超分子溶劑的形成研究文獻(xiàn)綜述目錄TOC\o"1-3"\h\u29230超分子溶劑的形成研究文獻(xiàn)綜述 1227881.1超分子溶劑的形成過程 1162591.2超分子溶劑的誘導(dǎo)因素 41.1超分子溶劑的形成過程超分子溶劑是由兩親分子溶液通過連續(xù)自組裝過程產(chǎn)生的。首先兩親分子在非共價相互作用下自發(fā)形成納/微米聚集體，然后發(fā)生凝聚現(xiàn)象，產(chǎn)生分散在連續(xù)相（通常為水）中的小液滴，最后通過離心等手段使分散的液滴聚集，從而達(dá)到分相現(xiàn)象。具體的形成過程如圖1.1所示ADDINEN.CITEADDINEN.CITE.DATA[\o"Melnyk,2014#178"8]，首先，在臨界聚集濃度（criticalaggregationconcentration,CAC）以上制備兩親分子的水性或有機(jī)膠體懸浮液。兩親分子自發(fā)形成三維納米聚集體，主要包括膠束（3-6nm）、反相膠束（4-8nm）和囊泡（30-500nm），其具體形態(tài)取決于兩親物和溶劑性質(zhì)。之后，通過凝聚誘導(dǎo)作用（例如pH、溫度、無機(jī)鹽、有機(jī)鹽或溶劑）來改變聚集體懸浮液的環(huán)境條件，以增加聚集體的尺寸。聚集體的生長引起凝聚現(xiàn)象，從而自發(fā)形成超分子液滴。這些液滴的密度與原本溶液的密度不同，這使其聚集或沉淀為新的液相（即超分子溶劑相），也可以通過外部提供離心力加速分離。液滴密度小于原本溶液的密度，則超分子溶劑會產(chǎn)生在上相，反之則會在下相。超分子溶劑是一種富含膠體的液相，在納米尺度和微米尺度范圍內(nèi)分布寬廣，并與本體溶液相（兩親分子濃度在CAC以上）保持平衡。圖1.1超分子溶劑的形成過程示意圖ADDINEN.CITEADDINEN.CITE.DATA[\o"Melnyk,2014#178"8]Figure1.1SchematicdiagramofSUPRASformationprocess.兩親分子自組裝成各種納米結(jié)構(gòu)聚集體是超分子溶劑形成中的第一步。達(dá)到臨界聚集濃度時，兩親分子會自發(fā)締合，最大程度地減少不利的疏溶劑性。在能量方面，兩親分子之間產(chǎn)生相互作用是有利于穩(wěn)定的ADDINEN.CITE<EndNote><Cite><Author>Ballesteros-Gómez</Author><Year>2010</Year><RecNum>151</RecNum><DisplayText>[9]</DisplayText><record><rec-number>151</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">151</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Ballesteros-Gómez,A.</author><author>Sicilia,M.D.</author><author>Rubio,S.</author></authors></contributors><auth-address>DepartmentofAnalyticalChemistry,FacultaddeCiencias,EdificioAnexoMarieCurie,CampusdeRabanales,14071Cordoba,Spain.</auth-address><titles><title>Supramolecularsolventsintheextractionoforganiccompounds.Areview</title><secondary-title>AnalyticaChimicaActa</secondary-title><alt-title>Analyticachimicaacta</alt-title></titles><periodical><full-title>AnalyticaChimicaActa</full-title></periodical><alt-periodical><full-title>AnalyticaChimicaActa</full-title></alt-periodical><pages>108-30</pages><volume>677</volume><number>2</number><dates><year>2010</year><pub-dates><date>Sep16</date></pub-dates></dates><isbn>1873-4324(Electronic) 0003-2670(Linking)</isbn><accession-num>20837178</accession-num><urls><related-urls><url>/pubmed/20837178</url></related-urls></urls><electronic-resource-num>10.1016/j.aca.2010.07.027</electronic-resource-num></record></Cite></EndNote>[\o"Ballesteros-Gómez,2010#151"9]。因此，自組裝聚集體的結(jié)構(gòu)源于溶質(zhì)-溶劑和溶質(zhì)-溶質(zhì)間微妙的相互作用。聚集體的形態(tài)取決于兩親分子頭基和烷基鏈的相對大小，可以通過Irsaelacvili提出的堆積參數(shù)（P）理論進(jìn)行預(yù)測ADDINEN.CITE<EndNote><Cite><Author>N.</Author><Year>1976</Year><RecNum>400</RecNum><DisplayText>[10]</DisplayText><record><rec-number>400</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">400</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Israelachvili,J.N.</author><author>Mitchell,D.J.</author><author>Ninham,B.W.</author></authors></contributors><titles><title>Theoryofself-assemblyofhydrocarbonamphiphilesintomicellesandbilayers</title><secondary-title>JournaloftheChemicalSocietyFaradayTransactions</secondary-title></titles><periodical><full-title>JournaloftheChemicalSocietyFaradayTransactions</full-title></periodical><pages>1525-1568</pages><volume>72</volume><dates><year>1976</year></dates><urls></urls></record></Cite></EndNote>[\o"Israelachvili,1976#400"10]。