CN113880892B - 一种小分子去垢剂 - Google Patents

一种小分子去垢剂 Download PDF

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CN113880892B
CN113880892B CN202010635979.5A CN202010635979A CN113880892B CN 113880892 B CN113880892 B CN 113880892B CN 202010635979 A CN202010635979 A CN 202010635979A CN 113880892 B CN113880892 B CN 113880892B
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陶厚朝
赵飞
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Abstract

本发明涉及有机化学领域，特别是涉及一种小分子去垢剂。本发明提供一种化合物或其盐、异构体、或溶剂化物，所述化合物的化学结构式如式(1)～(3)其中之一所示。本发明所提供的化合物在分子结构上是具有“预组装”特点的化合物，且可以具有两头两尾(或多头多尾)的特点。这些化合物在膜蛋白的热稳定性实验中能够显著提高膜蛋白的稳定性，且效果显著高于目前常用的去垢剂，具有良好的产业化前景。

Description

一种小分子去垢剂
技术领域
本发明涉及有机化学领域，特别是涉及一种小分子去垢剂。
背景技术
膜蛋白是一大类重要的药物靶标。人类基因组大约有20-30％表达的是膜蛋白，与此同时，当前FDA批准的药物中，大约有50％的靶标是膜蛋白。因此，对于膜蛋白的结构及生理功能的研究极其重要。然而，膜蛋白的研究难度却高于可溶性蛋白——膜蛋白只能在膜或拟膜的两亲环境中稳定存在并维持功能，不能在水中维持稳定。膜蛋白的研究也滞后于可溶性蛋白。全世界最大的结构生物学数据库RCSB中，膜蛋白的结构仅占全部收录蛋白的2％。限制膜蛋白研究的瓶颈之一是膜蛋白的纯化技术。膜蛋白的纯化是指利用拟膜试剂将生物膜上的膜蛋白萃取至水溶液中，并通过各种纯化手段使目标膜蛋白与其它组分分离。纯化得到的膜蛋白需维持自身的高级结构与功能活性与膜蛋白仍处在膜上的两亲环境相似，即“拟膜”的效果。在各种拟膜试剂中，最常用的是小分子去垢剂，具有适用范围广、对膜蛋白稳定性好、成本低廉等诸多优点。目前，针对各种不同家族的膜蛋白，人们已发展了多种去垢剂。其中，正辛基-β-D-吡喃葡萄糖苷(n-Octyl-β-D-Glucopyranoside，OG)、十二烷基-β-D-麦芽糖苷(n-Dodecyl-β-D-maltoside，DDM)、十二烷基新戊二醇麦芽糖苷(LaurylMaltose Neopentyl Glycol，LMNG)、磷酰胆碱系列(Fos-cholines)等是目前应用最为广泛的去垢剂。然而，膜蛋白的数量非常庞大，目前并没有证据表明存在单一的去垢剂能够很好的维持所有膜蛋白的稳定性。因此，为了应对膜蛋白的多样性，发展去垢剂的多样性具有重要的意义。
发明内容
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种小分子去垢剂，用于解决现有技术中的问题。
为实现上述目的及其他相关目的，本发明一方面提供一种化合物或其盐、异构体、或溶剂化物，所述化合物的化学结构式如下之一所示：
Figure BDA0002569419740000021
其中，A、B各自独立地选自戊糖或己糖的呋喃糖或吡喃糖构型所形成的单糖糖基或二糖糖基；
E、G各自独立地选自直链的C1～C20烷基。
在本发明一些实施方式中，A、B各自独立地选自己糖的吡喃糖构型所形成的单糖糖基或二糖糖基。
在本发明一些实施方式中，A、B各自独立地选自如下之一所示的基团：
Figure BDA0002569419740000022
在本发明一些实施方式中，式(3)中，A、B选自相同或不同的糖基。
在本发明一些实施方式中，E、G各自独立地选自直链的C1～C16烷基。
在本发明一些实施方式中，当A选自己糖的吡喃糖构型所形成的单糖糖基时，E选自直链的C1～C9烷基，当A选自己糖的吡喃糖构型所形成的二糖糖基时，E选自直链的C3～C13烷基。
在本发明一些实施方式中，当B选自己糖的吡喃糖构型所形成的单糖糖基时，G选自直链的C1～C9烷基，当B选自己糖的吡喃糖构型所形成的二糖糖基时，G选自直链的C3～C13烷基。
在本发明一些实施方式中，所述化合物的化学结构式如下之一所示：
Figure BDA0002569419740000023
n＝1～9，且n为整数；
Figure BDA0002569419740000031
n＝3～13，且n为整数；
Figure BDA0002569419740000032
n＝1～9，且n为整数；
Figure BDA0002569419740000033
n＝3～13，且n为整数；
Figure BDA0002569419740000034
m＝1～9，n＝1～9，且m、n为整数；
Figure BDA0002569419740000035
m＝1～9，n＝3～13，且m、n为整数；
Figure BDA0002569419740000041
m＝3～13，n＝1～9，且m、n为整数；
Figure BDA0002569419740000042
m＝3～13，n＝3～13，且m、n为整数。
本发明另一方面提供上述的化合物的制备方法，包括：将式(1)化合物的全乙酰化前体化合物水解，以提供式(1)化合物；或，
将式(2)化合物的全乙酰化前体化合物水解，以提供式(2)化合物；或，
将式(1)化合物的全乙酰化前体化合物和式(2)化合物的全乙酰化前体化合物进行Click反应，以提供式(3)化合物的全乙酰化前体化合物；
将式(3)化合物的全乙酰化前体化合物水解，以提供式(3)化合物。
本发明另一方面提供上述的化合物或其盐、异构体、或溶剂化物在膜蛋白纯化中的用途。
在本发明一些实施方式中，所述膜蛋白选自G蛋白偶联受体，更具体选自腺苷受体2A。
本发明另一方面提供一种组合物，包括上述的化合物或其盐、异构体、或溶剂化物。
附图说明
图1显示为本发明中预组装去垢剂对生物膜上的膜蛋白萃取并与之形成复合物的示意图，其中，单独的带有线段的蓝色球体及代表式(1)化合物，单独的带有线段的紫色球体代表式(2)化合物，带有线段的蓝色球体和带有线段的紫色球体预组装后所形成的即为式(3)化合物。
具体实施方式
本发明发明人经过大量研究，提供了一类新型的化合物，所述化合物在传统的去垢剂的亲水部分和疏水部分之间引入了可进一步发生化学反应的官能团，使去垢剂能在特定条件下发生化学反应，通过结构的变化改变去垢剂的性质，提高了其针对膜蛋白的稳定性，在此基础上完成了本发明。
本发明第一方面提供一种化合物或其盐、异构体、或溶剂化物，所述化合物的化学结构式如下之一所示：
Figure BDA0002569419740000051
其中，A、B可以各自独立地选自戊糖或己糖的呋喃糖或吡喃糖构型所形成的单糖或二糖糖基；
E、G可以各自独立地选自直链的C1～C20烷基。
本发明所提供的化合物包括亲水极性基团和疏水非极性基团，是一种双极性分子，这一类化合物也可以被称为去垢剂。所述化合物能够使脂膜解体释放膜蛋白，并在溶液中为去膜状态下的膜蛋白提供疏水环境，维持和保护膜蛋白的疏水跨膜结构，从而可以提高其所针对的膜蛋白的稳定性。
本发明中，术语“盐”应当被理解为由本发明使用的任何形式的活性化合物，其中所述化合物可以为离子形式或带电荷或被偶联到反离子(阳离子或阴离子)或在溶液中。这个定义还可以包括活性分子与其它分子和离子的季铵盐和络合物，特别是通过离子相互作用的络合物。
由上述本发明所提供的化合物可以包括取决于存在的手性中心的对映体或取决于存在的双键的异构体(例如Z,E)、单一异构体、对映异构体、非对映异构体、顺反异构体、几何异构体、互变异构体、旋转异构体、阻转异构体和它们的混合物(包括消旋体)均落入本发明的范围之内。
本发明中，术语“溶剂化物”通常指任何形式的根据本发明的活性化合物通过非共价键与另一分子(通常为极性溶剂)相结合，所获得的物质，具体可以是包括但不限于水化物和醇化物，例如甲醇化物。
本发明中，所述“烷基”通常指饱和脂肪族基团，它们可以是直链或支链。例如，C1-C20烷基通常指包括1个、2个、3个、4个、5个、6个、7个、8个、9个、10个、11个、12个、13个、14个、15个、16个、17个、18个、19个、20个碳原子的烷基基团，所述烷基基团具体可以是包括但不限于甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基等。
本发明所提供的化合物中，可以包括亲水极性基团，其作用主要是可以促进膜蛋白与胶束形成的复合物在水中的溶解。亲水极性基团具体可以是基团A和/或基团B。在本发明一具体实施例中，A、B可以各自独立地选自己糖的吡喃糖构型所形成的单糖糖基或二糖糖基。
在本发明另一具体实施例中，A、B可以各自独立地选自如下之一所示的基团：
Figure BDA0002569419740000061
在本发明另一具体实施例中，式(3)中，A、B可以选自相同或不同的糖基。
本发明所提供的化合物中，可以包括疏水非极性基团，其作用主要是可以维持和稳定膜蛋白的疏水结构。疏水非极性基团具体可以是基团E和/或基团G。在本发明一具体实施例中，E、G可以各自独立地选自直链的C1～C16烷基。
在本发明另一具体实施例中，当A选自己糖的吡喃糖构型所形成的单糖糖基时，E选自直链的C1～C9烷基，当A选自己糖的吡喃糖构型所形成的二糖糖基时，E选自直链的C3～C13烷基；
在本发明另一具体实施例中，当B选自己糖的吡喃糖构型所形成的单糖糖基时，G选自直链的C1～C9烷基，当B选自己糖的吡喃糖构型所形成的二糖糖基时，G选自直链的C3～C13烷基。
在本发明另一具体实施例中，所述化合物的化学结构式如下之一所示：
Figure BDA0002569419740000071
n＝1～9，且n为整数；
Figure BDA0002569419740000072
n＝3～13，且n为整数；
Figure BDA0002569419740000073
n＝1～9，且n为整数；
Figure BDA0002569419740000074
n＝3～13，且n为整数；
Figure BDA0002569419740000075
m＝1～9，n＝1～9，且m、n为整数；
Figure BDA0002569419740000076
m＝1～9，n＝3～13，且m、n为整数；
Figure BDA0002569419740000081
m＝3～13，n＝1～9，且m、n为整数；
Figure BDA0002569419740000082
m＝3～13，n＝3～13，且m、n为整数。
本发明第二方面提供本发明第一方面所提供的化合物的制备方法，包括：将式(1)化合物的全乙酰化前体化合物水解，以提供式(1)化合物；或，将式(2)化合物的全乙酰化前体化合物水解，以提供式(2)化合物；或，将式(3)化合物的全乙酰化前体化合物水解，以提供式式(3)化合物。式(1)化合物的全乙酰化前体化合物通常是指式(1)化合物中的羟基基团(-OH)全部被替换为(-OCOCH3)所形成的化学结构，式(2)化合物的全乙酰化前体化合物通常是指式(2)化合物中的羟基基团(-OH)全部被替换为(-OCOCH3)所形成的化学结构，式(3)化合物的全乙酰化前体化合物通常是指式(3)化合物中的羟基基团(-OH)全部被替换为(-OCOCH3)所形成的化学结构。合适的将乙酰化前体化合物进行水解的方法对于本领域技术人员来说应该是已知的。例如，乙酰化前体化合物的水解可以在碱存在的条件下进行，水解反应中所使用的碱具体可以是有机碱或无机碱等，更具体可以是醇钠等，碱的用量相对于乙酰化前体化合物来说通常是催化量、基本等量或者过量的。再例如，乙酰化前体化合物的水解可以在溶剂存在的条件下进行，水解反应中所使用的溶剂可以是质子性溶剂等，更具体可以是醇类溶剂等，更具体可以是甲醇等。再例如，水解反应通常可以在室温至溶剂沸点的温度条件下进行。
本发明所提供的制备方法中，还可以包括：将式(1)化合物的全乙酰化前体化合物和式(2)化合物的全乙酰化前体化合物进行Click反应，以提供式(3)化合物。合适的Click反应的条件对于本领域技术人员来说应该是已知的。例如，所述Click反应通常可以在硫酸铜/抗坏血酸钠体系中进行，硫酸铜和/或抗坏血酸钠的用量相对于式(1)化合物来说通常可以是催化量、基本等量或者过量的。再例如，式(2)化合物的用量相对于式(1)化合物来说通常是基本等量或者过量的，从而可以保证反应充分正向进行。再例如，Click反应可以在溶剂存在的条件下进行，Click反应中所使用的溶剂通常为反应体系的良溶剂，从而可以使反应原料和/或反应体系充分分散，Click反应中具体使用的溶剂可以包括水、甲醇、二氯甲烷等。再例如，Click反应通常可以在室温至溶剂沸点的温度条件下进行。
本发明第三方面提供本发明第一方面所提供的化合物或其盐、异构体、或溶剂化物在膜蛋白纯化中的用途。本发明所提供的化合物能够使脂膜解体释放膜蛋白，并在溶液中为去膜状态下的膜蛋白提供疏水环境，从而可以将生物膜上的膜蛋白萃取至水溶液中。此外，上述化合物可以在水中形成合适直径的胶束，且在上述化合物存在的条件下，膜蛋白热稳定性可以被明显改善。
本发明所提供的用途中，所述膜蛋白可以选自G蛋白偶联受体。G蛋白偶联受体的稳定性相对较差，一些传统的去垢剂很难有效稳定此类膜蛋白，而本申请所提供的化合物则对该类蛋白有较好的稳定作用。在本发明一具体实施例中，所述膜蛋白可以选自腺苷受体2A。
本发明第四方面提供一种组合物，包括本发明第一方面所提供的化合物或其盐、异构体、或溶剂化物。本发明所提供的组合物可以是一种膜蛋白分离制剂。所述组合物还可以包括脂质体化合物等，具体可以是例如胆固醇琥珀酸单酯等。
本发明第五方面提供一种膜蛋白纯化方法，包括：将包括目标膜蛋白的体系在本发明第一方面所提供的化合物存在的条件下孵育。所述包括目标膜蛋白的体系可以包括表达有目标膜蛋白的细胞或其破碎后所释放的细胞内容物等。合适的适用于膜蛋白分离的孵育体系和孵育条件对于本领域技术人员来说应该是已知的，例如，赋予体系通常可以包括合适的缓冲液、蛋白酶抑制剂等，再例如，通常在较低的温度下进行孵育。本领域技术人员可以选择合适的方法对孵育所得产物进行进一步纯化，例如，可以通过金属亲和固定树脂对孵育所得产物进行纯化，以提供目标膜蛋白的水溶液。
本发明所提供的化合物在分子结构上是具有“预组装”特点的化合物，且可以具有两头两尾(或多头多尾)的特点。这些化合物在膜蛋白的热稳定性实验中能够显著提高膜蛋白的稳定性，且效果显著高于目前常用的去垢剂，具有良好的产业化前景。
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。
须知，下列实施例中未具体注明的工艺设备或装置均采用本领域内的常规设备或装置。
此外应理解，本发明中提到的一个或多个方法步骤并不排斥在所述组合步骤前后还可以存在其他方法步骤或在这些明确提到的步骤之间还可以插入其他方法步骤，除非另有说明；还应理解，本发明中提到的一个或多个设备/装置之间的组合连接关系并不排斥在所述组合设备/装置前后还可以存在其他设备/装置或在这些明确提到的两个设备/装置之间还可以插入其他设备/装置，除非另有说明。而且，除非另有说明，各方法步骤的编号仅为鉴别各方法步骤的便利工具，而非为限制各方法步骤的排列次序或限定本发明可实施的范围，其相对关系的改变或调整，在无实质变更技术内容的情况下，当亦视为本发明可实施的范畴。
实施例1
小分子去垢剂及其合成
1、类型1的小分子去垢剂，其特征为直链烷基的1位具有一个乙炔基，其通式如下：
Figure BDA0002569419740000101
通过糖苷化反应合成类型1小分子去垢剂，其合成通式如下：
Figure BDA0002569419740000102
由于该类型小分子去垢剂的合成路线完全相同，下面仅举部分例子阐述合成路线。为便于表述，对合成最终得到的小分子去垢剂及其全乙酰化的合成前体命名如下：
小分子去垢剂命名由“烷基主链碳原子数”+“糖基缩写”+“yne”组成，G为β-D-吡喃葡萄糖基，M为β-D-麦芽糖基。
小分子去垢剂的全乙酰化前体命名由“Ac”+“小分子去垢剂名称”组成。
例如，下列两个小分子去垢剂及其全乙酰化前体的名称如下：
Figure BDA0002569419740000111
在干燥的、充满氮气的反应瓶中将12mmol三甲基硅基乙炔溶于50mL无水四氢呋喃(THF)中，将反应温度降至-78℃，向此溶液缓慢滴加8.6mL,2.4M的正丁基锂的正己烷溶液，继续在-78℃搅拌1小时。向此反应液滴加10mmol直链烷基醛，缓慢升至室温并搅拌1小时。反应结束后加入50mL饱和氯化铵溶液淬灭反应，分出有机相，水相用乙酸乙酯萃取三次，并入有机相，依次用饱和氯化铵水溶液和饱和食盐水洗涤，然后用无水硫酸钠干燥，过滤除去硫酸钠，浓缩得到粗产品。粗产品用柱层析(200-300目硅胶，洗脱剂为正己烷：乙酸乙酯＝50:1)分离得到纯净的中间体1-(三甲基硅基)-1-烷基炔-3-醇。
10mmol 1-(三甲基硅基)-1-烷基炔-3-醇溶于50mL甲醇中，加入30mmol(4.14g)无水碳酸钾，室温搅拌1小时。反应结束后加入100mL饱和氯化铵溶液淬灭反应，用乙酸乙酯萃取三次，有机相依次用饱和氯化铵水溶液和饱和食盐水洗涤，然后用无水硫酸钠干燥，过滤除去硫酸钠，浓缩得到粗产品。粗产品用柱层析(200-300目硅胶，洗脱剂为正己烷：乙酸乙酯＝20:1)分离得到纯净的中间体1-烷基炔-3-醇。
在干燥的、充满氮气的反应瓶中将5mmol 1-烷基炔-3-醇及7.5mmolβ-D-葡萄糖五乙酸酯(或β-D-麦芽糖八乙酸酯)溶于30mL无水二氯甲烷中，将反应温度降至0℃，向此溶液缓慢滴加1.3mL(10mmol)三氟化硼乙醚，缓慢升至室温并搅拌4-6小时。反应结束后加入2.8mL(20mmol)三乙胺淬灭反应。淬灭后的反应液依次用饱和碳酸氢钠水溶液和饱和食盐水洗涤，然后用无水硫酸钠干燥，过滤除去硫酸钠，浓缩得到粗产品。粗产品用柱层析(200-300目硅胶，全乙酰化葡萄糖苷的洗脱剂为正己烷：乙酸乙酯＝5:1，全乙酰化麦芽糖苷的洗脱剂为正己烷：乙酸乙酯＝3:1)分离得到纯净的去垢剂全乙酰化中间体。部分中间体表征数据如下：
Ac4Gyne
1H NMR(500MHz,CDCl3),δ(ppm)0.88(t,J＝7.0Hz,3H,CH3),1.65-1.82(m,2H,CH2),2.00-2.08(s,12H,CH3),2.55-2.56(m,1H,CH),3.73-3.78(m,1H,CH),4.11-4.15(m,1H,CH2),4.25-4.29(m,1H,CH2),4.34and 4.50(td,J＝6.5,2.0Hz,1H,CH),4.76and 4.87(d,J＝8.0Hz,1H,CH),4.97-5.02(m,1H,CH),5.05-5.10(m,1H,CH),5.20-5.27(m,1H,CH)；13C NMR(125MHz,CDCl3),δ(ppm)13.72,13.73,22.20,22.21,24.2,24.7,28.45,28.49,31.34,31.36,34.8,35.5,61.6,61.8,67.3,68.18,68.20,70.4,70.7,71.1,71.5,71.6,72.5,72.6,74.3,74.6,81.1,81.7,97.4,99.4,168.7,168.96,169.03,169.07,169.83,169.86,170.19,170.20；HRMS calcd for C20H28O10[M+Na]+:451.1575；found:451.1577.
