CN109575240B - 一种高荧光量子效率的红光聚合物及量子点溶液及用途 - Google Patents
一种高荧光量子效率的红光聚合物及量子点溶液及用途 Download PDFInfo
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Abstract
本发明公开了一种高荧光量子效率的红光聚合物及量子点溶液及用途，所述高荧光量子效率的红光聚合物的结构式为：
Description
技术领域
本发明属于聚合物制备领域，具体地涉及高荧光量子效率的红光聚合物及其量子点溶液及用途。
背景技术
有机聚合物作为新兴材料领域的热点受到许多研究人员的广泛关注。这主要是由于聚合物长的重复单元所构成的骨架能够实现良好的能量传递,从而使其具有强的光捕获能力和光学信号放大效应。与大多数小分子化合物相比，有机聚合物展示出更优良的光学性能、细胞兼容性、低毒性和易修饰等特点，这使其被广泛的应用于发光材料，化学生物传感及成像等领域。
在细胞生物学的研究中，为对感兴趣的结构和分子进行观察，最常用的方法是对其进行荧光标记。然而，传统的荧光探针在生物标记领域受到诸多限制。近红外荧光探针作为一种非侵袭性的荧光成像技术，对生命过程的探索具有重要意义。与传统的荧光染料相比，半导体聚合物量子点因为发光亮度高、辐射速率快、光稳定性好、生物相容性好等优异的特点，在生物荧光成像领域具有广泛应用。但是，现已报道的大部分半导体聚合物量子点荧光发射波长短，应用于活体成像时对组织细胞伤害大；荧光量子效率低，信噪比小，应用于荧光成像时准确性差。
发射近红外荧光的半导体聚合物量子点因为荧光发射波长长，对生物组织伤害小，信噪比高，成像精准度高，一直是研究的热点。然而，因为发射近红外荧光的半导体聚合物量子点结构设计过程复杂，合成制备困难，近年却少有报道，特别是发射波长位于生物组织的第一光学窗口(650-900nm)内的半导体聚合物量子点。因此，设计合成荧光发射峰位于650-900nm的具有新结构的易制备的聚合物很有必要。
发明内容
本发明的目的是克服现有技术的不足，提供一种高荧光量子效率的红光聚合物。
本发明的第二个目的是提供一种高荧光量子效率的红光聚合物的制备方法。
本发明的第三个目的是提供高荧光量子效率的红光聚合物量子点溶液。
本发明的第四个目的是提供高荧光量子效率的红光聚合物量子点溶液在制备细胞成像剂中的应用。
本发明的第五个目的是提供高荧光量子效率的红光聚合物量子点溶液在制备微管蛋白标记剂的应用。
本发明的技术方案概述如下：
一种高荧光量子效率的红光聚合物，所述聚合物的结构式为：
所述聚合物的重均分子量为35kg/mol。
上述一种高荧光量子效率的红光聚合物的制备方法，包括如下步骤：将化合物M1、M2、M3、NaHCO3、重蒸过的四氢呋喃和去离子水加入反应容器中，脱气，充氮气，加入催化剂Pd(PPh3)4，脱气，充氮气加热至回流，反应，冷却至室温，得到高荧光量子效率的红光聚合物；
反应式：
所述聚合物的重均分子量为35kg/mol。
优选地：M1、M2、M3、NaHCO3和Pd(PPh3)4的摩尔比为9:1:10:234:0.19，所述M1与重蒸过的四氢呋喃和去离子水的比例为36.6mg:6mL:3mL。
一种高荧光量子效率的红光聚合物量子点溶液，用下述方法制成：称取式(I)所示的重均分子量为35kg/mol的高荧光量子效率的红光聚合物溶于四氢呋喃配成浓度为0.5mg/mL的溶液为溶液一；称取数均分子量为1.7kg/mol的聚苯乙烯-顺丁烯二酸酐溶于四氢呋喃配成浓度为0.5mg/mL的溶液为溶液二；按体积比为5:1的比例，将溶液一和溶液二混合得前驱溶液，在超声条件下按体积比为3：10的比例将前驱溶液注入到去离子水中；并保持2-5min，在N2保护下加热至90-95℃，蒸发除去四氢呋喃，停N2，停止加热，降至室温，通过220nm的水系滤头，滤液为高荧光量子效率的红光聚合物量子点溶液。
