CN111961201B - 一锅法原位生成含氮阳离子的聚电解质及其应用 - Google Patents
一锅法原位生成含氮阳离子的聚电解质及其应用 Download PDFInfo
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- CN111961201B CN111961201B CN202010336658.5A CN202010336658A CN111961201B CN 111961201 B CN111961201 B CN 111961201B CN 202010336658 A CN202010336658 A CN 202010336658A CN 111961201 B CN111961201 B CN 111961201B
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Abstract
本发明提供了一种含氮阳离子的聚电解质的合成方法及其在荧光二维图案生成与抗菌方面的应用。该合成方法以简单易得的二炔、烯丙胺和极廉价的酸或盐为原料,在空气氛围中通过一锅法高效制备聚电解质,产率高达99%。与传统的聚电解质合成方法相比,该方法无需对聚合物进行后修饰,也不需要昂贵且种类有限的离子型单体。该方法不仅提供了新的聚电解质合成策略,还丰富了聚电解质的种类。
Description
技术领域
本发明涉及生物化学领域,特别是涉及一种新型聚电解质的简易合成方法、所得的含氮阳离子的聚电解质及其应用,如荧光二位图案,检测诸如微生物等目标分析物的应用(例如,快速对细菌染色)以及制备荧光探针、试剂盒,杀灭细菌,作为伤口敷料等的应用。
背景技术
聚电解质在生物系统及生产生活中都扮演着重要角色,因此聚电解质的合成及性质探索对于仿生和开发新材料有着重要意义。传统的聚电解质合成方法主要通过对非离子型的聚合物进行后修饰,然而后修饰的产率难以达到100%,造成的聚合物链段缺陷难以除去。某些聚电解质通过偶联反应(如Heck和Sonogashira)得到,但是这些方法需要的离子型单体种类有限且昂贵。
总之,发展一种简易高效地合成聚电解质的方法具有重要转化价值。
发明内容
本发明提供一种新型聚电解质的合成方法,成功制备出一系列多功能含氮阳离子的聚电解质。该聚合路线以简单易得的二炔、烯丙胺和极廉价的酸或盐为原料,在空气氛围中通过一锅法高效制备聚电解质,产率高达99%。与传统的聚电解质合成方法相比,该方法无需对聚合物进行后修饰,也不需要昂贵且种类有限的离子型单体。该方法不仅提供了新的聚电解质合成策略,还丰富了聚电解质的种类。
在聚合过程中原位生成的氮阳离子稠环有强烈的吸电子性质,因此通过引入不同给电子性质的单体,可以容易地调控所得聚电解质的发光波长。由于所得聚合物具有固态发光性质、优异的加工性、折光指数高且可调控,他们是制备二维荧光光刻图案的优秀材料,并在先进光电子器件中具有重要潜在应用。
此外,所得的含氮阳离子聚电解质在白光照射下具有很强的单线态氧产生能力,可用于光动力杀菌。该系列聚电解质可用于细菌成像和高效杀灭高致病性的耐甲氧西林金黄色葡萄球菌(MRSA)。
附图说明
图1所示为含氮阳离子聚电解质的合成示意图。
图2示出:(A)1a在D2O中的;(B)2a;(C)模型化合物2;(D)P1a/2a/3a在CD2Cl2中的1HNMR谱图。(E)1a在D2O中的;(F)2a;(G)模型化合物2;(H)P1a/2a/3a在CD2Cl2中的13C NMR谱图。
图3示出:(A)在手持式紫外线灯的365nm紫外线照射下拍摄的P1a/2d/3a在正己烷占比(fH)不同的二氯甲烷/正己烷混合溶液中的照片;(B)固态下聚合物P1/2/3的发光照片;(C)P1a/2d/3a在正己烷占比(fH)不同的二氯甲烷/正己烷混合溶液中的发射光谱;激发波长:380nm;(D)相对发射强度(I/I0)与P1a/2d/3a的二氯甲烷/正己烷不同组成的混合溶液的关系图;溶液浓度:10μM;(E)P1/2/3薄膜的发射光谱;激发波长:对于P1a/2e/3a,450nm;对于其他聚合物,380nm;(F-I)在紫外线照射下的P1a/2a/3a(F),P1a/2d/3a(G),P1a/2e/3a(H)和P1a/2d/3a(I)薄膜的二维荧光光刻图案;激发波长:330~385nm。
图4示出:(A-C)在(A)P1a/2e/3a、(B)P1a/2d/3a和(C)P1a/2c/3a存在的情况下ABDA的紫外-可见光吸收;(D)在P1/2/3和二碘曙红影响下ABDA的分解速率;A0和A分别是在聚苯乙烯存在的情况下在378nm的紫外照射前后的吸收。