Ac6Gyne
1H NMR(500MHz,CDCl3),δ(ppm)0.88and 0.89(t,J＝7.0Hz,3H,CH3),1.23-1.35(m,4H,CH2),1.38-1.48(m,2H,CH2),1.65-1.82(m,2H,CH2),2.00-2.08(s,12H,CH3),2.55-2.56(m,1H,CH),3.73-3.78(m,1H,CH),4.11-4.15(m,1H,CH2),4.25-4.29(m,1H,CH2),4.34and 4.50(td,J＝7.0,2.0Hz,1H,CH),4.76and 4.87(d,J＝8.0Hz,1H,CH),4.97-5.02(m,1H,CH),5.05-5.10(m,1H,CH),5.20-5.27(m,1H,CH)；13C NMR(125MHz,CDCl3),δ(ppm)13.7,20.26,20.28,20.30,20.32,20.39,20.40,22.17,22.20,23.9,24.4,30.98,31.01,34.7,35.5,61.6,61.8,67.3,68.19,68.21,70.4,70.7,71.1,71.5,71.6,72.5,72.6,74.3,74.6,81.1,81.7,97.4,99.4,168.8,168.99,169.05,169.09,169.85,169.89,170.22,170.23；HRMS calcd for C22H32O10[M+Na]+:479.1888；found:479.1889.
Ac8Gyne
1H NMR(500MHz,CDCl3),δ(ppm)0.88(t,J＝7.0Hz,3H,CH3),1.28-1.47(m,10H,CH2),1.65-1.82(m,2H,CH2),2.00-2.08(s,12H,CH3),2.57-2.58(m,1H,CH),3.74-3.79(m,1H,CH),4.10-4.14(m,1H,CH2),4.26-4.30(m,1H,CH2),4.34and 4.49(td,J＝6.5,2.0Hz,1H,CH),4.77and 4.88(d,J＝8.0Hz,1H,CH),4.97-5.01(m,1H,CH),5.05-5.10(m,1H,CH),5.20-5.27(m,1H,CH)；13C NMR(125MHz,CDCl3),δ(ppm)13.67,13.68,20.14,20.16,20.18,20.20,20.26,20.28,22.2,24.2,24.7,28.68,28.73,28.76,31.4,34.7,35.4,61.5,61.7,67.2,68.11,68.13,70.3,70.6,71.0,71.4,71.5,72.4,72.5,74.2,74.6,81.1,81.7,97.3,99.3,168.6,168.8,168.94,168.97,169.70,169.73,170.06,170.07；HRMS calcd forC24H36O10[M+Na]+:507.2201；found:507.2202.
Ac10Gyne
1H NMR(500 MHz,CDCl3),δ(ppm)0.88(t,J＝7.0 Hz,3H,CH3),1.24-1.47(m,14H,CH2),1.65-1.81(m,2H,CH2),2.00-2.08(s,12H,CH3),2.58-2.59(m,1H,CH),3.75-3.79(m,1H,CH)4.11-4.14(m,1H,CH2),4.26-4.30(m,1H,CH2),4.34 and 4.49(td,J＝6.5,2.0 Hz,1H,CH),4.77and 4.88(d,J＝8.0 Hz,1H,CH),4.97-5.01(m,1H,CH),5.05-5.10(m,1H,CH),5.20-5.27(m,1H,CH)；13C NMR(125 MHz,CDCl3),δ(ppm)13.67,13.68,20.11,20.14,20.16,20.22,20.24,22.2,24.2,24.6,28.72,28.76,28.86,28.87,29.06,29.07,29.08,31.44,31.45,34.7,35.4,61.5,61.7,67.2,68.09,68.12,70.2,70.6,71.0,71.37,71.44,72.4,72.5,74.2,74.6,81.0,81.6,97.3,99.3,168.6,168.8,168.94,168.97,169.69,169.72,170.05,170.06；HRMS calcd for C26H40O10[M+Na]+:535.2514；found:535.2516.
Ac12Gyne
1H NMR(500 MHz,CDCl3),δ(ppm)0.88(t,J＝7.0 Hz,3H,CH3),1.24-1.44(m,18H,CH2),1.65-1.82(m,2H,CH2),2.00-2.08(s,12H,CH3),2.57-2.58(m,1H,CH),3.74-3.78(m,1H,CH),4.10-4.14(m,1H,CH2),4.26-4.30(m,1H,CH2),4.34 and 4.49(td,J＝6.5,2.0 Hz,1H,CH),4.77and 4.87(d,J＝8.0 Hz,1H,CH),4.97-5.01(m,1H,CH),5.05-5.10(m,1H,CH),5.20-5.27(m,1H,CH)；13C NMR(125 MHz,CDCl3),δ(ppm)13.7,20.16,20.19,20.21,20.27,20.29,22.2,24.2,24.7,28.75,28.79,28.80,28.81,29.04,29.07,31.44,31.45,34.7,35.4,61.5,61.7,67.2,68.12,68.14,70.3,70.6,71.0,71.4,71.5,72.4,72.5,74.2,74.6,81.1,81.6,97.4,99.3,168.6,168.8,168.94,168.97,169.70,169.74,170.06,170.07；HRMS calcd for C28H44O10[M+Na]+:563.2827；found:563.2825.
Ac6Myne
1H NMR(500 MHz,CDCl3),δ(ppm)0.88(t,J＝7.0 Hz,3H,CH3),1.26-1.41(m,6H,CH2),1.64-1.80(m,2H,CH2),2.00-2.14(s,21H,CH3),2.49 and 2.51(d,J＝2.0 Hz,1H,CH),3.69-3.74(m,1H,CH),3.95-4.06(m,3H,CH2 and CH),4.22-4.50(m,4H,CH2 and CH),4.75-4.89(m,3H,CH),5.02-5.07(m,1H,CH),5.24-5.42(m,3H,CH)；13C NMR(125 MHz,CDCl3),δ(ppm)14.0,20.43,20.44,20.46,20.48,20.49,20.54,20.69,22.5,24.5,24.9,29.00,29.06,29.29,29.32,31.69,31.70,34.9,35.7,61.38,61.44,62.6,62.9,67.4,67.90,67.92,68.34,68.37,69.3,69.86,69.89,70.5,71.7,72.01,72.06,72.13,72.66,72.71,74.3,74.7,75.2,75.4,81.2,81.8,95.4,97.0,99.2,169.26,169.31,169.5,169.76,169.78,170.0,170.2,170.27,170.36,170.39；HRMS calcd for C34H48O18[M+Na]+:767.2733；found:767.2730.
Ac8Myne
1H NMR(500 MHz,CDCl3),δ(ppm)0.88(t,J＝7.0 Hz,3H,CH3),1.27-1.45(m,10H,CH2),1.64-1.80(m,2H,CH2),2.00-2.14(s,21H,CH3),2.47 and 2.50(d,J＝2.0 Hz,1H,CH),3.69-3.74(m,1H,CH),3.94-4.05(m,3H,CH2 and CH),4.21-4.50(m,4H,CH2 and CH),4.75-4.89(m,3H,CH),5.02-5.07(m,1H,CH),5.24-5.42(m,3H,CH)；13C NMR(125 MHz,CDCl3),δ(ppm)14.00,14.01,20.49,20.51,20.54,20.55,20.56,20.61,20.76,20.79,20.86,22.54,22.55,24.6,25.0,29.02,29.06,29.08,31.7,35.0,35.7,61.44,61.50,62.7,62.9,67.5,67.96,67.97,68.40,68.43,69.3,69.92,69.94,70.6,71.7,72.08,72.12,72.19,72.71,72.75,74.3,74.7,75.3,75.5,81.3,81.9,95.4,97.1,99.3,169.34,169.39,169.6,169.84,169.86,170.1,170.2,170.36,170.44,170.47；HRMS calcd forC36H52O18[M+Na]+:795.3046；found:795.3037.
Ac12Myne
1H NMR(500 MHz,CDCl3),δ(ppm)0.88(t,J＝7.0 Hz,3H,CH3),1.25-1.41(m,18H,CH2),1.64-1.79(m,2H,CH2),2.00-2.14(s,21H,CH3),2.47 and 2.50(d,J＝2.0 Hz,1H,CH),3.69-3.74(m,1H,CH),3.95-4.05(m,3H,CH2 and CH),4.21-4.50(m,4H,CH2 and CH),4.75-4.89(m,3H,CH),5.02-5.07(m,1H,CH),5.24-5.41(m,3H,CH)；13C NMR(125 MHz,CDCl3),δ(ppm)14.0,20.48,20.50,20.52,20.54,20.6,20.75,20.78,20.84,22.6,24.6,25.0,29.1,29.2,29.41,29.43,29.47,29.53,29.56,31.8,35.0,35.7,60.3,61.43,61.49,62.7,62.9,67.5,67.95,67.97,68.39,68.42,69.2,69.92,69.94,70.6,71.7,72.07,72.11,72.19,72.71,72.75,74.3,74.7,75.3,75.5,81.3,81.9,95.4,97.1,99.3,169.32,169.37,169.6,169.82,169.84,170.1,170.2,170.3,170.43,170.45；HRMS calcd forC40H60O18[M+Na]+:851.3672；found:851.3672.
Ac14Myne
1H NMR(500 MHz,CDCl3),δ(ppm)0.88(t,J＝7.0 Hz,3H,CH3),1.25-1.42(m,22H,CH2),1.64-1.80(m,2H,CH2),2.00-2.14(s,21H,CH3),2.50 and 2.52(d,J＝2.0 Hz,1H,CH),3.70-3.75(m,1H,CH),3.96-4.06(m,3H,CH2 and CH),4.22-4.50(m,4H,CH2 and CH),4.76-4.90(m,3H,CH),5.02-5.07(m,1H,CH),5.24-5.42(m,3H,CH)；13C NMR(125 MHz,CDCl3),δ(ppm)13.9,20.38,20.41,20.42,20.43,20.48,20.63,20.66,20.7,22.5,24.5,24.9,29.0,29.2,29.30,29.33,29.36,29.45,29.48,29.49,31.7,34.9,35.6,61.35,61.41,62.6,62.8,67.4,67.87,67.89,68.30,68.33,69.2,69.83,69.86,70.4,71.6,71.97,72.02,72.9,72.64,72.69,74.3,74.7,75.2,75.4,81.2,81.8,95.3,97.0,99.1,169.22,169.26,169.5,169.71,169.74,170.0,170.1,170.2,170.31,170.34；HRMS calcdfor C42H64O18[M+Na]+:879.3985；found:879.3973.
Ac16Myne
1H NMR(500MHz,CDCl3),δ(ppm)0.88(t,J＝7.0Hz,3H,CH3),1.25-1.42(m,26H,CH2),1.64-1.80(m,2H,CH2),2.00-2.14(s,21H,CH3),2.49and 2.52(d,J＝2.0Hz,1H,CH),3.70-3.75(m,1H,CH),3.95-4.06(m,3H,CH2 and CH),4.22-4.50(m,4H,CH2 and CH),4.75-4.89(m,3H,CH),5.02-5.07(m,1H,CH),5.24-5.42(m,3H,CH)；13C NMR(125MHz,CDCl3),δ(ppm)14.0,20.40,20.41,20.43,20.45,20.46,20.53,20.56,20.66,20.69,20.76,20.79,22.5,24.5,24.9,29.0,29.2,29.33,29.35,29.39,29.46,29.48,31.7,34.9,35.6,61.37,61.43,62.6,62.8,67.4,67.89,67.91,68.32,68.36,69.2,69.85,69.88,70.5,71.7,72.00,72.04,72.11,72.66,72.70,74.3,74.7,75.2,75.4,81.2,81.8,95.4,97.0,99.2,169.24,169.29,169.5,169.74,169.76,170.0,170.1,170.2,170.34,170.36；HRMS calcdfor C44H68O18[M+Na]+:907.4298；found:907.4298.
1mmol去垢剂全乙酰化前体溶于10mL甲醇中，加入50μL 30％甲醇钠的甲醇溶液，室温搅拌1小时。反应结束后加入阳离子交换树脂(安伯莱特IR120,氢型)调节溶液近中性，过滤除去树脂，浓缩得到粗产品。粗产品用柱层析(200-300目硅胶，葡萄糖苷的洗脱剂为二氯甲烷：甲醇＝10:1，麦芽糖苷的洗脱剂为二氯甲烷：甲醇＝5:1)分离得到纯净的小分子去垢剂。将纯化的小分子去垢剂溶于超纯水，冻干得到粉末状的去垢剂产品。部分化合物表征数据如下：
4Gyne
1H NMR(500MHz,CD3OD),δ(ppm)0.96(t,J＝7.0Hz,3H,CH3),1.34-1.58(m,2H,CH2),1.72-1.88(m,2H,CH2),2.90and 2.91(d,J＝2.0Hz,1H,CH),3.24-3.27(m,1H,CH),3.31-3.46(m,3H,CH2 and CH),3.70-3.75(m,1H,CH),3.88-3.93(m,1H,CH),4.48-4.69(m,2H,CH)；13C NMR(125MHz,CD3OD),δ(ppm)14.4,23.55,25.8,26.1,30.0,32.8,36.3,36.6,62.61,62.67,67.8,70.4,71.3,71.5,74.7,75.0,75.2,75.9,77.81,77.85,77.94,83.0,84.0,100.8,102.9；HRMS calcd for C12H20O6[M+Na]+:283.1152；found:283.1150.
6Gyne
1H NMR(500MHz,CD3OD),δ(ppm)0.94(t,J＝7.0Hz,3H,CH3),1.34-1.57(m,6H,CH2),1.70-1.86(m,2H,CH2),2.88and 2.89(d,J＝2.0Hz,1H,CH),3.21-3.24(m,1H,CH),3.28-3.43(m,3H,CH2 and CH),3.68-3.73(m,1H,CH),3.87-3.91(m,1H,CH),4.45-4.68(m,2H,CH)；13C NMR(125MHz,CD3OD),δ(ppm)14.3,23.6,25.6,25.9,32.63,32.65,36.3,36.6,62.68,62.74,67.8,70.4,71.4,71.6,74.8,75.09,75.13,75.9,77.92,77.96,78.04,83.1,84.1,100.9,103.0；HRMS calcd for C22H38O11[M+Na]+:501.2306；found:501.2295.；HRMScalcd for C14H24O6[M+Na]+:311.1465；found:311.1462.
8Gyne
1H NMR(500 MHz,CD3OD),δ(ppm)0.96(t,J＝7.0 Hz,3H,CH3),1.35-1.58(m,10H,CH2),1.73-1.88(m,2H,CH2),2.91 and 2.92(d,J＝2.0 Hz,1H,CH),3.25-3.28(m,1H,CH),3.31-3.47(m,3H,CH2 and CH),3.71-3.76(m,1H,CH),3.89-3.94(m,1H,CH),4.49-4.70(m,2H,CH)；13C NMR(125 MHz,CD3OD),δ(ppm)14.4,23.6,25.8,26.1,30.2,30.3,32.84,32.85,36.3,36.6,62.58,62.63,67.8,70.4,71.3,71.5,74.7,74.9,75.2,76.0,77.75,77.79,77.89,83.0,84.0,100.8,102.9；HRMS calcd for C16H28O6[M+Na]+:339.1778；found:339.1776.
10Gyne
1H NMR(500 MHz,CD3OD),δ(ppm)0.97(t,J＝7.0 Hz,3H,CH3),1.36-1.58(m,14H,CH2),1.74-1.90(m,2H,CH2),2.92 and 2.93(d,J＝2.0 Hz,1H,CH),3.27-3.30(m,1H,CH),3.33-3.49(m,3H,CH2 and CH),3.73-3.78(m,1H,CH),3.90-3.95(m,1H,CH),4.50-4.71(m,2H,CH)；13C NMR(125 MHz,CD3OD),δ(ppm)14.5,23.6,25.8,26.1,30.3,30.55,30.57,32.9,36.3,36.5,62.54,62.59,67.8,70.4,71.2,71.4,74.6,74.9,75.2,76.0,77.68,77.72,77.82,83.0,84.0,100.8,102.9；HRMS calcd for C18H32O6[M+Na]+:367.2091；found:367.2088.
12Gyne
1H NMR(500 MHz,CD3OD),δ(ppm)0.96(t,J＝7.0 Hz,3H,CH3),1.36-1.57(m,18H,CH2),1.73-1.89(m,2H,CH2),2.91 and 2.92(d,J＝2.0 Hz,1H,CH),3.26-3.29(m,1H,CH),3.32-3.47(m,3H,CH2 and CH),3.72-3.76(m,1H,CH),3.90-3.94(m,1H,CH),4.49-4.70(m,2H,CH)；13C NMR(125 MHz,CD3OD),δ(ppm)14.4,23.6,25.8,26.1,30.3,30.4,30.5,32.9,36.3,36.6,62.58,62.62,67.8,70.4,71.3,71.5,74.7,74.9,75.2,75.9,77.74,77.78,77.87,83.0,84.0,100.8,102.9；HRMS calcd for C20H36O6[M+Na]+:395.2404；found:395.2400.
6Myne
1H NMR(500 MHz,CD3OD),δ(ppm)0.94(t,J＝7.0 Hz,3H,CH3),1.34-1.53(m,6H,CH2),1.71-1.86(m,2H,CH2),2.90 and 2.92(d,J＝2.0 Hz,1H,CH),3.29-3.35(m,2H,CH),3.40-3.44(m,1H,CH),3.49-3.52(m,1H,CH),3.57-3.75(m,5H,CH2 and CH),3.83-3.94(m,3H,CH),4.49-4.69(m,2H,CH),5.22(d,J＝3.5 Hz,1H,CH)；13C NMR(125 MHz,CD3OD),δ(ppm)14.4,23.6,25.8,26.1,30.35,30.5,32.9,36.3,36.6,62.1,62.6,67.9,70.6,71.3,74.0,74.3,74.57,74.62,74.9,75.3,76.1,76.5,77.68,77.70,80.8,81.0,82.9,83.9,100.8,102.66,102.69,102.9；HRMS calcd for C20H34O11[M+Na]+:473.1993；found:473.1992.
8Myne
1H NMR(500 MHz,CD3OD),δ(ppm)0.92(t,J＝7.0 Hz,3H,CH3),1.32-1.52(m,10H,CH2),1.69-1.84(m,2H,CH2),2.88 and 2.89(d,J＝2.0 Hz,1H,CH),3.25-3.30(m,2H,CH),3.37-3.41(m,1H,CH),3.45-3.48(m,1H,CH),3.54-3.72(m,5H,CH2 and CH),3.81-3.92(m,3H,CH),4.46-4.67(m,2H,CH),5.18(d,J＝4.0 Hz,1H,CH)；13C NMR(125 MHz,CD3OD),δ(ppm)14.4,23.7,25.9,26.2,30.33,30.38,32.93,32.94,36.4,36.6,62.13,62.16,62.7,67.9,70.6,71.5,74.1,74.4,74.70,74.74,75.0,75.2,76.0,76.7,77.79,77.82,81.0,81.2,83.0,84.0,100.9,102.83,102.86,103.0；HRMS calcd for C22H38O11[M+Na]+:501.2306；found:501.2295.
