CN111433259A - 使用聚合物沉淀法大规模制备多个杰纳斯/两亲颗粒的方法 - Google Patents
使用聚合物沉淀法大规模制备多个杰纳斯/两亲颗粒的方法 Download PDFInfo
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Abstract
本发明提供一种制备大规模的两亲颗粒的方法。所述方法包含:将多个纳米颗粒添加到一聚碳酸酯基的溶液中;将一表面活性剂添加到所述溶液中,并同时进行超声波处理,以产生聚合物沉淀;产生至少一微球,所述微球上镶嵌有所述多个纳米颗粒;使所述多个被镶嵌的纳米颗粒的暴露的半球部分进行一进一步的多个两亲颗粒的相关改性;以及将所述至少一微球溶解在一聚碳酸酯基的溶液中,以便从所述至少一微球释放所述多个被镶嵌的纳米颗粒。
Description
相关申请的交叉引用
本申请与共同拥有的美国临时专利申请相关,并要求其优先权:美国临时专利申请第62/591,794号,标题为:使用聚合物沉淀法大规模制备杰纳斯/两亲颗粒的方法(Method for Large Scale Fabrication of Janus/amphiphilic particles usingPolymer Precipitation procedure),于2017年11月29日提交,其公开内容通过引用整体并入本文。
技术领域
本发明涉及生产微粒及纳米颗粒的领域。
背景技术
杰纳斯(Janus)颗粒是特殊类型的颗粒,由诺贝尔奖获得者P.G.de Gennes于1991年首次提出。这些各向异性的颗粒以罗马神杰纳斯(Janus)的名字命名,可以在单个颗粒内赋予截然不同的化学或物理性质及方向性。杰纳斯颗粒具有一系列不对称的颗粒结构,从球形到各种的哑铃形状,再到圆柱形或圆盘形,并且它们的物理性质及自组装行为已在各种应用领域中得到研究,例如用于乳液稳定的颗粒表面活性剂、调制型光学纳米探针及表面催化剂。
发明内容
本发明提供了一种使用聚合物沉淀技术来制备大量杰纳斯/两亲颗粒的方法。本发明的实施方式涉及用于制备大规模两亲颗粒的方法。所述方法包含:将多个纳米颗粒添加到一聚碳酸酯基的溶液中;将一表面活性剂添加到所述溶液中,并同时进行超声波处理,以产生一聚合物沉淀,所述聚合物沉淀配置为用以产生至少一微球,所述微球上镶嵌有所述多个纳米颗粒,所述多个纳米颗粒被镶嵌成使得所述多个纳米颗粒中的一个半球部分被暴露以便进一步改性;使所述多个被镶嵌的纳米颗粒的所述暴露的半球部分进行一进一步的多个两亲颗粒的相关改性;以及将所述至少一微球溶解在一聚碳酸酯基的溶液中,以便从所述至少一微球释放出所述多个被镶嵌的纳米颗粒。
可选地,所述方法还包含:使用离心过滤所述至少一微球;以及在将所述多个被镶嵌的纳米颗粒的所述暴露的半球部分进行一进一步的多个两亲颗粒的相关改性之前,使用去离子水润洗所述至少一微球,并在真空下将所述至少一微球进行干燥。
可选地,所述聚碳酸酯基的溶液包括四氢呋喃(tetrahydrofuran,THF)。
可选地,所述多个纳米颗粒是多个聚甲基倍半硅氧烷(polymethylsilsesquioxane,PMSQ)的纳米颗粒。
可选地,所述多个纳米颗粒是多个二氧化硅的纳米颗粒。
可选地,所述表面活性剂是在水中的双癸基二甲基溴化铵(Dimethyl didodecylammonium bromide,DDAB)。
可选地,所述进一步的多个两亲颗粒的相关改性选自于由以下组成的群组:在所述多个暴露的半球部分上形成多个胺基;在所述多个暴露的半球部分上形成多个羧基;以及将多个胺官能化的二氧化硅的纳米颗粒与多个聚甲基倍半硅氧烷-羧基(PMSQ-COOH)两亲的杰纳斯颗粒偶联。
