CN113702530A - 一种蠕虫状胶束的检测方法 - Google Patents

一种蠕虫状胶束的检测方法 Download PDF

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CN113702530A
CN113702530A CN202110995888.7A CN202110995888A CN113702530A CN 113702530 A CN113702530 A CN 113702530A CN 202110995888 A CN202110995888 A CN 202110995888A CN 113702530 A CN113702530 A CN 113702530A
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刘畅瑶
姚开心
孙立杰
龚佳妮
徐宝财
周雅文
张桂菊
刘红芹
赵莉
王策
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Abstract

本发明提供了一种蠕虫状胶束的检测方法，属于分析化学技术领域。本发明采用z‑ArN2 +为化学探针物质，将长链探针加入到试验溶液中，用于探测界面区域，将短链探针加入不含表面活性剂的对照溶液中，通过上述方法测定探针和不同亲核试剂的选择性，将得到的产物用高效液相色谱法测定产率，利用短链探针的选择性转化为界面摩尔数，通过测定产物的产率检测蠕虫状胶束。本发明利用化学探针的方式检测蠕虫状胶束，本发明方法制备简单、成本低、可实现实时检测，具有广泛的应用前景。

Description

一种蠕虫状胶束的检测方法
技术领域
本发明涉及分析化学技术领域，尤其涉及一种蠕虫状胶束的检测方法。
背景技术
蠕虫状胶束(wormlike micelles)是两亲分子在水溶液中的缔合结构之一，又被称为线状胶束(threadlike micelles)和巨胶束(giant micelles)，分子堆积参数P在1/2与1/3之间，蠕虫状胶束的直径通常在1～10nm之间，长度在101～104nm之间。蠕虫状胶束的长度与表面活性剂的结构和浓度，温度，盐度以及水溶液中的反离子有关。蠕虫状胶束的空间位阻抑制了溶液的自由旋转，因此蠕虫状胶束溶液表现为粘弹性流体，有独特的流变学性质。
蠕虫状胶束的形成过程，水环境与表面活性剂疏水链之间的排斥作用导致分子间自组装成为球状胶束；继续增大表面活性剂的浓度，胶束可以“生长”、变长，形成短棒状胶束；而在特定的熵条件下，从半无限圆柱体(通过断裂)产生两个半球形端盖所需的能量非常大，因此在一定条件下会沿着一维非轴向方向伸长，自组装成蠕虫状胶束；表面活性剂浓度到达临界缠绕浓度(C*)后，柔性的蠕虫状胶束之间相互叠加，形成动态的三维网络结构，并处于破坏和重组的平衡中，类似于柔性聚合物，因此，蠕虫状胶束又被称为“活”聚合物蠕虫状胶束的粘弹性质、聚集结构、微观形貌等主要采用旋转流变仪、小角度中子散射(SANS)、核磁、动态光散射(DLS)和cryo-TEM等仪器表征。
现有技术中通常使用流变仪或者原位冷冻透射电镜检测蠕虫状胶束的存在，但是检测仪器价格昂贵，导致检测不便且成本较高。
发明内容
有鉴于此，本发明提供了一种蠕虫状胶束的检测方法，利用化学探针的方式检测蠕虫状胶束，具有使用便利、成本低的特点。
一种蠕虫状胶束的检测方法，所述检测方法采用z-ArN2 +长链探针和z-ArN2 +短链探针对胶束进行检测，所述z-ArN2 +的结构如式Ⅰ所示：
Figure BDA0003234104680000021
式中z-ArN2+短链探针的z＝1，R为-CH3；所述z-ArN2+长链探针的z＝16，R为-C16H33；
所述蠕虫状胶束的检测方法包括如下步骤：
(1)将长链探针配制成浓度为0.005-0.05M的乙腈储备液，将短链探针配制成浓度为0.05-0.5M的乙腈储备液；
(2)在容量瓶中加入表面活性剂，用稀释液溶解定容，再加入步骤(1)所述的长链探针的储备液，得到试验溶液，所述试验溶液中，长链探针浓度为5×10-4–5×10-5M；表面活性剂的浓度为1×10-3–2M；
(3)用铵盐或磺酸盐替换步骤(2)中的表面活性剂，用稀释液溶解定容，再加入步骤(1)中所述的短链探针的储备液，得到对照溶液，所述对照溶液中短链探针的浓度为5×10-3–5×10-4M；
(4)将步骤(2)所述的试验溶液避光密封在25-60℃反应5-48h，反应结束后，用稀释液稀释，然后采用高效液相色谱法测量产物的收率；
(5)将步骤(3)对照溶液重复步骤(4)的操作；
(6)采用高效液相色谱法测定的产物的收率由三次或多次重复注射峰面积的平均值和十六烷基二甲基苯酚与十六烷基二甲基溴苯的校准曲线得出。
优选的，步骤(2)中所述的表面活性剂是十六烷基三甲基溴化铵。
