TW202304945A - 新穎槐糖脂質衍生物 - Google Patents
新穎槐糖脂質衍生物 Download PDFInfo
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- TW202304945A TW202304945A TW111112461A TW111112461A TW202304945A TW 202304945 A TW202304945 A TW 202304945A TW 111112461 A TW111112461 A TW 111112461A TW 111112461 A TW111112461 A TW 111112461A TW 202304945 A TW202304945 A TW 202304945A
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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 24
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Abstract
Description
本發明係關於一種新穎槐糖脂質衍生物及包含該衍生物之組成物。
親水基由糖所構成之糖型界面活性劑之中,為來自微生物之天然界面活性劑且安全性較高之糖型生物界面活性劑作為優異界面活性劑而為人所知。該等之中,槐糖脂質為糖脂質,具有兩親媒性結構,因此具有較強之界面活性作用,生物降解性與安全性較高,故作為生物界面活性劑之主角的用途開發正在進行。
作為生產槐糖脂質之酵母,具有代表性的是作為擔子菌酵母之球擬假絲酵母(Starmerella bombicola),由於其生物界面活性劑之生產力達到每1 L培養液400 g以上,因此用於商業基礎之生產。槐糖脂質係具有羥基脂肪酸於槐二糖之1位進行醚鍵結而形成之由下述式(3)所表示之內酯型(LSL)、及由下述式(4)所表示之酸型(ASL)之分子結構的糖脂質,該槐二糖係葡萄糖於2→1位進行醚鍵結而成之二糖。於微生物產物中該等係以包含一種或數種之混合物之形式存在。
關於槐糖脂質之內酯型(非離子型)與酸型(陰離子型),作為界面活性劑之性質大不相同,從而正在開發製作該等之組成不同之混合物或分開製作該等之方法等擴充槐糖脂質製品之結構及功能之多樣性的技術。例如,有報告指出,上述球擬假絲酵母(Starmerella bombicola)所生產之槐糖脂質一般以內酯型與酸型大致為6~8:2~4之混合物之形式獲得,作為主成分之內酯型與酸型相比濃度較低且表現出優異之表面張力降低能力(非專利文獻1),除此之外亦表現出較高之抗菌活性(非專利文獻2)。
另一方面,報告了一種藉由水解使內酯環開環而獲得化學上穩定之高純度之酸型槐糖脂質而將其調配所得之洗淨劑(專利文獻1),且報告了一種藉由將花假絲酵母(Candida floricola)作為生產菌進行培養而僅選擇性地製造酸型槐糖脂質之方法(專利文獻2)。又,除存在數個之官能基經改質之槐糖脂質衍生物以外,亦報告了分類不同於槐糖脂質聚合體等之內酯型、酸型之新穎結構之衍生物(專利文獻3、非專利文獻3)。進而,亦有報告稱,藉由將巴蒂斯塔念珠菌(Candida batistae)作為生產菌進行培養,可獲得與槐二糖鍵結之脂肪酸部分之結構不同之槐糖脂質(非專利文獻4)。
專利文獻1:日本專利特開2006-70231號公報
專利文獻2:日本專利特開2008-247845號公報
專利文獻3:國際公開第2015/20114號
[非專利文獻]
非專利文獻1:Journal of Oleo Science (2013) Vol.62, p.857-864
非專利文獻2:Journal of Microbiology and Biotechnology (2002) Vol.12, p.235-241
非專利文獻3:Carbohydrate Research (2012) Vol.348, p.33-41
