CN102933696A - 稳定性提高的腰果壳油 - Google Patents
稳定性提高的腰果壳油 Download PDFInfo
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- CN102933696A CN102933696A CN2011800274650A CN201180027465A CN102933696A CN 102933696 A CN102933696 A CN 102933696A CN 2011800274650 A CN2011800274650 A CN 2011800274650A CN 201180027465 A CN201180027465 A CN 201180027465A CN 102933696 A CN102933696 A CN 102933696A
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- Prior art keywords
- cashew nut
- acid
- shell oil
- nut shell
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Abstract
本发明可以提供一种组合物,其含有1种或者2种以上的酸与未加热的腰果壳油,通过上述1种或者2种以上的酸,抑制未加热腰果中含有的漆树酸的脱羧。
Description
技术领域
本发明涉及含有酸与未加热的腰果壳油且通过上述酸抑制未加热的腰果(CNSL)中含有的漆树酸脱羧的组合物、使用了这种组合物的未加热腰果壳油制剂以及饲料。同时本发明涉及抑制未加热腰果壳油中漆树酸的脱羧反应的方法,其特征在于在未加热腰果壳油中添加酸。
背景技术
腰果壳油是腰果树(Anacardium occidentale L.)的果壳中含有的油状液体。腰果壳油的成分主要有漆树酸、腰果酚、腰果二酚、甲基腰果二酚。
腰果壳油的制作法有加热法与溶剂提取法,通常,腰果壳油是在腰果生产地通过加热处理,将漆树酸转化为腰果酚后使用。
这是因为未加热的腰果壳油中,其成分漆树酸容易脱羧,运输中恐怕会存在起泡的问题。同时,未加热的腰果壳油在20℃时固化,其流动性消失,难以运输。从这些理由看,输送未加热的腰果壳油时有很大的限制,进一步地妨碍了工业使用。
作为在工业制品上的应用例的专利文献1-3,所使用的腰果壳油,均经过加热处理。
专利文献4-6虽涉及未加热的腰果壳油以及作为其成分的漆树酸在饲料用途上的活用,但因上述的稳定性、运输上的限制,包含物理以及经济的课题,实现它的障碍很大。同时,承认专利文献4-6中有关于未加热的腰果壳油的活用的记载,但是着眼于稳定性以及可操作性的提高并试图改善的见解却没有。
因此,期望发现可以稳定未加热的腰果壳油从而容易将它运输的方法。
专利文献7记载了含有漆树酸的腰果壳液中添加混合了碱使得漆树酸稳定的方法。然而,没有记载腰果壳液中添加酸使漆树酸稳定的情况。同时,也没有记载通过在添加酸的未加热腰果壳油中混合载体,可以防止在20℃左右时固化的情况。
现有技术文献
专利文献
专利文献1:日本专利特开2008-144171号公报
专利文献2:日本专利特开2006-111839号公报
专利文献3:日本专利特开2003-252893号公报
专利文献4:日本专利特开2003-238400号公报
专利文献5:日本专利特开2001-151675号公报
专利文献6:日本专利特开平8-231410号公报
专利文献7:日本专利特开2010-88363号公报
发明内容
本发明把未加热的腰果壳油特别是作为其成分的漆树酸不会脱羧从而容易搬运做为课题。本发明同时把大约20℃时固化的未加热的腰果壳油即使在低温时也容易运送做为课题。
本发明者为解决上述课题,经过深入研究,结果发现,通过在未加热腰果壳油中加入酸,可以抑制漆树酸的脱羧。