优选的，步骤(2)-步骤(4)中所述的稀释液是甲醇、乙腈或水中的至少一种。
优选的，步骤(3)中所述铵盐为四甲基铵盐、四乙基铵盐中的至少一种，所述磺酸盐为甲基磺酸盐。
优选的，步骤(4)和步骤(6)中所述高效液相色谱法检测的条件为：长度为25cm的C18色谱柱，65％甲醇：35％异丙醇(v/v)作为流动相，流速：0.4mL/min；λ＝220nm；注射量100μL。
长链探针和短链探针与水分子、醇和溴离子发生竞争性反应，生成脱氮产物z-ArOH，z-ArX和z-ArOR’，其中R’代表的是醇链长度，z-ArN2 +表示两种两亲性探针。z-ArN2 +与弱碱性亲核试剂在胶束溶液和参比溶液中发生的反应如下：
Figure BDA0003234104680000031
化学捕集法是基于化学探针的方法，将长链探针加入到胶束溶液中，用于探测界面区域，然后将短链探针加入不含表面活性剂的水溶液的参比溶液中，通过上述方法测定探针与不同亲核试剂的选择性，最后利用高效液相色谱法测定表面活性剂中得到的产物产率，利用短链探针的选择性，转化为界面摩尔数，通过测定产物的产率可知溶液中是否有蠕虫状胶束的生成。
与现有技术相比，本发明具有以下有益效果：本发明方法提供的蠕虫状胶束的检测方法操作简单、避免使用价格昂贵的检测仪器、可实现实时，具有广泛的应用前景。
附图说明
图1是本发明实施例1中胶体溶液的零剪切黏度随醇浓度变化趋势图；
图2是本发明实施例1中醇体系不同时，胶体溶液的弹性模量G'和粘性模量G"随振荡频率的变化曲线图；
图3是本发明实施例1中胶束界面区域醇、水和溴离子的浓度随醇浓度变化趋势图。
具体实施方式
下面结合实施例对本发明作进一步说明。下述实施例中所述试验方法或测试方法，如无特殊说明，均为常规方法；所述原料和助剂，如无特殊说明，均从常规商业途径获得，或以常规方法制备。
实施例1
(1)将长链探针16-ArN2BF4配制成浓度为0.01M的储备液置于乙腈中备用；取2ml0.1M CTAB/0.05M KBr/5-300mM肉桂醇体系备用；然后将20μL冰封在乙腈中的长链探针16-ArN2BF4的储备液加入2ml 0.1M CTAB/0.05M KBr/5-300mM肉桂醇体系中，得到浓度为1.2×10-5-2×10-4M的溶液，将上述溶液混匀后置于避光密封的环境中，25℃反应48h，反应结束后用甲醇稀释，然后用高效液相色谱法进行测量，其中采用高效液相色谱法测量的条件为：C18色谱柱，长度为25cm；流动相：65％甲醇：35％异丙醇(v/v)；流速：0.4mL/min；λ＝220nm；注射量100μL。
产物收率由三次或多次重复注射峰面积的平均值和十六烷基二甲基苯酚与十六烷基二甲基溴苯的校准曲线得出。
(2)将步骤(1)中的长链探针16-ArN2BF4替换为短链探针1-ArN2BF4，将步骤(1)中的0.1M CTAB/0.05M KBr/5-300mM肉桂醇体系替换成0.01-3M TMAB(四甲基溴化铵)的甲醇水溶液体系，其余操作和步骤(1)相同。
实施例2
将实施例1中的肉桂醇替换为苯甲醇，其余操作和实施例相同。
实施例3
将实施例1中的肉桂醇替换为苯乙醇，其余操作和实施例相同。
实施例4
将实施例1中的肉桂醇替换为茴香醇，其余操作和实施例相同。
在0.1M CTAB/0.05M KBr/5-300mM香料醇体系中，由流变学可得，在肉桂醇体系中，在肉桂醇浓度为50mM左右的区域中有蠕虫状胶束生成，而在苯乙醇、苯甲醇和茴香醇体系中则无蠕虫状胶束生成结果如图1所示。
为了进一步证明肉桂醇引发了体系中的椭球状胶束向蠕虫状胶束发生转变。我们分别研究了0.1M CTAB/0.05M KBr/5-300mM香料醇在25℃下的弹性模量G'和粘性模量G"随振荡频率的变化，如图2所示，有蠕虫状胶束生成的体系粘性模量G"在低频区大于弹性模量G’，而在高频区刚好相反，也就是G"和G’的曲线有交点，是蠕虫状胶束生成的标志。香料醇浓度全部选自图1中各醇η0值最高点对应的浓度，其中肉桂醇为55mM，苯乙醇、苯甲醇和茴香醇为40mM，由图2可知道，加入40mM苯乙醇、40mM苯甲醇和40mM茴香醇之后的体系总是表现出粘性行为，也说明了添加苯乙醇、苯甲醇和茴香醇的体系没有蠕虫状胶束的形成，而肉桂醇和动态流变相应在低频率表现为粘性行为，在高频率表现为弹性行为，说明有蠕虫状胶束存在。
利用化学探针检测以上四种0.1M CTAB/0.05M KBr/5-300mM香料醇体系中胶束界面区域的各化学组成结果如图3所示，有蠕虫状胶束生成的肉桂醇体系界面上醇的浓度显著提高，而其它三种醇体系界面上醇浓度变化幅度较小；同时有蠕虫状胶束生成的肉桂醇体系界面上水浓度降低，而另外三种醇体系界面水的浓度都略有增加。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (6)

