CN116261400A - 新型槐糖脂衍生物 - Google Patents
新型槐糖脂衍生物 Download PDFInfo
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- CN116261400A CN116261400A CN202280006101.2A CN202280006101A CN116261400A CN 116261400 A CN116261400 A CN 116261400A CN 202280006101 A CN202280006101 A CN 202280006101A CN 116261400 A CN116261400 A CN 116261400A
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- sophorolipid
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- ZTOKUMPYMPKCFX-CZNUEWPDSA-N (E)-17-[(2R,3R,4S,5S,6R)-6-(acetyloxymethyl)-3-[(2S,3R,4S,5S,6R)-6-(acetyloxymethyl)-3,4,5-trihydroxyoxan-2-yl]oxy-4,5-dihydroxyoxan-2-yl]oxyoctadec-9-enoic acid Chemical class OC(=O)CCCCCCC/C=C/CCCCCCC(C)O[C@@H]1O[C@H](COC(C)=O)[C@@H](O)[C@H](O)[C@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](COC(C)=O)O1 ZTOKUMPYMPKCFX-CZNUEWPDSA-N 0.000 title claims abstract description 34
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Abstract
Description
技术领域
本发明涉及一种新型槐糖脂衍生物及包含该衍生物的组合物。
背景技术
在亲水基由糖构成的糖型表面活性剂之中,作为优异的表面活性剂而为人所知的有来自微生物的天然表面活性剂且安全性高的糖型生物表面活性剂。这些中,槐糖脂为糖脂,其具有两亲性结构,因此具有较强的表面活性作用,生物降解性与安全性较高,所以正在开发其作为生物表面活性剂的主要成分的用途。
作为生产槐糖脂的酵母,具有代表性的是作为担子菌酵母的球拟假丝酵母(Starmerella bombicola),由于其生物表面活性剂的生产力达到每1L培养液400g以上,因此用于商业性的生产。槐糖脂是具有由下述式(3)所表示的内酯型(LSL)、及由下述式(4)所表示的酸型(ASL)的分子结构的糖脂质,其是在槐二糖的1位经醚键键合羟基脂肪酸而形成的,该槐二糖是葡萄糖在2→1位经醚键键合而成的二糖。作为在微生物产物中包含它们中的一种或多种的混合物的形式而存在。
关于槐糖脂的内酯型(非离子型)与酸型(阴离子型),作为表面活性剂的性质大不相同,从而正在开发它们的组成不同的混合物或分开制作它们的方法等扩充槐糖脂制品的结构及功能的多种技术。例如,有报告指出,上述球拟假丝酵母(Starmerella bombicola)所生产的槐糖脂一般以内酯型与酸型大致为6~8:2~4的混合物的形式获得,与酸型相比,作为主成分的内酯型能够在较低浓度下表现出优异的表面张力降低能力(非专利文献1),除此之外还表现出较高的抗菌活性(非专利文献2)。
另一方面,报告有,通过水解使内酯环开环而获得化学上稳定的高纯度的酸型槐糖脂,并将其调配而得到的清洁剂(专利文献1);并且报告有一种通过将居花假丝酵母(Candida floricola)作为生产菌进行培养而仅选择性地制造酸型槐糖脂的方法(专利文献2)。