非專利文獻4:Journal of Oleo Science (2008) Vol.57, p.359-369
(發明所欲解決之問題)
習知已知之槐糖脂質之結構大致僅有上述內酯型與酸型兩種形式,為了擴充物性、功能,要求擴展結構之多樣性。本發明之課題在於提供一種可應用於飼料、肥料、飲食品、農藥、醫藥品、準藥品、或化妝品等廣泛範圍之領域中之新穎槐糖脂質衍生物。又,本發明之課題在於提供一種包含新穎槐糖脂質之組成物,尤其是界面活性劑、洗淨劑、或乳化劑。
(解決問題之技術手段)
本發明人等藉由各種機器分析而確認到,於廣泛研究之槐糖脂質生產菌(例如球擬假絲酵母等)之培養產物中存在分子結構不同於習知已知之槐糖脂質之未知成分,將該等進行單離、精製,進行結構解析,可知其為新穎結構之槐糖脂質衍生物。根據物性解析,確認到該等新穎槐糖脂質衍生物表現出與習知之槐糖脂質不同之界面活性、自組織特性,作為優異之洗淨成分發揮功能,從而完成本發明。
本發明係關於下述(1)、(2)中所記載之槐糖脂質衍生物。
(1)一種槐糖脂質衍生物,其由下述式(1)之通式表示。
式(1)
[化1]
(式中,R
1~R
3分別獨立地為氫、碳數2~22之脂肪酸酯、或上述SL基,但R
1~R
3之至少一者為SL基。SL基中之R為相同或不同,分別表示氫或乙醯基,R
n表示碳數13~21之直鏈狀或支鏈狀之烷基或烯基)
(2)一種槐糖脂質衍生物,其係由下述式(2)之化學式所表示之任一化合物。
式(2)
[化2]
(式中之SL基與上述式(1)中之定義相同,R'表示碳數2~22之脂肪酸酯)
又,本發明係關於下述(3)、(
4)中所記載之界面活性劑、洗淨劑、分散劑、或乳化劑。
(3)一種界面活性劑、洗淨劑、分散劑、或乳化劑,其等包含如上述(1)或(2)中所記載之槐糖脂質衍生物。
(4)如上述(3)中所記載之界面活性劑、洗淨劑、分散劑、或乳化劑,其等用於飼料、肥料、飲食品、農藥、醫藥品、準藥品、或化妝品。
(對照先前技術之功效)
本發明之新穎槐糖脂質衍生物表現出與習知之槐糖脂質不同之界面活性及自集合特性,作為優異之洗淨成分發揮功能,因此可擴充槐糖脂質製品之結構、功能多樣性。與習知之槐糖脂質相比,作為水溶性較高之非離子型界面活性劑發揮功能。又,由於其為安全性較高之來自天然物之槐糖脂質衍生物,因此亦可提高各製品之安全性,可應用於飼料、肥料、飲食品、農藥、醫藥品、準藥品或化妝品等廣泛範圍之領域中。
本發明係關於一種新穎槐糖脂質衍生物及包含該衍生物之組成物。本發明之槐糖脂質衍生物(以下有時稱為「SL衍生物」)係由下述通式(1)表示。
式(1)
[化1]
此處,式中之R
1~R
3分別獨立地為氫、碳數2~22之任一脂肪酸酯、或上述SL基之任一者。其中,R
1~R
3之至少一者為SL基。碳數2~22之任一脂肪酸酯係由-(O)C-烴基表示,該烴基之碳數為1~21。又,SL基中之R可為相同或不同,表示氫或乙醯基,R
n表示碳數13~21之直鏈狀或支鏈狀之烷基或烯基。
本發明之SL衍生物可為由下述化學式(2)所表示之化合物之任一種。
式(2)
[化2]
此處,式中之SL基與上述式(1)中之定義相同。R'為碳數2~22之脂肪酸酯,由-(O)C-烴基表示,該烴基之碳數為1~21。
本發明之SL衍生物可自SL生產菌之培養物中獲得,但由於其為SL之甘油酯,因此可化學合成。
例如,可藉由如下方式製造:於非醇系有機溶劑(氯仿、甲苯、丙酮等)中或無溶劑下,以脂肪酶等固定化酶為觸媒,將SL與甘油進行酯化(酯交換或水解之逆反應),或使用植物油(三酸甘油酯)代替甘油,以相同之方式進行酯交換反應。尤其若使用反應性優異之內酯型(LSL),則藉由與甘油等混合並加熱攪拌,可製造本發明之SL衍生物。進而,SL基中之羥基即便在自培養物中獲得後,亦可藉由與乙酸酐等反應而乙醯化。藉由利用該反應,可製造向全部羥基導入乙醯基而提高親油性之SL衍生物(例如化學式(1)之SL基中之R全部為乙醯基)。
本發明之組成物可作為基於本發明之SL衍生物所具有之界面活性之界面活性劑,或作為乳化劑、分散劑,應用於飼料、肥料、飲食品、農藥、醫藥品、準藥品或化妝品、及該等之添加物中。本發明之組成物中所包含之SL衍生物之量並無特別限定,為0.01~100 wt%,較佳為0.1~50 wt%,更佳為1~30 wt%。於組成物中之SL衍生物之量如1 wt%以下等較少之情形時,水溶性變小,另一方面,於如50 wt%以上等較多之情形時,經濟性降低。
