液体混合物涂敷于一部分或全部谷粒上。然后用本领域已知的程序减少水分。最后,需要以一定比率预混强化后的谷粒和未经强化的谷粒,其比率应使单独一份混合后的谷粒能提供足够量的矿物质以满足对该特定金属最少量的日常需求。如果实施这一步骤,优选的强化谷粒对未强化谷粒的比率为按重量计约1∶1至约1∶10。然而,一些制备不需要这一步骤,因为涂层混合物的矿物质含量可能较低,或是因为较浓的混合物可涂敷于较大体积的谷粒。
在一个优选的制备强化谷粒的方法中,用以涂敷谷粒的液体混合物通过混合稳定剂载体和含水混合物直到形成均一液体来制备。接下来将食用酸、柠檬酸苹果酸钙和金属氨基酸螯合物加入到载体中直到形成均一的浆液。接下来,将包含调味剂成分或抗氧化剂成分的醇或醇混合物加入并充分混合。假如使用喷雾方法施加涂层,一个实施方案包括将谷粒置于涂层盘中,在谷粒上方通以热空气并在热空气流动时喷洒均一液体。这一过程持续到谷粒饱和到预定程度。非必需的步骤包括1)在将热空气吹入盘前用着色剂,例如二氧化钛,覆盖谷粒,和/或2)假如需要改变强化谷粒的颜色,在谷粒喷洒过均一液体后用着色剂覆盖谷粒。
假如涂层用浸泡方法施加,谷粒优选首先浸泡在上述的均一液体中,并且使用常规的干燥技术干燥直到水分达到预定的含量。如果必要,谷粒应该用摇动的方法进行筛选。非必需地,二氧化钛或其它着色剂可以与强化谷粒混合以改变谷粒的颜色。
强化大米的分析
感应耦合等离子体(ICP)光谱是一种快速有效的对强化大米的元素分析方法。这种方法对极低含量的金属,如钙和铁,有好的灵敏度。这允许使用小的样本尺寸,因而它们更容易处理和提供。不象原子吸收光谱(AA)和紫外光谱(UV),ICP光谱可用于同一分析时段内检测多种金属。它也是一种相对灵活的方法。硝酸是唯一所需的附加化学品。只要被分析物是液体,等离子体能迅速有效地分析被分析物的元素组分。大米通过微波分解易于转变为溶液。此方法的另一个好处是综合分析,是对整粒的分析。在UV和AA分析所需的提取或其它过程中可能造成损失,此方法可将这种损失最小化。UV或AA光谱还存在关于pH值、颜色稳定性和氧化状态方面的弱点,这些弱点在ICP光谱中也是最小的。
III.
实施例
以下实施例说明制备用于谷粒的柠檬酸苹果酸钙和金属氨基酸螯合物涂层的组合物及方法。具体地讲,实施例提出两种已知的涂层实施方案,即喷雾法和浸泡法,用于用可溶性铁螯合物和柠檬酸苹果酸钙强化谷粒。除非另有规定,用于这些实施例的CCM组合物具有的柠檬酸根与苹果酸根的摩尔比为约40∶60,和当量比为约1。在这些实施例中,由于加工规模较小,强化大米达到的强化水平产生了收率损失。大规模生产的应用将会有更有效的收率。这些实施例不应认为受本发明的限制,仅用以说明如何制备本发明的强化谷粒。
实施例1
以下是通过喷雾方法用二甘氨酸亚铁和柠檬酸苹果酸钙强化白米的方法。首先,将340g羟丙基甲基纤维素缓慢加入到17.625kg水中,在剧烈充分搅拌下混合。接下来,将4.49kg胶溶液倾倒入容器中,用以制备喷洒浆液。加入101g无水柠檬酸,充分搅拌(降低浆液的pH值到4.0或更低)。干混1030g柠檬酸苹果酸钙(按重量计20.8%的钙)和16g二甘氨酸亚铁。接着将这些干成分与胶体和酸混合物混合,高剪切搅拌直到成分全部很好分散。将另外551g食品级乙醇与16g粉状风味剂混合,将其另外搅拌加入到浆液中。
接下来,将40kg大米置于旋转盘中。将热空气吹进盘中,同时将3908g包含柠檬酸苹果酸钙和二甘氨酸亚铁的液体混合物喷洒在大米上。当所有的液体混合物被均匀施加后,允许涂敷大米干燥至水分低于14%和/或水活度小于0.65。由此方法,被二甘氨酸亚铁和柠檬酸苹果酸钙强化的40kg大米分别具有约48ppm的铁含量和约3000ppm的钙含量。成品将在每100g大米中提供300mg的钙和4.80mg的铁。此外,1份强化大米能与3份未强化大米混合,每100克(未煮的)混合大米提供1.2mg铁和75mg钙。
实施例2
以下是通过喷雾方法用二甘氨酸亚铁和柠檬酸苹果酸钙强化白米的方法。首先,将153g羟丙甲纤维素缓慢加入到3.76kg水中,在剧烈充分搅拌下混合。在另一个容器中,将74.9g柠檬酸加入到4.22kg水中,然后在剧烈充分搅拌下加入1844g柠檬酸苹果酸钙。在第三个容器中,将29g二甘氨酸亚铁和115g喷雾干燥风味剂加入到988g无水乙醇中。然后所有这些溶液都在充分搅拌下混合。