12Myne
1H NMR(500 MHz,CD3OD),δ(ppm)0.93(t,J＝7.0 Hz,3H,CH3),1.32-1.53(m,18H,CH2),1.70-1.85(m,2H,CH2),2.88 and 2.90(d,J＝2.0 Hz,1H,CH),3.26-3.31(m,2H,CH),3.38-3.42(m,1H,CH),3.46-3.48(m,1H,CH),3.55-3.73(m,5H,CH2 and CH),3.82-3.93(m,3H,CH),4.47-4.68(m,2H,CH),5.19(d,J＝3.5 Hz,1H,CH)；13C NMR(125 MHz,CD3OD),δ(ppm)14.4,23.7,25.9,26.2,30.43,30.45,30.66,30.67,30.68,30.73,30.76,33.0,36.4,36.7,62.13,62.16,62.7,67.9,70.6,71.4,74.1,74.4,74.69,74.73,75.0,75.2,76.0,76.6,77.77,77.80,81.0,81.2,83.0,84.0,100.9,102.82,102.86,103.0；HRMS calcd forC26H46O11[M+Na]+:557.2932；found:557.2914.
14Myne
1H NMR(500 MHz,CD3OD),δ(ppm)0.92(t,J＝7.0 Hz,3H,CH3),1.31-1.52(m,22H,CH2),1.70-1.85(m,2H,CH2),2.87 and 2.89(d,J＝2.0 Hz,1H,CH),3.26-3.35(m,2H,CH),3.38-3.42(m,1H,CH),3.45-3.48(m,1H,CH),3.54-3.73(m,5H,CH2 and CH),3.81-3.93(m,3H,CH),4.46-4.67(m,2H,CH),5.19(d,J＝4.0 Hz,1H,CH)；13C NMR(125 MHz,CD3OD),δ(ppm)14.4,23.7,25.9,26.2,30.44,30.46,30.66,30.68,30.69,30.75,30.77,30.78,33.0,36.4,36.7,62.12,62.16,62.7,68.0,70.6,71.4,74.1,74.4,74.69,74.73,75.0,75.2,76.0,76.6,77.77,77.80,81.0,81.2,83.0,84.0,100.9,102.82,102.85,103.0；HRMScalcd for C28H50O11[M+Na]+:585.3245；found:585.3231.
16Myne
1H NMR(500 MHz,CD3OD),δ(ppm)0.93(t,J＝7.0 Hz,3H,CH3),1.32-1.53(m,26H,CH2),1.70-1.86(m,2H,CH2),2.88 and 2.90(d,J＝2.0 Hz,1H,CH),3.27-3.34(m,2H,CH),3.39-3.43(m,1H,CH),3.46-3.49(m,1H,CH),3.56-3.74(m,5H,CH2 and CH),3.82-3.93(m,3H,CH),4.47-4.68(m,2H,CH),5.20(d,J＝3.5 Hz,1H,CH)；13C NMR(125 MHz,CD3OD),δ(ppm)14.4,23.7,25.9,26.2,30.42,30.44,30.65,30.66,30.68,30.73,30.74,30.76,33.0,36.4,36.6,62.10,62.13,62.7,67.9,70.6,71.4,74.1,74.4,74.65,74.69,75.0,75.2,76.0,76.6,77.73,77.76,80.9,81.2,83.0,84.0,100.8,102.77,102.80,103.0；HRMScalcd for C30H54O11[M+Na]+:613.3558；found:613.3559.
2、类型2的小分子去垢剂，其特征为直链烷基的2位具有一个叠氮基，其通式如下：
Figure BDA0002569419740000181
通过糖苷化反应合成类型2小分子去垢剂，其合成通式如下：
Figure BDA0002569419740000182
同样，该类型小分子去垢剂的合成路线完全相同，下面仅举部分例子阐述合成路线。该类型小分子去垢剂及其全乙酰化的合成前体命名如下：
小分子去垢剂命名由“烷基主链碳原子数”+“糖基缩写”+“azide”组成。
小分子去垢剂的全乙酰化前体命名由“Ac”+“小分子去垢剂名称”组成。
例如，下列两个小分子去垢剂及其全乙酰化前体的名称如下：
Figure BDA0002569419740000191
在干燥的反应瓶中将20mmol直链烷基羧酸溶于16mL二氯亚砜(SOCl2)中，加热回流6小时。反应结束后浓缩除去低沸点溶剂得到直链烷基酰氯的粗产品。粗产品中加入6mL液溴，加热至100℃搅拌10小时。反应结束后加入50mL饱和亚硫酸氢钠溶液淬灭反应，用乙酸乙酯萃取三次，有机相用饱和食盐水洗涤，然后用无水硫酸钠干燥，过滤除去硫酸钠，浓缩得到粗产品。粗产品用柱层析(200-300目硅胶，洗脱剂为正己烷：乙酸乙酯＝1:1)分离得到纯净的中间体2-溴直链烷基羧酸。
10mmol 2-溴直链烷基羧酸溶于30mL无水THF中，将反应温度降至0℃，向此溶液加入30mmol硼烷四氢呋喃溶液，缓慢升至室温并搅拌3小时。反应结束后在0℃下小心加入100mL饱和碳酸氢钠溶液淬灭反应，分出有机相。水相用乙酸乙酯萃取三次，并入有机相，依次用饱和碳酸氢钠水溶液和饱和食盐水洗涤，然后用无水硫酸钠干燥，过滤除去硫酸钠，浓缩得到粗产品。粗产品用柱层析(200-300目硅胶，洗脱剂为正己烷：乙酸乙酯＝20:1)分离得到纯净的中间体2-溴-1-烷基醇。
10mmol 2-溴-1-烷基醇溶于50mL二甲基亚砜(DMSO)中，向此溶液加入780mg(12mmol)叠氮化钠，加热回流6小时。反应结束后加入200mL饱和氯化钠溶液，用乙酸乙酯萃取三次，有机相用饱和食盐水洗涤，然后用无水硫酸钠干燥，过滤除去硫酸钠，浓缩得到粗产品。粗产品用柱层析(200-300目硅胶，洗脱剂为正己烷：乙酸乙酯＝10:1)分离得到纯净的中间体2-叠氮-1-烷基醇。
在干燥的、充满氮气的反应瓶中将5mmol 2-叠氮-1-烷基醇及7.5mmolβ-D-葡萄糖五乙酸酯(或β-D-麦芽糖八乙酸酯)溶于30mL无水二氯甲烷中，将反应温度降至0℃，向此溶液缓慢滴加1.3mL(10mmol)三氟化硼乙醚，缓慢升至室温并搅拌4-6小时。反应结束后加入2.8mL(20mmol)三乙胺淬灭反应。淬灭后的反应液依次用饱和碳酸氢钠水溶液和饱和食盐水洗涤，然后用无水硫酸钠干燥，过滤除去硫酸钠，浓缩得到粗产品。粗产品用柱层析(200-300目硅胶，全乙酰化葡萄糖苷的洗脱剂为正己烷：乙酸乙酯＝5:1，全乙酰化麦芽糖苷的洗脱剂为正己烷：乙酸乙酯＝3:1)分离得到纯净的去垢剂全乙酰化中间体。部分中间体表征数据如下：
Ac4Gazide
1H NMR(500MHz,CDCl3),δ(ppm)0.89and 0.90(t,J＝7.0Hz,3H,CH3),1.25-1.45(m,1H,CH2),1.48-1.59(m,1H,CH2),2.01-2.10(s,12H,CH3),3.38-3.47(m,1H,CH2 andCH),3.54-3.62(m,1H,CH2 and CH),3.70-3.74(m,1H,CH),3.88-3.99(m,1H,CH),4.14and4.17(d,J＝2.5Hz,1H,CH2),4.24-4.28(m,1H,CH2),4.58and 4.60(d,J＝4.5Hz,1H,CH),5.03(t,J＝8.0Hz,1H,CH),5.10(t,J＝9.5Hz,1H,CH),5.22(t,J＝9.5Hz,1H,CH)；13C NMR(125MHz,CDCl3),δ(ppm)13.8,20.47,20.56,20.61,22.33,30.2,30.6,31.33,31.36,61.0,61.67,61.73,61.9,68.16,68.20,70.92,70.94,71.2,71.72,71.74,72.65,72.66,72.75,100.4,100.7,169.2,169.3,170.2,170.5；HRMS calcd for C18H27N3O10[M+Na]+:468.1589；found:468.1587.
Ac6Gazide
1H NMR(500MHz,CDCl3),δ(ppm)0.91and 0.92(t,J＝7.0Hz,3H,CH3),1.31-1.44(m,5H,CH2),1.48-1.59(m,1H,CH2),2.01-2.09(s,12H,CH3),3.39-3.49(m,1H,CH2 andCH),3.55-3.64(m,1H,CH2 and CH),3.73-3.77(m,1H,CH),3.88-3.99(m,1H,CH),4.14-4.17(m,1H,CH2),4.26and 4.28(d,J＝4.5Hz,1H,CH2),4.61and 4.62(d,J＝3.5Hz,1H,CH),5.02(t,J＝8.0Hz,1H,CH),5.10(t,J＝9.5Hz,1H,CH),5.22(t,J＝9.5Hz,1H,CH)；13C NMR(125MHz,CDCl3),δ(ppm)13.53,13.55,20.17,20.26,20.31,22.02,22.05,27.64,27.67,29.7,30.1,60.7,61.46,61.50,61.6,67.95,67.98,70.70,70.73,71.0,71.45,71.46,72.40,72.42,72.47,100.1,100.4,168.89,168.96,169.02,169.8,170.2；HRMS calcd forC20H31N3O10[M+Na]+:496.1902；found:496.1906.
Ac8Gazide
1H NMR(500MHz,CDCl3),δ(ppm)0.89and 0.90(t,J＝7.0Hz,3H,CH3),1.24-1.43(m,9H,CH2),1.50-1.58(m,1H,CH2),2.01-2.09(s,12H,CH3),3.38-3.47(m,1H,CH2 andCH),3.54-3.62(m,1H,CH2 and CH),3.70-3.74(m,1H,CH),3.88-3.98(m,1H,CH),4.14and4.17(d,J＝2.5Hz,1H,CH2),4.24-4.28(m,1H,CH2),4.58and 4.60(d,J＝4.5Hz,1H,CH),5.02(t,J＝8.0Hz,1H,CH),5.10(t,J＝9.5Hz,1H,CH),5.22(t,J＝9.5Hz,1H,CH)；13C NMR(125MHz,CDCl3),δ(ppm)13.9,20.46,20.55,20.60,22.40,22.41,25.71,25.76,28.84,28.88,30.3,30.7,31.48,31.50,61.0,61.70,61.76,61.9,68.21,68.25,70.96,70.98,71.2,71.77,71.78,72.68,72.69,72.72,100.4,100.7,169.2,169.3,170.1,170.5；HRMScalcd for C22H35N3O10[M+Na]+:524.2215；found:524.2225.
Ac10Gazide
1H NMR(500 MHz,CDCl3),δ(ppm)0.88 and 0.89(t,J＝7.0 Hz,3H,CH3),1.27-1.43(m,13H,CH2),1.48-1.57(m,1H,CH2),2.01-2.09(s,12H,CH3),3.38-3.47(m,1H,CH2and CH),3.54-3.62(m,1H,CH2 and CH),3.71-3.74(m,1H,CH),3.88-3.99(m,1H,CH),4.14and 4.17(d,J＝2.5 Hz,1H,CH2),4.25-4.29(m,1H,CH2),4.58 and 4.60(d,J＝4.0 Hz,1H,CH),5.02(t,J＝8.0 Hz,1H,CH),5.10(t,J＝9.5 Hz,1H,CH),5.22(t,J＝9.5 Hz,1H,CH)；13C NMR(125 MHz,CDCl3),δ(ppm)13.9,20.39,20.48,20.53,22.4,25.68,25.74,28.98,29.00,29.11,29.16,29.18,29.21,30.2,30.6,31.61,31.62,60.9,61.61,61.67,61.8,68.10,68.14,70.86,70.89,71.2,71.66,71.68,72.59,72.60,72.7,100.3,100.6,169.1,169.19,169.20,170.1,170.4；HRMS calcd for C24H39N3O10[M+Na]+:552.2528；found:552.2532.
Ac12Gazide
1H NMR(500 MHz,CDCl3),δ(ppm)0.88 and 0.89(t,J＝7.0 Hz,3H,CH3),1.24-1.45(m,17H,CH2),1.49-1.57(m,1H,CH2),2.01-2.09(s,12H,CH3),3.38-3.47(m,1H,CH2and CH),3.52-3.62(m,1H,CH2 and CH),3.70-3.73(m,1H,CH),3.88-3.98(m,1H,CH),4.14and 4.17(d,J＝2.5 Hz,1H,CH2),4.24-4.28(m,1H,CH2),4.58 and 4.60(d,J＝4.5 Hz,1H,CH),5.02(t,J＝8.0 Hz,1H,CH),5.10(t,J＝9.5 Hz,1H,CH),5.21(t,J＝9.5 Hz,1H,CH)；13C NMR(125 MHz,CDCl3),δ(ppm)14.0,20.48,20.56,20.61,22.5,25.77,25.82,28.97,29.00,29.16,29.19,30.3,30.7,31.60,31.62,61.0,61.71,61.78,61.9,68.20,68.26,70.97,70.99,71.3,71.77,71.80,72.69,72.70,72.74,100.4,100.7,169.2,169.3,170.1,170.5；HRMS calcd for C26H43N3O10[M+Na]+:580.2841；found:580.2840.
Ac6Mazide
1H NMR(500 MHz,CDCl3),δ(ppm)0.88(t,J＝7.0 Hz,3H,CH3),1.27-1.57(m,6H,CH2),2.00-2.14(s,21H,CH3),3.37-3.62(m,2H,CH2 and CH),3.70-3.74(m,1H,CH),3.85-4.06(m,4H,CH2 and CH),4.22-4.28(m,2H,CH2),4.49-4.53(m,1H,CH),4.60(d,J＝8.0 Hz,1H,CH),4.84-4.87(m,2H,CH),5.06(t,J＝10.0 Hz,1H,CH),5.25 and 5.26(t,J＝9.0 Hz,1H,CH),5.34-5.42(m,2H,CH)；13C NMR(125 MHz,CDCl3),δ(ppm)13.7,20.16,20.25,20.40,20.49,25.50,25.53,28.69,28.71,28.88,28.91,30.0,30.4,31.3,60.7,61.2,61.6,62.27,62.33,67.7,68.1,68.9,69.6,71.1,71.57,71.59,71.8,72.3,72.4,72.6,74.9,95.2,99.5,100.0,169.0,169.16,169.23,169.5,169.8,169.98,170.05,170.08；HRMScalcd for C32H47N3O18[M+Na]+:784.2747；found:784.2749.
Ac8Mazide
1H NMR(500 MHz,CDCl3),δ(ppm)0.88(t,J＝7.0 Hz,3H,CH3),1.27-1.53(m,10H,CH2),2.01-2.15(s,21H,CH3),3.37-3.62(m,2H,CH2 and CH),3.68-3.72(m,1H,CH),3.85-4.06(m,4H,CH2 and CH),4.21-4.28(m,2H,CH2),4.50-4.54(m,1H,CH),4.62(d,J＝8.0 Hz,1H,CH),4.83-4.87(m,2H,CH),5.05(t,J＝10.0 Hz,1H,CH),5.25 and 5.26(t,J＝9.0 Hz,1H,CH),5.34-5.42(m,2H,CH)；13C NMR(125 MHz,CDCl3),δ(ppm)13.9,20.43,20.44,20.47,20.53,20.54,20.68,20.70,20.76,22.4,25.70,25.73,28.82,28.86,30.3,30.6,31.5,60.9,61.3,61.8,62.45,62.52,67.8,68.3,69.2,69.8,71.4,71.8,72.0,72.4,72.5,72.9,75.2,95.37,95.38,99.8,100.3,169.3,169.5,169.6,169.8,170.1,170.3,170.4；HRMScalcd for C34H51N3O18[M+Na]+:812.3060；found:812.3058.
Ac12Mazide
1H NMR(500 MHz,CDCl3),δ(ppm)0.88(t,J＝7.0 Hz,3H,CH3),1.26-1.53(m,18H,CH2),2.00-2.15(s,21H,CH3),3.36-3.61(m,2H,CH2 and CH),3.68-3.72(m,1H,CH),3.85-4.06(m,4H,CH2 and CH),4.21-4.27(m,2H,CH2),4.49-4.53(m,1H,CH),4.59 and 4.60(d,J＝8.0 Hz,1H,CH),4.84-4.87(m,2H,CH),5.06(t,J＝10.0 Hz,1H,CH),5.25 and 5.26(t,J＝9.0 Hz,1H,CH),5.34-5.42(m,2H,CH)；13C NMR(125 MHz,CDCl3),δ(ppm)14.0,20.46,20.48,20.54,20.56,20.70,20.72,20.78,22.6,25.51,25.53,29.17,29.18,29.20,29.24,29.30,29.33,29.40,29.42,29.44,30.3,30.7,31.8,61.0,61.4,61.9,62.51,62.57,67.9,68.4,69.2,69.9,71.4,71.9,72.1,72.47,72.55,72.9,75.2,95.4,99.8,100.3,169.3,169.47,169.55,169.8,170.1,170.28,170.38,170.39；HRMS calcd for C38H59N3O18[M+Na]+:868.3686；found:868.3680.
Ac14Mazide
1H NMR(500 MHz,CDCl3),δ(ppm)0.88(t,J＝7.0 Hz,3H,CH3),1.26-1.54(m,22H,CH2),2.00-2.14(s,21H,CH3),3.37-3.62(m,2H,CH2 and CH),3.69-3.73(m,1H,CH),3.85-4.06(m,4H,CH2 and CH),4.21-4.28(m,2H,CH2),4.49-4.53(m,1H,CH),4.62 and 4.61(d,J＝8.0 Hz,1H,CH),4.83-4.87(m,2H,CH),5.05(t,J＝10.0 Hz,1H,CH),5.25 and 5.26(t,J＝9.0 Hz,1H,CH),5.34-5.42(m,2H,CH)；13C NMR(125 MHz,CDCl3),δ(ppm)13.8,20.24,20.26,20.33,20.34,20.48,20.50,20.57,22.4,25.59,25.62,29.01,29.02,29.04,29.11,29.14,29.21,29.23,29.31,29.32,29.33,30.1,30.4,31.6,60.8,61.2,61.7,62.33,62.39,67.7,68.2,69.0,69.7,71.2,71.6,71.9,72.3,72.4,72.7,75.0,95.2,99.6,100.1,169.1,169.26,169.33,169.6,169.9,170.07,170.15,170.17；HRMS calcd for C40H63N3O18[M+Na]+:896.3999；found:896.3987.
Ac16Mazide1H NMR(500MHz,CDCl3),δ(ppm)0.88(t,J＝7.0Hz,3H,CH3),1.26-1.53(m,26H,CH2),2.00-2.14(s,21H,CH3),3.37-3.62(m,2H,CH2 and CH),3.72-3.74(m,1H,CH),3.85-4.06(m,4H,CH2 and CH),4.23-4.28(m,2H,CH2),4.50-4.52(m,1H,CH),4.63(d,J＝7.5Hz,1H,CH),4.82-4.86(m,2H,CH),5.05(t,J＝10.0Hz,1H,CH),5.26and 5.27(t,J＝9.0Hz,1H,CH),5.33-5.42(m,2H,CH)；13C NMR(125MHz,CDCl3),δ(ppm)13.6,20.03,20.11,20.26,20.27,20.4,22.2,25.42,25.44,28.84,28.87,28.95,28.96,29.04,29.05,29.12,29.9,30.7,31.4,60.6,61.1,61.5,62.23,62.28,67.6,68.0,68.8,69.6,71.0,71.48,71.51,71.7,72.3,72.4,72.5,74.8,95.1,99.4,99.9,168.8,168.99,169.06,169.3,169.7,169.81,169.87,169.93；HRMS calcd for C42H67N3O18[M+Na]+:924.4312；found:924.4308.