另外,除了所存在的多个官能基团经改性的槐糖脂衍生物以外,还报告有槐糖脂聚合体等的类型上不同于内酯型及酸型的新型结构的衍生物(专利文献3、非专利文献3)。
进一步,还报告有,通过将巴蒂斯塔假丝酵母(Candida batistae)作为生产菌进行培养,可获得与槐二糖键合的脂肪酸部分的结构不同的槐糖脂(非专利文献4)。
式(3)
式(4)
[现有技术文献]
[专利文献]
专利文献1:日本专利特开2006-70231号公报
专利文献2:日本专利特开2008-247845号公报
专利文献3:国际公开第2015/20114号
[非专利文献]
非专利文献1:《油脂科学杂志(Journal of Oleo Science)》(2013)第62卷,第857-864页
非专利文献2:《微生物学与生物技术杂志(Journal of Microbiology andBiotechnology)》(2002)第12卷,第235-241页
非专利文献3:《(碳水化合物研究Carbohydrate Research)》(2012)第348卷,第33-41页
非专利文献4:《油脂科学杂志(Journal of Oleo Science)》(2008)第57卷,第359-369页
发明内容
[发明所要解决的技术问题]
现有技术中已知的槐糖脂的结构大致仅有上述的内酯型与酸型两种形式,为了扩充物性及功能,要求扩展结构的多样性。
本发明的技术问题在于提供一种可应用于饲料、肥料、饮食品、农药、医药品、准药品、或化妆品等广泛范围的领域中的新型槐糖脂衍生物。
另外,本发明的技术问题在于提供一种包含新型槐糖脂的组合物,尤其是表面活性剂、清洁剂、或乳化剂。
[解决问题的技术手段]
本发明者们通过各种机器分析而确认到,在广泛研究的槐糖脂生产菌(例如球拟假丝酵母等)的培养产物中存在分子结构不同于现有已知的槐糖脂的未知成分,对它们进行了分离、精制,并进行了结构分析,确认了其为新型结构的槐糖脂衍生物。
通过物性分析确认到,这些新型槐糖脂衍生物表现出与现有的槐糖脂不同的表面活性、自组织特性,作为优异的清洁成分发挥功能,从而完成了本发明。
本发明涉及下述(1)、(2)中所记载的槐糖脂衍生物。
(1)一种槐糖脂衍生物,其由下述式(1)的通式表示。
式(1)
(式中,R1~R3分别独立地为氢、碳原子数2~22的脂肪酸酯、或上述SL基,并且R1~R3中的至少一个为SL基。SL基中的R为相同或不同,分别表示氢或乙酰基,Rn表示碳原子数13~21的直链状或支链状的烷基或烯基。)
(2)一种槐糖脂衍生物,其是由下述式(2)的化学式所表示的任一化合物。
式(2)
(式中的SL基与上述式(1)中的定义相同,R'表示碳原子数2~22的脂肪酸酯。)
另外,本发明涉及下述(3)、(4)中所记载的表面活性剂、清洁剂、分散剂、或乳化剂。
(3)一种表面活性剂、清洁剂、分散剂、或乳化剂,其由如上述(1)或(2)中所记载的槐糖脂衍生物构成。
(4)如上述(3)中所记载的表面活性剂、清洁剂、分散剂、或乳化剂,其用于饲料、肥料、饮食品、农药、医药品、准药品、或化妆品。
[发明效果]
本发明的新型槐糖脂衍生物表现出与已知的槐糖脂不同的表面活性及自集合特性,作为优异的清洁成分发挥功能,因此,能够扩充槐糖脂制品的结构及功能的多样性。与已知的槐糖脂相比,作为水溶性高的非离子型表面活性剂发挥功能。
另外,由于其为安全性高的来自天然物的槐糖脂衍生物,因此,也能够提高各种制品的安全性,能够应用于饲料、肥料、饮食品、农药、医药品、准药品或化妆品等广泛范围的领域中。
附图说明
图1表示实施例1中所取得的SL混合物固体的正相TLC分析的结果。
图2表示实施例1中所取得的SL混合物固体的逆相TLC分析的结果。
图3表示将实施例1中所取得的SL混合物固体提供给逆相柱层析法的层析图。