本发明者同时发现在加入酸抑制脱羧的未加热腰果壳油中,通过混合谷物粉、二氧化硅等的载体,即使在大约20℃以下的低温中也不会固化,可以实现未加热的腰果壳油的搬运。
本发明者至此,完成本发明。
即,本发明如下所述。
(1)一种组合物,其含有1种或者2种以上的酸与未加热的腰果壳油,通过上述1种或者2种以上的酸,抑制未加热腰果中含有的漆树酸的脱羧。
(2)根据(1)所述的组合物,其特征在于,酸的pKa在4.5以下。
(3).根据(1)或者(2)中记载的组合物,其中,酸的量与未加热腰果壳油的比在0.5重量%以上。
(4)一种未加热腰果壳油制剂,其含有(1)~(3)的任一项中记载的组合物与1种或者2种以上的载体。
(5)根据(4)中记载的未加热腰果壳油制剂,其特征在于,所述载体为二氧化硅。
(6)一种饲料,其通过加入(1)~(3)的任一项中记载的组合物以及/或者根据(4)或者(5)中记载的未加热腰果壳油制剂制成,其含有脱羧得到了抑制的未加热腰果壳油。
(7)一种抑制未加热腰果壳油中的漆树酸的脱羧反应的方法,其特征在于,在未加热腰果壳油添加了1种或者2种以上的酸。
(8)一种(4)或者(5)中记载的未加热腰果壳油制剂的制造方法,其特征在于,将1种或者2种以上的酸成分与1种或者2种以上的载体混合,以及将混合有酸成分的载体进一步地与未加热腰果壳油混合。
(9)一种抑制漆树酸的脱羧反应的方法,其特征在于,在漆树酸中添加了1种或者2种以上的酸。
发明的效果
通过在未加热腰果壳油中添加酸,可以抑制作为未加热腰果壳油成分的漆树酸的脱羧。同时,通过在添加了酸的未加热腰果壳油中混合载体,可以防止在20℃左右时固化。使得未加热腰果壳油在工业上容易利用。
附图说明
图1:图1表示使用1重量%的各种酸时未加热腰果壳油的脱羧反应的抑制。条形图由上至下表示腰果酚15:1,15:2,15:3,漆树酸15:1,15:2,15:3。
图2:图2表示使用10重量%的各种酸时未加热腰果壳油的脱羧反应的抑制。条形图由上至下表示腰果酚15:1,15:2,15:3,漆树酸15:1,15:2,15:3。
图3:图3表示使用各种浓度的硫酸时未加热腰果壳油的脱羧反应的抑制。图3A的条形图由上至下表示腰果酚15:1,漆树酸15:1,图3B的条形图,由上至下表示腰果酚15:3,漆树酸15:3。
图4:图4表示使用10重量%的磷酸时未加热腰果壳油制剂的脱羧反应的抑制(未加热腰果壳油中预先添加了酸)。条形图由上至下表示腰果酚15:3,漆树酸15:3。
图5:图5表示使用10重量%的硫酸时未加热腰果壳油制剂的脱羧反应的抑制(预先在载体中添加酸)。条形图上层由上至下表示腰果酚15:1,漆树酸15:1;下层由上至下表示腰果酚15:3,漆树酸15:3。
图6:图6表示使用10重量%的磷酸时饲料的脱羧反应的抑制。条形图由上至下表示腰果酚15:3,漆树酸15:3。
具体实施方式
本发明的组合物的特征在于,含有1种或者2种以上的酸与未加热的腰果壳油,通过所述1种或者2种以上的酸,抑制未加热腰果中含有的漆树酸的脱羧。
本发明中使用的腰果壳油是腰果树(Anacardium occidentale L.)的果壳中含有的油状液体。腰果壳油的成分有漆树酸、腰果酚、腰果二酚、甲基腰果二酚。
通过压榨腰果的壳提取出的非加热腰果壳油(以下称之为腰果壳油。),如J.Agric.Food Chem.2001,49,2548-2551中记载的,含有漆树酸55~80质量%,腰果酚5~20质量%,腰果二酚5~30质量%。
另外,漆树酸有在8,11,14位上存在3个双键(以下,15:3)、8,11位上具有2个双键(以下,15:2)以及在8位上具有1个双键(以下,15:1)3种。
同时,本发明还包含一种抑制漆树酸的脱羧反应的方法,其特征在于,在漆树酸中添加1种或者2种以上的酸。
本发明中使用的腰果壳油可以作为通过压榨腰果壳提取出的植物油来获得。同时,本发明中使用的腰果壳油也可以通过萃取,例如对腰果壳进行溶剂萃取来获得。进一步地,本发明中使用的腰果壳油,通过日本专利特开平8-231410号公报中记载的方法,例如,通过溶剂萃取法可以得到。