P其中，P代表堆積參數(shù)，V代表烷基鏈所占的空間體積，a0代表聚集體中兩親分子頭基的平均橫截面積，lc代表聚集體中烷烴鏈的最大伸展長度（如圖1.2）。參數(shù)P取決于兩親分子的分子幾何形狀，例如烷基鏈的碳原子個數(shù)和鏈飽和度（存在烯基或炔基），極性頭基的大小和所帶電荷。除此之外，溶液條件的影響，包括離子強(qiáng)度、pH、溫度、輔助表面活性劑濃度和添加劑都會間接影響V、a0和lc值。如圖1.2所示，一般來說，P<1/3時，形成球狀膠束或不連續(xù)的立方相；1/3<P<1/2時，形成橢球形、棒狀或蠕蟲狀膠束；1/2<P<1時，溶液形成囊泡或具有不同曲率的雙分子層結(jié)構(gòu)；P~1時，幾乎無曲率，形成碟狀膠束或雙分子層狀結(jié)構(gòu)；P>1時，會形成反向膠束結(jié)構(gòu)。兩親分子的聚集是一個起止過程，添加更多的兩親分子會導(dǎo)致形成更多相同的聚集體，而對于大多數(shù)典型的兩親物，終止過程源自頭基-頭基團(tuán)之間的相互排斥作用。圖1.2兩親分子堆積參數(shù)理論的超分子聚集體的結(jié)構(gòu)ADDINEN.CITE<EndNote><Cite><Author>Ballesteros-Gómez</Author><Year>2010</Year><RecNum>151</RecNum><DisplayText>[9]</DisplayText><record><rec-number>151</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">151</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Ballesteros-Gómez,A.</author><author>Sicilia,M.D.</author><author>Rubio,S.</author></authors></contributors><auth-address>DepartmentofAnalyticalChemistry,FacultaddeCiencias,EdificioAnexoMarieCurie,CampusdeRabanales,14071Cordoba,Spain.</auth-address><titles><title>Supramolecularsolventsintheextractionoforganiccompounds.Areview</title><secondary-title>AnalyticaChimicaActa</secondary-title><alt-title>Analyticachimicaacta</alt-title></titles><periodical><full-title>AnalyticaChimicaActa</full-title></periodical><alt-periodical><full-title>AnalyticaChimicaActa</full-title></alt-periodical><pages>108-30</pages><volume>677</volume><number>2</number><dates><year>2010</year><pub-dates><date>Sep16</date></pub-dates></dates><isbn>1873-4324(Electronic) 0003-2670(Linking)</isbn><accession-num>20837178</accession-num><urls><related-urls><url>/pubmed/20837178</url></related-urls></urls><electronic-resource-num>10.1016/j.aca.2010.07.027</electronic-resource-num></record></Cite></EndNote>[\o"Ballesteros-Gómez,2010#151"9]Figure1.2Schematicstructureofsupramolecularaggregatesaccordingtothepackingfactorofamphiphiles.改變懸浮液環(huán)境，導(dǎo)致聚集體尺寸的增加，是超分子溶劑形成的第二個重要步驟。在此步驟中，懸浮液中聚集體（膠束或囊泡等）體積增長，需要減少在第一個自組裝過程中停止聚集的頭部-頭部之間的排斥力，而如何實現(xiàn)此目標(biāo)取決于不同的兩親分子特性。在離子體系中，中和電荷數(shù)可以促進(jìn)聚集體的生長，通過添加具有較小頭基的輔助表面活性劑，電解質(zhì)或兩親性抗衡離子，以及通過改變pH來實現(xiàn)ADDINEN.CITE<EndNote><Cite><Author>H.Yin</Author><Year>2002</Year><RecNum>404</RecNum><DisplayText>[11,12]</DisplayText><record><rec-number>404</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">404</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>H.Yin,</author><author>M.Mao,</author><author>J.Huang,</author><author>H.Fu,</author></authors></contributors><titles><title>Two-phaseregionintheDTAB/SLmixedsurfactantsystem</title><secondary-title>Langmuir</secondary-title></titles><periodical><full-title>Langmuir</full-title></periodical><pages>9198-9203</pages><volume>18</volume><dates><year>2002</year></dates><urls></urls></record></Cite><Cite><Author>Casero</Author><Year>1999</Year><RecNum>155</RecNum><record><rec-number>155</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">155</