上述高荧光量子效率的红光聚合物量子点溶液在制备细胞成像剂中的应用。
上述高荧光量子效率的红光聚合物量子点溶液在制备微管蛋白标记剂的应用。
本发明的优点：
本发明的高荧光量子效率的红光聚合物在深红及近红外区(650nm-900nm)有荧光发射；利用纳米再沉淀法将本发明的聚合物制得粒径小于20nm的高荧光量子效率的红光聚合物量子点，成功实现了对细胞微管蛋白结构的有效标记。细胞毒性测试证明高荧光量子效率的红光聚合物量子点对细胞活性影响小，具有良好的生物相容性，是一种可用于活体成像的近红外荧光探针。
附图说明
图1为实施例1制备的红光聚合物的液体核磁氢谱图。
图2为实施例1制备的红光聚合物的液体核磁碳谱图。
图3为实施例1制备的红光聚合物的紫外吸收光谱图(a)和荧光发射光谱图(b)。
图4为实施例2制备的高荧光量子效率的红光聚合物量子点的紫外吸收光谱图(a)和荧光发射光谱图(b)。
图5为实施例2制备的高荧光量子效率的红光聚合物量子点的原子力显微镜图(a)和动态光散射图(b)。
图6为实施例2制备的高荧光量子效率的红光聚合物量子点的细胞微管成像图(a)和细胞毒性测试图(b)。
具体实施方式
下面结合具体实施例对本发明作进一步的说明，本发明的实施例是为了使本领域的技术人员能够更好地理解本发明，但并不能对本发明作任何限制。
实施例1
一种高荧光量子效率的红光聚合物的制备方法，包括如下步骤：
1、单体M1的制备步骤：
(1)将A1(2g,6.8mmol),、噻吩硼酸酯(3.57g,17mmol)、NaHCO3(5.72g,68mmol)、三(二亚苄基丙酮)二钯(0.31g,0.34mmol)、三(邻甲基苯基)膦(0.41g,1.36mmol)加入到四氢呋喃(80mL)和水(30mL)的混合溶液中，反复脱气，在在N2氛围下升温到90℃反应72h。
将反应液冷却到室温，用三氯甲烷和饱和食盐水萃取，收集有机相，加入无水硫酸镁干燥，旋干溶剂。过硅胶柱，粗产物用二氯甲烷和石油醚混合溶剂重结晶，得到橙红色固体B1(1.2g,60％)。
(2)将B1(130mg,0.43mmol)、N-溴代丁二酰亚胺(231.5mg,13.9mmol)加入到三氯甲烷(15mL)溶液中，室温搅拌12h。抽滤反应液，得到橙红色固体M1(177mg,89％)。
2、单体M2的制备步骤：
(1)将A2(16.79mmol,4.5g)、叔丁酰氯(31.45mmol,4.23g)、三乙胺(4mL)，加入到100mL四氢呋喃溶液中，室温搅拌12小时。减压旋出溶剂，加入二氯甲烷和水进行萃取洗涤，再用无水硫酸镁进行干燥，最后旋干。进行柱层析提纯,，洗脱剂为二氯甲烷：石油醚＝2：3,得白色固体化合物B2(6.17g,84％)。
(2)将B2(2.29mmol,1g)、噻吩硼酸酯(5.28mmol,1.11g)、NaHCO3(95.22mmol,8g)、四(三苯基膦)钯(0.07mmol,0.08g)加入到250mL的二口瓶中，抽气脱气三次，加入四氢呋喃(75mL)和水(30mL)的混合溶液中，抽气脱气三次，最终在氮气保护下，加热到70℃，回流24小时。冷却至室温，减压旋出溶剂，加入二氯甲烷和水进行萃取洗涤，再用无水硫酸镁进行干燥，最后旋干。进行柱层析提纯,洗脱剂为二氯甲烷：石油醚＝1：1,，得白色固体化合物C2(0.61g,61％)。
