CN115286563A - 一种具有聚集诱导发光性质的席夫碱类荧光粘度探针 - Google Patents
一种具有聚集诱导发光性质的席夫碱类荧光粘度探针 Download PDFInfo
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Abstract
本发明公开了具有聚集诱导发光性质的席夫碱类荧光粘度探针，其中，给体材料包括不同取代位的三苯胺、吲哚啉或咔唑，对位取代苯胺中的取代基为硝基、氰基或羧基，所述给体材料与对位取代苯胺通过碳氮双键连接。该探针在水溶液中具有较高的粘度检测稳定性。本发明还提供了该探针的制备方法，将带有醛基的给体材料与对位取代苯胺进行混合得到混合物，将所述混合物加入到有机溶剂中得到混合溶液，向所述混合溶液中加入冰乙酸或乙酸铵催化剂，并在室温下搅拌6‑12h，过滤得到滤饼，并在0‑10℃下洗涤所述滤饼2‑3次，将所述滤饼干燥后通过极性溶剂重结晶得到具有聚集诱导发光性质的席夫碱类荧光粘度探针。
Description
技术领域
本发明属于荧光探针技术领域，具体涉及一种具有聚集诱导发光性质的席夫碱类荧光粘度探针。
背景技术
粘度作为一个重要的物理参数，影响着生化过程、化学反应等中的传质行为。在生物体系中，粘度对组织和细胞的生物活性也有着重要的影响。例如在细胞中，粘度对营养物质和代谢产物运输过程有着重要的调控作用，也影响着细胞内/细胞间信号传递以及生物大分子间的相互作用。在食品工业中，粘度的大小通常是反映食品品质的一个关键参数，如食品加工过程的品质控制、食品保存中的变质等，都能从粘度数值中得到信息。在高分子科学中，粘度与聚合反应的转化率、聚合物的分子量、立构规整性、聚合物链动力学、聚合物交联、凝胶的形成等也存在着密切的关联。因此，粘度的即时、准确与便捷的测量对于生物、化学、医学和食品科学等领域的研究具有较为重要的意义。
目前常用的粘度测定方法包括毛细管法、落球法、旋转法和振动法。这些测量方法依赖于特定的设备，一般在实验室中完成，需耗费一定的时间与成本。上述粘度测定方法因设备尺寸、体积等限制，一般也不能检测细胞内等微环境中的流体粘度。因此，基于荧光探针的粘度测定方法因其灵敏度高、响应快、操作方便以及可在小体积样品中进行原位检测等特点，正逐渐受到人们的关注。
用于粘度检测的荧光探针一般具有分子转子的特征，包括尼罗红、硼-二吡咯亚甲基(BODIPY)衍生物、二苯乙烯衍生物、三芳胺系列化合物等。与这些探针分子相比，具有聚集诱导发光(AIE)性质的探针分子具有更高的灵敏度。AIE探针分子在溶液中的荧光强度很弱，而当聚集体形成或处于刚性环境中时，荧光强度显著增强。研究表明，AIE分子的发光性质源自分子内运动受限(RIM)机理。文献Chem.Eur.J.2015,21,907–914公开了，增加AIE分子中有效的“转子”部分可以显著提高其对粘度变化的灵敏度。
尽管AIE探针在粘度检测灵敏度上有优势，但现有的主要AIE分子结构(六苯基噻咯、四苯基乙烯等)对合成工艺的要求较高，制备成本相应也较高。近年来，亚胺(席夫碱)类AIE分子由于其便捷、低成本的制备工艺和较好的发光性能而受到关注。但席夫碱类分子存在的最大问题是其在水溶液中易发生水解，从而影响了探针的稳定性和检测效果。
尽管目前有报道采用水杨醛与氨基化合物反应制备水杨醛类席夫碱的案例，但该类席夫碱的发光机理属于光诱导分子内质子转移引起的分子结构改变。另外，水杨醛席夫碱由于苯环上羟基的存在，会限制其化学修饰和光谱调控的可能性。因此，开发水溶液中稳定的高性能席夫碱AIE荧光探针，并实现对其结构和光谱性能的系统性调控，对于AIE分子在检测等领域的低成本、便捷、广泛应用具有重要意义。
发明内容
本发明提供了一种具有聚集诱导发光性质的席夫碱类荧光粘度探针，该探针在水溶液中具有较高的粘度检测稳定性。