图5示出:(A)P1a/2e/3a水性分散下的流体力学直径分布及TEM图;(B)在有无光照条件下P1a/2e/3a对于MRSA的定量抗菌检测;(C)P1a/2e/3a处理过的MRSA的荧光图像,DIC图像以及其合并图像;(D)TEM观测的在不同处理条件下的MRSA的形态改变;(E)SEM观测的在不同处理条件下的MRSA的形态改变。
图6示出:(A)构建MRSA感染的小鼠烧伤模型和治疗概况的原理图;(B)治疗过程中在黑暗或光照条件下不同处理时感染MRSA的小鼠烧伤部位的典型照片;(C)第14天经过不同处理后的相对结痂大小分析;(D)受感染组织中的MRSA数量在第14天被量化;(E)不同组通过苏木精和曙红(H&E)染色的受MRSA感染的烧伤组织的组织分析;作为比较,商业万古霉素也同时被评估。
图7所示为单体2a-h的合成路线。
图8所示为模型化合物2的合成路线。
图9示出:(A)1a;(B)2a;(C)模型化合物2;(D)P1a/2a/3a的IR谱图。
图10示出:(A)P1a/2a/3a;(B)P1a/2a/3b;(C)P1a/2a/3c;(D)P1b/2a/3a;(E)P1b/2e/3a的IR谱图。
图11示出:(A)P1a/2b/3a;(B)P1a/2c/3a;(C)P1a/2d/3a;(D)P1b/2e/3a;(E)P1a/2f/3a的IR谱图。
图12示出氮气条件下加热速率10℃/min时记录的TGA热谱图。
图13示出氮气条件下加热速率10℃/min的第二个加热循环下记录的DSC热谱图。
图14示出P1/2/3在DCM溶液中的吸收光谱。浓度:10μM。
图15示出P1/2/3在DCM溶液中的发射光谱。溶液浓度:10μM。激发波长:对于P1a/2e/3a,450nm,对于其他聚合物,380nm。
图16示出P1/2/3薄膜的波长相关折射率。
图17示出P1a/2e/3a在正己烷占比(fH)不同的二氯甲烷/正己烷混合溶液中的发射光谱;插图:在手持式紫外线灯的365nm紫外线照射下拍摄的P1a/2e/3a在正己烷占比(fH)不同的二氯甲烷/正己烷混合溶液中的照片。
图18示出在白光照射不同次数水溶液中有无P1a/2c/3a、P1a/2d/3a和P1a/2e/3a时H2DCF-DA在525nm处荧光强度的改变;浓度:10×10-6M(聚合物)和3×10-5M(H2DCF-DA)。
图19示出在有二碘曙红的情况下ABDA的紫外-可见光谱。
图20示出(A)和(B):有无光照条件下,P1a/2e/3a对金黄色葡萄球菌和大肠杆菌的定量抗菌检测。
图21示出第14日进行各种处理后受感染烧伤组织对应的细菌菌群的照片。
图22示出在CD2Cl2中模型化合物2的1H NMR谱图。
图23示出在CD2Cl2中模型化合物2的13C NMR谱图。
图24示出在CD2Cl2中P1a/2a/3a的1H NMR谱图。
图25示出在CD2Cl2中P1a/2a/3a的13C NMR谱图。
图26示出在CD2Cl2中P1a/2a/3a的19F NMR谱图。
图27示出在CD2Cl2中P1a/2b/3a的1H NMR谱图。
图28示出在CD2Cl2中P1a/2b/3a的13C NMR谱图。
图29示出在CD2Cl2中P1a/2c/3a的1H NMR谱图。
图30示出在CD2Cl2中P1a/2c/3a的13C NMR谱图。
图31示出在CD2Cl2中P1a/2d/3a的1H NMR谱图。
图32示出在CD2Cl2中P1a/2d/3a的13C NMR谱图。
图33示出在CD2Cl2中P1a/2e/3a的1H NMR谱图。
图34示出在CD2Cl2中P1a/2e/3a的13C NMR谱图。
图35示出在CD2Cl2中P1a/2f/3a的1H NMR谱图。
图36示出在CD2Cl2中P1b/2a/3a的1H NMR谱图。
图37示出在CD2Cl2中P1b/2a/3a的13C NMR谱图。
图38示出在CD2Cl2中P1b/2e/3a的1H NMR谱图。
图39示出在CD2Cl2中P1b/2e/3a的13C NMR谱图。
图40示出在CD2Cl2中P1a/2a/3b的1H NMR谱图。
图41示出在CD2Cl2中P1a/2a/3b的13C NMR谱图。
图42示出在CD2Cl2中P1a/2a/3b的19F NMR谱图。
图43示出在CD2Cl2中P1a/2a/3b的31P NMR谱图。
图44示出在CD2Cl2中P1a/2a/3c的1H NMR谱图。
图45示出在CD2Cl2中P1a/2a/3c的13C NMR谱图。