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>I.Casero</author><author>D.Sicilia</author><author>S.Rubio</author><author>D.Pérez-Bendito</author></authors></contributors><titles><title>Anacid-inducedphasecloudpointseparationapproachusinganionicsurfactantsfortheextractionandpreconcentrationoforganiccompounds</title><secondary-title>AnalyticalChemistry</secondary-title></titles><periodical><full-title>AnalyticalChemistry</full-title></periodical><pages>4519-4526</pages><volume>71</volume><dates><year>1999</year></dates><urls></urls></record></Cite></EndNote>[\o"H.Yin,2002#404"11,\o"Casero,1999#155"12]。在非離子體系中，促進(jìn)聚集體生長的一種非常有效的方法是減少可用于溶劑化的溶劑分子的數(shù)量，這可以通過改變溫度或通過添加不良溶劑來實現(xiàn)ADDINEN.CITE<EndNote><Cite><Author>Hinze</Author><Year>1993</Year><RecNum>156</RecNum><DisplayText>[13,14]</DisplayText><record><rec-number>156</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">156</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Hinze,W.L.</author><author>Pramauro,E.</author></authors></contributors><titles><title>Acriticalreviewofsurfactant-mediatedphaseseparations(cloud-pointextractions):theoryandapplications</title><secondary-title>CriticalReviewsinAnalyticalChemistry</secondary-title></titles><periodical><full-title>CriticalReviewsinAnalyticalChemistry</full-title></periodical><pages>133-177</pages><volume>24</volume><number>2</number><dates><year>1993</year></dates><isbn>1040-8347 1547-6510</isbn><urls></urls><electronic-resource-num>10.1080/10408349308048821</electronic-resource-num></record></Cite><Cite><Author>Ruiz</Author><Year>2007</Year><RecNum>187</RecNum><record><rec-number>187</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">187</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Ruiz,F.</author><author>Rubio,S.</author><author>Pérez-Bendito,D.</author></authors></contributors><titles><title>Water-inducedcoacervationofalkylcarboxylicacidreversemicelles:phenomenondescriptionandpotentialfortheextractionoforganiccompounds</title><secondary-title>AnalyticalChemistry</secondary-title></titles><periodical><full-title>AnalyticalChemistry</full-title></periodical><pages>7473-7484</pages><volume>79</volume><dates><year>2007</year></dates><urls></urls></record></Cite></EndNote>[\o"Hinze,1993#156"13,\o"Ruiz,2007#187"14]。1.2超分子溶劑的誘導(dǎo)因素（1）溫度超分子溶劑的相行為對溫度非常敏感。與其他方法相比，溫度變化方便調(diào)控，且便于觀察和研究聚集體各個階段的轉(zhuǎn)變。動力學(xué)方面也可以通過控制加熱和冷卻速率來檢測。溫度對于基于非離子型表面活性劑的超分子溶劑體系相行為有很大的影響。當(dāng)表面活性劑溶液濃度大于臨界膠束濃度時，體系溫度升高且高于濁點時，膠束聚集體中表面活性劑與水分子間的氫鍵作用被破壞，水分子從膠束中逃逸，膠束發(fā)生脫水現(xiàn)象，從而在水中的溶解度降低，此時溶液會產(chǎn)生渾濁現(xiàn)象。進(jìn)一步升高溫度，渾濁溶液可發(fā)生相分離，生成澄清透明的液-液兩相，即膠體富集的超分子溶劑相和膠體含量少的水相（如圖1.3所示）ADDINEN.CITE<EndNote><Cite><Author>Ojeda</Author><Year>2009</Year><RecNum>160</RecNum><DisplayText>[15]</DisplayText><record><rec-number>160</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">160</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Ojeda,C.B.</author><author>Rojas,F.S.