一种具有聚集诱导发光性质的席夫碱类荧光粘度探针，包括如下结构式：
其中，给体材料(Donor)为不同取代位的三苯胺、吲哚啉或咔唑，R为硝基、氰基或羧基，所述给体材料与对位取代苯胺通过碳氮双键连接，所述给体材料(Donor)分别选自以下结构式：
其中，R1为无取代基、甲基或烷氧基。
本发明通过在芳亚氨基苯环对位引入吸电子基团R基，防止水解的发生，从而提高材料在水中的稳定性，拓展其在水溶液环境中的应用范围。通常亚氨基具有相对较高的pKa值，在水中容易分解成相应的醛和氨基化合物。水解过程主要包括亚胺氮原子的质子化、水的加成以及胺的离去。本发明所制备材料具有给体-受体结构，其中亚氨基苯环对位的吸电子基团可以降低亚胺N原子上的电子云密度，降低其质子化的可能性从而避免水解反应的进行。从而在水溶液中本发明提供的席夫碱类探针具有较好的荧光性。
所述的R1分别选自以下结构式：
R1＝H，CH3，O(CH2)nCH3(n＝0-9)。
所述的结构式Ⅱ至少包括一个三苯胺单元，且通过C-C单键连接；所述的结构式Ⅲ至少包括一个吲哚啉单元，且通过C-C单键连接；所述的结构式Ⅳ至少包括一个咔唑单元，且通过C-C单键连接。
本发明还提供了一种具有聚集诱导发光性质的席夫碱类荧光粘度探针的制备方法，包括：
进一步的，包括如下步骤：
将带有醛基的给体材料(Donor)与对位取代苯胺进行混合得到混合物，将所述混合物加入到有机溶剂中得到混合溶液，向所述混合溶液中加入冰乙酸或乙酸铵催化剂，并在室温下搅拌6-12h，过滤得到滤饼，在0-10℃下洗涤所述滤饼2-3次，将洗涤后的滤饼干燥后通过极性溶剂重结晶得到具有聚集诱导发光性质的席夫碱类荧光粘度探针。
极性溶剂重结晶为本席夫碱类分子制备的独有步骤：若采用一般的柱层析操作，会存在产物在硅胶柱中分解或在氧化铝柱中分离效果不佳的问题，因此采用重结晶法可保证产物纯度和收率；反应中极性较大的反应物对位取代苯胺相对于极性较小的给体部分过量1-1.5倍(摩尔比)，而苯胺中的伯胺基团与极性溶剂形成氢键的能力大于产物中的亚胺结构，故采用极性溶剂重结晶可最大限度溶解未反应的原料，同时因产物极性小于原料，在缓慢挥发过程中可结晶析出。
所述带有醛基的给体材料与对位取代苯胺的摩尔比为1:1-1:1.5。
所述有机溶剂为乙醇、乙腈、乙酸乙酯或四氢呋喃溶液。
所述冰乙酸或乙酸铵催化剂为带有醛基的给体材料2％-5％摩尔当量的冰乙酸、乙酸铵。
所述极性溶剂为乙醇、乙腈或丙酮。反应中极性较大的反应物对位取代苯胺相对于极性较小的给体部分过量1-1.5倍(摩尔比)，而苯胺中的伯胺基团与极性溶剂形成氢键的能力大于产物中的亚胺结构，故采用极性溶剂重结晶可最大限度溶解未反应的原料，同时因产物极性小于原料，在缓慢挥发过程中可结晶析出。
与现有技术相比，本发明的有益效果为：
(1)本发明通过在席夫碱(亚胺结构)两端链接给电子基团和吸电子基团，得到在水溶液或含水体系中稳定的具有聚集诱导发光性质的席夫碱类荧光粘度探针。该系列分子不易水解，可用于含水体系粘度等的稳定、可视化检测。
(2)本发明提供的具有聚集诱导发光性质的席夫碱类荧光粘度探针在聚集态下具有较强荧光发射强度(荧光量子产率大于0.49)，且易于通过改变给体结构或吸电子基团的方法制备具有不同结构的分子，不同结构的分子具有不同的发光波长范围，可适应各种用途的需要。
(3)本发明提供的具有聚集诱导发光性质的席夫碱类荧光粘度探针的制备方法，简单高效，周期短且收率高，收率为80-95％。
附图说明
图1为实施例1制备的DBSF-1吸收光谱和荧光发射光谱图；
图2为实施例1制备的DBSF-1在聚集态形成过程中光谱和荧光强度的变化图，其中，图2(a)为随着水体积比变化荧光发射强度与波长关系图；图2(b)为荧光发射强度与水体积比关系图；
图3为实施例1制备的DBSF-1在不同氘代试剂中的核磁共振氢谱图；