图46示出在CD2Cl2中P1a/2a/3c的19F NMR谱图。
具体实施方式
下面详细描述本发明的实施方案。下面描述的实施方案是示例性的,仅用于解释本发明,而不能理解为对本发明的限制。实施方案中未注明具体技术或条件的,按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者,均为可以通过市购获得的常规产品。
定义和一般术语
现在详细描述本发明的某些实施方案,其实例由随附的结构式和化学式说明。本发明意图涵盖所有的替代、修改和等同技术方案,它们均包括在如权利要求定义的本发明范围内。本领域技术人员应认识到,许多与本文所述类似或等同的方法和材料能够用于实践本发明。本发明绝不限于本文所述的方法和材料。在所结合的文献、专利和类似材料的一篇或多篇与本申请不同或相矛盾的情况下(包括但不限于所定义的术语、术语应用、所描述的技术,等等),以本申请为准。
应进一步认识到,本发明的某些特征,为清楚可见,在多个独立的实施方案中进行了描述,但也可以在单个实施例中以组合形式提供。反之,本发明的各种特征,为简洁起见,在单个实施方案中进行了描述,但也可以单独或以任意适合的子组合提供。
除非另外说明,本发明所使用的所有科技术语具有与本发明所属领域技术人员的通常理解相同的含义。本发明涉及的所有专利和公开出版物通过引用方式整体并入本发明。
除非另外说明,应当应用本文所使用的下列定义。出于本发明的目的,化学元素与元素周期表CAS版,和《化学和物理手册》,第75版,1994一致。此外,有机化学一般原理可参考“Organic Chemistry”,Thomas Sorrell,University Science Books,Sausalito:1999,和“March's Advanced OrganicChemistry”by Michael B.Smith and Jerry March,JohnWiley&Sons,NewYork:2007中的描述,其全部内容通过引用并入本文。
除非另有说明或者上下文中有明显的冲突,本文所使用的冠词“一”、“一个(种)”和“所述”旨在包括“至少一个”或“一个或多个”。因此,本文所使用的这些冠词是指一个或多于一个(即至少一个)宾语的冠词。例如,“一组分”指一个或多个组分,即可能有多于一个的组分被考虑在所述实施方案的实施方式中采用或使用。
术语“包含”为开放式表达,即包括本发明所指明的内容,但并不排除其他方面的内容。
另外,需要说明的是,除非以其他方式明确指出,在本发明中所采用的描述方式“各…独立地为”与“…各自独立地为”和“…独立地为”可以互换,均应做广义理解,其既可以是指在不同基团中,相同符号之间所表达的具体选项之间互相不影响,也可以表示在相同的基团中,相同符号之间所表达的具体选项之间互相不影响。
在本说明书的各部分,本发明公开化合物的取代基按照基团种类或范围公开。特别指出,本发明包括这些基团种类和范围的各个成员的每一个独立的次级组合。例如,术语“C1-18烷基”包括甲基、乙基、C3烷基、C4烷基、C5烷基和C6烷基。
本发明使用的术语“烃基”包括芳香族烃基和脂肪族烃基。脂肪族烃基包括“烷基”或“烷基基团”、烯基和炔基,它们可以是饱和或不饱和的直链或支链二价烃基基团。所述烃基可以任选地被一个或多个本发明描述的取代基所取代。在本发明的一个实施方案中,烷基基团含有1-18个碳原子。在另一实施方案中,烷基基团含有1-12个碳原子;在又一实施方案中,烷基基团含有1-6个碳原子;再一实施方案中,烷基基团含有1-4个碳原子;还在一实施方案中,烷基基团含有1-3个碳原子。
烷基基团的实例包含,但并不限于,C1-12烷基,如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、2-戊基、3-戊基、2-甲基-2-丁基、3-甲基-2-丁基、3-甲基-1-丁基、2-甲基-1-丁基、正己基、2-己基、3-己基、2-甲基-2-戊基、3-甲基-2-戊基、4-甲基-2-戊基、3-甲基-3-戊基、2-甲基-3-戊基、2,3-二甲基-2-丁基、3,3-二甲基-2-丁基、正庚基、正辛基、等等。
术语“烯基”表示碳原子的直链或支链一价烃基,其中至少有一个不饱和位点,即有一个碳-碳sp2双键,其中,所述烯基基团任选地被一个或多个本发明所描述的取代基所取代,其包括“cis”和“tans”的定位,或者"E"和"Z"的定位。在一实施方案中,烯基基团包含2-8个碳原子;在另一实施方案中,烯基基团包含2-6个碳原子;在又一实施方案中,烯基基团包含2-4个碳原子。烯基基团的实例包括,但并不限于,乙烯基、烯丙基等等。