图4表示实施例4中所分离的化合物A的LC/MS分析的结果。
图5表示实施例4中所分离的化合物B的LC/MS分析的结果。
图6表示实施例4中所分离的化合物C的LC/MS分析的结果。
图7表示化合物B的1H-NMR的结果。
图8表示化合物B的1H-NMR的结果(放大)。
图9表示化合物A的1H-NMR的结果。
图10表示化合物C的1H-NMR的结果。
图11是在化合物A、B、C中分别添加蒸馏水所得的0.1wt%水溶液的照片。
图12表示化合物A、B、C各自的表面张力降低能力。A为淡的●,B为○,C为●。
图13表示实施例1中所取得的SL混合物固体的MALDI-TOF/MS分析的结果。
图14表示化合物B的乙酰化反应前与反应后的HPLC分析的结果。
图15表示化合物B的乙酰化反应前与反应后的LC/MS分析的结果。
具体实施方式
本发明涉及一种新型槐糖脂衍生物及包含该衍生物的组合物。本发明的槐糖脂衍生物(以下,有时称为“SL衍生物”)由下述通式(1)表示。
式(1)
在此,式中的R1~R3分别独立地为氢、碳原子数2~22的任一脂肪酸酯、或上述SL基的任一个。其中,R1~R3的至少一个为SL基。
碳原子数2~22的任一个脂肪酸酯由-(O)C-烃基表示,该烃基的碳原子数为1~21。
另外,SL基中的R相同或不同,表示氢或乙酰基,Rn表示碳原子数13~21的直链状或支链状的烷基或烯基。
本发明的SL衍生物可以是由下述化学式(2)所表示的化合物的任一个。
式(2)
在此,式中的SL基与上述式(1)中的定义相同。R'为碳原子数2~22的脂肪酸酯,由-(O)C-烃基表示,该烃基的碳原子数为1~21。
本发明的SL衍生物能够从SL生产菌的培养物中获得,由于其是SL的甘油酯,因此能够化学合成。
例如,可通过如下方法制造:在非醇类有机溶剂(氯仿、甲苯、丙酮等)中或无溶剂下,以脂肪酶等固定化酶为催化剂,将SL与甘油进行酯化(酯交换或水解的逆反应);或者,使用植物油(甘油三酯)代替甘油,以相同的方式进行酯交换反应。尤其是,如果使用反应性优异的内酯型(LSL),则通过与甘油等进行混合并加热搅拌,而能够制造本发明的SL衍生物。进一步,对于SL基中的羟基而言,即便是在从培养物中获得之后,也可以通过与乙酸酐等进行反应而乙酰化。通过利用该反应,能够制造向全部羟基导入乙酰基而提高亲油性的SL衍生物(例如,化学式(1)的SL基中的R全部为乙酰基)。
本发明的组合物作为基于本发明的SL衍生物所具有的表面活性的表面活性剂,或作为乳化剂、分散剂,能够应用于饲料、肥料、饮食品、农药、医药品、准药品或化妆品、及它们的添加剂。
对于本发明的组合物中所包含的SL衍生物的量并没有特别的限定,为0.01~100wt%,优选为0.1~50wt%,更优选为1~30wt%。当组合物中的SL衍生物的量为如1wt%以下等较少的情况下,水溶性变小;另一方面,当组合物中的SL衍生物的量为如50wt%以上等较多的情况下,经济性降低。
[实施例]
以下,通过实施例对本发明进行更具体的说明,但本发明并不限定于下述的实施例。在实施例中,“%”是指“wt%”。
[实施例1]
槐糖脂的生产、回收
球拟假丝酵母(Starmerella bombicola)ATCC22214株的培养
(1)种培养
将保存于保存培养基(酵母萃取物10g/L、蛋白胨20g/L、葡萄糖20g/L、琼脂20g/L)的上述球拟假丝酵母(Starmerella bombicola)ATCC22214株接种1个白金耳至装有酵母萃取物10g/L、蛋白胨20g/L、葡萄糖20g/L的组成的液体培养基4mL的试验管中,在28℃下进行1天振荡培养。
(2)正式培养
将(1)中所获得的菌体培养液接种至装有10g/L酵母萃取物、20g/L蛋白胨、100g/L葡萄糖及100g/L菜籽油的组成的液体培养基30mL的三角烧瓶中,在28℃下进行7天振荡培养。
(3)槐糖脂的回收