接下来,将40kg大米置于旋转盘中。将热空气吹进盘中,同时将3908g包含二甘氨酸亚铁和柠檬酸苹果酸钙的液体混合物喷洒在大米上。当所有的液体混合物被均匀施加后,允许涂敷大米干燥至水分低于14%和/或水活度小于0.65。由此方法,被二甘氨酸亚铁和柠檬酸苹果酸钙强化的40kg大米分别具有约92ppm的铁含量和约6480ppm的钙含量。
实施例3
以下是通过喷雾方法用乙二胺四乙酸钠铁和柠檬酸苹果酸钙强化白米的方法。首先,将6.56g羟丙基甲基纤维素缓慢加入到345.8g水中,在剧烈充分搅拌下混合。接下来,将4.8g一水柠檬酸加入到胶溶液中。随后将79.3g柠檬酸苹果酸钙与1.88g乙二胺四乙酸钠铁(III)(例如,FERRAZONE,购自Azko-Nobel,Herkenbosch,TheNetherlands)混合,并在剧烈充分搅拌下加入到混合物中。将4.96g喷雾干燥风味剂和42.44g无水乙醇加入到混合物中,并在充分搅拌下混合。
接下来,将2kg大米置于旋转盘中。将热空气吹进盘中,同时将264.1g包含乙二胺四乙酸钠铁(III)和柠檬酸苹果酸钙的液体混合物喷洒在大米上。当所有的液体混合物被均匀施加后,允许涂敷大米干燥至水分低于14%和/或水活度小于0.65。由此方法,被乙二胺四乙酸钠铁(III)和柠檬酸苹果酸钙强化的2kg大米分别具有约48ppm的铁含量和约3200ppm的钙含量。
实施例4
以下是通过喷雾方法用二甘氨酸亚铁和柠檬酸苹果酸钙强化白米的方法。首先,将6.56g羟丙基甲基纤维素缓慢加入到345.8g水中,在剧烈充分搅拌下混合。接下来,将4.8g一水柠檬酸加入到胶溶液中。随后将79.3g柠檬酸苹果酸钙与1.24g二甘氨酸亚铁混合,并在剧烈充分搅拌下加入到混合物中。将4.96g喷雾干燥风味剂和42.44g无水乙醇加入到混合物中,并在充分搅拌下混合。
接下来,将2kg大米置于旋转盘中。将热空气吹进盘中,同时将264.1g包含二甘氨酸亚铁和柠檬酸苹果酸钙的液体混合物喷洒在大米上。当所有的液体混合物被均匀施加后,允许涂敷大米干燥至水分低于14%,和/或水活度小于0.65。随后将600g强化大米置于旋转盘中,将全部85.09g乙醇、13.53g水和1.38g玉米蛋白的混合物缓慢喷洒到大米上进行涂敷,而后干燥至水分低于14%和/或水活度小于0.65。由此方法,600g大米产生了光泽表面,并且被二甘氨酸亚铁和柠檬酸苹果酸钙强化,具有约48ppm的铁含量和约3200ppm的钙含量。
实施例5
以下是通过喷雾方法用二甘氨酸亚铁和柠檬酸苹果酸钙(用于本实施例的柠檬酸苹果酸钙组合物的柠檬酸根与苹果酸根的摩尔比为约50∶50,和当量比为约1)强化白米的方法。首先,将5.22g羟丙基甲基纤维素(HPMC)缓慢加入到269.38g水中,并在剧烈充分搅拌下混合。接下来,将20%阿拉伯树胶溶液(10g阿拉伯树胶和40g水)加入到HPMC溶液中并混合充分。将2.56g一水柠檬酸加入到胶溶液中。随后将63g柠檬酸苹果酸钙与0.905g二甘氨酸亚铁混合,并在剧烈充分搅拌下加入到混合物中。
接下来,将1kg大米置于旋转盘中。将热空气吹进盘中,同时将285g包含二甘氨酸亚铁和柠檬酸苹果酸钙的液体混合物喷洒在大米上。当所有的液体混合物被均匀施加后,允许涂敷大米干燥至水分低于14%,和/或水活度小于0.65。由此方法,被二甘氨酸亚铁和柠檬酸苹果酸钙强化的1kg大米具有约48ppm的铁含量和约3200ppm的钙含量。
尽管说明和描述了本发明的具体实施方案,但对于本领域的技术人员显而易见的是,在不背离本发明的精神和保护范围的情况下可作出许多其它的变化和修改。因此有意识地在附加的权利要求书中包括在本发明范围内的所有这些变化和修改。
参考文件
在发明详述中引用的所有文献的相关部分均引入本文以供参考;任何文献的引用并不可理解为是对其作为本发明的现有技术的认可。
Claims (10)
1.一种铁和钙强化的谷粒,其中所述钙为柠檬酸和苹果酸的钙盐形式。
2.如权利要求1所述的谷粒,其中所述铁选自以下形式:铁盐、亚铁盐、氨基酸螯合铁或氨基酸螯合亚铁、铁-糖-羧酸盐络合物,以及它们的混合物。
3.如权利要求2所述的谷粒,其中所述铁为氨基酸螯合亚铁形式,优选其中所述氨基酸螯合亚铁中的氨基酸是甘氨酸。
4.如权利要求3的任一项所述的谷粒,其中所述钙选自以下形式:柠檬酸钙和苹果酸钙的混合物,包含柠檬酸根和苹果酸根配体的钙络合物,钙盐与柠檬酸和苹果酸的混合物,以及它们的任何组合。
5.如权利要求1至4中任一项所述的谷粒,其中所述柠檬酸根与苹果酸根的摩尔比为10∶90至80∶20,优选为20∶80至70∶30;和所述当量比为0.5至2,优选为0.6至1.4。