术语“炔基”表示碳原子的直链或支链一价烃基,其中至少有一个不饱和位点,即有一个碳-碳sp三键,其中,所述炔基基团任选地被一个或多个本发明所描述的取代基所取代。在一实施方案中,炔基基团包含2-8个碳原子;在另一实施方案中,炔基基团包含2-6个碳原子;在又一实施方案中,炔基基团包含2-4个碳原子。炔基基团的实例包括,但并不限于,乙炔基、炔丙基、1-丙炔基等等。
术语“羧基”,无论是单独使用还是和其他术语连用,如“羧烷基”,表示-CO2H;术语“羰基”,无论是单独使用还是和其他术语连用,如“氨基羰基”或“酰氧基”,表示-(C=O)-。
术语“卤素”和“卤代”是指氟(F)、氯(Cl)、溴(Br)或碘(I)。
术语“芳香族基团”包括从芳香环中去掉两个氢原子从而与其他基团直接连接的基团。优选地,芳香族基团在成环原子中具有至少一个杂原子,例如N、O或S。
术语“芳香族环烃基”包括单环、双环和三环的芳基,其中,至少一个环体系是芳香族的,其中每一个环体系包含6-18个原子组成的环。芳基基团通常,但不必须地通过芳基基团的芳香性环与母体分子连接。术语“芳基”可以和术语“芳香环”或“芳环”交换使用。芳基基团的实例可以包括苯基、联苯基、萘基和蒽。所述芳基基团任选地被一个或多个本文所描述的取代基所取代。
在本发明中,取代基可以选自卤原子、羟基、醛基、羧基、氨基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的C2-C18烯基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的C2-C18炔基、任选地被一个或多个C6-C18芳香族环烃基或成环碳原子5-18的芳香族杂环基取代的的C1-C18烷基或烷氧基、成环碳原子6-18的芳香族环烃基、成环碳原子5-18的芳香族杂环基、巯基、氰基和硝基中的至少一者。
芳香族环烃基和芳香族杂环基的例子包括(例如)苯基、萘基、苯基、萘基、蒽基、菲基、并四苯基、芘基、苯并[c]菲基、苯并菲基、芴基、苯并芴基、二苯并芴基、联苯基、三联苯基、四联苯基、荧蒽基、吡咯基、吡嗪基、吡啶基、嘧啶基、三嗪基、吲哚基、异吲哚基、咪唑基、呋喃基、苯并呋喃基、异苯并呋喃基、二苯并呋喃基、二苯并噻吩基、喹啉基、异喹啉基、喹喔啉基、咔唑基、菲啶基、吖啶基、菲咯啉基、吩嗪基、吩噻嗪基、吩噁嗪基、噁唑基、噁二唑基、呋咱基、噻吩基、苯并噻吩基、二氢吖啶基、氮杂咔唑基、喹唑啉基等。
取代基的例子包括:
本发明提供一种新型聚电解质合成路线,成功制备出一系列多功能含氮阳离子的聚电解质。该聚合路线以简单易得的二炔、烯丙胺和极廉价的酸或盐为原料,在空气氛围中通过一锅法高效制备聚电解质,产率高达99%。与传统的聚电解质合成方法相比,该方法无需对聚合物进行后修饰,也不需要昂贵且种类有限的离子型单体。该方法不仅提供了新的聚电解质合成策略,还丰富了聚电解质的种类。
在聚合过程中原位生成的氮阳离子稠环有强烈的吸电子性质,因此通过引入不同给电子性质的单体,可以容易地调控所得聚电解质的发光波长。由于所得聚合物具有固态发光性质、优异的加工性、折光指数高且可调控,他们是制备二维荧光光刻图案的优秀材料,并在先进光电子器件中具有重要潜在应用。
此外,所得的含氮阳离子聚电解质在白光照射下具有很强的单线态氧产生能力,可用于光动力杀菌。该系列聚电解质可用于细菌成像和高效杀灭高致病性的耐甲氧西林金黄色葡萄球菌(MRSA)。
实施例
提供下述的例子来示意性描述以帮助本领域技术人员理解本发明。然而,本发明的以下例子不应被构建为不适当地限制本发明。在不脱离本发明发现的范围的情况下,本领域普通技术人员可以对所讨论的例子进行变化和修改。
通用方法
所得的聚合物的重均分子量(Mw)和数均分子量(Mn)以及多分散性指数(Mw/Mn)是通过Waters 1515凝胶渗透色谱系统估计而得的。DMF/LiBr的溶液(0.05M的LiBr)以1ml/min的流速用作洗脱剂。分子量范围为103-107g/mol的一组单分散聚苯乙烯用作分子量校准的标准。有关样品制备和实验设置的详细信息可以在我们之前的论文中找到。FT-IR光谱和高分辨率质谱(HRMS)分别记录在Bruker Vertex 70FT-IR光谱仪(KBr盘)和GCTPremierCAB 048质谱仪上。1H,13C,19F,和31P NMR谱图是用CD2Cl2,CDCl3或D2O做溶剂通过Bruker ARX 400NMR波谱仪获得。