1mmol去垢剂全乙酰化前体溶于10mL甲醇中，加入50μL 30％甲醇钠的甲醇溶液，室温搅拌1小时。反应结束后加入阳离子交换树脂(安伯莱特IR120,氢型)调节溶液近中性，过滤除去树脂，浓缩得到粗产品。粗产品用柱层析(200-300目硅胶，葡萄糖苷的洗脱剂为二氯甲烷：甲醇＝10:1，麦芽糖苷的洗脱剂为二氯甲烷：甲醇＝5:1)分离得到纯净的小分子去垢剂。将纯化的小分子去垢剂溶于超纯水，冻干得到粉末状的去垢剂产品。部分化合物表征数据如下：
4Gazide
1H NMR(500MHz,CD3OD),δ(ppm)0.91(t,J＝6.5Hz,3H,CH3),1.29-1.58(m,2H,CH2),3.18-3.38(m,4H,CH2 and CH),3.55-3.69(m,3H,CH2 and CH),3.86-3.96(m,1H,CH),4.28-4.31(m,1H,CH)；13C NMR(125MHz,CD3OD),δ(ppm)14.3,31.8,32.7,62.68,62.71,63.1,63.6,71.47,71.51,72.9,73.4,75.0,77.88,77.91,77.96,104.2,104.7；HRMS calcdfor C10H19N3O6[M+Na]+:300.1166；found:300.1167.
6Gazide
1H NMR(500MHz,CD3OD),δ(ppm)0.93(t,J＝7.0Hz,3H,CH3),1.28-1.60(m,6H,CH2),3.19-3.38(m,4H,CH2 and CH),3.55-3.69(m,3H,CH2 and CH),3.86-3.96(m,1H,CH),4.29-4.32(m,1H,CH)；13C NMR(125MHz,CD3OD),δ(ppm)14.3,23.5,29.2,31.6,62.66,62.67,63.1,63.5,71.44,71.49,72.9,73.3,75.0,77.85,77.88,77.93,104.1,104.7；HRMScalcd for C12H23N3O6[M+Na]+:328.1479；found:328.1487.
8Gazide
1H NMR(500 MHz,CD3OD),δ(ppm)0.89(t,J＝7.0 Hz,3H,CH3),1.30-1.58(m,10H,CH2),3.17-3.36(m,4H,CH2 and CH),3.53-3.67(m,3H,CH2 and CH),3.84-3.94(m,1H,CH),4.27-4.30(m,1H,CH)；13C NMR(125 MHz,CD3OD),δ(ppm)14.4,23.6,27.0,30.1,31.9,32.8,62.68,62.71,63.1,63.6,71.47,71.52,72.9,73.4,75.0,77.89,77.92,77.96,104.2,104.7；HRMS calcd for C14H27N3O6[M+Na]+:356.1792；found:356.1793.
10Gazide
1H NMR(500 MHz,CD3OD),δ(ppm)0.91(t,J＝7.0 Hz,3H,CH3),1.30-1.60(m,14H,CH2),3.20-3.40(m,4H,CH2 and CH),3.56-3.70(m,3H,CH2 and CH),3.87-3.97(m,1H,CH),4.30-4.33(m,1H,CH)；13C NMR(125 MHz,CD3OD),δ(ppm)14.5,23.7,27.0,30.3,30.45,30.47,30.54,31.87,31.88,62.65,62.68,63.1,63.6,71.42,71.46,72.9,73.3,74.9,77.83,77.86,77.91,104.1,104.6；HRMS calcd for C16H31N3O6[M+Na]+:384.2105；found:384.2105.
12Gazide
1H NMR(500 MHz,CD3OD),δ(ppm)0.89(t,J＝7.0 Hz,3H,CH3),1.29-1.57(m,18H,CH2),3.16-3.34(m,4H,CH2 and CH),3.53-3.67(m,3H,CH2 and CH),3.85-3.95(m,1H,CH),4.27-4.29(m,1H,CH)；13C NMR(125 MHz,CD3OD),δ(ppm)14.4,23.7,27.1,30.3,30.46,30.48,31.92,31.93,32.94,62.73,62.76,63.1,63.6,71.54,71.58,72.9,73.4,75.0,77.96,77.99,78.04,104.2,104.8；HRMS calcd for C18H35N3O6[M+Na]+:412.2418；found:412.2418.
6Mazide
1H NMR(500 MHz,CD3OD),δ(ppm)0.89(t,J＝7.0 Hz,3H,CH3),1.28-1.59(m,6H,CH2),3.24-3.27(m,2H,CH2),3.36-3.39(m,1H,CH),3.42-3.45(m,1H,CH),3.50-3.69(m,7H,CH2 andCH),3.77-3.84(m,2H,CH),3.87-3.94(m,2H,CH),4.31 and 4.32(d,J＝8.0 Hz,1H,CH),5.15(d,J＝4.0 Hz,1H,CH)；13C NMR(125 MHz,CD3OD),δ(ppm)14.4,23.7,27.0,30.3,30.4,31.9,32.9,62.11,62.14,62.6,63.1,63.6,71.4,73.0,73.4,74.0,74.6,74.7,75.0,76.58,76.61,77.72,77.76,81.13,81.15,102.8,104.1,104.6；HRMS calcd forC18H33N3O11[M+Na]+:490.2007；found:490.2010.
8Mazide
1H NMR(500 MHz,CD3OD),δ(ppm)0.90(t,J＝7.0 Hz,3H,CH3),1.31-1.60(m,10H,CH2),3.24-3.28(m,2H,CH2),3.37-3.40(m,1H,CH),3.43-3.46(m,1H,CH),3.51-3.70(m,7H,CH2 andCH),3.78-3.84(m,2H,CH),3.88-3.95(m,2H,CH),4.32 and 4.33(d,J＝7.5 Hz,1H,CH),5.16(d,J＝3.5 Hz,1H,CH)；13C NMR(125 MHz,CD3OD),δ(ppm)14.4,23.6,27.0,30.1,31.9,32.8,62.12,62.14,62.6,63.1,63.5,71.4,73.0,73.4,74.0,74.6,74.7,75.0,76.56,76.59,77.70,77.74,81.10,81.11,102.8,104.1,104.6；HRMS calcd forC20H37N3O11[M+Na]+:518.2320；found:518.2322.
12Mazide
1H NMR(500MHz,CD3OD),δ(ppm)0.92(t,J＝7.0Hz,3H,CH3),1.28-1.59(m,18H,CH2),3.26-3.31(m,2H,CH2),3.39-3.42(m,1H,CH),3.45-3.48(m,1H,CH),3.53-3.72(m,7H,CH2 and CH),3.81-3.87(m,2H,CH),3.91-3.98(m,2H,CH),4.34and 4.35(d,J＝8.0Hz,1H,CH),5.19(d,J＝4.0Hz,1H,CH)；13C NMR(125MHz,CD3OD),δ(ppm)14.4,23.7,27.0,30.4,30.48,30.49,30.61,30.67,30.70,31.9,33.0,62.19,62.21,62.7,63.2,63.6,71.5,73.0,73.4,74.1,74.7,74.8,75.0,76.66,76.68,77.78,77.81,81.21,81.23,102.9,104.2,104.7；HRMS calcd for C24H45N3O11[M+Na]+:574.2946；found:574.2948.
14Mazide
1H NMR(500MHz,CD3OD),δ(ppm)0.88(t,J＝7.0Hz,3H,CH3),1.27-1.59(m,22H,CH2),3.22-3.26(m,2H,CH2),3.35-3.38(m,1H,CH),3.41-3.44(m,1H,CH),3.49-3.68(m,7H,CH2 and CH),3.76-3.83(m,2H,CH),3.86-3.93(m,2H,CH),4.30and 4.31(d,J＝7.5Hz,1H,CH),5.14(d,J＝4.0Hz,1H,CH)；13C NMR(125MHz,CD3OD),δ(ppm)14.5,23.7,27.1,30.47,30.49,30.50,30.62,30.68,30.75,30.78,31.9,33.1,62.14,62.17,62.7,63.1,63.6,71.4,73.0,73.4,74.1,74.6,74.7,75.0,76.62,76.64,77.75,77.79,81.18,81.20,102.9,104.2,104.7；HRMS calcd for C26H49N3O11[M+Na]+:602.3259；found:602.3259.
16Mazide
1H NMR(500MHz,CD3OD),δ(ppm)0.88(t,J＝7.0Hz,3H,CH3),1.27-1.59(m,26H,CH2),3.23-3.27(m,2H,CH2),3.36-3.39(m,1H,CH),3.42-3.45(m,1H,CH),3.50-3.69(m,7H,CH2 and CH),3.77-3.83(m,2H,CH),3.87-3.94(m,2H,CH),4.30and 4.32(d,J＝8.0Hz,1H,CH),5.15(d,J＝4.0Hz,1H,CH)；13C NMR(125MHz,CD3OD),δ(ppm)14.5,23.7,27.0,30.46,30.48,30.49,30.62,30.67,30.74,31.9,33.0,62.12,62.15,62.7,63.1,63.6,71.4,73.0,73.4,74.1,74.6,74.7,75.0,76.60,76.63,77.74,77.77,81.16,81.18,102.8,104.2,104.6；HRMS calcd for C28H53N3O11[M+Na]+:630.3572；found:630.3570.
3、类型3的小分子去垢剂，其特征为两个直链烷基的1位及2位由一个1,2,3-三唑相连，其通式如下：
Figure BDA0002569419740000261
通过Click反应合成类型3小分子去垢剂，其合成通式如下：
Figure BDA0002569419740000262
该类型小分子去垢剂的合成路线完全相同，下面仅举部分例子阐述合成路线。该类型小分子去垢剂及其全乙酰化的合成前体命名如下：
小分子去垢剂命名由“类型1小分子去垢剂名称”-“yne”+“类型2小分子去垢剂名称”-“azide”组成。
小分子去垢剂的全乙酰化前体命名由“Ac”+“小分子去垢剂名称”组成。
例如，下列两个小分子去垢剂及其全乙酰化前体的名称如下：
Figure BDA0002569419740000271
将类型1和类型2的全乙酰化前体各0.5mmol溶于5mL甲醇和5mL二氯甲烷的混合溶剂中，加入1M硫酸铜水溶液1mL及1M抗坏血酸钠水溶液1mL，室温搅拌1小时。反应结束后加入10mL饱和氯化钠溶液，用二氯甲烷萃取三次，有机相用饱和食盐水洗涤，然后用无水硫酸钠干燥，过滤除去硫酸钠，浓缩得到粗产品。粗产品浓缩、柱层析(200-300目硅胶，洗脱剂为石油醚：乙酸乙酯＝3:1至1:1不等)分离纯化得到相应的类型3去垢剂的全乙酰化前体。部分中间体表征数据如下：
Ac4G4G
1H NMR(800MHz,CDCl3),δ(ppm)0.87(t,J＝7.2Hz,6H,CH3),1.06-1.15(m,1H,CH2),1.22-1.43(m,1H,CH2),1.80-1.92(m,4H,CH2),1.94-2.11(s,24H,CH3),3.58-3.82(m,2H,CH2and CH),3.86-4.29(m,6H,CH2 and CH),4.44-4.55(m,1H,CH),4.58-4.68(m,1H,CH),4.73-5.24(m,8H,CH),7.48,7.52,7.59and 7.62(s,1H,CH)；13C NMR(200MHz,CDCl3),δ(ppm)13.57,13.58,13.60,13.75,13.77,20.26,20.30,20.32,20.35,20.36,20.37,20.39,20.42,20.46,20.47,20.50,20.53,22.00,22.01,22.03,24.7,24.83,24.90,24.93,24.97,25.01,25.08,28.48,28.50,28.63,28.84,28.98,29.00,29.07,29.19,29.23,29.31,29.34,29.44,29.45,31.38,31.41,31.46,31.58,34.6,34.8,34.9,35.3,60.65,60.70,61.05,61.29,61.43,61.47,61.52,61.74,67.90,67.91,67.94,67.98,67.99,68.07,68.16,68.20,69.52,69.65,70.51,70.54,70.65,70.68,70.72,70.74,70.99,71.06,71.16,71.20,71.27,71.29,71.32,71.52,71.64,72.02,72.12,72.16,72.50,72.63,72.66,72.70,72.79,76.22,76.31,76.41,76.52,97.70,97.73,99.6,99.8,100.32,100.40,100.42,100.60,120.3,120.7,121.5,122.2,147.6,148.1,148.3,148.8,168.87,168.97,168.98,169.00,169.03,169.13,169.17,169.19,169.21,169.23,169.54,169.79,169.80,169.81,169.83,169.92,169.93,170.00,170.28,170.30,170.33,170.34,170.45,170.46；HRMS calcd for C38H55N3O20[M+Na]+:896.3271；found:896.3270.
Ac6G6G
1H NMR(800 MHz,CDCl3),δ(ppm)0.87(t,J＝7.2 Hz,6H,CH3),1.06-1.14(m,1H,CH2),1.22-1.39(m,9H,CH2),1.82-1.91(m,4H,CH2),1.94-2.11(s,24H,CH3),3.56-3.80(m,2H,CH2and CH),3.85-4.28(m,6H,CH2 and CH),4.42-4.52(m,1H,CH),4.58-4.63(m,1H,CH),4.73-5.23(m,8H,CH),7.45,7.49 and 7.59(s,1H,CH)；13C NMR(200 MHz,CDCl3),δ(ppm)13.95,13.96,13.98,13.99,20.44,20.45,20.47,20.48,20.51,20.54,20.56,20.57,20.60,20.64,20.66,20.68,20.71,22.48,22.49,22.53,25.0,25.1,25.2,25.42,25.46,25.49,25.56,25.64,28.89,28.93,28.96,29.02,29.07,29.08,29.14,29.16,29.18,29.29,29.36,29.38,29.41,29.44,29.45,29.48,29.55,29.62,31.3,31.4,31.61,31.63,31.73,31.74,34.8,35.05,35.11,35.5,61.58,61.61,61.68,61.9,68.06,68.09,68.13,68.23,68.32,68.36,69.77,69.86,70.62,70.67,70.76,70.80,70.87,70.97,71.17,71.21,71.32,71.33,71.46,71.49,71.7,71.8,72.18,72.29,72.31,72.80,72.84,72.87,97.87,97.92,99.8,100.0,100.4,100.58,100.60,100.8,120.3,121.6,122.4,168.98,169.09,169.10,169.12,169.14,169.15,169.25,169.29,169.31,169.34,169.6,169.94,169.96,169.97,169.99,170.07,170.09,170.16,170.42,170.47,170.49,170.58,170.59；HRMS calcd for C42H63N3O20[M+Na]+:952.3897；found:952.3899.
Ac6G10G
1H NMR(500 MHz,CDCl3),δ(ppm)0.86(t,J＝7.0 Hz,6H,CH3),1.07-1.14(m,1H,CH2),1.23-1.40(m,17H,CH2),1.78-1.91(m,3H,CH2),1.95-2.11(s,24H,CH3),3.55-3.82(m,2H,CH2and CH),3.87-4.06(m,2H,CH2 and CH),4.10-4.32(m,4H,CH2),4.43-4.54(m,1H,CH),4.58-4.63(m,1H,CH),4.72-5.24(m,8H,CH),7.45,7.49,7.56 and 7.59(s,1H,CH)；13C NMR(125 MHz,CDCl3),δ(ppm)13.77,13.84,13.97,20.32,20.35,20.42,20.45,20.48,20.52,20.59,20.79,22.27,22.32,22.36,24.5,24.6,24.8,25.40,25.47,25.54,28.79,28.82,28.86,28.90,29.03,29.07,31.08,31.18,31.21,31.25,31.31,31.34,31.5,34.7,34.9,35.0,35.4,60.1,60.5,60.6,61.9,68.00,68.04,68.08,68.17,68.27,68.31,69.63,69.72,70.58,70.62,70.73,70.75,70.80,71.16,71.25,71.39,71.62,71.76,72.1,72.21,72.24,72.72,72.76,97.80,97.86,99.7,99.9,100.5,100.7,168.86,168.95,168.97,169.00,169.12,169.17,169.20,169.5,169.79,169.81,169.83,169.91,170.00,170.26,170.31,170.44,170.8；HRMS calcd for C46H71N3O20[M+Na]+:1008.4523；found:1008.4520.
Ac8G8G
1H NMR(800 MHz,CD3OD),δ(ppm)0.89(t,J＝7.2 Hz,6H,CH3),0.97-1.08(m,1H,CH2),1.20-1.40(m,17H,CH2),1.83-1.93(m,4H,CH2),1.94-2.09(s,24H,CH3),3.56-3.82(m,2H,CH2and CH),3.86-4.28(m,6H,CH2 and CH),4.42-4.53(m,1H,CH),4.58-4.64(m,1H,CH),4.76-5.24(m,8H,CH),7.50,7.55 and 7.61(s,1H,CH)；13C NMR(200 MHz,CD3OD),δ(ppm)13.86,20.37,20.40,20.41,20.47,20.50,20.53,20.58,20.61,20.64,22.37,22.38,24.8,25.0,25.1,25.44,25.46,25.54,25.59,28.63,28.78,28.82,28.86,31.24,31.28,31.30,31.37,31.47,31.51,31.54,31.58,34.7,35.0,35.2,61.56,61.59,61.65,61.9,68.05,68.08,68.12,68.22,68.31,68.36,69.68,69.78,70.62,70.66,70.70,70.76,70.79,70.87,71.21,71.30,71.44,71.51,71.67,71.8,72.16,72.27,72.29,72.77,72.81,72.84,97.84,97.89,99.8,100.0,100.5,100.7,120.7,122.0,149.1,149.7,168.91,168.99,169.02,169.05,169.07,169.17,169.21,169.22,169.26,169.6,169.84,169.87,169.89,170.0,170.1,170.32,170.37,170.48,170.50；HRMS calcd for C46H71N3O20[M+Na]+:1008.4523；found:1008.4526.
Ac10G6G
1H NMR(800 MHz,CDCl3),δ(ppm)0.87(t,J＝7.2 Hz,6H,CH3),1.04-1.11(m,1H,CH2),1.25-1.45(m,17H,CH2),1.76-1.91(m,4H,CH2),1.94-2.11(s,24H,CH3),3.59-3.82(m,2H,CH2and CH),3.87-4.29(m,6H,CH2 and CH),4.43-4.52(m,1H,CH),4.56-4.62(m,1H,CH),4.77-5.23(m,8H,CH),7.48,7.52 and 7.54(s,1H,CH)；13C NMR(200 MHz,CDCl3),δ(ppm)13.66,13.68,13.70,13.99,14.00,20.46,20.48,20.49,20.50,20.51,20.52,20.55,20.56,20.58,20.60,20.62,20.64,20.69,20.71,20.72,21.99,22.01,22.34,22.58,22.55,22.56,25.0,25.1,25.3,27.61,27.66,27.69,27.76,29.12,29.19,29.21,29.32,29.43,29.44,29.47,29.48,29.51,29.57,30.07,30.08,31.01,31.10,31.11,31.12,31.15,31.33,31.39,31.76,31.77,34.5,34.9,61.65,61.67,61.72,61.99,62.02,62.04,68.14,68.17,68.20,68.22,68.29,68.39,68.44,69.81,70.70,70.74,70.83,70.84,70.87,71.29,71.38,71.39,71.50,71.77,71.78,71.90,71.91,72.25,72.35,72.37,72.87,72.88,72.93,97.90,97.96,99.8,100.1,100.57,100.60,100.73,100.78,120.5,149.4,169.09,169.12,169.14,169.17,169.18,169.26,169.30,169.32,169.33,169.34,169.36,169.6,169.95,169.98,169.99,170.10,170.16,170.44,170.48,170.59,170.61；HRMS calcd for C46H71N3O20[M+Na]+:1008.4523；found:1008.4522.