(3)将C2(1.13mmol,0.5g)、三氯氧磷(15mL)、五氧化二磷(23.25mmol,3.3g)加入到50mL单口圆底烧瓶中，加热到116℃，回流30小时。冷却至室温后，缓慢倒入冰水中，并用氢氧化钾调节PH至10，边调节边冷却。加入二氯甲烷进行萃取，再用无水硫酸镁干燥，最后旋干。过中性氧化铝柱，最终，用二氯和石油醚重结晶，得淡黄色固体化合物D2(0.32g,71％)。
(4)将二异丙胺(1mL)加入到四氢呋喃(20mL)中，冷冻除氧后，在-78℃条件下，缓慢加入正丁基锂(2.5mL)，维持低温1小时，取出，室温搅拌1小时，溶液呈黄色；然后，-78℃下，加D2(0.25mmol,0.1g)，维持低温1小时，取出，室温搅拌1小时，溶液呈绿色；然后，-78℃下，加入四溴化碳(2.6mmol,0.86g)，自然回温，过夜，溶液呈棕色。加水淬灭反应，旋出溶剂，加入二氯甲烷进行萃取，再用无水硫酸镁干燥，最后旋干。过中性氧化铝柱，最终，用二氯和石油醚重结晶，得纯白色固体化合物M2(0.12g,84％)。
其中，R1为叔丁基。
3、单体M3的制备步骤：
(1)将A3(12.0g,37mmol)、1-溴代正辛烷(15.7g,81.5mmol)、四丁基溴化铵(0.5g,1.6mmol)加入到NaOH的水溶液(50wt％,30mL)中，升温至70℃搅拌24h。将反应液冷却至室温，倒入饱和食盐水，用二氯甲烷萃取后收集有机相，用去离子水洗涤后，加入无水硫酸镁干燥，旋干溶剂。过硅胶柱，粗产物用乙醇重结晶，得到白色针状晶体B3(16g,80％)。
(2)将B3(1g,1.8mmol)、双联频哪醇硼酸酯(1.4g,5.4mmol)、PdCl2(dppf)(0.13g,0.18mmol)、醋酸钾(1.37g,13.96mmol)加入到1,4-二氧六环(30mL)中，反复脱气后，在N2氛围下升温到80℃反应12h。将反应液冷却到室温，加热旋去1,4-二氧六环，用二氯甲烷和饱和食盐水萃取，收集有机相，加入无水硫酸镁干燥，旋干溶剂。过硅胶柱，粗产物用正己烷重结晶，得到白色固体M3(0.8g,69％)。
4、一种高荧光量子效率的红光聚合物的制备：
将化合物M1(36.6mg,80.1μmol)、M2(5mg,8.9μmol)、M3(57.1mg,89μmol)、NaHCO3(175mg,2080μmol)、重蒸过的四氢呋喃(6mL)、去离子水(3mL)加入反应器中，反复脱气后，在氮气保护下迅速加入新制的催化剂Pd(PPh3)4(2mg,1.7μmol)，脱气数次，在氮气氛围下升温至反应液回流，反应72h后冷却至室温，加入饱和食盐水，用90mL CHCl3分三次萃取，合并有机层后用无水硫酸镁干燥。旋干溶剂，所得粗产物用甲醇沉降，过滤沉淀物后在真空下抽干，得到的聚合物为***固体(90mg,91％)。
图1和图2为本实施例获得的聚合物的液体核磁氢谱图和碳谱，该测试是在400MHzBrukerAV 400的核磁光谱仪上进行的。
聚合物在三氯甲烷溶液(浓度为1x 10-5mol/L-1)中的紫外吸收光谱图如图3(a)所示,该测试是在PerkinElmer Lambda 750UV/VIS/NIR的紫外光谱仪上进行的。聚合物的紫外吸收主要集中在在350nm-650nm的波长范围内，呈现两个显著的吸收峰，分别在397nm(摩尔吸光系数＝7.82x 104M-1cm-1)和552nm(摩尔吸光系数＝7.91x 104M-1cm-1)处。这两个吸收峰证明聚合物I分子内部存在两个嵌段。聚合物I分子在(420-600nm)具有紫外吸收，证明其可以被传统的生物友好型激光器激发(例如488nm的激光器或522nm的激光器)。