用CDCl3的δ7.26ppm(1H NMR)和δ77.16ppm(13C NMR),CD2Cl2的δ5.32ppm(1H NMR)和δ53.84ppm(13C NMR)和D2O的δ4.79ppm(1H NMR)作为内部参照来校准化学位移。TGA和DSC测量分别在氮气下以10℃/min的加热速率在TATGA Q5000和TAInstruments DSC Q1000进行。紫外-可见光谱和PL光谱分别在Milton RaySpectronic3000阵列分光光度计和PerkinElmer LS 55分光光度计测量。RI值由Woollam椭偏仪上使用Alpha-SE模型确定,波长可调范围为380至900nm。荧光照片图案在紫外光源(330-380nm)下由荧光光学显微镜(Nikon Eclipse的80i)拍摄而得。将聚合物的1,2-二氯乙烷溶液(~10mgmL-1)以700rpm的速度旋涂在硅片上1min,然后在真空烘箱中室温下干燥2h,制成用于RI测量的薄膜。通过在室温下在空气中通过光掩模对聚合物薄膜进行紫外线照射20min来生成光图案。具有网格图案的光掩模在正方形区域涂有铜,而网格线是透明的玻璃板。通过激光打印机将有“二维码”图案的光掩模印刷在不透明的纸上。用Oriel Mercury弧光灯的紫外线在25cm的距离下进行光照过程。入射光强度为~18.5mW cm-2,汞弧光灯的施加功率为180W。
ROS生成检测:H2DCF-DA被用作ROS检测剂。在实验中,将10μLH2DCF-DA储备溶液(1.0mM)加入到2mL聚合物悬浮液(10μM)中,并将白光(4.2mWcm-2)用作照射源。在不同的照射次数下记录H2DCF-DA在525nm处的发射。
1O2生成检测:ABDA被用作1O2检测剂。在实验中,将13μLABDA储备溶液(7.5mM)加入到2mL聚合物或二碘曙红的悬浮液(10μM)中,并将白光(4.2mWcm-2)用作照射源。在不同照射次数下记录ABDA在378nm处的吸收从而获得光敏过程的衰减率。
细菌抑制分析:按照标准程序测定P1a/2e/3a对金黄色葡萄球菌(ATCC6538),MRSA(ATCC 43300)和大肠杆菌(ATCC 25922)的MIC值。将初始装载量为5×105CFU/mL的细菌悬浮液(100μL)在96孔圆底微孔板上加入等体积(100μL)的在MH液体培养基中的聚合物分散液。在白光下照射或在黑暗中保持30min后,将混合物在37℃下进一步培养24h。使用酶标仪(Infinite M200,Tecan),通过600nm处的光密度值(OD600)记录细菌是否经过处理的浊度。将完全抑制金黄色葡萄球菌生长的最低P1a/2e/3a浓度定义为样品的MIC值。细菌生存力(%)=(OD600样品-24小时-OD600样品-0h)/(OD600对照-24小时-OD600对照-0h)×100%。
透射电子显微镜分析:在JEM-2100透射电子显微镜(JEOL,日本)下观察用P1a/2e/3a处理之前和之后的MRSA的形态。将细菌悬浮液(0.5mL)与0.5mL P1a/2e/3a胶束一起培养,其最终浓度为30μg/mL。对于光治疗组,将MRSA分散液暴露于白光(~4.2mW cm-2)下30min。之后,将混合物离心并用PBS洗涤,然后在室温下将一滴分散液置于经聚醋酸甲基乙烯酯/碳涂覆的200目铜栅上,最后通过TEM分析观察。
用P1a/2e/3a粘附细菌的荧光成像:将对数相细菌(5mL)以6000rpm离心5min,然后用磷酸盐缓冲溶液(PBS,0.01mol/L,pH 7.4)洗涤3次。倒掉上清液,并将剩余的细菌沉淀物重新悬浮于1.5mL PBS中,并将其稀释至OD600为0.1。用200μL P1a/2e/3a胶束(160μg/mL)处理细菌悬浮液(200μL)。在黑暗中培养5min,15min,30min和60min后,将分散液用冷PBS洗涤两次并离心。最后,将混合的悬浮液添加到带有封盖的各种载玻片上进行固定,并通过激光扫描共聚焦显微镜(Carl Zeiss LSM 510META)进行成像。
体内感染MRSA的小鼠烧伤模型:所有动物实验程序均已获得华南师范大学动物保护和使用委员会的批准。雌性Balb/c小鼠购自南方医科大学实验动物中心。将Balb/c小鼠(6-8周)的背毛剃毛,并形成直径约6mm的全层烧伤(n=5)。将MRSA悬浮液(2.5x 108CFU)接种到每个烧伤部位。在感染MRSA后12小时,隔天局部施用50μLPBS,P1a/2e/3a(2000μg/mL)和万古霉素(46.8μg/mL),共3次(图5A)。用游标卡尺测量伤口大小并拍照以追踪伤口闭合的进程。在第14天,将所有伤口切除,分离并均质化以进行进一步评估。通过琼脂平板稀释法评价每只小鼠的细菌负荷。此外,伤口组织也用10%福尔马林固定,并包埋在石蜡中。将4μm的垂直切片固定在载玻片上,并进行苏木精和曙红染色,并在Mshot MF 41显微镜(Micro-shot技术,中国广州)下观察载玻片。所有图像均通过Micro-shot数字成像系统获得。