通过将(2)中所得的培养液静置1小时而在下层产生SL相。回收该SL相,用氢氧化钠水溶液中和,用水清洗,由此将SL混合物以水溶液的状态回收。另外,为了对所得的SL混合物水溶液进行后续实验,通过添加己烷并进行搅拌、离心分离,从而在己烷相中提取并去除残存的油脂或脂肪酸,对水相进行冷冻干燥,回收SL混合物固体。
(4)内酯型槐糖脂、酸型槐糖脂样品的精制
为了在后续实验中用作样品,通过已知的精制方法将内酯型SL(LSL)及酸型SL(ASL)分离。即,将上述SL混合物固体溶解于丙酮中,提供给玻璃管柱中填充有硅胶(Wakogel C-200)的硅胶柱,通过以氯仿与丙酮的混合液作为展开溶剂的柱层析法进行精制。以氯仿与丙酮的比率为8:2的混合液分离回收LSL,接着,以氯仿与丙酮的比率为2:8的混合液分离回收酸型SL,通过下述薄层层析法分析而确认到各自回收的组分为目标LSL样品、ASL样品。
[实施例2]
槐糖脂的薄层层析法分析
针对实施例1中所得的SL混合物固体,将其溶解于甲醇中,进行薄层层析法(TLC)分析。
首先,使用硅胶TLC玻璃板(Merck公司制造的TLC硅胶60F254玻璃板),作为展开溶剂使用氯仿/甲醇/氨水=80/20/2混合溶剂,通过已知的正相系统进行TLC分析。当通过蒽酮硫酸指示剂检测成分时,检测到包含糖骨架的化合物为蓝绿色。其结果是,非极性的LSL在上部展开,高极性的ASL在下部展开(图1)。
其次,使用逆相改性硅胶TLC板(Merck公司制造的TLC硅胶60RP-18F254S玻璃板),作为展开溶剂使用甲醇/水=95/5混合溶剂,通过逆相系统进行分析,其结果,如预料的那样,与正相时相反,高极性的ASL在上部展开,非极性的LSL在中部展开,并且,进一步在下部检测到被视为通过已知方法未曾检测到的结构未知的糖脂的点(图2)。
根据该结果可知,实施例1中所得的SL混合物中包含与现有技术中已知的LSL、ASL不同的糖脂。
[实施例3]
槐糖脂的高效液相色谱法分析
针对实施例1中所获得的SL混合物固体,将其用甲醇溶解,进行高效液相色谱法(HPLC)分析。使用搭载有Corona带电粒子检测器(CAD)(Thermo公司制造的CoronaTM VeoTM)的HPLC(Thermo公司制造的Thermo Scientific Ultimate 3000HPLC),分析柱使用逆相ODS管柱(GL Science公司制造的InertSustainTM VC18),柱温为40℃,洗脱液为5mM甲酸铵甲醇/5mM甲酸铵水混合溶剂体系,将梯度程序设为甲醇70%(步骤0分钟→3分钟)、70%→100%(梯度3分钟→18分钟)、100%(步骤18分钟→25分钟)、70%(步骤25分钟→35分钟),以0.3mL/m的流速进行成分分析。将所得的色谱图示于图3中。
分析的结果为:在保持时间3分钟~10分钟时检测到ASL,在12分钟~16分钟时检测到LSL,之后,在18分钟前后、20分钟前后、22分钟前后分别检测到3个(A、B、C)未知成分的峰。该结果与实施例2的逆相TLC分析中在ASL、LSL后检测到未知糖脂的结果一致。
[实施例4]
结构未知糖脂的分离、精制
为了将实施例3中新检测到的3个峰的成分单独分离,通过硅胶柱层析法进行成分分离。首先,通过使用与实施例1(4)相同的氯仿/丙酮混合溶剂的正相管柱法,利用氯仿/丙酮=50/50溶剂使LSL组分几乎全量溶出,之后,利用100%丙酮或100%甲醇的溶剂回收ASL及混合存在目标的未知糖脂的剩余成分。其次,使用填充有经十八烷基改性的硅胶(Wakogel 100C18)的管柱,通过使用以甲醇/水混合溶剂作为展开溶剂的逆相柱层析法,通过将ASL与未知糖脂分离的2个阶段的管柱精制法,将未知糖脂分离并回收。通过逆相TLC分析及逆相HPLC分析确认到,所分离的各成分几乎为单一点、单一波峰的成分。
