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ergy in the aggregate).因此, ?N0 = (11/N) ?kT = ??0 + ?kT /Nwhere ??0 the bulk energy of a molecule in an infinite aggregate.這樣, as N 增加 , ?N0 下降 Fortherod,discandspherestructures,theinteractionfreeenergyofthemoleculescanbeexpressedas?N0 = ??0 + ?kT /NPwhererodlikep=1disclikeP=1/2sphereP=1/3Forallthesestructures,?N0 ? with N ?Monomer and aggregate concentrations as a function of total solute concentration. 聚集體形成的第二個(gè)條件 : aggregate 形成與濃度關(guān)系當(dāng) monomer濃度 增加時(shí),其濃度只能趨向某一值而不可能再增加, monomer的這個(gè)濃度定義為 criticalmicelleconcentration(CMC).兼性分子在水溶液中的聚集狀態(tài)與其濃度之間的關(guān)系單體濃度極低的情況下,兼性分子在溶液中以單體形式存在。逐漸加大兼性分子的濃度,自由單體濃度隨之增加,當(dāng)濃度達(dá)到一定值時(shí)溶液中的自由單體濃度停止增加,溶液中開始同時(shí)出現(xiàn)單體和微團(tuán)兩種形式。這個(gè)臨界濃度稱作臨界微團(tuán)濃度,簡稱CMC。 此后單體濃度保持不變,而兼性分子濃度的增加只能引起聚集體濃度的增加。 CMC 越高說明分子間的相互作用越弱,易于透析 !聚集體形成的第二個(gè)條件 : aggregate 形成與濃度關(guān)系由 XN=N{X1exp[(?10?N0)/kT]}N因?yàn)??N0= ??0+?kT/NP則有 XN=N{X1exp[?(11/NP)]}N?N{X1exp[?]}N對于一定的 ?值,總可以找到這樣的 X1值使 X1exp[?]??1,此時(shí), X1?X2?X3?…, 即多數(shù)分子處于monomer狀態(tài) .但是, 當(dāng) X1增加時(shí),由于 XN不可能大于 1, X1只能趨向 exp[?]的某一值而不可能再增加, monomer的這個(gè)濃度定義為 criticalmicelleconcentration(CMC).CMC 越高說明分子間的相互作用越弱,易于透析 !Amphiphilic molecule 在水中自組裝成聚集體的熱力學(xué)條件 是:? ?N0? ?10? 兼性分子濃度大于 CMC表 CMC、 n值兩親性物質(zhì) CMC(mmol/L)NSDS 62膽酸鈉 13?15 2?4脫氧膽酸鈉 5 7Triton X100 140棕櫚酰溶血卵磷脂 ?180DPPC ?1010mol/L 脂 質(zhì)分子幾何與聚集體的多型性幾何因子與脂質(zhì)聚集體的多型性? The major forces govern the selfassembly of amphiphiles into welldefined structurs: ? hydrophobic interaction induces the molecules to associate attractive hydrophobic forces ? the hydrophilic head group tends to be exposed to the aqueous phase repulsive forces ? These two forces pete in the interfacial region: the one tending to decrease and the other tending to increase the interfacial area per molecule.Repulsiveheadgroupforcesandattractivehydrophobicinterfacialforcesdeterminingtheoptimumheadgroupareaa0atwhich?N0isaminimum.自組裝中的裝配幾何 Geometric packing considerationsIsraelachviliet al.,(1979)Nature 277: 120.Basedupontheminimumsizedaggregateinwhichallthelipidshaveminimumfreeenergy.引入無量綱參數(shù) (critical packing parameter): v/a0lc where : v hydrophobic volume lc critical chain length a0 optimal area of the lipid.The value of v/a