另外,本发明所使用的腰果壳油也可以通过将腰果的壳粉碎、破碎而得到。
本发明所使用的腰果壳油也可以使用市售品。
本发明中使用的酸,优选pKa在4.5以下的酸,更优选4.0以下的。具体的酸,举例有蚁酸、苹果酸、柠檬酸、丁二酸、酒石酸、磷酸、硝酸、盐酸、草酸、丙二酸、戊二酸、己二酸、富马酸、马来酸、邻苯二甲酸、间苯二甲酸、植酸、硫酸、对苯二甲酸、乳酸、氨基磺酸、羟基乙酸、膦酸、葡萄糖酸,其中无特别限制。本发明中,pKa的值是以水为溶剂,在25℃时计算出来的值。
作为所用的酸的量,优选与腰果壳油(CNSL)之比为0.5重量%以上,更优选1~20重量%。另外,酸的pKa比2高时,添加的酸的量需要更多,例如可以在5~10重量%左右。
本发明的组合物可以通过在未加热腰果壳油中添加1种或者2种以上的酸来制造。
本发明的未加热腰果壳油制剂,优选含有本发明的组合物与1种或者2种以上的载体的制剂,例如,可以将本发明的组合物与1种或者2种以上的载体混合,作成未加热腰果壳油制剂。
作为无机载体,举例有硅酸以及其盐类(例如,二氧化硅),蛭石,硅藻土,滑石粉,高岭土,膨润土,但并不限定于这些。
作为无机载体,使用硅酸以及其盐类时,为了弱化氧化反应,其比表面积,优选500m3/g以下。作为无机载体,使用二氧化硅时,混合比(重量比)优选二氧化硅/未加热腰果壳油=1/3.0~1/0.1。使用其他的无机载体时,也可用同样的比表面积,混合比。另外,二氧化硅的比表面积可以通过BET法测定。
另外,可以使用谷物粉类或后述的玉米粒,玉米粉,西非高粱,豆饼,燕麦,小麦蛋糕粉,小麦粗粉,紫花苜蓿,三叶草,脱脂米糠,北洋鱼粉,沿岸鱼粉,酵母,糖蜜,肉片,骨粉等的饲料成分作为有机载体。
本发明的未加热腰果壳油制剂,只要含有未加热腰果壳油、1种或者2种以上的载体以及1种或者2种以上的酸成分,就没有特别限定。因此,可以预先混合酸成分与载体,将混合有酸成分的载体进一步地可以与未加热腰果壳油混合来制成上述制剂。通过载体中酸成分的影响,在酸与载体混合的状态下,可以抑制未加热腰果壳油的脱羧。
本发明的未加热腰果壳油制剂中除了含有未加热腰果壳油,载体以及酸成分,还可以含有1种或者2种以上的抗氧剂,举例有乙氧基喹啉、叔丁基羟基甲苯、叔丁基羟基苯甲醚、叔丁基对苯二酚、抗坏血酸及其酯、维生素E、没食子酸及其酯、异抗坏血酸、绿原酸、亚硫酸盐、硫代硫酸盐、亚磷酸盐、次亚磷酸盐、磷酸盐,但并不限定于这些。
本发明的未加热腰果壳油制剂中除了使用未加热腰果壳油,载体以及酸成分,还可使用1种或者2种以上的抗生素,举例有杆菌肽锌、阿维拉克林霉素、烷基三甲基铵钙氧四环素、依罗霉素、恩拉霉素、金霉素、赛地卡霉素、赛杜霉素、甲基盐霉素、那西肽、维吉霉素、二环霉素、富拉磷、浏阳霉素、莫能菌素、盐霉素、拉沙里菌素、溶胞菌素、罗奴霉素、阿伏霉素、硫酸黏菌素、磷酸泰乐菌素、氨丙啉·乙氧酰胺苯甲酯、氨丙啉·乙氧酰胺苯甲酯·磺胺喹恶啉、莫仑太尔柠檬酸、癸氧喹酯、双硝苯脲二甲嘧啶醇、卤夫酮聚苯乙烯磺酸、吉他霉素、硫代蛋白胨(tiopeptone),越霉素A、潮霉素B及其盐类等。
关于本发明的未加热腰果壳油制剂的剂形,可以通过含有谷物粉类、二氧化硅等载体,通过制剂化成为粉剂。即,本发明的未加热腰果壳油制剂可以如下制造,可以混合未加热腰果壳油、1种或者2种以上的载体、1种或者2种以上的酸成分以及根据需要的1种或者2种以上的任意成分,经制剂化制造成粉剂。这样的本发明的粉末状的制剂,不混合其他任意成分可以作为饲料
本发明的未加热腰果壳油制剂,可以是粉剂之外的颗粒剂等粒剂。此时,未加热腰果壳油中除了添加无机载体以及添加酸成分,还可以使用1种或者2种以上的硬化油。作为硬化油,可使用棕榈油,大豆油,菜籽油等硬化油。硬化油的熔点优选45~65℃。另外,可以使用通常的挤压造粒机使其颗粒化。