图4为实施例1制备的DBSF-1在乙醇-甘油体系中荧光强度随粘度变化情况图，其中，图4(a)为随着粘度变化荧光强度与波长关系图，图4(b)为荧光强度相对值与粘度对数值线性图；
图5为实施例1制备的DBSF-1在细胞质染色荧光图；
图6为实施例2制备的DBSF-2吸收光谱和荧光发射光谱图；
图7为实施例2制备的DBSF-2在聚集态形成过程中光谱和荧光强度的变化图，其中，图7(a)为随着水体积比变化荧光发射强度与波长关系图；图7(b)为荧光发射强度与水体积比关系图；
图8为实施例2制备的DBSF-2在丙烯酸聚合体系中荧光强度随粘度变化情况图，其中，图8(a)为随着粘度变化荧光强度与波长关系图，图8(b)为荧光强度相对值与粘度对数值线性图；
具体实施方式
下面结合附图和实施例，对本发明的具有聚集诱导发光性质的可逆力致变色材料及其制备方法作进一步说明：
实施例1
化合物DBSF-1的合成及表征实例：
将4-(二对甲苯氨基)苯甲醛(6.02g，20mmol)与对氨基苯甲腈(2.36g，20mmol)溶解于100mL乙腈中，再滴加3滴冰乙酸。投料完成后，反应混合液在室温下搅拌6小时。停止加热后，将反应液进行减压过滤，用0℃的乙腈洗涤滤饼。收集滤饼并用乙腈进行重结晶。过滤重结晶产物，收集所得固体并将其真空干燥，得到产物DBSF-1共7.62g，收率95％。化合物DBSF-1有关的结构表征数据如下：1H NMR(500MHz,CDCl3,δ):8.29(s,1H),7.71(d,J＝7.0Hz,2H),7.67(d,J＝7.0Hz,2H),7.22(d,J＝7.0Hz,2H),7.16(d,J＝7.0Hz,4H),7.09(d,J＝7.0Hz,4H),7.02(d,J＝7.0Hz,2H),2.37(s,6H).13C NMR(125MHz,CDCl3,δ):161.50,156.64,151.95,144.02,134.39,133.28,130.42,130.24,127.47,125.96,121.67,119.63,119.25,108.30,20.94.HRMS(ESI)m/z:[M]+calcd for C28H23N3,401.1892；found,401.1890.[M+Na]+calcd for C28H23N3,424.1784；found,424.1783.
实施例2
化合物DBSF-2的合成及表征实例：
将4-(对甲苯基)-1，2，3，3a，4，8b-六氢环戊二烯并[b]吲哚-7-甲醛(5.54g，20mmol)与对氨基苯甲腈(3.54g，30mmol)溶解于100mL乙醇中，再加入0.077g乙酸铵。投料完成后，反应混合液在80℃下搅拌12小时。停止加热后，将反应液进行减压过滤，用0℃的乙醇洗涤滤饼。收集滤饼并用乙醇进行重结晶。过滤重结晶产物，收集所得固体并将其真空干燥，得到产物DBSF-2共6.33g，收率80％。化合物DBSF-2有关的结构表征数据如下：1H NMR(500MHz,CDCl3,δ):8.28(s,1H),7.90(d,J＝8Hz,2H),7.59(d,J＝8.5Hz,2H),7.39(s,1H),7.18-7.13(m,5H),6.78(d,J＝8.0Hz,1H),4.85-4.83(m,1H),3.84-3.82(m,1H),2.30(s,3H),2.11-1.50(m,6H)；13C NMR(125MHz,CDCl3,δ):169.36,161.50,148.60,143.74,140.02,136.18,133.24,132.02,131.76,130.46,130.11,129.32,128.82,127.62,123.36,122.98,120.56,107.40,45.11,35.50,33.73,24.66,21.08.HRMS(ESI)m/z:[M+H]+calcdfor C28H23N3,397.1911；found,397.1918.
