表面活性剂与叶酸的相互作用及其对光氧化降解的影响
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摘要
表面活性剂与有机小分子作用不仅能提高表面活性剂的聚集能力,还能提高小分子的溶解度、稳定性等应用性能,因此研究二者之间的相互作用机理对于促进表面活性剂的发展和实际应用具有重要意义。本工作提出了一种利用功能有机小分子调控表面活性剂聚集行为,进而提高不稳定小分子自身稳定性的新策略。利用表面张力、紫外可见吸收光谱、荧光光谱、动态光散射、等温滴定量热和核磁共振技术研究了在p H为7.0时,叶酸分别与十二烷基硫酸钠(SDS)、十二烷基三甲基溴化铵(DTAB)、季铵盐Gemini 12-6-12和季铵盐线性三聚12-3-12-3-12四种表面活性剂之间的相互作用及其导致的叶酸光氧化降解性能的变化,结果表明,阴离子表面活性剂SDS抑制叶酸光氧化降解的效率较低,而阳离子表面活性剂都能够显著抑制叶酸的光氧化降解,且随着表面活性剂寡聚度的增加,抑制效果增强,所需表面活性剂的浓度显著降低,寡聚表面活性剂12-3-12-3-12的抑制效率高达96%。
Interactions between surfactants and small organic molecules not only enhance the surface activity of the surfactants and induce aggregate transitions in them, but also improve the solubility and stability of the organic molecules. Understanding the interaction between surfactants and small molecules will help in widening the scope of application of surfactants. Folic acid, a member of the vitamin B family, has a pteridine ring, paraaminobenzoic acid, and glutamic acid, and is crucial for many reactions inside the human body. The unique structure of folic acidalso facilitates the preparation of functional materials such as liquid crystals and gels. However, the poor solubility and precipitation of folic acid limit its applications. Therefore, it is essential to improve the solubility and stability of folic acid. Surfactants are efficient in solubilizing and stabilizing small molecules. The interactions of folic acid with four types of surfactants, namely, an anionic surfactant, sodium dodecyl sulfate(SDS); a cationic surfactant, dodecyl trimethylammonium bromide(DTAB); a cationic ammonium gemini surfactant, 12-6-12; and a cationic ammonium trimeric surfactant, 12-3-12-3-12; have been investigated at p H 7.0 by surface tension measurements, ultraviolet-visible(UV) absorption spectroscopy, dynamic light scattering, isothermal titration calorimetry, and nuclear magnetic resonance spectroscopy. At pH 7.0, the carboxylic acid groups of folic acid are deprotonated, so each folic acid molecule carries two negative charges. The addition of a small amount of folic acid sharply reduces the critical micelle concentration(CMC) of cationic surfactants and their surface tension at the CMC. However, the surface activity and aggregation of SDS show only minimal changes with the introduction of folic acid. In addition, the photodegradation of folic acid in the presence of different surfactants is studied by fluorescence and UV absorption spectroscopy. When irradiated with UV light, folic acid undergoes rapid degradation in aqueous solution, in the absence of any surfactants. In contrast, the degradation is greatly suppressed in the presence of surfactants. The extent of suppression by cationic surfactants is more significant than that by the anionic surfactant. The residual folic acid concentration increases from nearly 0 in the absence of any surfactant to 43%, 89%, 96%, and 96% in the presence of SDS, DTAB, 12-6-12, and 12-3-12-3-12, respectively, in the concentration range studied. The amount of surfactant required to prevent the degradation decreases with an increase in the degree of oligomerization of the cationic surfactants. The greater number of binding sites and hydrophobic tails in the gemini and oligomeric surfactants result in much stronger electrostatic and hydrophobic interactions with folic acid. In addition, the close and compact packing in these surfactant molecules prevents folic acid from coming in contact with oxygen, thereby retaining its stability and preserving its properties. This work provides a new methodology for regulating the surface activity of the surfactants and their aggregation in the presence of small functional molecules, which in turn improves the stability of the small molecules that are otherwise unstable.