6.如权利要求1至5中任一项所述的谷粒,所述谷粒包含按所述强化谷粒的总重量计0.03%至2%的钙,优选包含0.08%至1.5%的钙。
7.如权利要求1至6中任一项所述的谷粒,其中所述谷粒是大米。
8.如权利要求1至7中任一项所述的谷粒,其中(i)所述铁为氨基酸螯合亚铁形式;和(ii)所述钙选自以下形式:柠檬酸钙和苹果酸钙的混合物,包含柠檬酸根和苹果酸根配体的钙络合物,钙盐与柠檬酸和苹果酸的混合物,以及它们的任意组合。
9.一种铁和钙强化的大米,其中(i)所述铁是氨基酸螯合亚铁;(ii)所述钙为柠檬酸和苹果酸的钙盐形式,其中所述柠檬酸根与苹果酸根的摩尔比为20∶80至70∶30,所述当量比为0.6至约1.4;(iii)所述大米包含按所述大米的总重量计0.002%至0.005%的铁;和(iv)所述大米包含按所述大米的总重量计0.08%至1.5%的钙。
10.一种制备强化谷粒的方法,所述方法包括(a)提供谷粒,和(b)将所述谷粒与液体混合物混合,所述液体混合物包含铁和钙,所述钙为柠檬酸和苹果酸的钙盐形式。
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US20070269495A1 (en) * | 2006-05-18 | 2007-11-22 | Ashmead H Dewayne | Compositions and methods for enhancing mineral levels in animals with reduced environmental impact |
CN101489414B (zh) * | 2006-07-12 | 2013-05-22 | 普拉克生化公司 | 部分中和的酸涂层的食品级颗粒 |
WO2008020421A2 (en) * | 2006-08-17 | 2008-02-21 | The Procter & Gamble Company | Compositions comprising calcium citrate malate and methods for making the same |
JP2010110240A (ja) * | 2008-11-05 | 2010-05-20 | Satake Corp | 被覆剤及びその製造方法並びに装置 |
PL2758056T3 (pl) * | 2011-09-22 | 2021-04-06 | Albion Laboratories, Inc. | Buforowany promotor wchłaniania w górnym odcinku układu pokarmowego |
BR112014007022B1 (pt) * | 2011-09-22 | 2021-02-09 | Amip | composição farmacêutica, método e uso de uma composição farmacêutica |
US20140348983A1 (en) * | 2012-01-20 | 2014-11-27 | Otc Nutrition Llc | Edible Nutritional Compositions/Products Fortified with Iron (II) Mineral Sources |
WO2019100157A1 (en) * | 2017-11-27 | 2019-05-31 | Top Tier Foods Inc. | Sushi-style quinoa |
WO2019160500A1 (en) * | 2018-02-14 | 2019-08-22 | Profeat Biotechnology Co., Ltd. | Use of ferrous amino acid chelate to increase calcium absorption and bone mass, and to treat osteoporosis |
CN114957796B (zh) * | 2022-05-24 | 2023-11-21 | 浙江天石纳米科技股份有限公司 | 一种高稳定性低盐纳米碳酸钙浆料及在制备粉末化丁腈橡胶上的应用 |
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