除非本文另有定义,否则本文所用的所有技术及/或科学术语具有与本发明所属领域的普通技术人员通常所理解的相同含义。尽管与本文描述的那些类似或等同的方法及材料可以用于本发明的实施方式的实践或测试中,但是下面描述了示例性的方法及/或材料。如有抵触,以专利说明书及其定义为准。另外,材料、方法及示例仅是说明性的,并不意图必然是限制性的。
附图说明
本文仅通过示例的方式,参考附图描述了本发明的一些实施方式。具体地参考详细的附图,要强调的是,示出的细节是作为示例并且出于对本发明的实施方式的说明性讨论的目的。在这方面,结合附图的描述使本领域技术人员清楚地知道如何实践本发明的实施方式。
现在请注意附图,其中相同的附图标记或符号指示相应或类似的组件。
在附图中:
图1是根据本发明的一实施方式的系统及方法的示意图;
图2是扫描式电子显微镜(scanning electron microscope,SEM)的图像(A-D),示出了被镶嵌在聚合物沉淀物(核及壳)结构上的聚甲基倍半硅氧烷(polymethylsilsesquioxane,PMSQ);
图3是扫描式(scanning electron microscope,SEM)电子显微镜的图像(A-B),示出了聚合物沉淀物的截面结构;
图4是与聚甲基倍半硅氧烷杰纳斯(Janus)纳米颗粒相比的裸露的聚甲基倍半硅氧烷颗粒的傅立叶转换红外光谱(Fourier-transform infrared spectroscopy,FTIR)分析;
图5是说明两亲性以及均匀改性的纳米颗粒在氯仿-水系统中的位置的图像;以及
图6是特征性PMSQ-二氧化硅颗粒的高分辨率扫描式电子显微镜(High-Resolution Scanning Electron Microscopy,HRSEM)的显微照片(A-C)。
具体实施方式
本发明的应用不限于以下描述中阐述的结构细节和组件的布置。本发明能够具有其他实施方式,或者能够以各种方式被实践或执行。同样,应当理解,本文采用的措词及术语是出于描述的目的,而不应被认为是限制性的。
本发明提供了一种基于通过聚合物沉淀将纳米颗粒固定在PC微球上的大规模制备两亲杰纳斯颗粒的系统及方法。本发明涉及不受温度波动影响的杰纳斯颗粒的大规模生产。
图1是系统及方法100的示意图。最初,在容器102中(一标准反应容器),将多个纳米颗粒,例如:聚甲基倍半硅氧烷(polymethylsilsesquioxane,PMSQ)纳米颗粒添加到一聚碳酸酯基的溶液中,例如在四氢呋喃(Tetrahydrofuran,THF)中的聚碳酸酯中。例如,聚碳酸酯的使用,因为它具有非常高的机械性能,可以获得很高的产量,尤其是大规模生产中的制备工艺。此外,聚碳酸酯的高热稳定性使其能够获得对生产过程中可能出现的高温的恶劣热条件的高电阻。
在第二阶段,以约1mL/min的速率将一反溶剂或表面活性剂,例如水中的双癸基二甲基溴化铵(Dimethyl didodecyl ammonium bromide,DDAB)加入到所述容器102中。同时进行超声波处理,并且,例如,与双癸基二甲基溴化铵及水同时进行,以产生一聚合物沉淀。超声波处理由例如超声波液体处理器,例如超声波振动细胞(Sonics Vibra-cell)超声波液体处理器,型号VCX 750提供。超声波确保沉淀物均匀地分布,并使颗粒迅速地附着在聚合物的表面,与沉淀物的几何形状以及颗粒的紧密(致密)堆积有关。在此阶段,如所述容器104中所示,将多个纳米颗粒组装在多个聚碳酸酯(polycarbonate,PC)微球的表面上。
在第三阶段,例如通过离心过滤聚合物沉淀物,用去离子水冲洗以去除残留物以及微弱连接的纳米颗粒,并且例如在真空条件下在350℃下进行干燥3小时。
