CN108329460B - 一种光动力杀菌聚合物及其制备方法和应用 - Google Patents
一种光动力杀菌聚合物及其制备方法和应用 Download PDFInfo
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- CN108329460B CN108329460B CN201810189651.8A CN201810189651A CN108329460B CN 108329460 B CN108329460 B CN 108329460B CN 201810189651 A CN201810189651 A CN 201810189651A CN 108329460 B CN108329460 B CN 108329460B
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Abstract
本发明提供了一种光动力杀菌聚合物及其制备方法和应用。该聚合物由主链和侧链组成，侧链由末端季铵化的长烷基链构成，能够与带负电荷的细菌表面结合并形成紧密的组合体，使细菌膜通透；主链由苯、芴及噻吩组成，具有较强的刚性结构，在光照的条件下，受光激发敏化周围的空气产生活性氧，达到高效杀菌效果。该聚合物可作为抗菌剂应用，不仅能够杀死革兰氏阳性和何革兰氏阴性细菌，而且也能够杀死真菌，具有广谱抗菌的功能。该聚合物制备简单、反应温和、产率较高。该聚合物作为一种高效的光动力抗菌材料，杀菌所需浓度低、光剂量小，普通白光照射就能达到高效的杀菌效果。本发明聚合物在长波区发射荧光，还可用于生物荧光成像。
Description
技术领域
本发明涉及共轭聚合物，具体属于一种光动力杀菌聚合物及其制备方法和应用。
背景技术
自从青霉素被发现以来，许多抗生素接连被报道，在一段时间内起到了很好的杀菌效果。然而抗生素的广泛使用和滥用，导致耐药菌不断出现，人们迫切需要新的有效的抗感染方法。
与抗生素相比，光动力杀菌疗法利用光敏剂在光照下产生活性氧(包括单线态氧、超氧阴离子自由基、过氧化氢、以及羟基自由基等)来损伤细菌并致病菌死亡，且不会使细菌产生耐药性，优势更加突出。其中光敏剂是重要的一个元素，发展性能良好的光敏剂可减少使用剂量及光照强度，减少对正常组织的伤害。
共轭聚合物由于其良好的光电性质，近年来被广泛应用于生物医疗领域。在光照条件下，共轭聚合物可以直接敏化周围的氧气分子产生活性氧，从而发挥杀菌作用。季铵盐类化合物已经被证明能够与细菌膜发生静电吸引，增强细菌膜的通透性达到杀死细菌的目的。将共轭聚合物的光活性与季铵盐的杀菌活性结合，实现对细菌的快速杀伤，对于治疗因致病菌引起的感染有重要意义。然而，目前已经报道的季铵盐类化合物杀菌效果一般，杀菌范围有限，如只能杀细菌，不能杀真菌等，鉴于此，获得杀菌性能优良且广谱的抗菌材料是本发明的宗旨。
发明内容
本发明的目的是提供一种光动力杀菌聚合物及其制备方法和应用；所述的聚合物在光照射下具有高的杀菌活性，可作为光动力杀菌剂应用；所述聚合物制备方法操作简单、反应条件温和、产率较高。
本发明提供的一种光动力杀菌聚合物，其结构式为：
本发明提供的一种光动力杀菌聚合物的制备方法，包括如下步骤：
1)、按摩尔比1∶10∶3.6，将2,5-二溴对苯二酚、1,12-二溴十二烷和碳酸钾加入丙酮中，再加入催化量的18-冠-6相转移催化剂，搅拌下加热回流反应5h后，得到1,4-二溴-2,5-二(12-溴十二烷氧基)苯(II)；反应式如下：
2)、氮气保护下，按摩尔比1∶2.5∶6，将2,7-二溴芴、频哪醇硼酸酯和醋酸钾加入二氧六环中，再加入催化量的Pd(dppf)2Cl2，加热到110℃搅拌反应12h，得到2,7-二(4,4,5,5-四甲基-1,3,2-二氧杂硼酯)芴(III)；反应式如下：
3)、氮气保护下，按摩尔比1∶2∶1，将1,4-二溴-2,5-二(12-溴十二烷氧基)苯(II)、2,7-二(4,4,5,5-四甲基-1,3,2-二氧杂硼酯)芴(III)和4,7-二(2-溴-5-噻吩基)-2,1,3-苯并噻二唑加入体积比为1∶5的碳酸钾水溶液和甲苯的混合液中，再加入催化量的Pd(PPh3)4，加热回流反应48h得中间体产物，经甲醇沉淀后所得中间体产物加入含有10倍当量三甲胺的三氯甲烷溶液中，40℃下搅拌反应48h，得到聚合物(I)；反应式如下：
本发明光动力杀菌聚合物具有广谱抗菌的功效，对革兰氏阴性菌(大肠杆菌Top10)和革兰氏阳性菌(金黄色葡萄球菌ATCC6358)以及真菌(白色念珠菌)都具有杀菌活性，尤其是在光照下，杀菌率达到94％以上，可作为杀菌剂应用。
本发明光动力杀菌聚合物在长波区发射荧光，也可在生物荧光成像中应用。