本发明的未加热腰果壳油制剂,可以对其进行涂覆,例如,造粒后,使用玉米醇溶蛋白、紫胶、HPMC(羟基丙基甲基纤维素)、茁霉多糖、hemilose、葡萄糖、乳糖、海藻糖以及淀粉中选择1种或者2种以上的涂层剂来涂覆。此外,也可以用以这些为成分的片包覆。
本发明包含含有本发明的组合物和/或未加热腰果壳油制剂的饲料。本发明中,饲料中含有的未加热腰果壳油,通过1种或者2种以上的酸成分抑制脱羧。
本发明的饲料中,与本发明的组合物和/或腰果壳油制剂混合的饲料成分的种类或混合比例等没有特别限制,如果是以往供给各种动物的饲料均可以,例如,可以使用玉米粒、玉米粉、西非高粱、豆饼、燕麦、小麦蛋糕粉、小麦粗粉、紫花苜蓿、三叶草、脱脂米糠、北洋鱼粉,沿岸鱼粉、酵母、糖蜜、肉片、骨粉、碳酸钙、磷酸氢钙、黄油、维生素类、矿物类等的1种或者2种以上的饲料成分进行制作。
本发明的饲料,将未加热腰果壳油制剂直接地添加入饲料成分中,混合后可以制成。此时,使用粉末状、固体状的未加热腰果壳油制剂时,为了容易混合,可以将制剂制成液态或者凝胶状态。此时,可以使用水、豆油、菜籽油、玉米油等的植物油、液体动物油、聚乙烯醇或聚乙烯吡咯烷酮、聚丙烯酸等的水溶性高分子化合物的1种或者2种以上作为液体载体。同时,为了保持饲料中的腰果壳油的均一性,优选混合海藻酸、海藻酸钠、黄原胶、酪蛋白酸钠、阿拉伯胶、瓜尔胶、罗望子种子多糖类等的水溶性多糖类的1种或者2种以上。
本发明的饲料适宜用于饲养牛、猪、鸡、羊、马、山羊等家畜。摄取饲料的量可以根据动物的种类、体重、年龄、性别、健康状态、饲料的成分等适当地调节,此时饲料所含的腰果壳油优选0.005~500g/头·天,更优选0.05~100g/头·天。
摄取饲料的方法以及饲养的方法可以根据动物的种类,选择通常使用的方法。
实施例
实施例1.试料制作
从カシュー·トレーディング(株)得到腰果的壳500kg,通过压榨制造出腰果壳油(未加热腰果壳油)158kg。同时,作为载体使用的二氧化硅分以下2种等级使用。
Sipernat22(pH6.5)(エボニックデグサジャパン(株))
Carplex#1120(pH10.6)(エボニックデグサジャパン(株))
此外,所用酸的pKa如下所示。
硫酸(-3)
硝酸(-1.6)
磷酸(2.1)
蚁酸(3.8)
醋酸(4.8)
实施例2.HPLC测定
机器使用HPLC(Waters 600,日本ウォータース(株)),检测器(Waters 490E,日本ウォータース(株)),打印机(クロマトパツクC-R6A,岛津制作所),色谱柱(SUPELCOSILLC18,SUPELCO社)。条件为溶剂乙腈:水:醋酸=80:20:1(容量比),流速2mL/mL,温度25℃,吸光度280nm时测定。
pH测定
二氧化硅的pH通过下述方法测定。
通过离子交换水制成5重量%的二氧化硅水悬浮液,用玻璃电极测定电位作为pH。
实施例3.添加1重量%或者10重量%的各种酸时脱羧反应的抑制
各烧杯中分别取未加热腰果壳油10g,往里加入硫酸1重量%、硝酸1重量%、磷酸1重量%、10重量%、蚁酸1重量%、10重量%、醋酸1重量%、10重量%,搅拌均一。
分别密闭后静置在80℃的恒温槽中,4日后进行采样,通过HPLC进行组成分析。
由于漆树酸(AA)通过脱羧反应变为腰果酚(CD),所以表1、2中记载了恒温槽静置前后,漆树酸、腰果酚与腰果二酚的组成。漆树酸、腰果酚与腰果二酚,根据与芳香族环键合的碳原子数15的脂肪链具有的不饱和键的数量,各自分别主要以下述三类存在(漆树酸;AA15:1、AA15:2、AA15:3,腰果酚;CD15:1、CD15:2、CD15:3,腰果二酚;15:1,15:2,15:3)。
可知添加各种酸1重量%时(图1,表1),4日后的脱羧(漆树酸→腰果)的比例随着pKa的强度而变小。pKa4.8的醋酸时,添加1重量%的与无添加(对照组)的相比几乎没有变化。
另外,对于腰果二酚,只在表中记载,图中没有记载。
[表1-1]