聚合物在三氯甲烷溶液(浓度为1x 10-5mol/L-1)中的荧光发射光谱图(397nm激发)如图3(b)所示，该测试是在Hitachi F-7000的荧光光谱仪上进行的。聚合物I内部存在的两个嵌段发生了能量转移，使聚合物I分子的最大发射波长达653nm，与紫外吸收光谱相比具有较大斯托克位移(101nm)，荧光量子效率高达72.6％(以罗丹明B为参比)，该测试证明聚合物I分子的荧光发射已经延伸至近红外区域(600-800nm)。
证明：聚合物的结构如式I所示，
由AgilentTechnologies 1200凝胶渗透色谱仪器测得该聚合物的重均分子量为35kg/mol。
反应式：
实施例2
一种高荧光量子效率的红光聚合物量子点溶液，用下述方法制成：称取式I所示的高荧光量子效率的红光聚合物溶于四氢呋喃配成浓度为0.5mg/mL的溶液为溶液一；称取数均分子量为1.7kg/mol的聚苯乙烯-顺丁烯二酸酐溶于四氢呋喃配成浓度为0.5mg/mL的溶液为溶液二；按体积比为5:1的比例，将溶液一和溶液二混合得前驱溶液，在超声条件下按体积比为3：10的比例将前驱溶液注入到去离子水中；并保持2min(实验证明保持的时间在2-5min都可以)，在N2保护下加热至90℃(实验证明温度在90-95℃都可以)，蒸发除去四氢呋喃，停N2，停止加热，降至室温，通过220nm的水系滤头，滤液为高荧光量子效率的红光聚合物量子点溶液。
高荧光量子效率的红光聚合物量子点在水溶液中的紫外吸收光谱图如图4(a)所示。高荧光量子效率的红光聚合物量子点紫外吸收主要集中在在350nm-650nm的波长范围内，呈现两个显著的吸收峰，分别在369nm和515nm处。
高荧光量子效率的红光聚合物量子点在水溶液中的荧光发射光谱图(515nm激发)如图4(b)所示。高荧光量子效率的红光聚合物量子点在深红及近红外区域(580-850nm)处具有显著发射，最大发射波长为677nm，绝对荧光量子效率高达6.2％，证明本发明所得的高荧光量子效率的红光聚合物量子点是一种高荧光量子效率的红光聚合物量子点。
高荧光量子效率的红光聚合物量子点的原子力显微镜图如图5(a)所示，该测试是在Bruker Mutimode 8的原子力显微镜上进行的。高荧光量子效率的红光聚合物量子点的动态光散射图如图5(b)所示，该测试是在Malvern Zetasizer NanoS的动态光散射仪上进行的。图5证明高荧光量子效率的红光聚合物通过纳米再沉淀法得到了粒径均一、紧凑的球形量子点，平均粒径为13nm。
实施例3
高荧光量子效率的红光聚合物量子点的生物化。
将20μL的5％重量/体积的聚乙二醇水溶液(重均分子量＝3.35kg/mol)和20μL的HEPES(羟乙基哌嗪乙硫磺酸)缓冲液(1M,pH＝7.2)添加到1mL 50μg/mL的高荧光量子效率的红光聚合物量子点水溶液中，加入链霉亲和素(1mg/mL，60μL)，混合。加入20μL新鲜配置的EDC(1-乙基3-[3-二甲基氨基丙基〕碳化二亚胺盐酸盐)溶液(5mg/mL，在Milli-Q水中)，混合，将上述混合液室温下搅拌4小时。用超滤离心管(截留分子量＝100,000)离心分离，得到链霉亲和素生物化的红光聚合物的量子点。
实施例4高荧光量子效率的红光聚合物量子点链霉亲和素的微管标记
37℃下在5％CO2中，用添加了10％牛血清蛋白(FBS)和1％PenStrep(5000单位/mL盘尼西林G，50μg/mL链霉亲和素硫酸盐，在0.85％NaCl中)的DMEM完全培养基(一种含各种氨基酸和葡萄糖的培养基)培养人***细胞(Hela细胞)。在实验之前预培养细胞，直至达到聚集。