Interactions between surfactants and small organic molecules not only enhance the surface activity of the surfactants and induce aggregate transitions in them, but also improve the solubility and stability of the organic molecules. Understanding the interaction between surfactants and small molecules will help in widening the scope of application of surfactants. Folic acid, a member of the vitamin B family, has a pteridine ring, paraaminobenzoic acid, and glutamic acid, and is crucial for many reactions inside the human body. The unique structure of folic acidalso facilitates the preparation of functional materials such as liquid crystals and gels. However, the poor solubility and precipitation of folic acid limit its applications. Therefore, it is essential to improve the solubility and stability of folic acid. Surfactants are efficient in solubilizing and stabilizing small molecules. The interactions of folic acid with four types of surfactants, namely, an anionic surfactant, sodium dodecyl sulfate(SDS); a cationic surfactant, dodecyl trimethylammonium bromide(DTAB); a cationic ammonium gemini surfactant, 12-6-12; and a cationic ammonium trimeric surfactant, 12-3-12-3-12; have been investigated at p H 7.0 by surface tension measurements, ultraviolet-visible(UV) absorption spectroscopy, dynamic light scattering, isothermal titration calorimetry, and nuclear magnetic resonance spectroscopy. At pH 7.0, the carboxylic acid groups of folic acid are deprotonated, so each folic acid molecule carries two negative charges. The addition of a small amount of folic acid sharply reduces the critical micelle concentration(CMC) of cationic surfactants and their surface tension at the CMC. However, the surface activity and aggregation of SDS show only minimal changes with the introduction of folic acid. In addition, the photodegradation of folic acid in the presence of different surfactants is studied by fluorescence and UV absorption spectroscopy. When irradiated with UV light, folic acid undergoes rapid degradation in aqueous solution, in the absence of any surfactants. In contrast, the degradation is greatly suppressed in the presence of surfactants. The extent of suppression by cationic surfactants is more significant than that by the anionic surfactant. The residual folic acid concentration increases from nearly 0 in the absence of any surfactant to 43%, 89%, 96%, and 96% in the presence of SDS, DTAB, 12-6-12, and 12-3-12-3-12, respectively, in the concentration range studied. The amount of surfactant required to prevent the degradation decreases with an increase in the degree of oligomerization of the cationic surfactants. The greater number of binding sites and hydrophobic tails in the gemini and oligomeric surfactants result in much stronger electrostatic and hydrophobic interactions with folic acid. In addition, the close and compact packing in these surfactant molecules prevents folic acid from coming in contact with oxygen, thereby retaining its stability and preserving its properties. This work provides a new methodology for regulating the surface activity of the surfactants and their aggregation in the presence of small functional molecules, which in turn improves the stability of the small molecules that are otherwise unstable.
引文
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(2)Juzeniene,A.;Tam,T.T.T.;Iani,V.;Moan,J.T.J.Photochem.Photobiol.B 2013,126,11.doi:10.1016/j.jphotobiol.2013.05.011
(3)Hu,J.M.;Qian,Y.F.;Wang,X.F.;Liu,T.;Liu,S.Y.Langmuir 2012,28,2073.doi:10.1021/la203992q
(4)Leamon,C.P.;Reddy,J.A.Adv.Drug Deliv.Rev.2004,56,1127.doi:10.1016/j.addr.2004.01.008
(5)Li,W.J.;Shi,J.;Zhang,C.;Li,M.;Gan,L.;Xu,H.B.;Yang.X.L.J.Mater.Chem.B 2014,2,4901.doi:10.1039/c4tb00502c
(6)Zhu,J.;Liao,L.;Zhu,L.N.;Kong,J.L.;Liu,B.H.Acta Chim.Sinica 2013,71,69.[朱杰,廖蕾,朱丽娜,孔继烈,刘宝红.化学学报,2013,71,69.]doi:10.6023/A12090680
(7)Bonazzi,S.;DeMorais,M.M.;Gottarelli,G.;Mariani,P.;Spada,G.P.Angew.Chem.Int.Ed.1993,32,248.doi:10.1002/anie.199302481
(8)Xing,P.Y.;Chu,X.X.;Du,G.Y.;Li,M.Z.;Su,J.;Hao,A.Y.;Hou,Y.H.;Li,S.Y.;Ma,M.F.;Wu,L.;et al.RSC Adv.2013,3,15237.doi:10.1039/c3ra42129e
(9)Xing,P.Y.;Chu,X.X.;Ma,M.F.;Li,S.Y.;Hao,A.Y.Phys.Chem.Chem.Phys.2014,16,8346.doi:10.1039/c4cp00367e
(10)Xing,P.Y.;Chu,X.X.;Ma,M.F.;Li,S.Y.;Zhang,Y.M.;Hao,A.Y.RSC Adv.2014,4,36633.doi:10.1039/c4ra04585h
(11)Akhtar,M.J.;Khan,M.A.;Ahmad,I.J.Pharm.Biomed.Anal.1999,19,269.doi:10.1016/S0731-7085(98)00038-7
(12)Thomas,A.H.;Suárez,G.;Cabrerizo,F.M.;Martino,R.;Capparelli,A.L.J.Photochem.Photobiol.A:Chem.2000,135,147.doi:10.1016/S1010-6030(00)00304-X
(13)Jamil Akhtar,M.;Ataullah Khan,M.;Ahmad,I.J.Pharm.Biomed.Anal.1999,19,269.doi:10.1016/S0731-7085(98)00038-7
(14)Vorobey,P.;Steindal,A.E.;Off,M.K.;Vorobey,A.;Moan,J.Photochem.Photobiol.2006,82,817.doi:10.1562/2005-11-23-RA-739
(15)Liang,L.;Subirade,M.J.Phys.Chem.B 2010,114,6707.doi:10.1021/jp101096r
(16)Bourassa,P.;Tajmir-Riahi,H.A.J.Phys.Chem.B 2012,116,513.doi:10.1021/jp2083677
(17)Tavares,G.M.;Croguennec,T.;Le,S.;Lerideau,O.;Hamon,P.;Carvalho,A.F.;Bouhallab,S.Langmuir 2015,31,12481.doi:10.1021/acs.langmuir.5b02299
(18)Madziva,H.;Kailasapathy,K.;Phillips,M.J.Microencapsul.2005,22,343.doi:10.1080/02652040500100931
(19)Drummond,C.J.;Fong,C.Curr.Opin.Colloid Interface Sci.1999,4,449.doi:10.1016/S1359-0294(00)00020-0
(20)Zhang,H.X.;Annunziata,O.Langmuir 2008,24,10680.doi:10.1021/la802080t
(21)Bhat,P.A.;Rather,G.M.;Dar,A.A.J.Phys.Chem.B 2009,113,997.doi:10.1021/jp807229c.