0天 | 0天(%) | 4天 | 4天(%) | |
对照组漆树酸C15:3 | 1878 | 16.9 | 753 | 5.4 |
漆树酸C15:2 | 1335 | 12.0 | 311 | 2.2 |
漆树酸C15:1 | 3849 | 34.5 | 955 | 6.8 |
腰果酚C15:3 | 533 | 4.8 | 4213 | 30.0 |
腰果酚C15:2 | 213 | 1.9 | 1320 | 9.4 |
腰果酚C15:1 | 591 | 5.3 | 4281 | 30.5 |
腰果二酚C15:3 | 1784 | 16.0 | 1700 | 12.1 |
腰果二酚C15:2 | 542 | 4.9 | 524 | 3.7 |
腰果二酚C15:1 | 422 | 3.8 | 0 | 0.0 |
总计 | 11147 | 100.0 | 14058 | 100.0 |
0天 | 0天(%) | 4天 | 4天(%) | |
1%硫酸漆树酸C15:3 | 2865 | 25.7 | 2600 | 22.4 |
漆树酸C15:2 | 1140 | 10.2 | 1099 | 9.5 |
漆树酸C15:1 | 3522 | 31.7 | 3176 | 27.4 |
腰果酚C15:3 | 453 | 4.1 | 1119 | 9.6 |
腰果酚C15:2 | 200 | 1.8 | 396 | 3.4 |
腰果酚C15:1 | 530 | 4.8 | 1214 | 10.5 |
腰果二酚C15:3 | 1601 | 14.4 | 1507 | 13.0 |
腰果二酚C15:2 | 451 | 4.1 | 483 | 4.2 |
腰果二酚C15:1 | 365 | 3.3 | 0 | 0.0 |
总计 | 11126 | 100.0 | 11594 | 100.0 |
0天 | 0天(%) | 4天 | 4天(%) | |
1%硝酸漆树酸C15:3 | 3485 | 25.8 | 1743 | 12.5 |
漆树酸C15:2 | 1464 | 10.9 | 753 | 5.4 |
漆树酸C15:1 | 4176 | 31.0 | 2142 | 15.3 |
腰果酚C15:3 | 578 | 4.3 | 3149 | 22.5 |
腰果酚C15:2 | 239 | 1.8 | 976 | 7.0 |
腰果酚C15:1 | 628 | 4.7 | 3097 | 22.2 |
腰果二酚C15:3 | 1873 | 13.9 | 1607 | 11.5 |
腰果二酚C15:2 | 581 | 4.3 | 509 | 3.6 |
腰果二酚C15:1 | 458 | 3.4 | 0 | 0.0 |
总计 | 13483 | 100.0 | 13976 | 100.0 |
[表1-2]
0天 | 0天(%) | 4天 | 4天(%) | |
1%磷酸漆树酸C15:3 | 5077 | 37.1 | 2530 | 17.5 |
漆树酸C15:2 | 1189 | 8.7 | 1075 | 7.5 |
漆树酸C15:1 | 3633 | 26.6 | 3143 | 21.8 |
腰果酚C15:3 | 485 | 3.5 | 1871 | 13.0 |
腰果酚C15:2 | 199 | 1.5 | 565 | 3.9 |
腰果酚C15:1 | 550 | 4.0 | 2994 | 20.8 |
腰果二酚C15:3 | 1699 | 12.4 | 1722 | 11.9 |
腰果二酚C15:2 | 477 | 3.5 | 521 | 3.6 |
腰果二酚C15:1 | 373 | 2.7 | 0 | 0.0 |
总计 | 13680 | 100.0 | 14421 | 100.0 |
0天 | 0天(%) | 4天 | 4天(%) | |
1%蚁酸漆树酸C15:3 | 3003 | 25.7 | 1157 | 10.1 |