</author></authors></contributors><titles><title>Separationandpreconcentrationbyacloudpointextractionprocedurefordeterminationofmetals:anoverview</title><secondary-title>AnalyticalandBioanalyticalChemistry</secondary-title></titles><periodical><full-title>AnalyticalandBioanalyticalChemistry</full-title></periodical><pages>759-782</pages><volume>394</volume><number>3</number><dates><year>2009</year></dates><isbn>1618-2642 1618-2650</isbn><urls></urls><electronic-resource-num>10.1007/s00216-009-2660-9</electronic-resource-num></record></Cite></EndNote>[\o"Ojeda,2009#160"15]。例如常見的Triton系列（聚氧乙烯叔辛基苯基醚）或PONPE系列（聚氧乙烯壬基苯醚）表面活性劑溶液在濁點溫度以上，非離子膠束相出現(xiàn)分相情況ADDINEN.CITE<EndNote><Cite><Author>Hinze</Author><Year>1993</Year><RecNum>156</RecNum><DisplayText>[13]</DisplayText><record><rec-number>156</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">156</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Hinze,W.L.</author><author>Pramauro,E.</author></authors></contributors><titles><title>Acriticalreviewofsurfactant-mediatedphaseseparations(cloud-pointextractions):theoryandapplications</title><secondary-title>CriticalReviewsinAnalyticalChemistry</secondary-title></titles><periodical><full-title>CriticalReviewsinAnalyticalChemistry</full-title></periodical><pages>133-177</pages><volume>24</volume><number>2</number><dates><year>1993</year></dates><isbn>1040-8347 1547-6510</isbn><urls></urls><electronic-resource-num>10.1080/10408349308048821</electronic-resource-num></record></Cite></EndNote>[\o"Hinze,1993#156"13]。圖1.3溫度升高引發(fā)非離子型表面活性劑溶液分相的示意圖ADDINEN.CITE<EndNote><Cite><Author>Ojeda</Author><Year>2009</Year><RecNum>160</RecNum><DisplayText>[15]</DisplayText><record><rec-number>160</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">160</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Ojeda,C.B.</author><author>Rojas,F.S.</author></authors></contributors><titles><title>Separationandpreconcentrationbyacloudpointextractionprocedurefordeterminationofmetals:anoverview</title><secondary-title>AnalyticalandBioanalyticalChemistry</secondary-title></titles><periodical><full-title>AnalyticalandBioanalyticalChemistry</full-title></periodical><pages>759-782</pages><volume>394</volume><number>3</number><dates><year>2009</year></dates><isbn>1618-2642 1618-2650</isbn><urls></urls><electronic-resource-num>10.1007/s00216-009-2660-9</electronic-resource-num></record></Cite></EndNote>[\o"Ojeda,2009#160"15]Figure1.3Schematicdiagramofphaseseparationofnon-ionicsurfactantsolutioncausedbytemperatureincrease.對于陰陽離子表面活性劑復(fù)配超分子溶劑體系，溫度的影響則更為復(fù)雜。通常情況下，溫度升高，聚集體尺寸會減小。在大多數(shù)囊泡體系中，溫度升高伴隨著囊泡到膠束的相轉(zhuǎn)變ADDINEN.CITE<EndNote><Cite><Author>Yin</Author><Year>2005</Year><RecNum>402</RecNum><DisplayText>[16,17]</DisplayText><record><rec-number>402</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">402</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>H.Yin</author><author>J.Huang</author><author>Y.Lin</author><author>Y.Zhang</author><author>S.Qiu</author><author>J.Ye</author></authors></contributors><titles><title>Heating-inducedmicelletovesicletransitioninthecationic-anionicsurfactantsystems:comprehensivestudyandunderstanding</title><secondary-title>JournalofPhysicalChemistryB</secondary-title></titles><periodical><full-title>JournalofPhysicalChemistryB</full-title><abbr-1>JournalofPhysicalChemistryB</abbr-1></periodical><pages>4104-4110</pages><volume>109</volume><dates><year>2005</year></dates><urls></urls></record></Cite><Cite><Author>Buwalda</Author><Year>2000</Year><RecNum>403</RecNum><record><rec-number>403</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">403</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Buwalda,R.T.</author><author>Stuart,M.C.A.</author><author>Engberts,J.B.F.N.</author></authors></contributors><titles><title>Wormlikemicellarandvesicularphasesinaqueoussolutionsofsingle-tailedsurfactantswitharomaticcounterions</title><secondary-title>Langmuir</secondary-title></titles><periodical><full-title>Langmuir</full-title></periodical><pages>6780-6786</pages><volume>16</volume><dates><year>2000</year></dates><urls></urls></record></Cite></EndNote>[\o"Yin,2005#402"16,\o"Buwalda,2000#403"17]。例如在十二烷基三甲基溴化銨（dodecyltrimethylammoniumbromide,DTAB)/月桂酸鈉(sodiumlaurate,SL)體系中，可觀察到隨著溫度的增加，膠體富集相的體積逐漸增加，最后兩相之間的界面在一定溫度下消失。用動態(tài)光散射追蹤溫度影響時，發(fā)現(xiàn)聚集體的結(jié)構(gòu)以及它們之間的相互作用隨著溫度的升高而變化。溫度由21oC上升到30-40oC，小聚集體的平均粒徑不變，而大粒徑聚集體（囊泡）的含量則急劇下降。當(dāng)溫度達(dá)到50oC時，較大的聚集體平均直徑僅為47.6nmADDINEN.CITE<EndNote><Cite><Author>H.Yin</Author><Year>2002</Year><RecNum>404</RecNum><DisplayText>[11]</DisplayText><record><rec-number>404</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">404</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>H.Yin,</author><author>M.Mao,</author><author>J.Huang,</author><author>H.Fu,</author></authors></contributors><titles><title>Two-phaseregionintheDTAB/SLmixedsurfactantsystem</title><secondary-title>Langmuir</secondary-title></titles><periodical><full-title>Langmuir</full-title></periodical><pages>9198-9203</pages><volume>18</volume><dates><year>2002</year></dates><urls></urls></record></Cite></EndNote>[\o"H.Yin,2002#404"11]。引起這一現(xiàn)象有兩個可能的原因，一是聚集體縮小，二是在溫度升高時聚集體的聚集程度減少。近年來，也在陰陽離子表面活性劑復(fù)配體系中，觀察到溫度誘導(dǎo)的膠束向囊泡相轉(zhuǎn)換現(xiàn)象。加熱后脂質(zhì)囊泡中表面活性劑的溶解能力下降被認(rèn)為是相轉(zhuǎn)變的原因。例如在制備十二烷基硫酸鈉（sodiumdodecylsulfate,SDS）/十二烷基三乙基溴化銨（dodecyltriethylammoniumbromide,DTEAB）混合的陰陽離子表面活性劑體系（摩爾比為2:1，表面活性劑總濃度為10mM）中，當(dāng)溫度從30oC升高到50oC，濁度檢查可以觀察到明顯的渾濁度增加，粒徑測量也表明聚集體由膠束向囊泡的轉(zhuǎn)變。然而此體系的升溫過程未能觀察到如非離子表面活性劑所展現(xiàn)出來的相分離或是沉淀ADDINEN.CITE<EndNote><Cite><Author>Yin</Author><Year>2003</Year><RecNum>405</RecNum><DisplayText>[18]</DisplayText><record><rec-number>405</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">405</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Yin,H.</author><author>Zhou,Z.</author><author>Huang,J.</author><author>Zheng,R.</author><author>Zhang,Y.</author></authors></contributors><titles><title>Temperature-inducedmicelletovesicletransitioninthesodiumdodecylsulfate/dodecyltriethylammoniumbromidesystem</title><secondary-title>AngewandteChemieInternationalEdition</secondary-title></titles><periodical><full-title>AngewandteChemieInternationalEdition</full-title></periodical><pages>2188-2191</pages><volume>42</volume><number>19</number><dates><year>2003</year></dates><isbn>14337851 15213773</isbn><urls></urls><electronic-resource-num>10.1002/anie.200350913</electronic-resource-num></record></Cite></EndNote>[\o"Yin,2003#405"18]。