合成及表征
模型化合物合成
向25mL的Schlenk管中加入丙烯胺(0.2mmol),二苯乙炔(0.4mmol),乙酸铜(1mmol),[Cp*RhCl2]2(5mol%),四氟硼酸(48%的水溶液,0.3mmol)和1mL DCM/MeOH(1:1)。将所得溶液在130℃下搅拌6h,用无水MgSO4干燥,过滤,并将滤液真空浓缩。通过使用柱色谱法(DCM:MeOH=1:1)提纯获得产率80%的模型化合物2(黄色固体)。1H NMR(400MHz,CD2Cl2)δ8.83(d,J=6.9Hz,1H),8.36(d,J=7.5Hz,1H),8.05(d,J=8.7Hz,1H),7.90(t,J=7.2Hz,1H),7.77(t,J=7.7Hz,1H),7.72–7.01(m,17H);13C NMR(100MHz,CD2Cl2))δ,143.90,142.99,141.43,139.97,138.65,137.92,136.22,134.37,134.16,133.99,131.37,131.28,130.87,130.67,130.61,130.44,130.38,130.30,130.18,129.12,128.99,128.86,128.83,127.75,125.21,123.25;IR(净):3128,3057,1627,1602,1599,1575,1490,1442,1411,1325,1280,1174和1074(νB-F)cm-1。
聚合物合成
在所有聚合反应中均采用标准Schlenk技术,下面以P1a/2a/3a(表1,条目3)的合成步骤为例。向25mL Schlenk管中加入丙烯胺1a(0.1mmol),内二炔2a(0.1mmol),乙酸铜(0.5mmol),[Cp*RhCl2]2(5mol%),四氟硼酸3a(48%的水溶液,0.15mmol)和0.50mL DCM/MeOH(1:1)。将所得溶液在130℃下搅拌24h。真空下溶剂蒸发后,将5ml DCM加入至粗产物,然后过滤。将滤液逐滴滴加到50ml乙醚中,过滤后最终收集沉淀物,用甲醇洗涤并在室温下真空干燥至恒重。结构表征的结果如下:
P1a/2a/3a的表征数据:黄色粉末;93%(表1,条目7)。Mn:20400;Mw:28700;Mw/Mn:1.41(GPC,聚苯乙烯校正)。IR(KBr),ν(cm-1):3136,3047,2937,1606,1510,1442,1408,1245,1174和1083(νB-F)cm-1。1H NMR(400MHz,CD2Cl2),δ(ppm):8.84,8.75,8.66,8.34-6.87(芳香环质子),4.11(CH质子),3.95(CH质子),1.81-1.45(CH质子)。13C NMR(100MHz,CDCl3),δ(ppm):160.89,159.48,144.05,142.97,142.12,141.25,140.35,140.14,139.33,138.81,135.79,135.55,134.53,133.81,133.32,132.81,131.78,131.68,131.36,130.60,130.46,130.32,130.03,128.98,128.76,128.37,127.67,125.52,123.21,121.68,119.08,116.54,116.14,114.97,68.64,29.50,26.19。19F NMR(376MHz,CD2Cl2)δ-148.69,-153.84。
P1a/2b/3a的表征数据:黄色粉末;60%(表1,条目2)。Mn:11900;Mw:14900;Mw/Mn:1.25(GPC,聚苯乙烯校正)。IR(KBr),ν(cm-1):1602,1512,1444,1406,1249,1217,1124和1083(νB-F)cm-1。1H NMR(400MHz,CD2Cl2),δ(ppm):8.84,8.77,8.70,8.34-6.95(芳香环质子),4.54-4.30(CH质子)。13C NMR(100MHz,CDCl3),δ(ppm):160.44,144.17,143.01,140.41,136.95,135.71,133.95,133.45,133.07,131.83,131.37,130.67,130.10,128.80,127.73,125.49,123.24,121.98,116.80,116.36,114.97,109.74,67.15,36.63,31.45。