漆树酸C15:2 | 1207 | 10.3 | 505 | 4.4 |
漆树酸C15:1 | 3637 | 31.1 | 1453 | 12.6 |
腰果酚C15:3 | 503 | 4.3 | 1706 | 14.8 |
腰果酚C15:2 | 207 | 1.8 | 1096 | 9.5 |
腰果酚C15:1 | 550 | 4.7 | 3495 | 30.4 |
腰果二酚C15:3 | 1687 | 14.4 | 1607 | 14.0 |
腰果二酚C15:2 | 512 | 4.4 | 494 | 4.3 |
腰果二酚C15:1 | 395 | 3.4 | 0 | 0.0 |
总计 | 11701 | 100.0 | 11515 | 100.0 |
0天 | 0天(%) | 4天 | 4天(%) | |
1%醋酸漆树酸C15:3 | 3006 | 25.5 | 840 | 6.1 |
漆树酸C15:2 | 1263 | 10.7 | 352 | 2.6 |
漆树酸C15:1 | 3641 | 30.9 | 1133 | 8.2 |
腰果酚C15:3 | 518 | 4.4 | 3945 | 28.7 |
腰果酚C15:2 | 208 | 1.8 | 1250 | 9.1 |
腰果酚C15:1 | 558 | 4.7 | 4065 | 29.6 |
腰果二酚C15:3 | 1687 | 14.3 | 1670 | 12.1 |
腰果二酚C15:2 | 515 | 4.4 | 493 | 3.6 |
腰果二酚C15:1 | 396 | 3.4 | 0 | 0.0 |
总计 | 11792 | 100.0 | 13747 | 100.0 |
另一方面,pKa较弱的酸,将添加量增加到10重量%进行研究时(图2,表2),发现pKa3.8的蚁酸4日后的腰果成分含量非常低,可认定添加量的增加引起的效果显著。
另外,对于腰果二酚,只在表中记载,图中没有记载。
[表2]
0天 | 0天(%) | 4天 | 4天(%) | |
对照组漆树酸C15:3 | 1878 | 16.9 | 753 | 5.4 |
漆树酸C15:2 | 1335 | 12.0 | 311 | 2.2 |
漆树酸C15:1 | 3849 | 34.5 | 955 | 6.8 |
腰果酚C15:3 | 533 | 4.8 | 4213 | 30.0 |
腰果酚C15:2 | 213 | 1.9 | 1320 | 9.4 |
腰果酚C15:1 | 591 | 5.3 | 4281 | 30.5 |
腰果二酚C15:3 | 1784 | 16.0 | 1700 | 12.1 |
腰果二酚C15:2 | 542 | 4.9 | 524 | 3.7 |
腰果二酚C15:1 | 422 | 3.8 | 0 | 0.0 |
总计 | 11147 | 100.0 | 14058 | 100.0 |
0天 | 0天(%) | 4天 | 4天(%) | |
1%磷酸漆树酸C15:3 | 2891 | 25.7 | 3277 | 26.0 |
漆树酸C15:2 | 1218 | 10.8 | 1440 | 11.4 |
漆树酸C15:1 | 3467 | 30.8 | 3924 | 31.2 |
腰果酚C15:3 | 474 | 4.2 | 593 | 4.7 |
腰果酚C15:2 | 185 | 1.6 | 249 | 2.0 |
腰果酚C15:1 | 516 | 4.6 | 601 | 4.8 |
腰果二酚C15:3 | 1614 | 14.4 | 1612 | 12.8 |
腰果二酚C15:2 | 489 | 4.4 | 504 | 4.0 |
腰果二酚C15:1 | 386 | 3.4 | 381 | 3.0 |
总计 | 11240 | 100.0 | 12580 | 100.0 |
0天 | 0天(%) | 4天 | 4天(%) | |
1%蚁酸漆树酸C15:3 | 3004 | 25.8 | 2376 | 23.5 |
漆树酸C15:2 | 1216 | 10.4 | 990 | 9.8 |
漆树酸C15:1 | 3626 | 31.1 | 2869 | 28.4 |
腰果酚C15:3 | 503 | 4.3 | 832 | 8.2 |
腰果酚C15:2 | 207 | 1.8 | 291 | 2.9 |
腰果酚C15:1 | 541 | 4.6 | 863 | 8.5 |
腰果二酚C15:3 | 1679 | 14.4 | 1237 | 12.3 |
腰果二酚C15:2 | 475 | 4.1 | 382 | 3.8 |
腰果二酚C15:1 | 396 | 3.4 | 257 | 2.5 |
总计 | 11646 | 100.0 | 10098 | 100.0 |
0天 | 0天(%) | 4天 | 4天(%) | |
1%醋酸漆树酸C15:3 | 2786 | 25.6 | 1872 | 15.0 |
漆树酸C15:2 | 1114 | 10.2 | 804 | 6.4 |
漆树酸C15:1 | 3384 | 31.1 | 2307 | 18.5 |
腰果酚C15:3 | 462 | 4.2 | 2435 | 19.5 |
腰果酚C15:2 | 177 | 1.6 | 741 | 5.9 |
腰果酚C15:1 | 519 | 4.8 | 2295 | 18.4 |
腰果二酚C15:3 | 1567 | 14.4 | 1555 | 12.4 |
腰果二酚C15:2 | 495 | 4.6 | 479 | 3.8 |
腰果二酚C15:1 | 375 | 3.4 | 0 | 0.0 |
总计 | 10878 | 100.0 | 12488 | 100.0 |
实施例4.添加各种浓度的硫酸(pKa=-3)时脱羧反应的抑制
各烧杯中分别取未加热腰果壳油10g,往里加入硫酸0.1重量%、0.3重量%、0.6重量%、1重量%,搅拌均一。
分别密闭后静置在80℃的恒温槽中,3日后进行采样,通过HPLC进行组成分析。分析结果分为漆树酸15:1与漆树酸15:3,记为分析时的浓度(nmol/L)(表3左栏,右栏,图3A,B)。根据图,可知硫酸添加量为0.6重量%时,脱羧反应减少,添加1重量%时,结果十分显著。
[表3]
AA15:1 AA15:3
0.0%硫酸 0.0%硫酸
0.1%硫酸 0.1%硫酸
0.6%硫酸 0.6%硫酸
1.0%硫酸 1.0%硫酸
实施例5.未加热腰果壳油制剂中的脱羧反应抑制(未加热腰果壳油中预先添加磷酸)
采取二氧化硅(Sipernat22,Carplex#1120)各10g置入烧杯中,往里添加未加热腰果壳油20g或者含有10重量%磷酸的未加热腰果壳油20g,搅拌均一,混合。分别密闭后静置在80℃的恒温槽中,3日后进行采样,通过HPLC进行组成分析。HPLC分析如下进行,将采取试样在醋酸乙酯中浓度调整为5mg(含有二氧化硅)/ml后,在15,000rpm下进行5min的离心分离,测定上清。分析结果中,对于漆树酸15:3,作为分析时的浓度(nmol/L)记载(表4,图4)。
可以确认,载体使用二氧化硅时,pH在中性左右的Sipernat22与不使用载体时比较,脱羧的比例大致相同或者降低,但载体使用碱性的Carplex#1120时,脱羧的比例增加。
另一方面,可以确认,使用含有10重量%磷酸的未加热腰果壳油时,与有无使用载体、载体中所用的二氧化硅的pH无关,抑制了脱羧反应。结果在下表4中所示。
[表4]
不添加二氧化硅,未加热腰果壳油 不添加二氧化硅,未加热腰果壳油、10%磷酸
pH6.5(Sipernat22.未加热腰果壳油) pH6.5(Sipernat22.未加热腰果壳油,10%磷酸)
pH10.6(Carplex#1120.未加热腰果壳油,10%磷
pH10.6(Carplex#1120.未加热腰果壳油) 酸)
实施例6.