与现有技术相比本发明的有益效果：本发明得到的光动力杀菌聚合物由主链和侧链组成，侧链由末端季铵化的长烷基链构成，能够与带负电荷的细菌表面结合并形成紧密的组合体，使细菌膜通透；主链由苯、芴及噻吩组成，具有较强的刚性结构，在光照的条件下，受光激发敏化周围的空气产生活性氧，达到高效杀菌效果。该聚合物可作为杀菌剂应用，具有光谱抗菌的能力，不仅能够杀伤真菌，而且对细菌也有强的杀伤能力。该聚合物制备方法简单、反应条件温和、产率较高。该聚合物杀菌所需浓度低、光剂量小，普通白光照射就能达到高效的杀菌效果。本发明聚合物在长波区发射荧光，还可用于生物荧光成像。
附图说明
图1聚合物(I)在DMSO中的荧光发射和紫外吸收图；
图2聚合物(I)产生活性氧能力测试图；
图3聚合物(I)对大肠杆菌的杀菌性能图；
图4聚合物(I)对金黄色葡萄球菌的杀菌性能图；
图5聚合物(I)对白色念珠菌的杀菌性能图；
图6聚合物(I)与大肠杆菌作用荧光成像图；
图7聚合物(I)与金黄色葡萄球菌作用荧光成像图；
图8聚合物(I)与白色念珠菌作用荧光成像图。
具体实施方式
实施例1聚合物(I)的制备
1)、在100mL圆底烧瓶中，依此加入2.68g 2,5-二溴对苯二酚(10.0mmol),32.8g1,12-二溴十二烷(100mmol),4.97g碳酸钾(36.0mmol)和100mL丙酮。在催化量的18-冠-6相转移催化剂下，搅拌加热回流反应5h。停止反应，减压旋除大量溶剂后，加入200mL二氯甲烷，所得有机相用蒸馏水洗涤3次(3×100mL)，经无水硫酸钠干燥，除去溶剂得粗产品。粗产品经柱色谱分离(洗脱剂为二氯甲烷/石油醚＝1/2,v/v)得到1,4-二溴-2,5-二(12-溴十二烷氧基)苯(II)2.68g(产率35.1％)。1H NMR(400MHz,CDCl3,ppm)δ:1.23-1.49(m,32H),1.77-1.89(m,8H),3.36(t,JJ＝7.2Hz,4H),3.94(t,JJ＝8.0Hz,4H),7.08(s,2H)；13C NMR(100MHz,CDCl3,ppm)δ:25.88,28.15,28.68,29.14,29.28,29.54,29.78,32.26,34.11,70.28,110.96,118.56,150.12；MALDI-TOF-MS(m/z):762.6[M+],801.3[M++K]。
2)、氮气保护下，向100mL的四口瓶中，依次3.24g 2,7-二溴芴(10.0mmol)、6.35g频那醇硼酸酯(25.0mmol)、5.88g乙酸钾(60.0mmol)、催化量的Pd(dppf)2Cl2和60mLDMSO溶剂，搅拌下加热至80℃反应12h。反应结束后，自然冷却至室温，将反应液倒入大量冰水中，快速搅拌，有大量固体析出，过滤，收集滤饼，滤饼经干燥后，柱色谱分离(乙酸乙酯/石油醚＝1/10,v/v)得2,7-二(4,4,5,5-四甲基-1,3,2-二氧杂硼酯)芴(III)3.56g，产率85.2％。1H NMR(CDCl3,400MHz)δ8.02(s,2H),7.88(d,J＝8.8Hz,4H),3.91(s,2H),1.34(s,24H)；13CNMR(CDCl3,100MHz)δ24.94,36.64,83.81,119.64,131.29,133.38,143.11,144.38；LCEI-MS(m/z)418.2[M+]。
3)、氮气保护下，向100mL圆底烧瓶中依此加入0.762g 1,4-二溴-2,5-二(12-溴十二烷氧基)苯(II)(1.00mmol),0.836g 2,7-二(4,4,5,5-四甲基-1,3,2-二氧杂硼酯)芴(III)(2.00mmol),0.458g 4,7-二(5-溴噻吩)-1,2,5-苯并噻二唑(1.00mmol)，2.0mL的碳酸钾水溶液(2.0mol/L)，10mL甲苯及催化量的Pd(PPh3)4，100℃搅拌反应48h。停止反应，减压旋除溶剂，用100mL三氯甲烷溶解，蒸馏水洗涤有机相三次(3×100mL)，无水硫酸钠干燥后，减压旋除溶剂到2-3mL。在搅拌下，将上述溶液缓慢滴入50mL甲醇中，析出大量沉淀，离心得固体。将所的固体溶解在3mL三氯甲烷中，再滴入50mL甲醇中，离心得固体。重复上述操作3次。然后，将所得中间产物溶解在30mL三氯甲烷中，再加入10当量的三甲胺，40℃下搅拌反应48h。反应结束后，减压旋除溶剂，真空干燥得到共轭聚合物(I)0.146g产率29.3％。1HNMR(400MHz,d-DMSO,ppm)δ:1.21-1.53(br,32H),1.62-1.78(m,8H),3.06-3.18(br,22H),4.02-4.13(m,8H),6.52(s,2H),7.32-7.38(br,4H),7.58-7.72(br,8H),8.03-8.09(m,6H)；Mn＝12846,Mw＝21083,PDI＝1.64.