在分子相互作用較強(qiáng)、膠束聚集數(shù)較大的陰陽離子表面活性劑體系中，熱致膠束向囊泡相轉(zhuǎn)變現(xiàn)象更容易發(fā)生ADDINEN.CITE<EndNote><Cite><Author>Yin</Author><Year>2005</Year><RecNum>402</RecNum><DisplayText>[16]</DisplayText><record><rec-number>402</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">402</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>H.Yin</author><author>J.Huang</author><author>Y.Lin</author><author>Y.Zhang</author><author>S.Qiu</author><author>J.Ye</author></authors></contributors><titles><title>Heating-inducedmicelletovesicletransitioninthecationic-anionicsurfactantsystems:comprehensivestudyandunderstanding</title><secondary-title>JournalofPhysicalChemistryB</secondary-title></titles><periodical><full-title>JournalofPhysicalChemistryB</full-title><abbr-1>JournalofPhysicalChemistryB</abbr-1></periodical><pages>4104-4110</pages><volume>109</volume><dates><year>2005</year></dates><urls></urls></record></Cite></EndNote>[\o"Yin,2005#402"16]。（2）pH研究表明pH值對于基于離子型表面活性劑的超分子溶劑形成有顯著影響。圖1.4顯示了室溫下鹽酸濃度與陰離子表面活性劑濃度，包括十二烷基硫酸鈉（SDS）、十二烷基苯磺酸鈉（sodiumdodecylbenzenesulphonate,SDBSA）、十二烷磺酸鈉（sodiumdodecylsulfonate,SDSA）和二辛基磺基琥珀酸鈉（AerosolOT）的相圖。可觀察到三個不同的區(qū)域，即均勻的液體區(qū)域（L），兩個共存的各向同性相（L-L）和固體區(qū)域（S）。在所有測試的陰離子表面活性劑中均觀察到酸誘導(dǎo)的液-液相分離，因此，推測酸誘導(dǎo)相分離是這類表面活性劑的一般性質(zhì)ADDINEN.CITE<EndNote><Cite><Author>Casero</Author><Year>1999</Year><RecNum>155</RecNum><DisplayText>[12]</DisplayText><record><rec-number>155</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">155</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>I.Casero</author><author>D.Sicilia</author><author>S.Rubio</author><author>D.Pérez-Bendito</author></authors></contributors><titles><title>Anacid-inducedphasecloudpointseparationapproachusinganionicsurfactantsfortheextractionandpreconcentrationoforganiccompounds</title><secondary-title>AnalyticalChemistry</secondary-title></titles><periodical><full-title>AnalyticalChemistry</full-title></periodical><pages>4519-4526</pages><volume>71</volume><dates><year>1999</year></dates><urls></urls></record></Cite></EndNote>[\o"Casero,1999#155"12]?？紤]到表面活性劑在酸性介質(zhì)中可能會逐漸氧化，需避免使用硝酸或高氯酸等強(qiáng)氧化性酸，因而鹽酸被認(rèn)為是獲得兩相分離的最合適的介質(zhì)。在獲得兩個各向同性相的鹽酸濃度下，陰離子表面活性劑中的硫酸根和磺酸根均應(yīng)質(zhì)子化，說明酸性介質(zhì)會將陰離子表面活性劑轉(zhuǎn)化為非離子表面活性劑。尤其對于基于烷酸的超分子溶劑體系，通常需要將溶液pH值調(diào)節(jié)至酸性環(huán)境，使部分烷酸維持電中性，在氫鍵作用力下生成超分子溶劑。例如，在pH為4.5的30mL水樣中加入0.2g癸酸可獲得超分子溶劑ADDINEN.CITE<EndNote><Cite><Author>Safari</Author><Year>2015</Year><RecNum>279</RecNum><DisplayText>[19]</DisplayText><record><rec-number>279</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">279</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Safari,M.</author><author>Yamini,Y.</author><author>Tahmasebi,E.</author><author>Ebrahimpour,B.