P1a/2c/3a的表征数据:黄色粉末;99%(表2,条目3)。Mn:17900:Mw:24000;Mw/Mn:1.34(GPC,聚苯乙烯校正)。IR(KBr),ν(cm-1):2920,2877,1606,1510,1450,1247,1122和1083(νB-F)cm-1。1H NMR(400MHz,CD2Cl2),δ(ppm):8.84,8.75,8.68,8.33-6.88(芳香环质子),4.24-3.64(CH质子),1.85-0.87(CH质子)。13C NMR(100MHz,CDCl3),δ(ppm):160.48,145.08,142.93,142.15,140.17,139.12,136.98,135.60,133.33,132.72,132.40,131.79,131.64,131.39,131.13,130.02,129.07,128.77,123.21,121.96,119.32,116.52,116.20,115.44,115.02,114.80,70.86,69.75,68.20,31.95,23.02,14.26。
P1a/2d/3a的表征数据:橘黄色粉末;71%(表2,条目4)。Mn:14000:Mw:20000;Mw/Mn:1.43(GPC,聚苯乙烯校正)。IR(KBr),ν(cm-1):3057,3022,1625,1597,1490,1440,1415,1122和1083(νB-F)cm-1。1HNMR(400MHz,CD2Cl2),δ(ppm):8.75,8.28-7.14(芳香环质子)。13CNMR(100MHz,CDCl3),δ(ppm)):143.94,143.27,143.05,134.04,133.26,132.77,131.58,130.71,130.25,129.84,128.81,128.47,128.14,127.44,123.78,123.26,122.97。
P1a/2e/3a的表征数据:红色粉末;74%(表2,条目5)。Mn:18900;Mw:22700;Mw/Mn:1.20(GPC,聚苯乙烯校正)。IR(KBr),ν(cm-1):3053,1589,1508,1494,1442,1409,1323,1271,1122,1083(νB-F)和1029cm-1。1H NMR(400MHz,CD2Cl2),δ(ppm):9.08,8.84,8.65,8.39-6.79(芳香环质子)。13C NMR(100MHz,CDCl3),δ(ppm):147.71,132.95,131.75,130.70,130.36,130.11,129.98,128.77,126.04,123.65,53.84。
P1a/2f/3a的表征数据:橘色粉末;78%(表2,条目6)。Mn:5700;Mw:8100;Mw/Mn:1.43(GPC,聚苯乙烯校正)。IR(KBr),ν(cm-1):1637,1610,1444,1415,1126,1083(νB-F)和1031cm-1。1H NMR(400MHz,CD2Cl2),δ(ppm):8.86,8.42-7.40(芳香环质子)。
P1b/2a/3a的表征数据:黄色粉末;52%(表2,条目7)。Mn:17700;Mw:26000;Mw/Mn:1.47(GPC,聚苯乙烯校正)。IR(KBr),ν(cm-1):2933,2858,1608,1512,1469,1431,1284,1242,1174和1083(νB-F)cm-1。1H NMR(400MHz,CD2Cl2),δ(ppm):8.60,8.50,8.42,8.18-6.83(芳香环质子),2.52-2.46(CH质子),4.12-3.94(CH质子),1.84-1.47(CH质子)。13C NMR(100MHz,CDCl3),δ(ppm):162.96,160.82,159.41,144.77,144.02,142.08,140.65,140.27,139.55,138.98,138.45,137.68,134.39,133.76,133.32,132.70,132.05,131.75,131.64,131.36,131.08,130.73,130.45,129.76,128.97,127.62,126.51,125.49,119.19,116.48,116.03,114.75,109.19,109.02,100.38,68.66,68.52,68.34,29.45,25.96,18.91。