[實施例]
以下,藉由實施例對本發明更具體地進行說明,但本發明並不限定為以下實施例。於實施例中,「%」意指「wt%」。
[實施例1]
槐糖脂質之生產、回收
球擬假絲酵母(Starmerella bombicola)ATCC22214株之培養
(1)種培養
將保存於保存培養基(酵母萃取物10 g/L、蛋白腖20 g/L、葡萄糖20 g/L、瓊脂20 g/L)之上述球擬假絲酵母(Starmerella bombicola)ATCC22214株接種1白金耳至裝有酵母萃取物10 g/L、蛋白腖20 g/L、葡萄糖20 g/L之組成之液體培養基4 mL的試驗管中,於28℃下進行1天振盪培養。
(2)正式培養
將(1)中所獲得之菌體培養液接種至裝有10 g/L酵母萃取物、20 g/L蛋白腖、100 g/L葡萄糖及100 g/L菜籽油之組成之液體培養基30 mL的三角燒瓶中,於28℃下進行7天振盪培養。
(3)槐糖脂質之回收
藉由將(2)中所得之培養液靜置1小時而於下層產生SL相。回收該SL相,用氫氧化鈉水溶液中和,用水洗淨,藉此將SL混合物以水溶液之狀態回收。又,為了對所得之SL混合物水溶液進行後續實驗,藉由添加己烷並進行攪拌、離心分離,而於己烷相中提取、去除殘存油脂或脂肪酸,對水相進行冷凍乾燥,回收SL混合物固體。
(4)內酯型槐糖脂質、酸型槐糖脂質樣品之精製
為了於後續實驗中用作樣品,藉由已知之精製方法將內酯型SL(LSL)及酸型SL(ASL)分離。即,將上述SL混合物固體溶解於丙酮中,供於玻璃柱管中填充有矽膠[和光膠C-200(Wakogel® C-200)]之矽膠管柱,藉由以氯仿與丙酮之混合液作為展開溶劑之管柱層析法進行精製。以氯仿與丙酮之比率為8:2對LSL進行分離回收,繼而以2:8對酸型SL進行分離回收,藉由下述薄層層析法解析而確認到各自回收之組分為目標LSL樣品、ASL樣品。
[實施例2]
槐糖脂質之薄層層析法解析
針對實施例1中所得之SL混合物固體,將其溶解於甲醇中,進行薄層層析法(TLC)解析。首先,使用矽膠TLC玻璃板(Merck公司製造之TLC矽膠60F254玻璃板),藉由展開溶劑使用氯仿/甲醇/氨水=80/20/2混合溶劑之習知之正相系統進行TLC分析。當藉由蒽酮硫酸指示劑檢測成分時,檢測到包含糖骨架之化合物為藍綠色。結果非極性LSL於上部展開,高極性ASL於下部展開(圖1)。其次,使用逆相改質矽膠TLC板(Merck公司製造之TLC矽膠60RP-18F254S玻璃板),藉由展開溶劑使用甲醇/水=95/5混合溶劑之逆相系統進行分析,結果如預料般與正相時相反,高極性ASL於上部展開,非極性LSL於中部展開,且進而於下部檢測到被視為藉由習知法未檢測到之結構未知之糖脂質的點(圖2)。根據該結果可知,實施例1中所得之SL混合物中包含與習知已知之LSL、ASL不同之糖脂質。
[實施例3]
槐糖脂質之高效液相層析法解析
針對實施例1中所獲得之SL混合物固體,將其用甲醇溶解,進行高效液相層析法(HPLC)解析。使用搭載有Corona帶電粒子檢測器(CAD)(Thermo公司製造之Corona
TMVeo
TM)之HPLC(Thermo公司製造之Thermo Scientific Ultimate 3000 HPLC),分析管柱使用逆相系ODS管柱(GL Science公司製造之InertSustain
TMVC18),管柱溫度為40℃,溶離液為5 mM甲酸銨甲醇/5 mM甲酸銨水混合溶劑系統,將梯度程式設為甲醇70%(步驟0分鐘→3分鐘)、70%→100%(梯度3分鐘→18分鐘)、100%(步驟18分鐘→25分鐘)、70%(步驟25分鐘→35分鐘),以0.3 mL/m之流速進行成分分析。將所得之層析圖示於圖3中。分析之結果為,於保持時間3分鐘~10分鐘檢測到ASL,於12分鐘~16分鐘檢測到LSL後,於18分鐘前後、20分鐘前後、22分鐘前後分別檢測到3個(A、B、C)未知成分之峰。該等結果與實施例2之逆相TLC解析中於ASL、LSL後檢測到未知糖脂質之結果一致。