Ac10G10G
1H NMR(800 MHz,CDCl3),δ(ppm)0.87(t,J＝7.2 Hz,6H,CH3),1.04-1.15(m,1H,CH2),1.25-1.43(m,25H,CH2),1.77-1.92(m,4H,CH2),1.94-2.10(s,24H,CH3),3.55-3.82(m,2H,CH2and CH),3.85-4.28(m,6H,CH2 and CH),4.42-4.53(m,1H,CH),4.58-4.63(m,1H,CH),4.72-5.24(m,8H,CH),7.45,7.48,7.55 and 7.58(s,1H,CH)；13C NMR(200 MHz,CDCl3),δ(ppm)13.79,13.80,13.87,13.88,20.39,20.43,20.48,20.51,20.54,20.58,20.60,20.62,20.65,22.29,22.39,24.82,24.96,25.10,25.35,25.38,25.45,25.53,28.48,28.50,28.52,28.55,28.63,28.77,28.88,29.12,31.25,31.29,31.31,31.4,31.51,31.54,31.59,34.7,35.0,35.1,35.5,60.7,61.1,61.4,61.57,61.60,61.66,61.9,68.06,68.10,68.14,68.23,68.32,68.37,69.74,69.82,70.47,70.63,70.67,70.78,70.80,70.85,70.90,71.11,71.17,71.22,71.31,71.36,71.45,71.48,71.7,71.8,72.2,72.28,72.30,72.72,72.78,72.82,72.84,73.0,97.86,97.90,99.8,100.0,100.4,100.5,100.7,120.3,121.4,122.4,148.0,148.6,168.9,169.01,169.04,169.07,169.18,169.22,169.24,169.27,169.6,169.86,169.88,169.90,170.00,170.08,170.34,170.39,170.49,170.51；HRMS calcd for C50H79N3O20[M+Na]+:1064.5149；found:1064.5150.
Ac12G12G
1H NMR(500 MHz,CDCl3),δ(ppm)0.87(t,J＝7.0 Hz,6H,CH3),1.04-1.16(m,1H,CH2),1.22-1.46(m,33H,CH2),1.76-1.91(m,4H,CH2),1.94-2.10(s,24H,CH3),3.55-3.81(m,2H,CH2and CH),3.84-4.28(m,6H,CH2 and CH),4.42-4.53(m,1H,CH),4.58-4.64(m,1H,CH),4.71-5.24(m,8H,CH),7.44,7.48,7.55 and 7.58(s,1H,CH)；13C NMR(125 MHz,CDCl3),δ(ppm)13.89,13.91,20.37,20.41,20.46,20.49,20.52,20.56,20.58,20.60,20.64,22.42,22.45,24.9,25.0,25.2,25.40,25.43,25.50,25.58,28.84,28.87,28.90,28.95,29.00,29.01,29.08,29.12,29.22,29.29,29.31,29.36,29.45,29.47,29.50,31.25,31.39,31.55,31.57,31.65,31.66,34.8,35.03,35.09,35.47,60.6,60.7,61.0,61.3,61.55,61.59,61.64,61.9,68.05,68.08,68.13,68.22,68.31,68.36,69.76,69.84,70.60,70.66,70.76,70.79,70.84,70.93,71.13,71.20,71.31,71.41,71.45,71.67,71.80,72.16,72.29,72.76,72.81,72.83,73.0,97.86,97.90,99.8,100.0,100.4,100.5,100.7,120.3,120.6,121.4,122.2,147.8,148.2,148.3,148.8,168.89,168.98,169.00,169.01,169.04,169.15,169.19,169.21,169.24,169.6,169.83,169.85,169.87,169.96,169.98,170.05,170.30,170.36,170.45,170.46,170.49；HRMS calcd for C54H87N3O20[M+Na]+:1120.5775；found:1120.5776.
Ac6G8M
1H NMR(500 MHz,CDCl3),δ(ppm)0.86(t,J＝7.0 Hz,6H,CH3),1.07-1.14(m,1H,CH2),1.23-1.44(m,13H,CH2),1.80-1.90(m,4H,CH2),1.92-2.16(s,33H,CH3),3.54-3.80(m,2H,CH2and CH),3.86-4.27(m,10H,CH2 and CH),4.44-4.62(m,3H,CH),4.73-4.90(m,3H,CH),4.96-5.27(m,5H,CH),5.32-5.40(m,2H,CH),7.43,7.45,7.53 and 7.56(s,1H,CH)；13C NMR(125 MHz,CDCl3),δ(ppm)13.82,13.86,14.04,20.36,20.41,20.43,20.51,20.59,20.62,20.66,20.68,20.87,22.28,22.31,22.33,22.38,22.42,24.5,24.6,24.8,25.36,25.38,25.47,25.54,25.58,28.52,28.54,28.57,31.1,31.30,31.31,31.33,31.35,31.40,31.49,60.2,61.3,61.56,61.60,61.9,62.30,62.37,62.49,63.1,67.84,67.85,68.06,68.17,68.35,68.38,69.11,69.14,69.81,69.85,69.89,69.93,70.99,71.06,71.23,71.34,71.43,71.52,71.64,72.10,72.12,72.3,72.45,72.47,72.50,72.79,72.83,72.85,74.68,74.76,74.80,74.82,95.38,95.44,95.51,95.58,97.96,98.02,98.7,99.4,99.6,100.17,100.23,100.36,100.48,100.53,169.01,169.09,169.22,169.24,169.26,169.28,169.35,169.37,169.76,169.83,169.85,169.88,170.01,170.08,170.14,170.18,170.24,170.33,170.36,170.52,170.9；HRMS calcd for C56H83N3O28[M+Na]+:1268.5055；found:1268.5050.
Ac8G12M
1H NMR(800 MHz,CDCl3),δ(ppm)0.87(t,J＝7.2 Hz,6H,CH3),1.04-1.13(m,1H,CH2),1.18-1.42(m,25H,CH2),1.76-1.90(m,4H,CH2),1.91-2.15(s,33H,CH3),3.54-3.80(m,2H,CH2and CH),3.84-4.27(m,10H,CH2 and CH),4.46-4.62(m,3H,CH),4.69-4.87(m,3H,CH),4.93-5.26(m,5H,CH),5.34-5.41(m,2H,CH),7.41,7.43,7.52 and 7.53(s,1H,CH)；13C NMR(200 MHz,CDCl3),δ(ppm)13.94,13.95,13.97,20.38,20.43,20.44,20.46,20.48,20.50,20.54,20.62,20.64,20.65,20.68,20.69,20.70,20.72,20.73,22.48,22.50,22.52,24.9,25.1,25.2,25.46,25.49,25.58,25.64,28.94,28.96,28.98,28.99,29.00,29.04,29.07,29.11,29.12,29.14,29.16,29.20,29.23,29.24,29.37,29.39,29.40,31.34,31.37,31.40,31.45,31.64,31.66,31.68,31.73,31.74,34.86,35.04,35.21,35.55,60.6,60.7,61.1,61.32,61.35,61.38,61.41,61.58,61.59,61.62,61.92,61.93,62.32,62.39,62.41,62.52,67.87,67.89,68.09,68.20,68.38,68.41,69.14,69.18,69.84,69.88,70.00,71.04,71.09,71.23,71.26,71.37,71.38,71.40,71.46,71.53,71.55,71.66,71.67,72.13,72.15,72.30,72.47,72.51,72.53,72.82,72.83,72.86,72.88,72.95,73.17,74.72,74.81,74.84,74.86,95.41,95.43,95.48,98.00,98.06,99.4,99.77,100.2,100.4,100.53,100.60,120.2,120.6,121.3,122.0,147.9,148.3,148.5,148.9,169.03,169.04,169.10,169.23,169.24,169.26,169.28,169.30,169.31,169.36,169.40,169.78,169.79,169.85,169.88,169.90,170.03,170.05,170.12,170.16,170.19,170.20,170.26,170.34,170.36,170.38,170.40,170.52,170.54；HRMScalcd for C62H95N3O28[M+Na]+:1352.5994；found:1352.5999.
Ac10G14M
1H NMR(500 MHz,CDCl3),δ(ppm)0.88(t,J＝7.0 Hz,6H,CH3),1.04-1.13(m,1H,CH2),1.21-1.42(m,33H,CH2),1.75-1.90(m,4H,CH2),1.92-2.15(s,33H,CH3),3.54-3.80(m,2H,CH2and CH),3.83-4.27(m,10H,CH2 and CH),4.46-4.63(m,3H,CH),4.70-4.86(m,3H,CH),4.93-5.27(m,5H,CH),5.33-5.41(m,2H,CH),7.42,7.44,7.52 and 7.54(s,1H,CH)；13C NMR(125 MHz,CDCl3),δ(ppm)13.91,20.31,20.36,20.38,20.43,20.46,20.54,20.57,20.61,20.63,22.46,24.8,25.0,25.1,25.38,25.42,25.51,25.57,28.86,28.89,28.91,28.99,29.00,29.11,29.13,29.18,29.21,29.32,29.35,29.37,29.41,29.43,31.23,31.26,31.30,31.32,31.37,31.66,31.67,31.69,34.8,35.0,35.15,35.5,60.5,60.7,61.06,61.26,61.28,61.32,61.51,61.57,61.8,62.26,62.34,62.46,67.80,67.82,68.01,68.13,68.30,68.34,69.07,69.10,69.78,69.81,69.93,70.98,71.03,71.15,71.18,71.31,71.39,71.46,71.48,71.60,72.06,72.07,72.23,72.40,72.47,72.75,72.79,72.81,72.88,73.10,73.13,74.64,74.72,74.77,74.79,95.34,95.36,95.41,97.91,97.97,99.3,99.6,100.1,100.34,100.45,100.53,120.2,120.5,121.2,122.0,147.8,148.2,148.4,148.8,168.93,168.95,169.01,169.15,169.17,169.22,169.28,169.31,169.68,169.77,169.79,169.82,169.94,169.95,170.02,170.06,170.09,170.11,170.17,170.25,170.26,170.29,170.31,170.40,170.43,170.45；HRMS calcd forC66H103N3O28[M+Na]+:1408.6620；found:1408.6617.
Ac8M6G
1H NMR(800 MHz,CDCl3),δ(ppm)0.87(t,J＝7.2 Hz,6H,CH3),1.05-1.13(m,1H,CH2),1.22-1.42(m,13H,CH2),1.76-2.16(m,37H,CH2 and CH3),3.54-3.88(m,2H,CH2 andCH),3.90-4.28(m,9H,CH2 and CH),4.43-4.64(m,3H,CH),4.71-5.09(m,7H,CH),5.14-5.42(m,4H,CH),7.44,7.46,7.55 and 7.60(s,1H,CH)；13C NMR(200 MHz,CDCl3),δ(ppm)13.69,13.71,13.96,13.98,20.44,20.47,20.48,20.49,20.54,20.56,20.58,20.62,20.63,20.64,20.71,20.74,20.81,20.82,20.83,22.02,22.05,22.08,22.51,22.53,25.0,25.19,25.21,25.25,27.61,27.62,27.70,27.77,29.05,29.06,29.09,29.10,29.14,29.17,29.28,29.54,29.58,30.04,30.09,31.01,31.03,31.10,31.21,31.33,31.40,31.66,31.68,31.70,34.72,34.76,34.85,35.09,35.20,35.61,60.6,60.8,61.1,61.3,61.41,61.43,61.64,61.68,61.75,62.26,62.34,62.8,67.87,67.90,67.94,68.14,68.21,68.22,68.23,68.26,68.32,68.34,69.23,69.24,69.26,69.28,69.87,69.92,69.93,69.99,70.73,70.82,70.88,70.89,70.99,71.75,71.76,71.82,71.88,71.95,72.08,72.17,72.20,72.27,72.31,72.37,72.40,72.43,72.79,72.83,72.91,73.00,73.02,75.32,75.38,75.40,75.48,95.34,95.38,95.42,95.43,97.44,97.52,99.8,100.1,100.2,100.57,100.65,100.78,121.6,123.4,149.4,169.02,169.06,169.16,169.27,169.31,169.34,169.44,169.48,169.49,169.51,169.57,169.76,169.79,170.00,170.01,170.08,170.09,170.17,170.23,170.34,170.35,170.36,170.40,170.41,170.44,170.46,170.49,170.50；HRMS calcd for C56H83N3O28[M+Na]+:1268.5055；found:1268.5052.
Ac12M8G
1H NMR(800 MHz,CDCl3),δ(ppm)0.88(t,J＝7.2 Hz,6H,CH3),1.04-1.14(m,1H,CH2),1.20-1.43(m,25H,CH2),1.76-2.16(m,37H,CH2 and CH3),3.53-3.87(m,2H,CH2 andCH),3.89-4.29(m,9H,CH2 and CH),4.42-4.65(m,3H,CH),4.71-5.10(m,7H,CH),5.13-5.44(m,4H,CH),7.42,7.46,7.55 and 7.60(s,1H,CH)；13C NMR(200 MHz,CDCl3),δ(ppm)13.88,13.89,13.91,14.30,20.45,20.47,20.48,20.49,20.50,20.52,20.55,20.57,20.58,20.59,20.60,20.63,20.65,20.66,20.74,20.75,20.76,20.82,20.83,20.84,22.37,22.38,22.39,22.57,22.58,25.01,25.22,25.25,25.29,25.43,25.44,25.53,25.60,28.56,28.58,28.59,28.63,29.14,29.16,29.20,29.21,29.23,29.24,29.25,29.26,29.35,29.36,29.48,29.50,29.52,29.53,29.56,29.57,29.58,31.31,31.34,31.38,31.39,31.48,31.79,31.80,31.82,34.8,35.1,35.2,35.6,60.6,60.7,61.0,61.2,61.36,61.38,61.40,61.60,61.66,61.71,61.74,62.18,62.30,62.7,67.80,67.84,67.87,67.88,68.09,68.15,68.17,68.20,68.22,68.28,68.31,69.19,69.21,69.23,69.26,69.81,69.88,69.90,69.96,70.67,70.77,70.84,70.88,71.04,71.70,71.72,71.76,71.85,71.89,72.03,72.16,72.17,72.19,72.23,72.25,72.26,72.29,72.36,72.37,72.40,72.73,72.79,72.83,73.03,75.30,75.36,75.38,75.47,95.30,95.34,95.40,95.42,97.41,97.51,99.8,100.07,100.17,100.58,100.66,100.77,120.3,120.8,121.5,122.8,147.8,148.1,148.3,148.7,169.02,169.05,169.19,169.27,169.31,169.32,169.35,169.44,169.48,169.51,169.52,169.61,169.77,169.80,169.99,170.01,170.02,170.09,170.10,170.19,170.21,170.34,170.37,170.41,170.43,170.44,170.45,170.47,170.50,170.52；HRMS calcd for C62H95N3O28[M+Na]+:1352.5994；found:1352.5999.
Ac14M10G
1H NMR(800 MHz,CDCl3),δ(ppm)0.88(t,J＝7.2 Hz,6H,CH3),1.05-1.14(m,1H,CH2),1.22-1.42(m,33H,CH2),1.78-2.16(m,37H,CH2 and CH3),3.55-3.87(m,2H,CH2 andCH),3.89-4.28(m,9H,CH2 and CH),4.43-4.65(m,3H,CH),4.72-5.09(m,7H,CH),5.14-5.43(m,4H,CH),7.43,7.46,7.56 and 7.61(s,1H,CH)；13C NMR(200 MHz,CDCl3),δ(ppm)14.00,14.03,14.12,20.47,20.49,20.50,20.54,20.56,20.58,20.59,20.61,20.64,20.66,20.67,20.75,20.77,20.83,20.85,20.87,22.54,22.55,22.60,25.06,25.26,25.28,25.33,25.53,25.55,25.63,25.71,28.95,29.96,28.99,29.02,29.07,29.08,29.17,29.19,29.20,29.21,29.27,29.28,29.39,29.52,29.56,29.57,29.59,29.60,29.62,29.63,29.64,30.09,30.11,31.36,31.39,31.42,31.51,31.66,31.68,31.69,31.83,34.89,35.22,60.3,60.6,60.8,61.27,61.42,61.44,61.66,61.71,61.77,61.79,62.23,62.34,62.8,67.88,67.91,67.96,68.16,68.22,68.24,68.27,68.36,69.28,69.30,69.33,69.94,69.96,70.02,70.74,70.84,70.90,70.97,71.79,71.82,71.83,71.84,71.92,72.08,72.10,72.22,72.25,72.29,72.33,72.35,72.42,72.44,72.46,72.58,72.60,72.79,72.82,72.84,72.92,72.96,75.33,75.38,75.41,75.50,95.36,95.40,95.45,95.47,97.48,97.58,99.8,100.12,100.29,100.66,100.68,100.80,120.8,121.4,150.0,169.05,169.08,169.21,169.29,169.33,169.35,169.37,169.46,169.50,169.52,169.54,169.63,169.78,169.80,169.82,170.01,170.02,170.03,170.09,170.11,170.12,170.18,170.19,170.23,170.29,170.33,170.36,170.39,170.43,170.44,170.47,170.49,170.51,170.52；HRMS calcd for C66H103N3O28[M+Na]+:1408.6620；found:1408.6617.
Ac6M6M
1H NMR(800 MHz,CDCl3),δ(ppm)0.87(t,J＝7.2 Hz,6H,CH3),1.06-1.14(m,1H,CH2),1.20-1.43(m,9H,CH2),1.77-2.16(m,46H,CH2 and CH3),3.54-3.86(m,2H,CH2 andCH),3.89-4.09(m,7H,CH2 and CH),4.12-4.28(m,5H,CH),4.43-4.63(m,4H,CH),4.69-4.96(m,6H,CH),5.03-5.09(m,2H,CH),5.17-5.28(m,2H,CH),5.32-5.42(m,4H,CH),7.43,7.53 and 7.57(s,1H,CH)；13C NMR(200 MHz,CDCl3),δ(ppm)13.93,13.95,13.98,20.40,20.43,20.44,20.46,20.47,20.49,20.53,20.54,20.57,20.66,20.71,20.72,20.73,20.75,20.80,20.82,20.86,22.42,22.44,22.45,22.50,22.52,25.0,25.17,25.19,25.24,25.50,25.60,25.66,28.84,28.87,28.88,28.92,28.94,29.04,29.05,29.08,29.09,29.13,29.17,29.24,29.28,29.57,31.38,31.39,31.48,31.56,31.57,31.66,31.68,31.70,34.8,35.2,60.3,60.5,61.22,61.24,61.26,61.33,61.35,61.40,61.42,61.7,62.16,62.22,62.34,62.42,62.45,62.58,62.73,62.76,67.89,67.91,67.93,68.21,68.24,68.33,68.38,68.40,68.43,69.17,69.19,69.21,69.23,69.25,69.81,69.86,69.88,69.91,69.96,69.99,71.05,71.54,71.60,71.63,71.69,72.15,72.20,72.26,72.30,72.43,72.52,72.58,72.80,72.87,72.91,74.77,74.87,74.94,75.31,75.36,75.38,75.46,95.29,95.34,95.42,95.46,97.51,97.63,99.4,99.5,99.7,100.21,100.25,100.40,100.48,120.3,147.9,169.29,169.30,169.33,169.34,169.42,169.44,169.45,169.46,169.48,169.50,169.51,169.74,169.75,169.76,169.81,169.83,169.87,169.91,169.94,170.06,170.07,170.15,170.17,170.20,170.24,170.25,170.28,170.31,170.32,170.34,170.40,170.41,170.42,170.45；HRMS calcd for C66H95N3O36[M+Na]+:1528.5587；found:1528.5590.