</author></authors></contributors><titles><title>MagneticnanoparticleassistedsupramolecularsolventextractionoftriazineherbicidespriortotheirdeterminationbyHPLCwithUVdetection</title><secondary-title>MicrochimicaActa</secondary-title></titles><periodical><full-title>MicrochimicaActa</full-title></periodical><pages>203-210</pages><volume>183</volume><number>1</number><dates><year>2015</year></dates><isbn>0026-3672 1436-5073</isbn><urls></urls><electronic-resource-num>10.1007/s00604-015-1607-4</electronic-resource-num></record></Cite></EndNote>[\o"Safari,2015#279"19]。又如，四氫呋喃（tetrahydrofuran,THF）或六氟異丙醇（hexafluoroisopropanol,HFIP）介導(dǎo)的烷酸體系均需要在酸性條件下形成ADDINEN.CITEADDINEN.CITE.DATA[\o"Ruiz,2007#187"14,\o"Zong,2018#19"20]。進(jìn)一步研究酸誘導(dǎo)陰離子表面活性劑的相分離行為發(fā)現(xiàn)，烷基磺酸鹽的臨界鹽酸濃度（發(fā)生兩相分離所需的最低酸濃度）隨著陰離子表面活性劑的烷基鏈長度從10到14的增加而增加ADDINEN.CITE<EndNote><Cite><Author>Sicilia</Author><Year>2002</Year><RecNum>406</RecNum><DisplayText>[21]</DisplayText><record><rec-number>406</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">406</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Sicilia,D.</author><author>Rubio,S.</author><author>Pérez-Bendito,D.</author></authors></contributors><titles><title>Evaluationofthefactorsaffectingextractionoforganiccompoundsbasedontheacid-inducedphasecloudpointapproach</title><secondary-title>AnalyticaChimicaActa</secondary-title></titles><periodical><full-title>AnalyticaChimicaActa</full-title></periodical><pages>13-22</pages><volume>460</volume><dates><year>2002</year></dates><urls></urls></record></Cite></EndNote>[\o"Sicilia,2002#406"21]。圖1.4在室溫下鹽酸-陰離子表面活性劑溶液相圖ADDINEN.CITE<EndNote><Cite><Author>Casero</Author><Year>1999</Year><RecNum>155</RecNum><DisplayText>[12]</DisplayText><record><rec-number>155</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">155</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>I.Casero</author><author>D.Sicilia</author><author>S.Rubio</author><author>D.Pérez-Bendito</author></authors></contributors><titles><title>Anacid-inducedphasecloudpointseparationapproachusinganionicsurfactantsfortheextractionandpreconcentrationoforganiccompounds</title><secondary-title>AnalyticalChemistry</secondary-title></titles><periodical><full-title>AnalyticalChemistry</full-title></periodical><pages>4519-4526</pages><volume>71</volume><dates><year>1999</year></dates><urls></urls></record></Cite></EndNote>[\o"Casero,1999#155"12]Figure1.4Phasediagramofhydrochloricacid-anionicsurfactantsolutionatroomtemperature.陰陽離子表面活性劑體系中的分子自組裝主要歸因于帶相反電荷的頭基之間的強(qiáng)靜電吸引力，這極大地促進(jìn)了聚集體中表面活性劑分子的致密堆積。pH值的改變，能改變離子表面活性劑頭基的電荷量，而電荷量的變化對陰離子-陽離子表面活性劑之間的靜電作用力有顯著影響，從而會改變聚集體的類型。例如具有pH響應(yīng)的單鏈陰離子表面活性劑正癸基磷酸（decylphosphonicacid,DPA），其具有兩個pKa值2.67和7.04，可以通過調(diào)節(jié)pH值使得正癸基磷酸帶一個或兩個負(fù)電荷（如圖1.5所示）。隨著pH值的變化，DPA的中和度從2.0變?yōu)?.0，在表面活性劑摩爾比相同時，十六烷基三甲基溴化銨（CTAB）和DPA的混合物可以從“1-2”表面活性劑對變?yōu)椤?-1”表面活性劑對。