[實施例4]
結構未知糖脂質之分離、精製
為了將實施例3中新檢測到之3個峰成分單離,藉由矽膠管柱層析法進行成分分離。首先藉由使用與實施例1(4)相同之氯仿/丙酮混合溶劑之正相管柱法,利用氯仿/丙酮=50/50溶劑使LSL組分幾乎全量溶出,其後利用丙酮100%或甲醇100%溶劑回收ASL及混合存在目標之未知糖脂質之剩餘成分。其次使用填充有經十八烷基改質之矽膠(和光膠100C18)之管柱,藉由以甲醇/水混合溶劑作為展開溶劑之逆相管柱層析法,藉由將ASL與未知糖脂質分離之2個階段之管柱精製法,將未知糖脂質分離、回收。藉由逆相TLC解析及逆相HPLC解析確認到,所分離之各成分幾乎為單一點、單一波峰之成分。之後,按照自逆相管柱溶出之順序設為化合物A、B、C。化合物A為透明黏稠之固體,B為較A硬質之透明固體,C為蠟狀白色固體。
[實施例5]
結構未知糖脂質之質譜解析
對實施例4中所分離之化合物A、B、C進行液體層析/質譜(LC/MS)解析。使用連結有電噴灑游離質譜儀(ESI-MS)(Thermo公司製造之Exactive Plus)之實施例3中所記載之HPLC,在分離條件與實施例3相同之條件下進行LC/MS解析,將所得之結果分別示於圖4~6中。化合物A之主成分為m/z=1468,B為m/z=2157,C為m/z=1731(所有檢測均為負模式),混合存在其他自各主成分-42之成分(1426、2115、1689)。其係糖脂質型生物界面活性劑中常見之形式,預計係去除了一個乙醯基之化合物。進而,亦混合存在各成分+114之成分(1582、2271、1845)或自其-42之成分,預計該等均為主成分之官能基經部分改質者。預計化合物A~C中混合存在基本骨架相同且脂肪酸組成不同者。
[實施例6]
結構未知糖脂質之結構解析
對實施例4中所分離之化合物A、B、C,藉由核磁共振光譜(NMR)解析進行化學結構之鑑定。使用Bruker公司製造之NMR(AV-400),首先對含量最多之化合物B進行
1H-NMR解析,結果確認到其為與結構已知之ASL幾乎相同形式之光譜(圖7)。另一方面,將糖骨架部分之光譜放大而比較,結果確認到於5.3 ppm附近出現與ASL不同之新波峰,並且與4.1~4.4 ppm附近之峰面積比成為標準波峰之槐二糖1位之波峰相比明顯較大。為了對該等波峰更詳細地進行解析而進行
1H-
1HCOSY解析,結果可知原本於4.1~4.4 ppm附近出現之與來自槐二糖6位之波峰不同之新波峰於該位置處重疊,該等與5.3 ppm附近之新波峰相關(圖8)。
將化合物B之NMR資料示於表1中。
[表1]
13C-NMR | 1H-NMR | ||
δ(ppm) | δ(ppm) | ||
糖骨架 | |||
C-1' | 101.2 | H-1' | 4.45 d |
C-2' | 82.4 | H-2' | 3.36 m |
C-3' | 76.4 | H-3' | 3.30-3.60 m |
C-4' | 70.0 | H-4' | 3.30-3.60 m |
C-5' | 73.5 | H-5' | 3.30-3.60 m |
C-6' | 63.5 | H-6'a | 4.19 m |
H-6'b | 4.36 m | ||
C-1'' | 104.3 | H-1'' | 4.55 d |
C-2'' | 74.7 | H-2'' | 3.25 m |
C-3'' | 76.1 | H-3'' | 3.30-3.60 m |
C-4'' | 70.0 | H-4'' | 3.30-3.60 m |
C-5'' | 74.2 | H-5'' | 3.30-3.60 m |
C-6'' | 63.5 | H-6''a | 4.19 m |
H-6''b | 4.36 m | ||
乙醯基 -C=O(C-6',6'') | 171.3 | ||
-CH 3(C-6',6'') | 19.4,19.6 | 2.05,2.06 s | |
甘油骨架 | |||