在第四阶段,对所述多个被镶嵌的纳米颗粒的暴露的半球部分进行化学改性,以添加多个两亲颗粒的相关改性,例如,添加胺基。如容器106所示,使用例如(3-氨丙基)三乙氧基硅烷(APTES)来进行改性。(3-氨丙基)三乙氧基硅烷是一种氨基硅烷,用于通过将胺基团添加到暴露的半球部分上来硅烷化所述多个被镶嵌的纳米颗粒的暴露的半球部分。
在最后阶段,将聚合物溶解在有机溶剂中,例如聚碳酸酯以及四氢呋喃,以将所述多个纳米颗粒从所述多个聚碳酸酯微球分离出来。容器108中所示的现在分离的颗粒可以进行额外的化学改性,例如添加羧基。
如容器104中所示,所制备的微球将颗粒冻结至固定位置。这防止了在上述化学改性阶段中颗粒的运动,并且防止了颗粒在液-液界面处的旋转。在两阶段化学改性中,所制备的微球消除了寻找反应物仅可溶于一种液体的液-液组合(liquid-liquidcombination)的需要。此外,所制备的微球使分离以及纯化过程变得更加有效。
尽管上面提供了前述阶段,然而其顺序是示例性的,并且这些阶段的其他顺序也是被允许的。
图2是扫描式电子显微镜的图像(A-D),示出了被镶嵌在聚合物沉淀物(核及壳)结构上的聚甲基倍半硅氧烷(PMSQ)。图像A-C是从水中滤出的球形聚合物沉淀物不同比例尺的显微照片。比例尺为500μm(A)、50μm(B)、10μm(C)。图像D是在一聚碳酸酯微球的表面上的多个聚甲基倍半硅氧烷颗粒单层的放大图。比例尺为5μm(D)。
图3是扫描式电子显微镜图像(A-B),示出了聚合物沉淀物的截面结构。这些沉淀物的图像表明没有可见的未附着的颗粒。这表明未附着的颗粒仅存在于水相中,并且所述多个颗粒被镶嵌在聚合物沉淀物的表面上而不是内部。
示例
以下示例并不意味以任何方式限制权利要求的范围。以下示例被提出以向本领域普通技术人员提供关于如何制备及使用所描述的发明的完整公开及描述,并且不旨在限制本发明的范围,也不旨在表示以下实验是全部或仅进行的实验。除非另有说明,否则份数是重量份,分子量是重均分子量,温度是摄氏度,压力是大气压或接近大气压。
示例1-聚碳酸酯/聚甲基倍半硅氧烷(PC/PMSQ)微球的制备:
聚合物的沉淀特性可用于制备聚甲基倍半硅氧烷两亲杰纳斯颗粒。将0.2g的PMSQ颗粒添加到四氢呋喃(2mL)中的10wt%的PC溶液中。在超声波场(振幅为20%,超声波振动细胞(Sonics Vibra-cell)超声波液体处理器,型号VCX 750,纽敦(Newtown),康乃狄克州,美国)下,以1mL/min的速度向混合物中缓慢加入5mL DDAB水溶液(反溶剂)(60mg/L),导致微米级PC的沉淀物在其表面吸附有PMSQ颗粒,从而形成PC/PMSQ微球。随后,将微球进行过滤并使用去离子水进行润洗,以去除多余的且微弱附着的PMSQ颗粒。然后,将所述PC/PMSQ微球在真空下于350℃干燥3小时。
示例2-PMSQ-NH2两亲杰纳斯颗粒的制备:
为了将APTES分子(胺边缘基团)硅烷化到PMSQ颗粒的暴露的半球部分,将10mmol的甲醇溶液中的2mmol的APTES加至干燥的PC/PMSQ微球,并在常温下以500rpm搅拌48小时,而在暴露的半球部分上形成胺基。硅烷化后,将反应混合物在250℃下以9000rpm离心10分钟。随后,将PC/PMSQ-NH2微球使用甲醇冲洗5次,以去除过量的未反应APTES。然后,通过使用THF溶解PC核,将PMSQ-NH2颗粒与PC沉淀物分离,然后进行五次连续的离心以及THF润洗循环。进行两次离心以及乙醇润洗循环,以从PMSQ-NH2颗粒去除PC、物理地附着的APTES以及DDAB。然后将得到的颗粒在真空下于350℃干燥3小时。
示例3-PMSQ-COOH两亲杰纳斯颗粒的制备:
通过胺基与琥珀酸酐的酰胺化反应,对PMSQ-NH2杰纳斯颗粒的暴露的半球部分的进行改性以引入羧基,以形成N-[3-(三乙氧基硅基)丙基]琥珀酰胺酸配体,其包含羧基边缘基团(PMSQ-COOH)。将0.1g的PMSQ-NH2颗粒与10mL乙腈与0.02mL的EDIPA一起加入2mL的70mg琥珀酸酐在10mL的乙腈中的储备溶液中。然后将溶液在常温下搅拌3小时。通过三次连续的离心以及使用水及乙腈润洗的循环来收集PMSQ-COOH颗粒。然后将PMSQ-COOH颗粒在真空下于350℃干燥3小时。
示例4-PMSQ-COOH两亲杰纳斯颗粒的荧光标记:
分别在10mL的0.05M MES(pH 6.1)缓冲液中分别制备100mg的EDC以及1mg的6-氨基荧光素(6-aminofluorescein)染料的储备液。在EDC的存在下,连接到PMSQ颗粒上的配体的羧基边缘基团与染料的胺边缘基团反应形成酰胺键。将0.05g的PMSQ-COOH两亲性杰纳斯颗粒添加到1mL的一混合物中,所述混合物包括300μL的EDC、100μL的染料溶液及600μL的MES缓冲液。然后将溶液在常温下通过振荡进行混合1小时。随后,将混合物离心,并使用MES缓冲液进行润洗以除去多余的反应物。EDC用作一交联剂,主要通过与羧基反应并产生胺反应性的O-酰基硫脲,将PMSQ-COOH两亲杰纳斯粒子化学连接到6-氨基荧光素染料上。此中间产物与染料的氨基反应生成酰胺键,释放出荧光标记的PMSQ颗粒以及尿素作为副产物。
示例5-胺官能化二氧化硅纳米颗粒的合成:
通过机械混合将1g的二氧化硅的纳米颗粒分散在40mL的甲醇中。将2mM的APTES缓慢地添加到溶液中。反应在常温下进行45分钟。通过四次离心循环收集胺官能化的二氧化硅颗粒,然后使用乙醇润洗。然后将纳米颗粒在真空下于350℃干燥3小时。
示例6-胺官能化的二氧化硅的纳米颗粒与PMSQ-COOH两亲杰纳斯颗粒的偶联:
胺官能化的二氧化硅的纳米颗粒与PMSQ-COOH颗粒的偶联通过EDC/羟基琥珀酰亚胺酰胺化(根据示例4中所述的方法)进行。二氧化硅的纳米颗粒的胺基与PMSQ-COOH颗粒的羧基反应,从而可以通过高分辨率扫描式电子显微镜直接观察偶联的二氧化硅颗粒,从而表征羧基的位置。将0.005g的PMSQ-COOH颗粒以及0.002g的胺官能化的二氧化硅的纳米颗粒添加到1mL的300μL的EDC以及700μL的MES缓冲液的混合物中。然后在常温下将溶液搅拌3小时。通过八次离心分离循环,将PMSQ-二氧化硅杰纳斯颗粒与反应试剂分离,然后使用水及乙腈确实地搅拌,以确保仅共价键合的颗粒保留在PMSQ-COOH颗粒的表面。然后将颗粒在真空下于350℃干燥3小时。
示例7-确认杰纳斯特征:
为了证实聚甲基倍半硅氧烷球的表面上存在不同的官能基,使用了傅里叶转换红外光谱(Fourier-Transform Infrared spectroscopy,FTIR)分析。图4是与聚甲基倍半硅氧烷杰纳斯纳米颗粒相比,裸露的聚甲基硅倍半硅氧烷的傅里叶转换红外光谱分析。图4A显示了裸露的聚甲基倍半硅氧烷球的FT-IR光谱。酰胺化后,在1900及1300cm-1处的吸收峰代表裸露的聚甲基倍半硅氧烷及(3-氨丙基)三乙氧基硅烷(APTES)。图4B显示了在1425、1575-1585cm-1处氨基的不对称变形振动,表明氨基已成功固定在聚甲基倍半硅氧烷颗粒的表面上。此外,在2865-2875cm-1及2930-3100cm-1范围内的峰值分别归因于CH2及CH拉伸振动。通过羧酸盐的峰的出现,以及在1725及1461cm-1处的峰,均对应于-COOH的振动峰,在FT-IR光谱中可以看到使用琥珀酸酐对聚甲基倍半硅氧烷(PMSQ)-NH2颗粒进行了进一步改性,以引入羧基功能。这表明在聚甲基倍半硅氧烷球的表面发生了顺序的改性。