(22)Xie,H.J.;Liu,C.C.;Sun,Q.;Gu,Q.;Lei,Q.F.;Fang,W.J.Acta Phys.-Chim.Sin.2016,32,295.[谢湖均,刘程程,孙强,顾青,雷群芳,方文军.物理化学学报,2016,32,295.]doi:10.3866/PKU.WHXB201609231
(23)Treger,J.S.;Ma,V.Y.;Gao,Y.;Wang,C.C.;Jeon,S.;Robinson,J.M.;Wang,H.L.;Johal,M.S.Langmuir 2008,24,13127.doi:10.1021/la802080t
(24)Carlotti,M.E.;Sapino,S.;Vione,D.;Pelizzetti,E.;Trotta,M.J.Dispersion Sci.Technol.2004,25,193.doi:10.1081/dis-120030666
(25)Leung,M.H.M.;Colangelo,H.;Kee,T.W.Langmuir 2008,24,5672.doi:10.1021/la800780w
(26)Wan,Z.Z.;Ke,D.;Hong,J.X.;Wang,X.Y.;Shen,W.G.Colloids Surf.,A Physicochem.Eng.Aspects 2012,414,267.doi:10.1016/j.colsurfa.2012.08.046
(27)Wang,M.N.;Wu,C.X.;Tang,Y.Q.;Fan,Y.X.;Han,Y.C.;Wang,Y.L.Soft Matter 2014,10,3432.doi:10.1039/c4sm00086b
(28)Shikata,T.;Hirata,H.;Kotaka,T.Langmuir 1989,5,398.doi:10.1021/la00086a020
(29)Hassan,P.;Yakhmi,J.Langmuir 2007,23,10044.doi:10.1021/la701542k
(30)Wattebled,L.;Laschewsky.Langmuir 2000,16,7187.doi:10.1021/la000517o
(31)Yu,D.F.;Huang,X.;Deng,M.L.;Wang,Y.L.J.Phys.Chem.B 2010,114,14955.doi:10.1021/jp106031d
(32)Jiang,L.X.;Huang,J.B.;Bahramian,A.;Li,P.X.;Thomas,R.K.;Penfold,J.Langmuir 2012,28,327.doi:10.1021/la2040938
(33)Wang,R.J.;Tian,M.Z.;Wang,Y.L.Soft Matter 2014,10,1705.doi:10.1039/c3sm52819g
(34)Wang,M.N.;Fan,Y.X.;Han,Y.C.;Nie,Z.X.;Wang,Y.L.Langmuir 2013,29,14839.doi:10.1021/la403582y
(35)Laschewsky,A.;Wattebled,L.;Arotarena,M.;Habib-Jiwan,J.;Rakotoaly,R.H.Langmuir 2005,21,7170.doi:10.1021/la050952o
(36)Hou,Y.B.;Han,Y.C.;Deng,M.L.;Wang,Y.L.Langmuir 2008,26,28.doi:10.1021/la903672r
(37)In,M.;Bec,V.;Aguerre-Chariol,O.;Zana,R.Langmuir 2000,16,141.doi:10.1021/la990645g
(38)Fan,Y.X.;Han,Y.C.;Wang,Y.L.Acta Phys.-Chim.Sin.2016,32,214.[范雅珣,韩玉淳,王毅琳.物理化学学报,2016,32,214.]doi:10.3866/PKU.WHXB201511022
(39)Zana,R.;Levy,H.;Papoutsi,D.;Beinert,G.Langmuir 1995,11,3694.doi:10.1021/la00010a018
(40)Lou,P.X.;Wang,Y.J.;Bai,G.Y.;Fan,C.Y.;Wang,Y.L.Acta Phys.-Chim.Sin.2013,29,1401.[娄朋晓,王玉洁,白光月,范朝英,王毅琳.物理化学学报,2013,29,1401.]doi:10.3866/PKU.WHXB201304282