-CH 2O- | 61.9 | 4.17,4.35 m | |
-CHO- | 70.0 | 5.28 m | |
脂肪酸鏈 | |||
-C=O | 173.4 | ||
-CO- CH 2 - | 33.5 | 2.33 m | |
-CO-CH 2 CH 2 - | 24.9 | 1.60 b | |
-(CH 2) n- | 24.5-29.6 | 1.25-1.46 b | |
-CH=CH- CH 2 - | 26.8 | 2.00-2.10 b | |
-CH=CH- | 129.5 | 5.35 m | |
-OCH(CH 3)- CH 2 - | 36.5 | 1.60 b | |
-O CH(CH 3)- | 77.2 | 3.74 m | |
-CH 3 | 20.5 | 1.20 d |
根據以上結果可知,化合物B為除ASL之結構外還具有表示該等2種波峰之化學結構的SL衍生物。作為該等於5.3 ppm附近及4.1~4.4 ppm附近出現波峰之典型化合物之例,可例舉油脂(脂肪酸三甘油酯)之甘油骨架。基於以上,推定化合物B為甘油之3個羥基與ASL進行酯鍵結而成之化學式(6)之化合物。實施例5中確認到之化合物B之主成分為m/z=2157,其與脂肪酸部位為C18:1之2個ASL、C18:2之1個ASL與1個甘油進行酯鍵結而成之三酸甘油酯結構的化合物之分子量完全一致。綜合以上,鑑定化合物B為化學式(6)之化合物。
式(6)
[化6]
對化合物A及C進行相同之解析。將化合物A及C之
1H-NMR解析之結果示於圖9及10中。又,將化合物A或C之NMR資料示於表2或表3中。
[表2]
13C-NMR | 1H-NMR | ||
δ(ppm) | δ(ppm) | ||
糖骨架 | |||
C-1' | 101.2 | H-1' | 4.45 d |
C-2' | 82.4 | H-2' | 3.36 m |
C-3' | 76.4 | H-3' | 3.30-3.60 m |
C-4' | 70.0 | H-4' | 3.30-3.60 m |
C-5' | 73.5 | H-5' | 3.30-3.60 m |
C-6' | 63.5 | H-6'a | 4.19 m |
H-6'b | 4.36 m | ||
C-1'' | 104.3 | H-1'' | 4.55 d |
C-2'' | 74.7 | H-2'' | 3.25 m |
C-3'' | 76.1 | H-3'' | 3.30-3.60 m |
C-4'' | 70.0 | H-4'' | 3.30-3.60 m |
C-5'' | 74.2 | H-5'' | 3.30-3.60 m |
C-6'' | 63.5 | H-6''a | 4.19 m |
H-6''b | 4.36 m | ||
乙醯基 -C=O(C-6',6'') | 171.3 | ||
-CH 3(C-6',6'') | 19.4,19.6 | 2.05,2.06 s | |
甘油骨架 | |||
-CH 2O- | 64.6 | 4.11 m | |
-CHO- | 67.0 | 4.02 m | |
脂肪酸鏈 | |||
-C=O | 173.8 | ||
-CO- CH 2 - | 33.5 | 2.35 m | |
-CO-CH 2 CH 2 - | 24.9 | 1.60 b | |
-(CH 2) n- | 24.5-29.6 | 1.25-1.46 b | |
-CH=CH- CH 2 - | 26.8 | 2.00-2.10 b | |
-CH=CH- | 129.5 | 5.35 m | |
-OCH(CH 3)- CH 2 - | 36.5 | 1.60 b | |
-O CH(CH 3)- | 77.2 | 3.74 m | |
-CH 3 | 20.5 | 1.20 d |
[表3]
13C-NMR | 1H-NMR | ||
δ(ppm) | δ(ppm) | ||
糖骨架 | |||
C-1' | 101.2 | H-1' | 4.45 d |