化合物性能测试：
DBSF-1性能测试：
如图1所示，化合物DBSF-1的紫外-可见吸收峰为393nm，最大发射峰为529nm。材料的固态荧光量子产率为0.49，表明其在固态下具有较好发光效率。
如图2(a)所示，在不同水体积比(fw)的四氢呋喃/水溶液中测试DBSF-1的荧光发射光谱。如图2(b)所示，在纯四氢呋喃溶液及水体积比小于70％的混合溶液中，DBSF-1的荧光发射强度呈现逐渐降低趋势；当水体积比fw大于70％后，由于聚集体的形成，DBSF-1的荧光发射强度显著上升。
如图3的a所示，DBSF-1在氘代二甲基亚砜中未发生化学反应，如图3的b所示，DBSF-1在10％重水的氘代二甲基亚砜中未发生化学反应，也未出现反应物对应的信号峰，如图3的c所示，当反应物醛和对氨基苯甲腈以1：1(摩尔比)混合时，在化学位移9.7处出现一单峰，为醛基质子的特征峰。该峰在图3的a和b中均未出现，表明DBSF-1在纯氘代二甲基亚砜和含有重水的氘代二甲基亚砜中未发生化学变化，进一步证明了该材料在水中的稳定性。
如图4(a)所示，当甘油含量增加，体系粘度上升时，DBSF-1荧光强度显著提升。如图4(b)所示，529nm处荧光强度对数值与粘度对数值呈现较好的线性关系(R2＝0.993)。这表明DBSF-1可用于流体粘度的定量检测，且具有较高的可靠性。
如图5所示，化合物DBSF-1可以进入到细胞中，并将细胞质染色。在含DBSF-1的溶液中培养的细胞在荧光显微镜下(激发波长405nm)可见明细的绿色荧光，如图5中sample所示。而在对照组(control)中未见荧光发射。
如图6所示，化合物DBSF-2的紫外-可见吸收峰为399nm，最大发射峰为527nm。Stokes位移为130nm。分子荧光发射峰处于绿光区域，对于大部分小分子发光和生物背景荧光具有抗干扰能力。
如图7(a)所示，在0-90％水体积比(fw)的四氢呋喃/水溶液中测试DBSF-2的荧光发射光谱。如图7(b)所示，在纯四氢呋喃溶液及水体积比小于80％的混合溶液中，DBSF-2的荧光发射强度呈现逐渐降低趋势；当水体积比fw大于80％后，由于聚集体的形成，DBSF-2的荧光发射强度显著上升。
如图8(a)所示，当聚合度增加，体系粘度上升时，DBSF-2荧光强度显著提升。如图8(b)所示，其中，527nm处荧光强度对数值与粘度对数值呈现较好的线性关系(R2＝0.994)。这表明DBSF-2可用于聚合过程粘度变化的可视化定量检测，且具有较高的可靠性。
Claims (9)
1.一种具有聚集诱导发光性质的席夫碱类荧光粘度探针，其特征在于，包括如下结构式：
其中，给体材料为不同取代位的三苯胺、吲哚啉或咔唑，R为硝基、氰基或羧基，所述给体材料与对位取代苯胺通过碳氮双键连接，所述给体材料分别选自以下结构式：
其中，R1为无取代基、甲基或烷氧基。
2.根据权利要求1所述的具有聚集诱导发光性质的席夫碱类荧光粘度探针，其特征在于，所述的R1分别选自以下结构式：
R1＝H，CH3，O(CH2)nCH3(n＝0-9)。
3.根据权利要求1所述的具有聚集诱导发光性质的席夫碱类荧光粘度探针，其特征在于，所述的结构式Ⅱ至少包括一个三苯胺单元，且通过C-C单键连接；所述的结构式Ⅲ至少包括一个吲哚啉单元，且通过C-C单键连接；所述的结构式Ⅳ至少包括一个咔唑单元，且通过C-C单键连接。
4.根据权利要求1-3任一项所述的具有聚集诱导发光性质的席夫碱类荧光粘度探针的制备方法，其特征在于，包括：
5.根据权利要求4所述的具有聚集诱导发光性质的席夫碱类荧光粘度探针的制备方法，其特征在于，包括：
将带有醛基的给体材料与对位取代苯胺进行混合得到混合物，将所述混合物加入到有机溶剂中得到混合溶液，向所述混合溶液中加入冰乙酸或乙酸铵催化剂，并在室温下搅拌6-12h，过滤得到滤饼，在0-10℃下洗涤所述滤饼2-3次，将洗涤后的滤饼干燥后通过极性溶剂重结晶得到具有聚集诱导发光性质的席夫碱类荧光粘度探针。
6.根据权利要求5所述的具有聚集诱导发光性质的席夫碱类荧光粘度探针的制备方法，其特征在于，所述带有醛基的给体材料与对位取代苯胺的摩尔比为1:1-1:1.5。
7.根据权利要求5所述的具有聚集诱导发光性质的席夫碱类荧光粘度探针的制备方法，其特征在于，所述有机溶剂为乙醇、乙腈、乙酸乙酯或四氢呋喃溶液。
8.根据权利要求5所述的具有聚集诱导发光性质的席夫碱类荧光粘度探针的制备方法，其特征在于，所述冰乙酸或乙酸铵催化剂为所述带有醛基的给体材料2％-5％摩尔当量的冰乙酸或乙酸铵。
9.根据权利要求5所述的具有聚集诱导发光性质的席夫碱类荧光粘度探针的制备方法，其特征在于，所述极性溶剂为乙醇、乙腈或丙酮。
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