示例8-杰纳斯颗粒的特殊界面活性:
将PMSQ-COOH两亲杰纳斯颗粒添加到水-氯仿的两相系统中。图5描绘了裸露的PMSQ(图5A)以及PMSQ-COOH两亲杰纳斯颗粒(图5B)的快照,这些颗粒已添加到水-氯仿的两相系统中。在图5B中,在水-氯仿界面处观察到的雾度是由颗粒的自组装引起的,表明它们的两亲性。相比之下,裸露的PMSQ颗粒不会在界面处自组装,因此不会显示雾度(图5A)。为了进一步查明PMSQ-COOH颗粒的两亲性,将代表亲水性表面的玻璃尖端(图5C、图5D)以及代表疏水性表面的聚丙烯尖端(图5E、图5F)分别浸入两相系统中,其含有裸露的PMSQ颗粒或PMSQ-COOH两亲杰纳斯颗粒。在玻璃及聚丙烯的情况下,颗粒皆吸附到尖端的表面(图5D、图5F)。PMSQ-COOH两亲颗粒吸附到极性的玻璃尖端是由于其亲水性半球部分(COOH基团)与玻璃表面(图5D)的相互作用引起的;反之亦然,在聚丙烯尖端,如图5F所示,颗粒被其疏水性半球部分(未处理/原始PMSQ)吸附。在将裸露的PMSQ颗粒添加到水-氯仿的两相系统中的任何一种情况下,都不会发生吸附,如图5C、图5E所示。
示例9-使用荧光染料标记的聚甲基倍半硅氧烷杰纳斯颗粒的分析:
图6A描绘了特征性PMSQ-二氧化硅颗粒的高分辨率扫描式电子显微镜的显微照片。在一给定的PMSQ-COOH颗粒的半球部分上选择性地观察到二氧化硅的纳米颗粒的修饰,这清楚地证实了所制备的颗粒的杰纳斯特性;也就是说,被镶嵌在PC沉淀物上的同时以APTES硅烷化的期间,它们的暴露的半球部分被选择性地官能化。这些发现最终证实了成功制备出具有亲水侧(包含COOH)及原始疏水侧的两亲杰纳斯PMSQ颗粒。图6B、图6C中显示了特征性PMSQ-COOH颗粒的共聚焦显微镜的图像,这些颗粒通过其羧基进行了荧光标记。6-氨基荧光素与PMSQ-COOH颗粒的羧基进行反应,产生选择性荧光标记。图6C描绘了仅显示荧光素信号的图像,这些图像进一步证实了PMSQ-COOH颗粒的杰纳斯特性,由于与官能化的半球部分不同,被镶嵌的半球部分不显示任何荧光信号。为了通过共聚焦显微镜捕获单个两亲杰纳斯颗粒,所述颗粒必须位于焦平面中正确的方向。图6B、图6C描绘了位于焦平面中的多个特征性PMSQ颗粒,因此可以清楚地观察到它们的对称制动。这些颗粒是以截面的角度被捕获的。
尽管已经相对有限的实施方式描述了本发明,但是应当理解,可以做出本发明的许多变型、修改及其他应用。因此,如所附权利要求书所述的要求保护的发明不限于本文所述的实施方式。
Claims (7)
1.一种制备大规模的两亲颗粒的方法,其特征在于,所述方法包含:
将多个纳米颗粒添加到一聚碳酸酯基的溶液中;
将一表面活性剂添加到所述溶液中,并同时进行超声波处理,以产生一聚合物沉淀,所述聚合物沉淀配置为用以产生至少一微球,所述微球上镶嵌有所述多个纳米颗粒,所述多个纳米颗粒被镶嵌成使得所述多个纳米颗粒中的一个半球部分被暴露以便进一步改性;
使所述多个被镶嵌的纳米颗粒的所述暴露的半球部分进行一进一步的多个两亲颗粒的相关改性;以及
将所述至少一微球溶解在一聚碳酸酯基的溶液中,以便从所述至少一微球释放出所述多个被镶嵌的纳米颗粒。
2.根据权利要求1所述的方法,其特征在于:所述方法还包含:使用离心过滤所述至少一微球;以及在将所述多个被镶嵌的纳米颗粒的所述暴露的半球部分进行一进一步的多个两亲颗粒的相关改性之前,使用去离子水润洗所述至少一微球,并在真空下将所述至少一微球进行干燥。
3.根据权利要求1所述的方法,其特征在于:所述聚碳酸酯基的溶液包括四氢呋喃。
4.根据权利要求1所述的方法,其特征在于:所述多个纳米颗粒是多个聚甲基倍半硅氧烷的纳米颗粒。
5.根据权利要求1所述的方法,其特征在于:所述多个纳米颗粒是多个二氧化硅的纳米颗粒。