1.一种蠕虫状胶束的检测方法，其特征在于，所述检测方法采用z-ArN2 +长链探针和z-ArN2 +短链探针对胶束进行检测，所述z-ArN2 +的结构如式Ⅰ所示：
Figure FDA0003234104670000011
其中z-ArN2 +短链探针的z＝1，R为-CH3；所述z-ArN2 +长链探针的z＝16，R为-C16H33。
2.根据权利要求1所述蠕虫状胶束的检测方法，其特征在于，包括以下步骤：
(1)将长链探针配制成浓度为0.005-0.05M的乙腈储备液，将短链探针配制成浓度为0.05-0.5M的乙腈储备液；
(2)在容量瓶中加入表面活性剂，用稀释液溶解定容，再加入步骤(1)所述的长链探针的储备液，得到试验溶液，所述试验溶液中，长链探针浓度为5x10-4–5x10-5M；表面活性剂的浓度为1x10-3–2M；
(3)用铵盐或磺酸盐替换步骤(2)中的表面活性剂，用稀释液溶解定容，再加入步骤(1)中所述的短链探针的储备液，得到对照溶液，所述对照溶液中短链探针的浓度为5x10-3-5x10-4M；
(4)将步骤(2)所述的试验溶液避光密封在25–60℃反应5-48h，反应结束后，用稀释液稀释，然后采用高效液相色谱法测量产物的收率；
(5)将步骤(3)对照溶液重复步骤(4)的操作；
(6)采用高效液相色谱法测定的产物的收率由三次或多次重复注射峰面积的平均值和十六烷基二甲基苯酚和十六烷基二甲基溴苯的校准曲线得出。
3.根据权利要求2所述的蠕虫状胶束的检测方法，其特征在于，步骤(2)中所述的表面活性剂是十六烷基三甲基溴化铵。
4.根据权利要求2所述的蠕虫状胶束的检测方法，其特征在于，步骤(2)-步骤(4)中所述的稀释液是甲醇、乙腈或水中的至少一种。
5.根据权利要求2所述的蠕虫状胶束的检测方法，其特征在于，步骤(3)中所述铵盐为四甲基铵盐、四乙基铵盐中的至少一种，所述磺酸盐为甲基磺酸盐。
6.根据权利要求2所述的蠕虫状胶束的检测方法，其特征在于，所述高效液相色谱法检测的条件为：长度为25cm的C18色谱柱，65％甲醇：35％异丙醇(v/v)作为流动相，流速：0.4mL/min；λ＝220nm；注射量100μL。
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