加入1.5mL提取液(PIPES(1,4-哌嗪二乙磺酸)的浓度为0.1M、EGTA(乙二醇双(2-氨基乙基醚)四乙酸)的浓度为1mM、MgCl2的浓度为1mM、TritonX-100((聚乙二醇辛基苯基醚-100)的体积分数为0.2％)没过HeLa细胞，提取5min，然后对提取得到的HeLa细胞用PBS(磷酸缓冲盐溶液)洗涤三次。然后，用1.5mL PBS溶液(多聚甲醛，体积分数为4％，戊二醛，体积分数为0.1％)在室温下浸泡HeLa细胞15分钟，对细胞进行固定，继续用PBS溶液洗涤三次，然后用1.5mLTriton-X 100溶液(体积分数为0.5％)对细胞进行通透化处理。加入阻断缓冲溶液(牛血清蛋白，体积分数为5％，Triton-X 100，体积分数为0.1％)的缓冲溶液没过细胞，30分钟。把连接有链霉亲和素的微管蛋白抗体用阻断缓冲溶液稀释至5μg/mL加入到HeLa细胞培养皿中，在室温下培养1小时后，用PBS清洗，去除多余抗体。继续加入10μL链霉亲和素生物化的红光聚合物水溶液(50μg/mL)，在室温下培养1小时，然后用PBS水溶液洗涤细胞三次。最后用全内反射荧光显微镜(用405nm的激光激发)观测细胞微管成像。
高荧光量子效率的红光聚合物量子点的细胞微管成像图如图6(a)所示，该测试是在Olympus IX71的全内反射荧光显微镜上进行的，该图证明高荧光量子效率的红光聚合物量子点可以实现有效标记细胞的微管蛋白。
实施例5
高荧光量子效率的红光聚合物量子点的细胞毒性分析
利用MTT实验进行毒性测试，配置含有高荧光量子效率的红光聚合物量子点的生长基溶液(浓度分别为0,10,20,40,80,100μg/mL)，在96孔板中用生长基溶液培养HeLa细胞24小时后，观察存活细胞数量。
高荧光量子效率的红光聚合物量子点的细胞毒性测试图如图6(b)所示，该测试是在BioTek Instruments Inc的成像阅读器上进行的，该图证明当高荧光量子效率的红光聚合物量子点的浓度为10-100ppm时，基本对细胞无毒害作用，显示出较好的生物相容性。
Claims (6)
1.一种高荧光量子效率的红光聚合物，其特征是所述聚合物的结构式为：
所述聚合物的重均分子量为35kg/mol。
2.权利要求1的一种高荧光量子效率的红光聚合物的制备方法，其特征是包括如下步骤：将化合物M1、M2、M3、NaHCO3、重蒸过的四氢呋喃和去离子水加入反应容器中，脱气，充氮气，加入催化剂Pd(PPh3)4，脱气，充氮气加热至回流，反应，冷却至室温，得到高荧光量子效率的红光聚合物；
反应式：
所述聚合物(I)的重均分子量为35kg/mol。
3.根据权利要求2所述的方法，其特征是所述M1、M2、M3、NaHCO3和Pd(PPh3)4的摩尔比为9:1:10:234:0.19，所述M1与重蒸过的四氢呋喃和去离子水的比例为36.6mg:6mL:3mL。
4.一种高荧光量子效率的红光聚合物量子点溶液，其特征是用下述方法制成：称取重均分子量为35kg/mol的权利要求1所述的高荧光量子效率的红光聚合物，溶于四氢呋喃配成浓度为0.5mg/mL的溶液为溶液一；称取数均分子量为1.7kg/mol的聚苯乙烯-顺丁烯二酸酐溶于四氢呋喃配成浓度为0.5mg/mL的溶液为溶液二；按体积比为5:1的比例，将溶液一和溶液二混合得前驱溶液，在超声条件下按体积比为3：10的比例将前驱溶液注入到去离子水中；并保持2-5min，在N2保护下加热至90-95℃，蒸发除去四氢呋喃，停N2，停止加热，降至室温，通过220nm的水系滤头，滤液为高荧光量子效率的红光聚合物量子点溶液。
5.权利要求4的高荧光量子效率的红光聚合物量子点溶液在制备细胞成像剂中的应用。
6.权利要求4的高荧光量子效率的红光聚合物量子点溶液在制备微管蛋白标记剂的应用。
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