在“1-1”表面活性劑對體系中形成體積更大的聚集體（如囊泡，層狀結(jié)構(gòu)等），而在“1-2”表面活性劑對中僅觀察到小聚集體（如球形膠束或蠕蟲狀膠束等）ADDINEN.CITE<EndNote><Cite><Author>Y.Lin</Author><Year>2008</Year><RecNum>407</RecNum><DisplayText>[22]</DisplayText><record><rec-number>407</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">407</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Y.Lin,</author><author>X.Han,</author><author>X.Cheng,</author><author>J.Huang,</author><author>D.Liang,</author><author>C.Yu</author></authors></contributors><titles><title><styleface="normal"font="default"size="100%">pH-regulatedmolecularself-assembliesinacationic#anionicsurfactantsystem:froma</style><styleface="normal"font="default"charset="134"size="100%">“1#2”</style><styleface="normal"font="default"size="100%">s</style><styleface="normal"font="default"charset="134"size="100%">urfactant</style><styleface="normal"font="default"size="100%">p</style><styleface="normal"font="default"charset="134"size="100%">airtoa“1#1”</style><styleface="normal"font="default"size="100%">s</style><styleface="normal"font="default"charset="134"size="100%">urfactant</style><styleface="normal"font="default"size="100%">p</style><styleface="normal"font="default"charset="134"size="100%">air</style></title><secondary-title>Langmuir</secondary-title></titles><periodical><full-title>Langmuir</full-title></periodical><pages>13918-13924</pages><volume>24</volume><dates><year>2008</year></dates><urls></urls></record></Cite></EndNote>[\o"Y.Lin,2008#407"22]。圖1.5pH值對陰陽離子表面活性劑聚集體結(jié)構(gòu)的影響ADDINEN.CITE<EndNote><Cite><Author>Y.Lin</Author><Year>2008</Year><RecNum>407</RecNum><DisplayText>[22]</DisplayText><record><rec-number>407</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">407</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Y.Lin,</author><author>X.Han,</author><author>X.Cheng,</author><author>J.Huang,</author><author>D.Liang,</author><author>C.Yu</author></authors></contributors><titles><title><styleface="normal"font="default"size="100%">pH-regulatedmolecularself-assembliesinacationic#anionicsurfactantsystem:froma</style><styleface="normal"font="default"charset="134"size="100%">“1#2”</style><styleface="normal"font="default"size="100%">s</style><styleface="normal"font="default"charset="134"size="100%">urfactant</style><styleface="normal"font="default"size="100%">p</style><styleface="normal"font="default"charset="134"size="100%">airtoa“1#1”</style><styleface="normal"font="default"size="100%">s</style><styleface="normal"font="default"charset="134"size="100%">urfactant</style><styleface="normal"font="default"size="100%">p</style><styleface="normal"font="default"charset="134"size="100%">air</style></title><secondary-title>Langmuir</secondary-title></titles><periodical><full-title>Langmuir</full-title></periodical><pages>13918-13924</pages><volume>24</volume><dates><year>2008</year></dates><urls></urls></record></Cite></EndNote>[\o"Y.Lin,2008#407"22]Figure1.5TheeffectofpHontheaggregatestructuresofanionicandcationicsurfactants.（3）無機(jī)鹽對于大多數(shù)非離子表面活性劑而言，鹽的存在可促進(jìn)相分離，因為它們會增加水相的密度。鹽的添加也可以降低非離子表面活性劑的濁點溫度，使用的電解質(zhì)濃度通常很高（超過0.1M），可以用所謂的鹽溶和鹽析作用（salting-inandsalting-outeffects）來解釋這一現(xiàn)象ADDINEN.CITE<EndNote><Cite><Author>Wang</Author><Year>2006</Year><RecNum>408</RecNum><DisplayText>[23]</DisplayText><record><rec-number>408</rec-number><foreign-keys><keyapp="EN"db-id="f02aarrpvad9f9eve0m5d2zrvsz0d552vwtz">408</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contrib