C-2' | 82.4 | H-2' | 3.36 m |
C-3' | 76.4 | H-3' | 3.30-3.60 m |
C-4' | 70.0 | H-4' | 3.30-3.60 m |
C-5' | 73.5 | H-5' | 3.30-3.60 m |
C-6' | 63.5 | H-6'a | 4.19 m |
H-6'b | 4.36 m | ||
C-1'' | 104.3 | H-1'' | 4.55 d |
C-2'' | 74.7 | H-2'' | 3.25 m |
C-3'' | 76.1 | H-3'' | 3.30-3.60 m |
C-4'' | 70.0 | H-4'' | 3.30-3.60 m |
C-5'' | 74.2 | H-5'' | 3.30-3.60 m |
C-6'' | 63.5 | H-6''a | 4.19 m |
H-6''b | 4.36 m | ||
乙醯基 -C=O(C-6',6'') | 171.3 | ||
-CH 3(C-6',6'') | 19.4,19.6 | 2.05,2.06 s | |
甘油骨架 | |||
-CH 2O- | 61.9 | 4.17,4.35 m | |
-CHO- | 70.0 | 5.28 m | |
脂肪酸鏈 | |||
-C=O | 173.4 | ||
-CO- CH 2 - | 33.5 | 2.33 m | |
-CO-CH 2 CH 2 - | 24.9 | 1.60 b | |
-(CH 2) n- | 24.5-29.6 | 1.25-1.46 b | |
-CH=CH- CH 2 - | 26.8 | 2.00-2.10 b | |
-CH=CH- | 129.5 | 5.35 m | |
-OCH(CH 3)- CH 2 - | 36.5 | 1.60 b | |
-O CH(CH 3)- | 77.2 | 3.74 m | |
-CH 3(SL) | 20.5 | 1.20 d | |
-CH 3(脂肪酸) | 13.2 | 0.91 m |
作為根據NMR測定結果推定之可能性最高之代表性結構的化合物,推定化合物A為甘油與2個ASL鍵結所得之化學式(5)之化合物,化合物C為甘油與2個ASL及1個長鏈脂肪酸鍵結所得之化學式(7)之化合物。該等均與實施例5中確認到之各化合物主成分之分子量一致,支持該結構解析之結果。但生產菌培養物中所包含之衍生物並不限定於該等。
式(5)
[化5]
式(7)
[化7]
[實施例7]
新穎槐糖脂質衍生物A~C之水溶液
對實施例4中所分離之化合物A、B、C,分別稱取10 mg放入量瓶中,添加蒸餾水而定容,藉此製備1 mg/mL(0.1 wt%)水溶液(圖11)。化合物A、B完全溶解而獲得透明之水溶液,但C產生白濁。進而對A、B利用相同之方法製備10 mg/mL(1 wt%)水溶液,結果A產生白濁,B完全溶解。進而,將白濁之化合物A、C之水溶液靜置於冰箱中,結果均完全溶解而成為透明之水溶液。該根據溫度之水溶液之狀態變化係可逆之現象,表示其於室溫(25℃以下)以下具有濁點。即支持化合物A及C如實施例6中確定結構般為非離子性界面活性劑。又,根據以上之結果,確認到與長鏈脂肪酸所鍵結之化合物C相比,未鍵結之化合物A表現出較高之水溶性,進而化合物B係與該等相比分子量較高但水溶性極高之非離子性界面活性劑。
[實施例8]
新穎SL衍生物A~C之表面張力降低能力
對實施例4中所分離之化合物A、B、C,製備各濃度之水溶液,使用接觸角計(協和界面科學公司製造之DMo-500)藉由懸滴法[楊-拉普拉斯(Young Laplhas)法]進行水溶液之表面張力測定。將對水溶液濃度-表面張力進行對數繪圖所得之圖表示於圖12中。關於化合物C,無論濃度多少,水溶液之表面張力值幾乎無變化,但關於A、B,隨著濃度之增加而表面張力大幅降低。又,均確認到隨著濃度之增加,圖表中存在2個階段之反曲點,當根據表面張力值固定之後半段之反曲點算出臨界微胞濃度(CMC)時,化合物A為CMC=1.91 g/L(約1.3×10