之后,按照从逆相管柱溶出的顺序设为化合物A、B、C。化合物A为透明粘稠的固体,B为比A硬质的透明固体,C为蜡状白色固体。
[实施例5]
结构未知糖脂的质谱分析
对实施例4中所分离的化合物A、B、C进行液相色谱/质谱(LC/MS)分析。使用连结有电喷雾电离质谱仪(ESI-MS)(Thermo公司制造的Exactive Plus)的实施例3中所记载的HPLC,在分离条件与实施例3相同的条件下进行LC/MS分析,将所得的结果分别示于图4~6中。
化合物A的主成分为m/z=1468,B为m/z=2157,C为m/z=1731(所有检测均为负模式),混合存在其他的“各主成分-42”的成分(1426、2115、1689)。这是糖脂型生物表面活性剂中常见的形式,预计是去除了一个乙酰基的化合物。进一步,还混合存在“各成分+114”的成分(1582、2271、1845)或该值-42的成分,预计这些均为主成分的官能基经部分改性后的成分。预计化合物A~C中混合存在基本骨架相同且脂肪酸组成不同的成分。
[实施例6]
结构未知糖脂的结构分析
对实施例4中所分离的化合物A、B、C,通过核磁共振波谱(NMR)分析进行化学结构的鉴定。使用Bruker公司制造的NMR(AV-400),首先对含量最多的化合物B进行1H-NMR分析,结果,确认到其为与结构已知的ASL几乎相同图案的波谱(图7)。
另一方面,将糖骨架部分的波谱放大而进行比较,结果,确认到在5.3ppm附近出现了与ASL不同的新波峰,并且,与4.1~4.4ppm附近的峰面积比成为标准波峰的槐二糖1位的波峰相比明显较大。为了对该波峰更详细地进行分析而进行1H-1HCOSY分析,结果,确认到原本在4.1~4.4ppm附近出现的与来自槐二糖6位的波峰不同的新波峰在该位置处重叠,这些与5.3ppm附近的新波峰相关(图8)。
将化合物B的NMR资料示于表1中。
[表1]
根据以上结果可知,化合物B为在ASL的结构上还具有表示这些2种波峰的化学结构的SL衍生物。作为这些在5.3ppm附近及4.1~4.4ppm附近出现波峰的典型化合物的例,可例举油脂(脂肪酸甘油三酯)的甘油骨架。鉴于上述结果,推测化合物B为甘油的3个羟基与ASL经酯键键合而成的化学式(6)的化合物。
实施例5中确认到的化合物B的主成分为m/z=2157,其与脂肪酸部位为C18:1的2个ASL和脂肪酸部位为C18:2的1个ASL与1个甘油经酯键键合而成的甘油三酯结构的化合物的分子量完全一致。综上所述,确定了化合物B为化学式(6)的化合物。
式(6)
对化合物A及C进行相同的分析。将化合物A及C的1H-NMR分析的结果示于图9及10中。另外,将化合物A或C的NMR资料示于表2或表3中。
[表2]
[表3]
作为根据NMR测定结果所推测的可能性最高的代表性结构的化合物,推测化合物A为甘油与2个ASL键合所得的化学式(5)的化合物,化合物C为甘油与2个ASL及1个长链脂肪酸键合所得的化学式(7)的化合物。这些均与实施例5中确认到的各化合物主成分的分子量一致,支持该结构分析的结果。但生产菌培养物中所包含的衍生物并不限定于这些。
式(5)
式(7)
[实施例7]
新型槐糖脂衍生物A~C的水溶液
对实施例4中所分离的化合物A、B、C,分别称取10mg放入量瓶中,添加蒸馏水而定容,由此制备1mg/mL(0.1wt%)水溶液(图11)。
化合物A、B完全溶解而获得透明的水溶液,但C产生白浊。进一步,对A、B利用相同的方法制备10mg/mL(1wt%)水溶液,结果A产生白浊,B完全溶解。进一步,将白浊的化合物A、C的水溶液静置于冰箱中,结果均完全溶解而成为透明的水溶液。
该根据温度而发生的水溶液的状态变化是可逆的现象,表示其在室温(25℃以下)以下具有浊点。即,支持了如下事实:如实施例6中所确定的结构那样,化合物A及C是非离子性表面活性剂。另外,根据以上的结果,确认到:与键合有长链脂肪酸的化合物C相比,未键合有长链脂肪酸的化合物A表现出更高的水溶性,进一步,化合物B是与这些相比分子量高但水溶性极高的非离子性表面活性剂。