P1b/2e/3a的表征数据:红色粉末;53%(表2,条目8)。Mn:18800;Mw:23700;Mw/Mn:1.26(GPC,聚苯乙烯校正)。IR(KBr),ν(cm-1):3033,1591,1508,1489,1427,1325,1269,1124,1174,1083(νB-F)和1028cm-1。1H NMR(400MHz,CD2Cl2),δ(ppm):8.81,8.67,8.60,8.24-6.80(芳香环质子),2.62-2.46(CH质子)。13C NMR(100MHz,CDCl3),δ(ppm):146.62,144.67,134.71,132.08,131.68,131.40,130.61,130.19,129.92,128.92,127.65,125.42,125.05,124.66,124.26,18.71,8.82。
P1a/2a/3b的表征数据:黄色粉末;64%(表2,条目9)。Mn:13100;Mw:21500;Mw/Mn:1.64(GPC,聚苯乙烯校正)。IR(KBr),ν(cm-1):2939,2854,1604,1512,1440,1408,1249,1174和843(νP-F)cm-1。1HNMR(400MHz,CD2Cl2),δ(ppm):8.81,8.72,8.65,8.31-6.86(芳香环质子),4.06-3.93(CH质子),1.81-1.73(CH质子)。13C NMR(100MHz,CDCl3),δ(ppm):160.88,144.17,142.97,140.33,139.34,138.81,135.82,133.83,133.36,132.80,131.78,131.24,130.47,130.03,128.97,128.39,127.72,125.53,123.26,121.67,119.86,116.54,116.13,114.96,109.09,68.66,30.09,29.41,26.22。19F NMR(376MHz,CD2Cl2)δ-72.45,-74.34。31PNMR(162MHz,CD2Cl2)δ-136.09,-140.48,-144.88,-149.27,-153.66。
P1a/2a/3c的表征数据:黄色粉末;75%(表2,条目10)。Mn:16800;Mw:25100;Mw/Mn:1.49(GPC,聚苯乙烯校正)。IR(KBr),ν(cm-1):2941,1604,1512,1442,1415,1253,1180,1155和1029cm-1。1H NMR(400MHz,CD2Cl2),δ(ppm):8.83,8.74,8.64,8.33-6.85(芳香环质子),4.12(CH质子),3.94(CH质子),1.81-1.46(CH质子)。13C NMR(100MHz,CDCl3),δ(ppm):160.93,159.47,144.06,138.80,135.54,133.35,132.72,131.79,131.26,130.39,128.88,128.74,125.49,123.11,116.42,116.15,114.80,68.40,29.53,26.22。19F NMR(376MHz,CD2Cl2)δ-78.87。
表1环化聚合反应的条件优化
a除特别说明外,聚合反应均在空气中130℃下进行24h,[3a]=0.3M,在MeOH,DCM或二者的混合物中(1:1)。b在线性聚苯乙烯校正的基础上由在DMF中的GPC估算而得。cMeOH/DMSO=8:2(条目2),6:4(条目3)。d反应时间18h(条目12),12h(条目13)。
表2不同单体的环化聚合反应结果
a除特别说明外,聚合反应均在空气中130℃下进行24h,[1]=[2]=0.2M,[3]=0.3M,[Rh]=5mol%,[Cu]=5equiv。溶剂:DCM/MeOH=1:1.b在线性聚苯乙烯校正的基础上由在DMF中的GPC估算而得。c反应时间36h。d部分不溶解。
表3聚合物的折射率和色散
a缩写:n=折射率,νD=阿贝数=(nD-1)/(nF-nC),其中nD,nF和nC是弗劳恩霍夫D、F和C光谱线的波长,即分别在589.2,486.1和656.3nm处的n值;D=色散=1/νD。νD和D的定义在文献中可找到2。
Claims (5)
5.根据权利要求4所述的应用,其特征在于,所述革兰氏阳性菌为耐甲氧西林金黄色葡萄球菌。
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