Ac8M8M
1H NMR(800 MHz,CDCl3),δ(ppm)0.87(t,J＝7.2 Hz,6H,CH3),1.07-1.12(m,1H,CH2),1.24-1.39(m,17H,CH2),1.78-2.17(m,46H,CH2 and CH3),3.54-3.87(m,2H,CH2 andCH),3.89-4.09(m,7H,CH2 and CH),4.13-4.27(m,5H,CH),4.43-4.65(m,4H,CH),4.71-4.94(m,6H,CH),5.03-5.09(m,2H,CH),5.18-5.29(m,2H,CH),5.31-5.44(m,4H,CH),7.42,7.43,7.53 and 7.58(s,1H,CH)；13C NMR(200 MHz,CDCl3),δ(ppm)13.96,20.35,20.42,20.43,20.49,20.52,20.62,20.69,20.76,22.51,24.9,25.16,25.21,25.39,25.43,25.55,25.62,27.02,28.88,28.92,28.95,29.07,29.15,29.18,29.20,29.28,29.36,29.41,29.43,29.48,29.58,31.31,31.34,31.42,31.71,31.73,34.74,35.09,35.15,35.54,60.54,60.66,61.01,61.15,61.26,61.29,61.37,62.04,62.14,62.24,62.35,62.49,62.65,67.78,67.82,68.12,68.14,68.25,68.30,68.34,69.08,69.12,69.16,69.72,69.78,69.83,69.89,69.91,70.99,71.05,71.44,71.51,71.54,71.60,71.64,71.68,71.84,71.96,72.05,72.10,72.20,72.29,72.31,72.38,72.45,72.64,72.74,72.78,72.97,74.67,74.78,74.86,75.22,75.26,75.30,75.38,95.19,95.25,95.32,95.37,97.40,97.52,99.2,99.6,100.14,100.18,100.34,100.45,120.2,120.7,121.4,122.6,147.8,148.1,148.2,148.7,169.24,169.27,169.29,169.38,169.41,169.70,169.77,169.82,169.86,169.89,170.01,170.03,170.13,170.14,170.20,170.26,170.29,170.36；HRMS calcd for C70H103N3O36[M+Na]+:1584.6213；found:1584.6210.
Ac8M14M
1H NMR(800 MHz,CDCl3),δ(ppm)0.87(t,J＝7.2 Hz,6H,CH3),1.04-1.14(m,1H,CH2),1.21-1.41(m,29H,CH2),1.75-2.16(m,46H,CH2 and CH3),3.52-3.86(m,2H,CH2 andCH),3.89-4.10(m,7H,CH2 and CH),4.12-4.28(m,5H,CH),4.43-4.64(m,4H,CH),4.69-4.93(m,6H,CH),5.03-5.08(m,2H,CH),5.18-5.28(m,2H,CH),5.32-5.42(m,4H,CH),7.40,7.42,7.52 and 7.56(s,1H,CH)；13C NMR(200 MHz,CDCl3),δ(ppm)13.99,14.01,14.03,20.44,20.48,20.49,20.50,20.51,20.52,20.56,20.58,20.61,20.70,20.75,20.78,20.79,20.83,20.85,22.54,22.56,22.60,25.0,25.20,25.23,25.27,25.54,25.66,25.73,29.00,29.03,29.04,29.06,29.08,29.09,29.12,29.14,29.17,29.21,29.24,29.29,29.32,29.46,29.47,29.48,29.50,29.52,29.53,31.43,31.45,31.54,31.70,31.72,31.74,31.81,34.8,35.1,35.3,35.6,60.6,60.75,60.84,61.09,61.27,61.29,61.38,61.41,61.42,61.45,61.47,62.19,62.26,62.27,62.30,62.37,62.46,62.48,62.52,62.61,62.77,62.79,67.92,67.93,67.96,68.25,68.27,68.37,68.41,68.44,68.46,69.21,69.23,69.25,69.27,69.29,69.89,69.91,69.94,71.00,71.03,71.08,71.11,71.64,71.67,71.72,71.77,71.81,71.95,71.97,72.10,72.19,72.20,72.24,72.26,72.29,72.33,72.46,72.48,72.55,72.60,72.74,72.81,72.88,72.96,73.14,74.80,74.91,74.98,75.35,75.40,75.42,75.49,95.32,95.38,95.44,95.49,95.51,97.59,97.70,99.4,99.8,100.23,100.29,100.44,100.50,120.2,120.8,121.4,122.5,147.9,148.2,148.3,148.7,169.33,169.35,169.38,169.46,169.48,169.50,169.54,169.79,169.80,169.82,169.87,169.92,169.95,169.96,169.98,170.10,170.12,170.30,170.32,170.36,170.38,170.44,170.46,170.47,170.50；HRMS calcd for C76H115N3O36[M+Na]+:1668.7152；found:1668.7150.
Ac12M12M
1H NMR(800 MHz,CDCl3),δ(ppm)0.88(t,J＝7.2 Hz,6H,CH3),1.06-1.14(m,1H,CH2),1.22-1.40(m,33H,CH2),1.75-2.16(m,46H,CH2 and CH3),3.51-3.86(m,2H,CH2 andCH),3.88-4.10(m,7H,CH2 and CH),4.12-4.28(m,5H,CH),4.42-4.64(m,4H,CH),4.68-4.94(m,6H,CH),5.03-5.10(m,2H,CH),5.17-5.27(m,2H,CH),5.30-5.43(m,4H,CH),7.39,7.41,7.51 and 7.55(s,1H,CH)；13C NMR(200 MHz,CDCl3),δ(ppm)14.04,14.05,20.49,20.52,20.62,20.77,20.80,20.85,22.59,22.61,25.54,25.66,25.73,29.04,29.06,29.19,29.20,29.22,29.24,29.27,29.29,29.41,29.44,29.47,29.52,29.55,29.58,29.62,29.63,31.46,31.81,31.83,31.84,35.7,61.09,61.23,61.28,61.41,61.50,61.63,62.65,62.77,67.92,67.93,67.96,68.37,68.46,69.21,69.26,69.27,69.30,69.89,69.94,70.03,71.29,71.40,71.51,72.09,72.18,72.26,72.34,74.82,74.92,74.99,75.28,75.41,75.44,75.51,95.11,95.33,95.44,95.46,95.50,97.53,97.69,99.4,99.8,100.09,100.24,100.29,100.45,100.53,100.68,120.9,147.9,169.33,169.35,169.38,169.45,169.48,169.50,169.53,169.79,169.86,169.95,170.10,170.20,170.23,170.29,170.32,170.35,170.37,170.45,170.47,170.50；HRMS calcd for C78H119N3O36[M+Na]+:1696.7465；found:1696.7466.
Ac14M8M
1H NMR(800 MHz,CDCl3 and CD3OD),δ(ppm)0.89(t,J＝7.2 Hz,6H,CH3),1.04-1.14(m,1H,CH2),1.22-1.42(m,29H,CH2),1.78-2.18(m,46H,CH2 and CH3),3.63-3.87(m,2H,CH2 and CH),3.90-4.11(m,7H,CH2 and CH),4.12-4.30(m,5H,CH),4.36-4.67(m,4H,CH),4.74-4.94(m,6H,CH),5.04-5.08(m,2H,CH),5.22-5.32(m,2H,CH),5.34-5.42(m,4H,CH),7.61,7.65,7.69 and7.74(s,1H,CH)；13C NMR(200 MHz,CDCl3 and CD3OD),δ(ppm)13.03,13.05,13.14,19.50,19.58,19.59,19.63,19.69,19.71,19.84,19.86,19.87,19.90,19.93,19.94,19.95,19.96,19.98,21.78,21.96,24.35,24.60,24.63,24.84,24.92,24.97,27.99,28.00,28.04,28.05,28.51,28.53,28.65,28.66,28.75,28.89,28.90,28.92,28.94,28.95,29.98,29.00,30.67,30.70,30.72,30.81,30.82,30.84,30.85,30.86,31.24,34.4,34.5,34.8,60.7,60.97,61.07,61.11,61.32,61.94,62.07,62.15,62.20,62.34,67.62,67.65,67.73,67.75,67.84,67.87,67.89,67.90,68.75,68.78,68.79,69.61,69.64,69.70,71.26,71.27,71.33,71.35,71.68,71.75,71.80,72.57,72.74,74.28,74.42,74.46,74.77,74.83,74.85,75.40,75.48,94.90,94.94,94.98,95.03,96.68,96.88,98.8,99.1,99.71,99.84,99.92,99.94,118.8,148.3,169.22,169.26,169.27,169.32,169.40,169.42,169.44,169.45,169.49,169.50,169.60,169.64,169.69,169.71,169.72,169.75,169.76,169.80,169.84,169.85,169.89,169.94,170.14,170.17,170.18,170.23,170.26,170.32,170.42,170.43,170.46,170.49；HRMS calcd forC76H115N3O36[M+Na]+:1668.7152；found:1668.7150.
Ac14M14M
1H NMR(800 MHz,CDCl3),δ(ppm)0.88(t,J＝7.2 Hz,6H,CH3),1.04-1.14(m,1H,CH2),1.22-1.39(m,41H,CH2),1.81-2.16(m,46H,CH2 and CH3),3.55-3.86(m,2H,CH2 andCH),3.90-4.07(m,7H,CH2 and CH),4.12-4.27(m,5H,CH),4.44-4.65(m,4H,CH),4.71-4.94(m,6H,CH),5.03-5.08(m,2H,CH),5.18-5.29(m,2H,CH),5.32-5.42(m,4H,CH),7.40,7.42,7.57 and7.61(s,1H,CH)；13C NMR(200 MHz,CDCl3),δ(ppm)14.06,20.47,20.50,20.53,20.54,20.59,20.60,20.63,20.68,20.70,20.74,20.77,20.79,20.81,20.84,20.86,20.90,22.62,22.63,25.26,25.30,25.56,25.58,25.68,25.75,29.02,29.07,29.09,29.21,29.26,29.28,29.30,29.31,29.32,29.34,29.39,29.49,29.51,29.54,29.59,29.61,29.64,29.65,29.66,31.85,31.87,34.8,35.0,61.0,61.23,61.28,61.38,61.44,61.46,61.62,62.11,62.21,62.46,62.78,67.94,67.96,67.98,68.25,68.27,68.36,68.39,68.45,68.48,68.52,68.59,68.63,68.89,69.08,69.23,69.30,69.32,69.91,69.93,69.95,69.97,69.99,70.03,70.05,70.41,70.58,71.07,71.58,71.74,72.26,72.29,72.35,72.37,72.48,72.90,74.83,74.93,75.09,75.29,75.35,75.44,75.52,95.39,95.46,95.47,95.53,97.60,97.69,98.8,99.5,99.8,100.14,100.20,100.30,100.42,120.3,148.5,169.14,169.26,169.34,169.35,169.38,169.43,169.50,169.57,169.63,169.73,169.78,169.80,169.85,169.87,169.89,170.09,170.21,170.30,170.36,170.39,170.43,170.45,170.47,170.50,170.51；HRMS calcd for C82H127N3O36[M+Na]+:1752.8091；found:1752.8089.
Ac16M16M
1H NMR(800 MHz,CDCl3),δ(ppm)0.88(t,J＝7.2 Hz,6H,CH3),1.04-1.14(m,1H,CH2),1.22-1.40(m,49H,CH2),1.76-2.16(m,46H,CH2 and CH3),3.52-3.86(m,2H,CH2 andCH),3.90-4.10(m,7H,CH2 and CH),4.12-4.28(m,5H,CH),4.43-4.64(m,4H,CH),4.69-4.93(m,6H,CH),5.03-5.08(m,2H,CH),5.18-5.28(m,2H,CH),5.32-5.43(m,4H,CH),7.40,7.43,7.52 and7.56(s,1H,CH)；13C NMR(200 MHz,CDCl3),δ(ppm)13.54,13.91,13.92,18.99,20.31,20.34,20.37,20.39,20.41,20.43,20.45,20.47,20.58,20.62,20.63,20.64,20.65,20.66,20.71,20.72,22.46,22.48,24.9,25.11,25.13,25.18,25.4,25.52,25.58,27.0,28.85,28.88,28.90,28.92,29.04,29.05,29.08,29.10,29.11,29.14,29.15,29.26,29.30,29.31,29.32,29.33,29.38,29.40,29.42,29.44,29.48,29.49,29.50,30.38,31.31,31.33,31.41,31.67,31.71,34.7,35.1,35.2,35.5,60.5,60.6,61.0,61.17,61.19,61.28,61.32,62.08,62.16,62.26,62.35,62.38,62.51,62.66,67.82,67.86,68.13,68.15,68.26,68.30,68.33,68.35,69.08,69.11,69.12,69.13,69.15,69.17,69.73,69.78,69.80,69.83,69.90,69.91,70.96,71.02,71.46,71.52,71.55,71.61,71.65,71.69,71.84,71.98,72.07,72.11,72.13,72.19,72.22,72.37,72.39,72.47,72.48,72.52,72.72,72.79,72.82,72.98,74.68,74.79,74.87,75.22,75.27,75.29,75.37,95.20,95.26,95.33,95.34,95.38,95.39,97.40,97.52,99.3,99.6,100.12,100.16,100.33,100.42,120.2,120.6,121.3,122.5,147.7,148.10,148.14,148.6,169.18,169.19,169.22,169.24,169.31,169.34,169.36,169.38,169.62,169.63,169.64,169.70,169.74,169.77,169.81,169.83,169.95,169.97,170.06,170.08,170.12,170.14,170.19,170.22,170.27,170.28,170.30,170.31,170.34；HRMS calcd for C86H135N3O36[M+Na]+:1808.8717；found:1808.8715.
0.3mmol去垢剂全乙酰化前体溶于5mL甲醇中，加入25μL 30％甲醇钠的甲醇溶液，室温搅拌1小时。反应结束后加入阳离子交换树脂(安伯莱特IR120,氢型)调节溶液近中性，过滤除去树脂，浓缩得到粗产品。粗产品用柱层析(200-300目硅胶，洗脱剂为二氯甲烷：甲醇＝5:1至1:1不等)分离得到纯净的小分子去垢剂。将纯化的小分子去垢剂溶于超纯水，冻干得到粉末状的去垢剂产品。部分化合物表征数据如下：
4G4G
1H NMR(500MHz,CD3OD),δ(ppm)0.86(t,J＝7.0Hz,6H,CH3),1.06-1.13(m,1H,CH2),1.24-1.40(m,1H,CH2),1.86-2.03(m,4H,CH2),3.11-3.16(m,1H,CH),3.19-3.39(m,8H,CH2and CH),3.58-3.78(m,2H,CH),3.84-3.89(m,2H,CH2),3.97-4.47(m,3H,CH),4.79-4.83(m,1H,CH),4.91-5.08(m,1H,CH),8.08,8.11and 8.13(s,1H,CH)；13C NMR(125MHz,CD3OD),δ(ppm)14.26,14.37,14.38,23.42,23.44,23.6,25.70,25.74,25.95,25.99,26.33,26.38,26.39,32.38,32.43,32.68,32.69,32.77,32.78,35.45,35.53,36.97,37.02,62.67,62.70,62.73,62.80,62.88,62.98,63.43,63.49,71.45,71.50,71.52,71.61,71.63,71.8,72.2,72.5,72.6,72.86,72.93,74.85,75.08,75.14,75.16,75.31,77.75,77.76,77.81,77.86,77.90,77.95,101.14,101.24,103.66,103.71,104.1,104.3,104.91,104.95,123.90,124.25,124.51,124.59,149.07,149.18,149.94,150.23；HRMScalcd for C22H39N3O12[M+Na]+:560.2426；found:560.2424.
6G6G
1H NMR(800MHz,CD3OD),δ(ppm)0.88(t,J＝7.2Hz,6H,CH3),1.03-1.11(m,1H,CH2),1.19-1.40(m,9H,CH2),1.85-2.03(m,4H,CH2),3.11-3.15(m,1H,CH),3.19-3.37(m,8H,CH2and CH),3.58-3.77(m,2H,CH),3.84-3.88(m,2H,CH2),3.97-4.46(m,3H,CH),4.80-4.83(m,1H,CH),4.91-5.07(m,1H,CH),8.07,8.10,8.12and 8.13(s,1H,CH)；13C NMR(200MHz,CD3OD),δ(ppm)14.20,14.22,14.24,14.35,14.36,14.38,23.18,23.20,23.60,23.61,25.72,25.76,25.98,26.02,28.94,28.95,28.96,28.99,32.07,32.16,32.18,32.23,32.70,32.71,32.79,32.80,35.49,35.57,36.98,37.03,62.71,62.74,62.77,62.82,62.83,62.92,63.00,63.45,63.51,71.49,71.55,71.57,71.65,71.67,71.8,72.2,72.5,72.6,72.9,73.0,74.89,74.90,75.12,75.18,75.21,75.4,77.80,77.81,77.85,77.86,77.87,77.92,77.96,78.00,78.01,78.04,101.20,101.29,103.73,103.78,104.1,104.3,104.95,104.99,124.30,124.50,124.57,124.66；HRMS calcd for C26H47N3O12[M+Na]+:616.3052；found:616.3050.
6G10G
1H NMR(500 MHz,CD3OD),δ(ppm)0.88(t,J＝7.0 Hz,6H,CH3),1.04-1.14(m,1H,CH2),1.24-1.40(m,17H,CH2),1.87-2.03(m,4H,CH2),3.11-3.17(m,1H,CH),3.20-3.39(m,8H,CH2and CH),3.59-3.78(m,2H,CH),3.84-3.90(m,2H,CH2),3.96-4.47(m,3H,CH),4.79-4.84(m,1H,CH),4.91-5.08(m,1H,CH),8.08,8.11 and 8.14(s,1H,CH)；13C NMR(125 MHz,CD3OD),δ(ppm)14.39,14.40,14.43,23.60,23.65,25.69,25.74,25.95,25.99,26.68,26.72,26.74,30.08,30.20,30.22,30.42,30.44,30.45,30.46,32.28,32.39,32.43,32.47,32.69,32.70,32.77,32.78,32.92,35.45,35.52,36.96,37.03,62.69,62.72,62.78,62.87,62.99,63.44,63.50,71.43,71.48,71.51,71.60,71.62,71.8,72.2,72.5,72.6,72.89,72.94,74.84,75.07,75.11,75.14,75.32,77.75,77.78,77.84,77.88,77.94,101.15,101.24,103.64,103.69,104.0,104.3,104.89,104.92,123.89,124.18,124.53,124.63；HRMS calcd for C30H55N3O12[M+Na]+:672.3678；found:672.3677.
8G8G
1H NMR(800 MHz,CD3OD),δ(ppm)0.87(t,J＝7.2 Hz,6H,CH3),1.04-1.12(m,1H,CH2),1.21-1.38(m,17H,CH2),1.85-2.03(m,4H,CH2),3.11-3.16(m,1H,CH),3.19-3.37(m,8H,CH2and CH),3.59-3.79(m,2H,CH),3.84-3.89(m,2H,CH2),3.97-4.46(m,3H,CH),4.79-4.83(m,1H,CH),4.91-5.07(m,1H,CH),8.07,8.10,8.12 and 8.13(s,1H,CH)；13C NMR(200MHz,CD3OD),δ(ppm)14.36,14.43,23.51,23.52,23.68,23.69,26.05,26.30,26.34,26.66,26.68,26.70,26.71,29.77,29.78,29.79,30.35,30.36,30.44,30.45,30.55,30.56,32.33,32.43,32.51,32.72,32.74,32.76,32.93,32.94,32.96,35.51,35.60,37.03,37.10,62.72,62.74,62.77,62.83,62.84,62.90,63.01,63.47,63.51,71.50,71.54,71.58,71.66,71.68,71.9,72.2,72.5,72.7,72.89,72.94,74.89,75.13,75.17,75.20,75.34,77.80,77.81,77.85,77.92,77.95,77.96,77.97,78.01,78.02,78.04,101.18,101.27,103.69,103.75,104.1,104.4,104.95,104.98,124.21,124.64,149.08,149.23；HRMS calcd for C30H55N3O12[M+Na]+:672.3678；found:672.3674.