[实施例8]
新型SL衍生物A~C的表面张力降低能力
对实施例4中所分离的化合物A、B、C,制备各浓度的水溶液,使用接触角测量仪(协和界面科学公司制造的DMo-500)通过悬滴法[杨-拉普拉斯(Young Laplhas)法]进行水溶液的表面张力测定。将对水溶液浓度-表面张力进行对数绘图所得的图表示于图12中。对于化合物C而言,无论浓度多少,水溶液的表面张力值几乎无变化;对于A、B而言,随着浓度的增加,表面张力大幅降低。另外,均确认到:随着浓度的增加,图表中存在2个阶段的拐点(inflection point)。当根据表面张力值固定的后半段的拐点计算出临界微胞浓度(CMC)的结果:化合物A为CMC=1.91g/L(约1.3×10-3M),此时的表面张力值(γCMC)为40.4mN/m;化合物B为CMC=2.99g/L(约1.4×10-3M),γCMC为41.4mN/m。根据文献记载,LSL、ASL的这些值分别为LSL:CMC=1.4×10-5M、γCMC=32.3mN/m,ASL:CMC=1.2×10-4M、γCMC=37.1mN/m,此次所发现的新型SL衍生物与这些相比虽为非离子性表面活性剂,但水溶性极高,表现出平稳的表面张力降低能力,即,表示其为非常适合在水系中使用的表面活性剂。
[实施例9]
槐糖脂的基质辅助激光解吸电离飞行时间质谱(MALDI-TOF/MS)分析
针对实施例1中所得的SL混合物固体,使用日本分光公司制造的JMS-3000SpiralTOF-MS,基质使用2',4',6'-三羟基苯乙酮(THAP)进行MALDI-TOF/MS分析(图13)。
检测到了与已知的LSL、ASL不同的m/z=803.4的结构未鉴定化合物的波峰。参考SL与甘油经酯键键合而成的化合物A~C的结构,根据分子量计算,则推测为如化学式(8)所示的脂肪酸部位为C18:1的1个ASL与甘油经酯键键合而得的化合物(Na加成体)。
式(8)
[实施例10]
槐糖脂衍生物的乙酰化反应
称取20mg实施例4中所得的化合物B放入小玻璃瓶中,添加丙酮1mL使其溶解。分别添加乙酸酐200μL、三乙胺10μL,在室温下静置一晚。反应结束后,通过减压干燥而将溶剂类全部去除,回收反应产物。
进行反应前后的化合物的逆相TLC分析,其结果,检测到因乙酰化反应比作为起始物的化合物B移动度小(即疏水性较高)的化合物,确认到反应的进行。其次,通过与实施例3及5相同的方法进行了产物的HPLC、LC/MS分析。
HPLC分析的结果是,与逆相TLC分析的结果同样地确认到:产物的波峰向保持时间较长的一侧(即,疏水性的一侧)移动(图14)。进一步,确认到:产物的主成分的分子离子峰为2536、2578、2494、…等,分别为化合物B的糖骨架上键合9个、10个、8个、…乙酰基而成的乙酰化物(图15)。根据NMR测定的结果,在2.0ppm附近的来自乙酰基的波峰增加,因此,也确认到:糖骨架中追加导入了乙酰基。
如果使用相同的方法,则对化合物A、C也能够将任意数量的乙酰基导入到糖骨架中。根据以上结果确认到,本发明的新型SL衍生物通过乙酰化反应能够转换为糖骨架中导入有任意数量的乙酰基的衍生物(式(1))。
(产业上的可利用性)
本发明的新型SL衍生物的水溶性、降低表面张力的能力、自组织特性优异,并且是安全性高的来自天然物的槐糖脂衍生物,因此,能够应用于饲料、肥料、饮食品、农药、医药品、准药品及化妆品等范围较广的领域中。
Claims (4)
3.一种表面活性剂、清洁剂、分散剂、或乳化剂,其由权利要求1或2所述的槐糖脂衍生物构成。
4.如权利要求3所述的表面活性剂、清洁剂、分散剂、或乳化剂,其用于饲料、肥料、饮食品、农药、医药品、准药品、或化妆品。
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