未加热腰果壳油制剂中的脱羧反应抑制(载体中预先添加磷酸)
采取Sipernat 22150g在塑料袋中,边搅拌边喷雾85%磷酸9ml。测定制作的添加了磷酸Sipernat 22的pH为2.0。
取二氧化硅(Sipernat 22,添加了磷酸Sipernat 22,Carplex#1120)各10g置入烧杯中,往里添加未加热腰果壳油20g,搅拌均一,混合。分别密闭后静置于80℃的恒温槽中,3日后采样,通过HPLC进行组成分析。HPLC分析如下进行,将采取试样在醋酸乙酯中浓度调整为5mg(含有二氧化硅)/ml后,在15,000rpm下进行5min的离心分离,测定上清。分析结果中,对于漆树酸15:1以及漆树酸15:3,作为分析时的浓度(nmol/L)记载(表5,图5)。
评价结果如下述表5所示。
[表5]
AA15:1不添加二氧化硅 AA15:3不添加二氧化硅
pH6.5(Sipernat22) pH6.5(Sipernat22)
pH2.0(Sipernat22,磷酸) pH2.0(Sipernat22,磷酸)
pH10.6(Carplex#1120) pH10.6(Carplex#1120)
由此可知,载体(二氧化硅)的pH低,脱羧反应会受抑制。
由以上内容可知,脱羧反应中使用的酸,无需预先添加到未加热腰果壳油,可以预先添加到载体。
实施例7.饲料中脱羧反应的抑制
饲料(幼龄牛饲养用标准饲料:SDC No.2日本配合饲料(株))100g中添加实施例5制作的二氧化硅剂2种(Sipernat 2210g+未加热腰果壳油20g或者含有10重量%磷酸的未加热腰果壳油20g)1重量%,制成含有未加热腰果壳油的饲料。
分别密闭后静置在80℃的恒温槽中,3日后进行采样,通过HPLC进行组成分析。
HPLC分析如下进行,用醋酸乙酯从试验中使用的饲料中萃取出可溶份后,滤过,干燥,调整浓度为5mg/ml之后测定。分析结果显示了对于漆树酸15:3,恒温槽静置前后其中漆树酸与腰果酚的组成(表6,图6)。评价结果如下述表6所示。
[表6]
由此可知,使用含有10重量%磷酸的未加热腰果壳油时,饲料中没有脱羧反应,可以稳定地存在。
实施例8.添加未加热腰果壳油的饲料的制作(使用有机载体)
使用标准饲料作为载体,制作成鸡以及牛用饲料。混合例不局限于以下各例。
(1)童子鸡用饲料制作
童子鸡肥育前期用标准饲料:
SDB No.1日本配合饲料(株) 99.5重量%
未加热腰果壳油(10重量%磷酸) 0.05重量%
通过混合上述物质成为粉体,可以防止在20℃左右时固化。
(2)牛用饲料制作
幼龄牛培养用标准饲料:
SDC No.2日本配合饲料(株) 99.5重量%
未加热腰果壳油(10重量%磷酸) 0.05重量%
通过混合上述物质成为粉体,可以防止在20℃左右时固化。
产业上的可利用性
通过在未加热腰果壳油中添加酸,可以抑制脱羧引起的起泡。同时,通过在添加了酸的未加热腰果壳油中混合无机载体,可以防止在20℃左右时固化。因此,未加热腰果壳油在工业上容易利用。
Claims (9)
1.一种组合物,其含有1种或者2种以上的酸与未加热的腰果壳油,通过所述1种或者2种以上的酸,抑制未加热腰果中含有的漆树酸的脱羧。
2.根据权利要求1所述的组合物,其特征在于,酸的pKa在4.5以下。
3.根据权利要求1或者2中记载的组合物,其中,酸的量与未加热腰果壳油的比在0.5重量%以上。
4.一种未加热腰果壳油制剂,其含有权利要求1~3的任一项中记载的组合物与1种或者2种以上的载体。
5.根据权利要求4中记载的未加热腰果壳油制剂,其特征在于,所述载体为二氧化硅。
6.一种饲料,其通过加入权利要求1~3的任一项中记载的组合物以及/或者权利要求4或者5中记载的未加热腰果壳油制剂制成,其含有脱羧得到了抑制的未加热腰果壳油。
7.一种抑制未加热腰果壳油中的漆树酸的脱羧反应的方法,其特征在于,在未加热腰果壳油中添加1种或者2种以上的酸。
8.一种权利要求4或者5中记载的未加热腰果壳油制剂的制造方法,其特征在于,将1种或者2种以上的酸成分与1种或者2种以上的载体混合,以及将混合有酸成分的载体进一步地与未加热腰果壳油混合。
9.一种抑制漆树酸的脱羧反应的方法,其特征在于,在漆树酸中添加1种或者2种以上的酸。
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