10G6G
1H NMR(800 MHz,CD3OD),δ(ppm)0.89(t,J＝7.2 Hz,6H,CH3),1.03-1.10(m,1H,CH2),1.19-1.39(m,17H,CH2),1.85-2.02(m,4H,CH2),3.11-3.16(m,1H,CH),3.20-3.38(m,8H,CH2and CH),3.59-3.77(m,2H,CH),3.84-3.90(m,2H,CH2),3.97-4.47(m,3H,CH),4.79-4.83(m,1H,CH),4.91-5.07(m,1H,CH),8.08,8.11,8.13 and 8.14(s,1H,CH)；13C NMR(200MHz,CD3OD),δ(ppm)14.25,14.44,23.17,23.69,26.04,26.08,26.29,26.32,28.92,30.40,30.64,32.04,32.15,33.01,35.50,35.58,37.00,37.04,62.72,62.81,62.89,62.97,63.43,63.47,71.52,71.63,71.85,72.2,72.5,72.6,72.88,72.94,74.85,75.09,75.15,75.33,77.76,77.81,77.92,77.96,101.15,101.24,103.68,103.72,104.1,104.3,104.93,123.92,124.24,124.53,124.62,149.10,150.29；HRMS calcd for C30H55N3O12[M+Na]+:672.3678；found:672.3677.
10G10G
1H NMR(800 MHz,CD3OD),δ(ppm)0.89(t,J＝7.2 Hz,6H,CH3),1.04-1.11(m,1H,CH2),1.18-1.40(m,25H,CH2),1.85-2.03(m,4H,CH2),3.11-3.16(m,1H,CH),3.20-3.38(m,8H,CH2and CH),3.59-3.77(m,2H,CH),3.84-3.90(m,2H,CH2),3.96-4.47(m,3H,CH),4.79-4.83(m,1H,CH),4.91-5.07(m,1H,CH),8.07,8.11 and 8.13(s,1H,CH)；13C NMR(200 MHz,CD3OD),δ(ppm)14.44,14.45,23.68,23.71,26.04,26.09,26.28,26.33,26.70,26.73,26.74,26.76,30.10,30.11,30.12,30.24,30.26,30.43,30.44,30.46,30.48,30.49,30.50,30.58,30.60,30.64,30.66,30.68,30.69,30.70,32.30,32.42,32.46,32.51,32.95,32.96,33.04,35.50,35.58,37.02,37.10,62.69,62.72,62.73,62.75,62.81,62.83,62.89,62.99,63.00,63.46,63.49,71.46,71.51,71.52,71.53,71.64,71.65,71.9,72.2,72.5,72.6,72.91,72.94,74.84,74.86,74.87,75.11,75.14,75.17,75.18,75.32,77.76,77.70,77.78,77.80,77.82,77.89,77.91,77.92,77.94,77.97,77.98,77.99,78.00,101.17,101.26,103.65,103.71,104.1,104.3,104.92,104.95,123.82,124.15,124.58,124.71,149.03,149.25,149.93；HRMS calcd for C34H63N3O12[M+Na]+:728.4304；found:728.4302.
12G12G
1H NMR(800 MHz,CD3OD),δ(ppm)0.87(t,J＝7.2 Hz,6H,CH3),1.05-1.15(m,1H,CH2),1.23-1.37(m,33H,CH2),1.87-2.01(m,4H,CH2),3.11-3.17(m,1H,CH),3.20-3.38(m,8H,CH2and CH),3.59-3.77(m,2H,CH),3.84-3.89(m,2H,CH2),3.97-4.47(m,3H,CH),4.78-4.82(m,1H,CH),4.92-5.07(m,1H,CH),8.08,8.11 and 8.13(s,1H,CH)；13C NMR(200 MHz,CD3OD),δ(ppm)14.44,23.62,23.70,26.03,26.08,26.28,26.31,26.73,30.05,30.17,30.42,30.66,32.29,32.42,32.81,33.02,35.49,35.57,37.01,37.08,62.72,62.81,62.98,63.46,71.50,71.63,71.85,72.2,72.5,72.6,72.92,74.84,75.15,75.31,77.79,77.91,77.95,101.15,101.24,103.64,103.68,104.1,104.3,104.91,123.82,124.15,124.56,124.70,149.01,149.22,149.91,150.26；HRMS calcd for C38H71N3O12[M+Na]+:784.4930；found:784.4928.
6G8M
1H NMR(500 MHz,CD3OD),δ(ppm)0.87(t,J＝7.0 Hz,6H,CH3),1.04-1.11(m,1H,CH2),1.24-1.40(m,13H,CH2),1.86-2.03(m,4H,CH2),3.17-3.31(m,6H,CH2 and CH),3.35-3.38(m,1H,CH),3.43-3.53(m,2H,CH2 and CH),3.57-3.67(m,5H,CH),3.74-3.90(m,5H,CH2and CH),3.97-4.47(m,3H,CH),4.75-4.83(m,1H,CH),4.91-5.08(m,1H,CH),5.14-5.17(m,1H,CH),8.08,8.11 and 8.13(s,1H,CH)；13C NMR(125 MHz,CD3OD),δ(ppm)14.36,14.38,14.40,23.51,23.62,25.72,25.77,25.96,26.01,26.64,26.68,26.70,29.72,29.76,32.30,32.37,32.40,32.46,32.66,32.70,32.72,32.79,32.80,35.48,35.53,36.97,37.05,62.17,62.69,62.74,62.80,62.82,62.91,63.48,63.50,63.51,71.44,71.46,71.53,71.58,71.64,71.66,72.2,72.5,72.7,72.88,72.92,74.08,74.16,74.19,74.43,74.46,74.7,75.0,75.09,75.13,75.17,75.33,76.55,76.61,76.64,77.54,77.56,77.61,77.64,77.69,77.78,77.83,77.92,77.95,77.99,80.95,80.98,81.13,81.16,101.20,101.26,102.80,102.84,103.70,103.76,104.0,104.8,123.90,124.32,124.51,124.65；HRMS calcd for C34H61N3O17[M+Na]+:806.3893；found:806.3895.
8G12M
1H NMR(800 MHz,CD3OD),δ(ppm)0.89(t,J＝7.0 Hz,6H,CH3),1.04-1.14(m,1H,CH2),1.24-1.38(m,25H,CH2),1.87-2.03(m,4H,CH2),3.19-3.31(m,6H,CH2 and CH),3.35-3.37(m,1H,CH),3.43-3.54(m,2H,CH2 and CH),3.59-3.70(m,5H,CH),3.74-3.90(m,5H,CH2and CH),3.97-4.47(m,3H,CH),4.78-4.81(m,1H,CH),4.91-5.07(m,1H,CH),5.15-5.17(m,1H,CH),8.08,8.11 and 8.13(s,1H,CH)；13C NMR(200 MHz,CD3OD),δ(ppm)14.45,23.62,23.70,26.30,26.71,26.73,26.76,30.09,30.15,30.26,30.44,30.52,30.58,30.71,32.94,33.03,35.52,37.01,37.11,62.12,62.16,62.68,62.79,62.82,62.91,63.02,71.44,71.64,71.90,72.90,74.06,74.42,74.45,74.72,74.99,75.08,75.16,75.32,76.62,77.52,77.58,77.64,77.70,77.79,77.81,77.91,77.98,81.12,101.26,102.80,102.83,103.67,104.0,104.2,104.8,123.88,124.69,149.04,150.29；HRMS calcd forC40H73N3O17[M+Na]+:890.4832；found:890.4834.
10G14M
1H NMR(800 MHz,CD3OD),δ(ppm)0.89(t,J＝7.2 Hz,6H,CH3),1.03-1.11(m,1H,CH2),1.24-1.38(m,33H,CH2),1.86-2.03(m,4H,CH2),3.17-3.31(m,6H,CH2 and CH),3.35-3.39(m,1H,CH),3.43-3.53(m,2H,CH2 and CH),3.57-3.70(m,5H,CH),3.74-3.90(m,5H,CH2and CH),3.97-4.46(m,3H,CH),4.79-4.83(m,1H,CH),4.91-5.07(m,1H,CH),5.14-5.17(m,1H,CH),8.08,8.11,8.12 and 8.13(s,1H,CH)；13C NMR(200 MHz,CD3OD),δ(ppm)14.46,23.72,26.05,26.11,26.29,26.34,26.75,30.10,30.46,30.59,30.74,32.30,32.39,33.06,35.56,35.69,37.02,37.12,62.18,62.71,62.84,62.92,63.03,63.52,71.47,71.66,71.92,72.3,72.92,74.09,74.47,74.74,75.02,75.12,75.32,76.64,77.56,77.70,77.82,77.93,78.02,80.94,81.15,101.22,101.27,102.70,102.82,103.66,103.73,104.0,104.3,104.8,123.82,124.23,124.71,124.77,148.98；HRMS calcd for C37H67N3O17[M+Na]+:946.5458；found:946.5455.
8M6G
1H NMR(800 MHz,CD3OD),δ(ppm)0.88(t,J＝7.2 Hz,6H,CH3),1.03-1.10(m,1H,CH2),1.19-1.40(m,13H,CH2),1.86-2.03(m,4H,CH2),3.12-3.17(m,1H,CH),3.24-3.36(m,7H,CH2and CH),3.42-3.45(m,1H,CH),3.51-3.70(m,6H,CH),3.74-3.92(m,4H,CH2 andCH),3.98-4.48(m,3H,CH),4.79-4.83(m,1H,CH),4.90-5.06(m,1H,CH),5.15-5.17(m,1H,CH),8.08,8.11,8.12 and 8.14(s,1H,CH)；13C NMR(200 MHz,CD3OD),δ(ppm)14.24,14.42,23.17,23.65,26.04,26.09,26.29,26.35,28.94,30.31,30.40,30.51,32.07,32.15,32.21,32.90,35.61,35.65,36.88,36.96,62.21,62.70,62.88,62.97,63.44,63.49,64.25,71.49,71.80,72.2,72.6,72.94,74.08,74.69,74.85,74.93,74.99,75.58,75.62,76.40,76.53,76.55,77.73,77.81,77.94,80.93,81.00,81.08,101.04,101.11,102.55,102.74,103.71,104.1,104.3,104.91,105.02,123.88,124.38,124.53,124.61,148.99,149.95,150.28；HRMS calcd for C34H61N3O17[M+Na]+:806.3893；found:806.3894.
12M8G
1H NMR(800 MHz,CD3OD),δ(ppm)0.89(t,J＝7.2 Hz,6H,CH3),1.04-1.12(m,1H,CH2),1.19-1.40(m,25H,CH2),1.86-2.04(m,4H,CH2),3.12-3.16(m,1H,CH),3.24-3.36(m,7H,CH2and CH),3.42-3.44(m,1H,CH),3.50-3.70(m,6H,CH),3.72-3.92(m,4H,CH2 andCH),3.97-4.48(m,3H,CH),4.79-4.82(m,1H,CH),4.90-5.06(m,1H,CH),5.14-5.17(m,1H,CH),8.07,8.10,8.12 and 8.13(s,1H,CH)；13C NMR(200 MHz,CD3OD),δ(ppm)14.39,14.41,14.44,23.52,23.53,23.72,26.04,26.10,26.29,26.36,26.67,26.69,26.71,26.72,29.77,29.78,30.46,30.48,30.50,30.58,30.59,30.60,30.68,30.70,30.71,30.74,30.77,30.78,32.35,32.37,32.45,32.52,32.73,32.76,33.77,33.06,35.62,35.66,36.92,37.02,62.15,62.21,62.23,62.24,62.71,62.73,62.74,62.76,62.90,63.48,63.53,71.47,71.49,71.50,71.53,71.55,71.58,71.8,72.2,72.68,72.96,74.13,74.66,74.69,74.70,74.72,74.77,74.80,74.89,74.91,74.96,74.97,75.04,75.56,75.63,76.26,76.43,76.47,76.54,76.56,76.60,77.68,77.75,77.81,77.86,77.92,77.95,77.97,77.99,78.01,81.00,81.08,81.19,101.07,101.13,102.61,102.79,102.81,103.71,103.73,104.1,104.4,104.95,105.06,123.82,124.34,124.60,124.68,148.63,148.86,149.03,150.34；HRMS calcd for C40H73N3O17[M+Na]+:890.4832；found:890.4835.
14M10G
1H NMR(800 MHz,CD3OD),δ(ppm)0.89(t,J＝7.2 Hz,6H,CH3),1.02-1.12(m,1H,CH2),1.18-1.39(m,33H,CH2),1.87-2.03(m,4H,CH2),3.13-3.17(m,1H,CH),3.25-3.37(m,7H,CH2and CH),3.43-3.45(m,1H,CH),3.50-3.70(m,6H,CH),3.73-3.92(m,4H,CH2 andCH),3.97-4.49(m,3H,CH),4.79-4.82(m,1H,CH),4.90-5.06(m,1H,CH),5.15-5.17(m,1H,CH),8.08,8.11,8.12 and 8.13(s,1H,CH)；13C NMR(200 MHz,CD3OD),δ(ppm)14.45,14.46,23.68,23.70,26.02,26.09,26.26,26.34,26.70,26.72,26.73,26.75,30.08,30.09,30.23,30.25,30.44,30.47,30.50,30.59,30.68,30.70，30.73,30.77,30.78,32.30,32.33,32.43,32.49,32.95,32.96,33.03,35.58,35.62,36.88,37.00,62.12,62.16,62.22,62.65,62.70,62.88,62.99,63.46,63.51,71.38,71.48,71.50,71.54,71.8,72.2,72.64,72.68,72.93,72.97,74.07,74.63,74.66,74.68,74.73,74.75,74.82,74.84,74.86,74.92,74.99,75.50,75.58,76.38,76.41,76.48,76.50,76.54,77.71,77.76,77.80,77.87,77.89,77.94,80.90,80.93,81.02,81.10,101.03,101.09,102.53,102.72,102.75,103.62,103.65,104.1,104.3,104.90,105.01,123.76,124.30,124.65,124.75,149.03,149.44,150.34,150.93；HRMS calcd for C44H81N3O17[M+Na]+:946.5458；found:946.5455.
6M6M
1H NMR(800 MHz,CD3OD),δ(ppm)0.88(t,J＝7.2 Hz,6H,CH3),1.04-1.13(m,1H,CH2),1.21-1.42(m,9H,CH2),1.85-2.04(m,4H,CH2),3.19-3.23(m,1H,CH),3.25-3.39(m,6H,CH2and CH),3.43-3.55(m,4H,CH),3.58-3.70(m,8H,CH),3.73-3.92(m,6H,CH2 andCH),3.94-4.48(m,3H,CH),4.78-4.82(m,1H,CH),4.89-5.06(m,1H,CH),5.14-5.16(m,2H,CH),8.08,8.11,8.12 and 8.13(s,1H,CH)；13C NMR(200 MHz,CD3OD),δ(ppm)14.43,23.63,23.68,26.05,26.12,26.25,26.35,26.74,30.04,30.18,30.35,30.43,30.55,32.13,32.22,32.36,32.46,32.81,32.93,35.65,35.71,36.97,37.17,62.16,62.21,62.70,62.80,62.94,63.03,63.48,71.39,71.46,72.0,72.31,72.39,72.67,72.97,74.10,74.41,74.70,74.74,75.02,76.46,76.55,76.62,77.59,77.65,77.75,80.96,81.06,81.22,81.34,81.44,81.52,101.04,101.10,102.80,102.87,103.78,104.1,104.3,104.86,104.91,123.77,124.33,124.74,149.21,149.62,149.90,150.40；HRMS calcd forC38H67N3O22[M+Na]+:940.4108；found:940.4110.
8M8M
1H NMR(800 MHz,CD3OD),δ(ppm)0.88(t,J＝7.2 Hz,6H,CH3),1.02-1.13(m,1H,CH2),1.20-1.41(m,17H,CH2),1.85-2.04(m,4H,CH2),3.19-3.23(m,1H,CH),3.26-3.40(m,6H,CH2and CH),3.44-3.56(m,4H,CH),3.58-3.70(m,8H,CH),3.73-3.92(m,6H,CH2 andCH),3.94-4.48(m,3H,CH),4.79-4.82(m,1H,CH),4.89-5.06(m,1H,CH),5.14-5.16(m,2H,CH),8.08,8.11,8.12 and 8.13(s,1H,CH)；13C NMR(200 MHz,CD3OD),δ(ppm)14.37,14.44,23.48,23.50,23.66,23.67,26.03,26.11,26.24,26.33,26.66,26.68,26.72,29.73,29.74,30.32,30.33,30.34,30.41,30.44,30.53,30.54,32.13,32.22,32.35,32.45,32.70,32.73,32.90,32.92,32.93,35.63,35.70,36.95,37.14,62.15,62.16,62.20,62.24,62.28,62.65,62.68,62.92,63.01,71.35,71.42,71.44,72.0,72.3,72.65,72.70,72.92,72.95,74.06,74.09,74.37,74.39,74.40,74.45,74.65,74.68,74.71,74.72,74.73,74.76,74.93,74.99,75.00,75.02,75.56,75.70,76.38,76.43,76.44,76.47,76.52,76.59,77.52,77.58,77.59,77.63,77.64,77.69,77.72,77.74,80.92,81.02,81.16,81.19,81.30,81.33,81.39,81.40,81.48,101.01,101.02,101.08,102.75,102.77,102.82,102.86,102.88,102.92,103.75,104.1,104.3,104.82,123.78,124.73,124.90；HRMS calcd forC42H75N3O22[M+Na]+:996.4734；found:996.4731.
8M14M
1H NMR(800 MHz,CD3OD and CDCl3),δ(ppm)0.89(t,J＝7.2 Hz,6H,CH3),1.03-1.14(m,1H,CH2),1.23-1.41(m,29H,CH2),1.87-2.06(m,4H,CH2),3.14-3.24(m,1H,CH),3.25-3.39(m,6H,CH2 and CH),3.43-3.56(m,4H,CH),3.58-3.70(m,8H,CH),3.72-3.92(m,6H,CH2 and CH),3.94-4.48(m,3H,CH),4.77-4.84(m,1H,CH),4.90-5.06(m,1H,CH),5.13-5.16(m,2H,CH),8.07,8.10,8.11 and 8.12(s,1H,CH)；13C NMR(200 MHz,CD3OD andCDCl3),δ(ppm)14.46,14.48,23.66,23.67,26.01,26.09,26.20,26.32,26.69,26.70,26.76,26.86,28.05,30.03,30.05,30.33,30.35,30.41,30.43,30.45,30.47,30.50,30.51,30.52,30.54,30.66,30.69,30.72,32.00,32.12,32.28,32.40,32.90,32.91,32.92,33.00,35.56,35.66,36.90,37.16,62.04,62.09,62.10,62.11,62.13,62.20,62.60,62.64,62.86,62.97,63.42,71.26,71.34,71.37,72.0,72.3,72.60,72.68,72.80,72.88,74.00,74.26,74.29,74.30,74.35,74.58,74.62,74.65,74.71,74.85,74.94,75.46,75.63,76.30,76.33,76.35,76.43,76.51,77.42,77.46,77.48,77.54,77.60,77.65,80.90,81.03,81.16,81.19,81.29,81.34,81.43,81.54,100.91,100.96,102.75,102.83,102.90,102.94,103.69,104.0,104.2,104.78,104.84,123.63,124.20,124.73,124.95,148.70,149.16,149.78,150.35；HRMS calcd for C48H87N3O22[M+Na]+:1080.5673；found:1080.5671.