6.根据权利要求1所述的方法,其特征在于:所述表面活性剂是在水中的双癸基二甲基溴化铵。
7.根据权利要求1所述的方法,其特征在于:所述进一步的多个两亲颗粒的相关改性选自于由以下组成的群组:在所述多个暴露的半球部分上形成多个胺基;在所述多个暴露的半球部分上形成多个羧基;以及将多个胺官能化的二氧化硅的纳米颗粒与多个聚甲基倍半硅氧烷-羧基两亲的杰纳斯颗粒偶联。
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CN113462425B (zh) * | 2021-06-16 | 2022-09-23 | 中国石油大学(华东) | 一种高效Janus型两亲硅基破乳剂及其制备方法 |
CN115261003B (zh) * | 2022-08-16 | 2023-06-06 | 长江大学 | 一种两亲Janus片状材料及其制备方法和应用 |
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US20080234394A1 (en) * | 2007-03-23 | 2008-09-25 | Liang Hong | System for forming janus particles |
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US10836918B2 (en) * | 2014-12-24 | 2020-11-17 | National Research Council Of Canada | Microparticles and apparatus for smart ink production |
US11440927B2 (en) * | 2017-11-28 | 2022-09-13 | International Business Machines Corporation | Hydroxyapatite janus particles |
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2018
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- 2018-11-29 EP EP18883815.5A patent/EP3717547A4/en active Pending
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DE19742759A1 (de) * | 1997-09-27 | 1999-04-01 | Gerd Dr Rossmy | Verfahren zur Herstellung amphiphiler anisotroper Teilchen |
US20080234394A1 (en) * | 2007-03-23 | 2008-09-25 | Liang Hong | System for forming janus particles |
CN101422621A (zh) * | 2007-10-31 | 2009-05-06 | 韩国科学技术研究院 | 通过早期引入不规则结构,生产生物成像的纳米颗粒及其制造方法 |
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US20200291236A1 (en) | 2020-09-17 |
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