-3M),此時之表面張力值(γCMC)為40.4 mN/m,化合物B為CMC=2.99 g/L(約1.4×10
-3M),γCMC為41.4 mN/m。LSL、ASL之該等值根據文獻分別為LSL:CMC=1.4×10
-5M、γCMC=32.3 mN/m,ASL:CMC=1.2×10
-4M、γCMC=37.1 mN/m,此次所發現之新穎SL衍生物與該等相比雖為非離子性界面活性劑,但水溶性極高,表現出平穩之表面張力降低能力,即表示其為非常適合在水系中使用之界面活性劑。
[實施例9]
槐糖脂質之基質輔助雷射脫附游離飛行時間質譜(MALDI-TOF/MS)解析
針對實施例1中所得之SL混合物固體,使用日本分光公司製造之JMS-3000 Spiral TOF-MS,基質使用2',4',6'-三羥基苯乙酮(THAP)進行MALDI-TOF/MS解析(圖13)。檢測到與習知之LSL、ASL不同之m/z=803.4之結構未鑑定化合物之波峰。推定其若參考SL與甘油進行酯鍵結而成之化合物A~C之結構,根據分子量算出,則為如化學式(8)之脂肪酸部位為C18:1之1個ASL與甘油進行酯鍵結所得之化合物(Na加成體)。
式(8)
[化8]
[實施例10]
槐糖脂質衍生物之乙醯化反應
稱取20 mg實施例4中所得之化合物B放入小玻璃瓶中,添加丙酮1 mL使其溶解。分別添加乙酸酐200 μL、三乙胺10 μL,於室溫下靜置一晚。反應結束後,藉由減壓乾燥而將溶劑類全部去除,回收反應產物。
進行反應前後之化合物之逆相TLC分析,結果檢測到因乙醯化反應較作為起始物之化合物B移動度小、即疏水性較高之化合物,確認到反應進行。其次,藉由與實施例3及5相同之方法進行產物之HPLC、LC/MS分析。HPLC分析之結果與逆相TLC分析之結果同樣地確認到產物之波峰轉移至保持時間較長之側、即疏水性側(圖14)。進而確認到,產物之主成分之分子離子峰為2536、2578、2494、…等,為9個、10個、8個、…乙醯基與各化合物B之糖骨架鍵結而成之乙醯化物(圖15)。根據NMR測定之結果,亦確認到由於2.0 ppm附近之來自乙醯基之波峰增加,因此糖骨架中追加導入了乙醯基。
若使用相同之方法,則可對化合物A、C亦將任意數量之乙醯基導入糖骨架中。根據以上結果確認到,本發明之新穎SL衍生物藉由乙醯化反應可轉換為糖骨架中導入有任意數量之乙醯基之衍生物(式(1))。
(產業上之可利用性)
由於本發明之新穎SL衍生物係水溶性、降低表面張力之能力、自組織特性優異且為來自安全性較高之天然物的槐糖脂質衍生物,因此可應用於飼料、肥料、飲食品、農藥、醫藥品、準藥品及化妝品等範圍較廣之領域中。
圖1表示實施例1中所取得之SL混合物固體之正相TLC分析之結果。
圖2表示實施例1中所取得之SL混合物固體之逆相TLC分析之結果。
圖3表示將實施例1中所取得之SL混合物固體供於逆相管柱層析法之層析圖。
圖4表示實施例4中所分離之化合物A之LC/MS解析之結果。
圖5表示實施例4中所分離之化合物B之LC/MS解析之結果。
圖6表示實施例4中所分離之化合物C之LC/MS解析之結果。
圖7表示化合物B之
1H-NMR之結果。
圖8表示化合物B之
1H-NMR之結果(放大)。
圖9表示化合物A之
1H-NMR之結果。
圖10表示化合物C之
1H-NMR之結果。
圖11係於化合物A、B、C中分別添加蒸餾水所得之0.1 wt%水溶液之照片。
圖12表示化合物A、B、C各自之表面張力降低能力。A為較淡之●,B為○,C為●。
圖13表示實施例1中所取得之SL混合物固體之MALDI-TOF/MS解析之結果。
圖14表示化合物B之乙醯化反應前與反應後之HPLC分析之結果。
圖15表示化合物B之乙醯化反應前與反應後之LC/MS解析之結果。
Claims (4)
- 一種界面活性劑、洗淨劑、分散劑、或乳化劑,其等包含請求項1或2之槐糖脂質衍生物。
- 如請求項3之界面活性劑、洗淨劑、分散劑、或乳化劑,其等用於飼料、肥料、飲食品、農藥、醫藥品、準藥品、或化妝品。
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