12M12M
1H NMR(800 MHz,CD3OD),δ(ppm)0.89(t,J＝7.2 Hz,6H,CH3),1.02-1.13(m,1H,CH2),1.23-1.40(m,33H,CH2),1.85-2.05(m,4H,CH2),3.18-3.23(m,1H,CH),3.24-3.40(m,6H,CH2and CH),3.42-3.54(m,4H,CH),3.55-3.70(m,8H,CH),3.72-3.92(m,6H,CH2 andCH),3.94-4.48(m,3H,CH),4.78-4.84(m,1H,CH),4.90-5.06(m,1H,CH),5.13-5.16(m,2H,CH),8.08,8.11 and 8.13(s,1H,CH)；13C NMR(200 MHz,CD3OD),δ(ppm)14.48,23.75,23.76,26.04,26.13,26.24,26.37,26.75,26.76,26.82,26.93,28.10,30.10,30.11,30.33,30.34,30.50,30.51,30.54,30.56,30.59,30.60,30.62,30.66,30.73,30.76,30.77,30.79,30.83,32.10,32.20,32.37,32.47,33.09,33.10,35.60,35.69,36.53,36.95,37.20,62.14,62.20,62.27,62.66,62.69,62.94,63.06,63.50,64.27,71.35,71.43,71.46,72.07,72.35,72.68,72.76,72.86,72.94,73.46,74.10,74.37,74.40,74.41,74.46,74.68,74.72,74.76,74.81,74.94,75.01,75.03,75.51,75.68,76.39,76.44,76.53,76.61,77.53,77.58,77.63,77.71,77.74,80.97,81.09,81.22,81.26,81.33,81.38,81.49,81.59,101.02,101.07,102.83,102.91,102.96,103.02,103.76,104.1,104.3,104.88,104.93,123.72,124.31,124.83,125.04,148.76,149.21,149.86,150.43；HRMS calcd for C50H91N3O22[M+Na]+:1108.5986；found:1108.5986.
14M8M
1H NMR(800 MHz,CD3OD),δ(ppm)0.89(t,J＝7.2 Hz,6H,CH3),1.02-1.12(m,1H,CH2),1.21-1.40(m,29H,CH2),1.84-2.05(m,4H,CH2),3.18-3.23(m,1H,CH),3.24-3.40(m,6H,CH2and CH),3.43-3.55(m,4H,CH),3.57-3.70(m,8H,CH),3.72-3.92(m,6H,CH2 andCH),3.93-4.48(m,3H,CH),4.78-4.83(m,1H,CH),4.90-5.06(m,1H,CH),5.14-5.16(m,2H,CH),8.08,8.11,8.12 and 8.13(s,1H,CH)；13C NMR(200 MHz,CD3OD),δ(ppm)14.42,14.46,23.53,23.54,23.55,23.72,26.03,26.12,26.24,26.35,26.68,26.70,26.75,26.91,28.08,29.76,29.78,30.30,30.32,30.46,30.47,30.51,30.58,30.60,30.61,30.64,30.68,30.71,30.72,30.76,30.78,30.80,32.12,32.21,32.35,32.46,32.74,32.76,32.77,33.06,35.62,35.69,36.94,37.16,62.13,62.18,62.21,62.26,62.67,62.91,63.02,63.46,63.47,71.34,71.42,72.0,72.3,72.67,72.73,72.84,72.90,74.08,74.35,74.38,74.39,74.44,74.67,74.70,74.73,74.74,74.79,74.93,74.99,75.01,75.54,75.69,76.37,76.42,76.45,76.51,76.58,77.52,77.55,77.58,77.63,77.69,77.73,80.93,81.05,81.18,81.22,81.34,81.38,81.44,81.53,100.97,101.03,102.79,102.81,102.87,102.89,102.92,102.97,103.77,104.1,104.3,104.85,104.91,123.75,124.34,124.78,124.97,148.77,149.14,149.87,150.40；HRMS calcd for C48H87N3O22[M+Na]+:1080.5673；found:1080.5670.
14M14M
1H NMR(800 MHz,CD3OD),δ(ppm)0.89(t,J＝7.2 Hz,6H,CH3),1.02-1.12(m,1H,CH2),1.23-1.40(m,41H,CH2),1.87-2.04(m,4H,CH2),3.19-3.23(m,1H,CH),3.25-3.39(m,6H,CH2and CH),3.43-3.56(m,4H,CH),3.58-3.70(m,8H,CH),3.73-3.92(m,6H,CH2 andCH),3.94-4.49(m,3H,CH),4.79-4.83(m,1H,CH),4.90-5.06(m,1H,CH),5.14-5.16(m,2H,CH),8.07,8.11 and 8.12(s,1H,CH)；13C NMR(200 MHz,CD3OD),δ(ppm)14.46,23.72,26.01,26.11,26.20,26.33,26.74,26.75,26.80,30.08,30.09,30.10,30.47,30.48,30.52,30.53,30.55,30.58,30.60,30.70,30.72,30.74,30.77,30.79,30.80,30.82,32.10,32.21,32.37,32.48,33.06,35.60,36.93,37.16,62.13,62.16,62.20,62.23,62.29,62.66,62.70,62.94,63.06,63.49,71.37,71.45,71.47,72.0,72.3,72.64,72.92,74.08,74.36,74.40,74.66,74.70,74.74,74.76,74.78,74.94,75.00,75.02,75.52,76.44,76.45,76.53,76.60,77.57,77.64,77.71,77.74,80.91,81.05,81.17,81.20,81.29,81.33,81.44,81.53,101.00,101.07,102.77,102.84,102.92,102.96,103.71,104.08,104.11,104.3,104.84,104.91,124.87,125.08,148.73,149.81,150.00；HRMScalcd for C54H99N3O22[M+Na]+:1164.6612；found:1164.6610.
16M16M
1H NMR(800MHz,CD3OD),δ(ppm)0.89(t,J＝7.2Hz,6H,CH3),1.01-1.12(m,1H,CH2),1.23-1.40(m,49H,CH2),1.86-2.04(m,4H,CH2),3.19-3.23(m,1H,CH),3.25-3.39(m,6H,CH2and CH),3.44-3.56(m,4H,CH),3.58-3.70(m,8H,CH),3.73-3.92(m,6H,CH2 andCH),3.94-4.49(m,3H,CH),4.79-4.83(m,1H,CH),4.90-5.06(m,1H,CH),5.14-5.16(m,2H,CH),8.08,8.12and 8.13(s,1H,CH)；13C NMR(200MHz,CD3OD),δ(ppm)14.47,23.72,26.02,26.12,26.21,26.33,26.73,26.74,26.80,30.09,30.46,30.55,30.57,30.60,30.69,30.71,30.74,30.76,30.80,32.08,32.36,32.46,33.06,35.60,35.68,36.93,37.15,62.12,62.18,62.21,62.27,62.64,62.68,62.94,63.05,63.49,64.25,71.37,71.45,71.47,72.0,72.3,72.74,72.91,74.06,74.36,74.39,74.44,74.66,74.69,74.72,74.74,74.78,74.92,75.00,75.50,75.64,75.67,75.71,76.37,76.41,76.44,76.58,77.55,77.62,77.69,77.70,77.73,80.90,81.03,81.16,81.18,81.32,81.42,81.52,101.01,101.06,102.77,102.84,102.95,103.02,103.70,104.1,104.3,104.83,104.88,124.84,125.11,147.21,148.15,148.62,149.79；HRMS calcd for C58H107N3O22[M+Na]+:1220.7238；found:1220.7239.
实施例2
挑选部分小分子去垢剂表征其临界胶束浓度(critical micelleconcentration，CMC)及胶束大小。为简洁直观的列出实施例中的稳定性测试数据，所挑选的168个化合物使用二维表给出，各化合物的数据在表中的位置如表1所示：
表1
Figure BDA0002569419740000461
Figure BDA0002569419740000471
类型1去垢剂如表1中的第二列所示，具体为6Gyne、7Gyne……10Gyne；8Myne、9Myne……14Myne，共12个化合物。
类型2去垢剂如表1中的第二行所示，具体为6Gazide、7Gazide……10Gazide；8Mazide、9Mazide……14Mazide，共12个化合物。
类型3去垢剂如表1中的第三行至第十四行的第三列至第十四列所示，具体为：
Figure BDA0002569419740000472
共144个化合物。
CMC测定具体步骤：用10μM的荧光染料8-苯胺基萘-1-磺酸(ANS)的水溶液溶解小分子去垢剂配制成储液。将储液用10μM ANS的水溶液稀释成不同的浓度梯度，按浓度由低至高顺序加入96孔板中，每个浓度梯度三复孔，每个孔加入80μL去垢剂溶液。全部加入后在室温下孵育30分钟，使用Envision酶标仪(PerkinElmer)对荧光值(激发波长405nm，发射波长465nm)进行测定。平行测定三组数据，通过拟合得到荧光值随浓度变化的拐点，对应浓度即为该去垢剂的CMC。CMC测定结果如表2所示(单位：mM)：
表2
Figure BDA0002569419740000473
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Figure BDA0002569419740000481
胶束大小测定具体步骤：将去垢剂固体溶于超纯水配制成溶液，若去垢剂CMC小于0.1mM，则溶液浓度为1mM；反之，溶液浓度为10*CMC。用动态光散射仪(Malvin ZetasizerNano ZS)测定胶束的直径。胶束直径测定结果如表3所示(单位：nm)：
表3
Figure BDA0002569419740000482
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Figure BDA0002569419740000491
实施例3
分别对实施例2中表征的小分子去垢剂进行膜蛋白热稳定性实验：
1、A2AR的表达、纯化与热稳定性测试。
腺苷受体2A(A2AR)是一种G蛋白偶联受体。在此实施例中使用的是人工改造过的A2AR-BRIL-ΔC结构(PDB：4EIY，以下简称A2AR)。通过杆状病毒侵染昆虫细胞Sf9的方式将A2AR表达在细胞中。将细胞培养至2×106个/mL浓度，然后使用6000g转速离心10分钟收集细胞。
将细胞用低盐缓冲液(10mM MgCl2,20mM KCl,蛋白酶抑制剂(Roche),10mM 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid(HEPES),pH 7.5)重悬并破碎，使用35000rpm转速离心30分钟，弃去上清液，底部的沉淀重复上述低盐洗涤2次，然后使用高盐缓冲液(1M NaCl,10mM MgCl2,20mM KCl,10mM HEPES,pH 7.5)重复上述洗涤-离心步骤2次。这样最终得到含有A2AR的固体膜用重悬缓冲液(10mM MgCl2,20mM KCl,30％(v/v)glycerol,100μM ZM241385(4-[2-[[7-amino-2-(2-furanyl)[1,2,4]-triazolo[1,5-a][1,3,5]triazin-5-yl]amino]ethyl]phenol),2mg/mL碘乙酰胺,10mM HEPES,pH 7.5)重悬，在4℃下孵育1小时。之后重悬液加入等体积的溶膜缓冲液(800mM NaCl,1％(w/v)DDM,50mM HEPES,pH 7.5)，继续在4℃下孵育2.5小时。将此悬浊液用35000rpm转速离心30分钟，收集上清液，加入20mM咪唑、TALON金属亲和固定树脂(Clontech)，孵育过夜。如此操作后，A2AR被收集并固定在树脂上。此树脂依次用洗涤缓冲液I(800mM NaCl,10％甘油,8mM三磷酸腺苷(ATP),10mM MgCl2,20mM咪唑,100μM ZM241385,0.1％DDM,50mM HEPES,pH 7.5)及洗涤缓冲液II(500mM NaCl,10％甘油,20mM咪唑,100μM ZM241385,0.05％DDM,50mMHEPES,pH 7.5)洗涤，然后用洗脱缓冲液(500mM NaCl,10％甘油,250mM咪唑,100μMZM241385,0.025％DDM,25mM HEPES,pH 7.5)洗脱得到膜蛋白A2AR的DDM溶液。
A2AR在不同去垢剂样品的制备：将去垢剂缓冲液与A2AR的DDM溶液混合，使50μL样品中含有1μg A2AR、40μM ZM241385、0.2％(w/v)去垢剂、500mM NaCl、10％甘油、25mMHEPES，pH 7.5。将荧光染料N-([4-(7-diethylamino-4-methyl-3-coumarinyl)phenyl]-maleimide(CPM)的DMSO储液(4mg/mL)加入上述样品中，使荧光染料的终浓度为2μg/mL，在4℃下孵育15分钟。之后将样品置于高通量荧光分光光度计(Rotor-Gene Q，Qiagen)中逐渐升温并记录荧光值随温度变化的结果，激发波长365nm，发射波长460nm，升温速率1℃/min。使用Graph Pad Prism处理数据，使用玻尔兹曼S型函数(Boltzmann sigmoidal)拟合数据并得到每个样品的Tm值。测试同时使用DDM和LMNG作为对照去垢剂。
A2AR在各种去垢剂中的Tm值测定结果如表4所示(单位：℃)：
表4
Figure BDA0002569419740000501
对照用去垢剂结果：DDM：47.22℃；LMNG：50.97℃。
上述实施例中大部分的去垢剂在膜蛋白热稳定性实验的结果优于对照去垢剂DDM。部分去垢剂甚至优于LMNG，后者被认为对于多种膜蛋白的稳定性具有非常优异的表现。这一现象在类型3去垢剂中尤为显著。
综上所述，本发明有效克服了现有技术中的种种缺点而具高度产业利用价值。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (6)

1.一种化合物或其盐，所述化合物的化学结构式如下之一所示：
Figure FDA0004178709810000011
其中，A、B各自独立地选自戊糖或己糖的的呋喃糖或吡喃糖构型所形成的单糖糖基或二糖糖基；
E、G各自独立地选自直链的C1～C20烷基；
其中，所述化合物选自1-(1--D-葡萄糖基己烷-2-基)-4-(1--D-葡萄糖基己烷基)-1H-1,2,3-三氮唑、1-(1--D-葡萄糖基庚烷-2-基)-4-(1--D-葡萄糖基己烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基辛烷-2-基)-4-(1--D-葡萄糖基己烷基)-1H-1,2,3-三氮唑、1-(1--D-葡萄糖基庚烷-2-基)-4-(1--D-葡萄糖基己烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十三烷-2-基)-4-(1--D-葡萄糖基庚烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十四烷-2-基)-4-(1--D-葡萄糖基庚烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十二烷-2-基)-4-(1--D-葡萄糖基辛烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十三烷-2-基)-4-(1--D-葡萄糖基辛烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十四烷-2-基)-4-(1--D-葡萄糖基辛烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十二烷-2-基)-4-(1--D-葡萄糖基壬烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十三烷-2-基)-4-(1--D-葡萄糖基壬烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十四烷-2-基)-4-(1--D-葡萄糖基壬烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基癸烷-2-基)-4-(1--D-葡萄糖基癸烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十一烷-2-基)-4-(1--D-葡萄糖基癸烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十二烷-2-基)-4-(1--D-葡萄糖基癸烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十三烷-2-基)-4-(1--D-葡萄糖基癸烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十四烷-2-基)-4-(1--D-葡萄糖基癸烷基)-1H-1,2,3-三氮唑、1-(1--D-葡萄糖基己烷-2-基)-4-(1--D-麦芽糖基辛烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十二烷-2-基)-4-(1--D-麦芽糖基辛烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十三烷-2-基)-4-(1--D-麦芽糖基辛烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十四烷-2-基)-4-(1--D-麦芽糖基辛烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十二烷-2-基)-4-(1--D-麦芽糖基壬烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十三烷-2-基)-4-(1--D-麦芽糖基壬烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十四烷-2-基)-4-(1--D-麦芽糖基壬烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十二烷-2-基)-4-(1--D-麦芽糖基癸烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十三烷-2-基)-4-(1--D-麦芽糖基癸烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十四烷-2-基)-4-(1--D-麦芽糖基癸烷基)-1H-1,2,3-三氮唑、1-(1--D-葡萄糖基癸烷-2-基)-4-(1--D-麦芽糖基十一烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基壬烷-2-基)-4-(1--D-麦芽糖基十一烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基癸烷-2-基)-4-(1--D-麦芽糖基十一烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十一烷-2-基)-4-(1--D-麦芽糖基十一烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十二烷-2-基)-4-(1--D-麦芽糖基十一烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十三烷-2-基)-4-(1--D-麦芽糖基十一烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十四烷-2-基)-4-(1--D-麦芽糖基十一烷基)-1H-1,2,3-三氮唑、1-(1--D-葡萄糖基辛烷-2-基)-4-(1--D-麦芽糖基十二烷基)-1H-1,2,3-三氮唑、1-(1--D-葡萄糖基壬烷-2-基)-4-(1--D-麦芽糖基十二烷基)-1H-1,2,3-三氮唑、1-(1--D-葡萄糖基癸烷-2-基)-4-(1--D-麦芽糖基十二烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基辛烷-2-基)-4-(1--D-麦芽糖基十二烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基壬烷-2-基)-4-(1--D-麦芽糖基十二烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基癸烷-2-基)-4-(1--D-麦芽糖基十二烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十一烷-2-基)-4-(1--D-麦芽糖基十二烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十二烷-2-基)-4-(1--D-麦芽糖基十二烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十三烷-2-基)-4-(1--D-麦芽糖基十二烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十四烷-2-基)-4-(1--D-麦芽糖基十二烷基)-1H-1,2,3-三氮唑、1-(1--D-葡萄糖基庚烷-2-基)-4-(1--D-麦芽糖基十三烷基)-1H-1,2,3-三氮唑、1-(1--D-葡萄糖基辛烷-2-基)-4-(1--D-麦芽糖基十三烷基)-1H-1,2,3-三氮唑、1-(1--D-葡萄糖基壬烷-2-基)-4-(1--D-麦芽糖基十三烷基)-1H-1,2,3-三氮唑、1-(1--D-葡萄糖基癸烷-2-基)-4-(1--D-麦芽糖基十三烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基辛烷-2-基)-4-(1--D-麦芽糖基十三烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基壬烷-2-基)-4-(1--D-麦芽糖基十三烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基癸烷-2-基)-4-(1--D-麦芽糖基十三烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十一烷-2-基)-4-(1--D-麦芽糖基十三烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十二烷-2-基)-4-(1--D-麦芽糖基十三烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十三烷-2-基)-4-(1--D-麦芽糖基十三烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十四烷-2-基)-4-(1--D-麦芽糖基十三烷基)-1H-1,2,3-三氮唑、1-(1--D-葡萄糖基庚烷-2-基)-4-(1--D-麦芽糖基十四烷基)-1H-1,2,3-三氮唑、1-(1--D-葡萄糖基辛烷-2-基)-4-(1--D-麦芽糖基十四烷基)-1H-1,2,3-三氮唑、1-(1--D-葡萄糖基壬烷-2-基)-4-(1--D-麦芽糖基十四烷基)-1H-1,2,3-三氮唑、1-(1--D-葡萄糖基癸烷-2-基)-4-(1--D-麦芽糖基十四烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基辛烷-2-基)-4-(1--D-麦芽糖基十四烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基壬烷-2-基)-4-(1--D-麦芽糖基十四烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基癸烷-2-基)-4-(1--D-麦芽糖基十四烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十一烷-2-基)-4-(1--D-麦芽糖基十四烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十二烷-2-基)-4-(1--D-麦芽糖基十四烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十三烷-2-基)-4-(1--D-麦芽糖基十四烷基)-1H-1,2,3-三氮唑、1-(1--D-麦芽糖基十四烷-2-基)-4-(1--D-麦芽糖基十四烷基)-1H-1,2,3-三氮唑。
2.如权利要求1所述的化合物的制备方法，包括：
将式(1)化合物的全乙酰化前体化合物和式(2)化合物的全乙酰化前体化合物进行Click反应，以提供式(3)化合物的全乙酰化前体化合物；
将式(3)化合物的全乙酰化前体化合物水解，以提供式(3)化合物；
Figure FDA0004178709810000031
3.如权利要求1所述的化合物或其盐在膜蛋白纯化中的用途。
4.如权利要求3所述的用途，其特征在于，所述膜蛋白选自G蛋白偶联受体。
5.如权利要求3所述的用途，其特征在于，所述膜蛋白选自腺苷受体2A。
6.一种组合物，包括如权利要求1所述的化合物或其盐。
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