实施例2聚合物(I)的荧光发射光谱和紫外吸收光谱的测试
将聚合物(I)溶于DMSO中，配制成浓度为0.02mg/mL的溶液。准确移取上述溶液2.0mL加入紫外样品池中，以DMSO溶剂为参比，在HITACHI UH5300紫外吸收仪上测定，所得最大吸收峰为540nm。同样准确移取上述浓度为0.02mg/mL的DMSO溶液加入2.0mL荧光样品池中，在HITACHI F-4600荧光仪上测定，激发和发射狭缝宽度为5n，激发波长为513nm，所得最大发射波长为665nm。所得结果归一化图谱见图1。
实施例3聚合物(I)的产生活性氧能力测试
取50μL 10.0mM的2,7-二氯荧光素二乙酸盐乙醇溶液，加入450μL乙醇稀释，再加入2.0mL 0.01M NaOH水溶液后室温避光活化30min。活化后加入10mL 1×PBS缓冲溶液，混合后的DCFH溶液最终浓度为40μM。
在比色皿中加入1.0mL活化的DCFH(40μM)溶液和52.4μL聚合物(I)(100μM)的水溶液，混合均匀后，将所得溶液在白光(1.0mW/cm2)下照射5min，每分钟记录激发波长为488nm的DCFH溶液在500-700nm的荧光发射光谱，空白组为未添加任何待测活化的DCFH溶液(40μM)，在相同光照处理后用同样的方法检测其荧光发射光谱。所得测试结果见图2。
实施例4聚合物(I)对大肠杆菌(Top10)的杀菌性能测试
1)、大肠杆菌(Top10)的培养
取出一支50mL离心管，吸取10mL LB液体培养基到50mL无菌离心管中，加入10μL浓度为50mg/mL的氨苄西林钠和10μL大肠杆菌菌种，37℃下180rpm震荡培养8小时。
2)、对大肠杆菌的杀菌率测试
将在LB液体培养基中培养8小时的大肠杆菌吸取2mL菌液进行离心(7100rpm,2min)，对大肠杆菌进行沉淀，将沉淀的大肠杆菌用1×PBS洗涤后再次离心沉淀，重复两次后，弃去上清液，将菌液重新悬浮于1×PBS中，调OD600为1.0。
在1.5mL离心管中，加入100μL的菌液(OD600＝1.0)和一定量共轭聚合物(I)(最终浓度分别为2μM,4μM,5μM,10μM)，用无菌1×PBS将体积补充到500μL，并在暗处37℃下孵育20min，每个浓度各两组，分别为非光照和光照组，同时做空白组(不加药)为参照。孵育结束后，非光照组稀释1×104倍后吸取100μL菌液均匀涂布于90mm LB固体培养基(含50mg/mL的氨苄西林钠)，37℃培养18h后计数菌落形成单位。
光照组在25mW/cm2的400～1000nm白光下照射15min后稀释涂板，其它操作与非光照组相同。
3)、在聚合物(I)浓度为4μM时，光照条件下对大肠杆菌的杀菌率能达到95.3％，非光照条件下只能达到36.4％；浓度为10μM时光照条件下的杀菌率达到99.9％，非光照条件下只能达到53.4％；测试结果见图3。
实施例5聚合物(I)对金黄色葡萄球菌(ATCC6358)的杀菌性能测试
1)、金黄色葡萄球菌(ATCC6358)的培养
取出一支50mL离心管，吸取10mL NB液体培养基到50mL无菌离心管中，加入10μL金黄色葡萄球菌菌种，37℃下180rpm震荡培养8小时。
2)、对金黄色葡萄球菌(ATCC6358)的杀菌率测试
将在NB液体培养基中培养8小时的金黄色葡萄球菌吸取2mL菌液进行离心(7100rpm,2min)，对金黄色葡萄球菌进行沉淀，将沉淀的金黄色葡萄球菌用1×PBS洗涤后再次离心沉淀，重复两次后，弃去上清液，将菌液重新悬浮于1×PBS中，调OD600为1.0。
在1.5mL离心管中，加入100μL的菌液(OD600＝1.0)和一定量聚合物(I)(最终浓度分别为5μM,10μM,15μM,20μM)，用无菌1×PBS将体积补充到500μL，并在暗处37℃下孵育20min，每个浓度各两组，分别为非光照和光照组，同时做空白组(不加聚合物)为参照。孵育结束后，非光照组稀释1×104倍后吸取100μL菌液均匀涂布于90mm NA培养基，37℃培养18h后计数菌落形成单位。
光照组在25mW/cm2的400～1000nm白光下照射15min后稀释涂板，其它操作与非光照组相同。
3)、在聚合物(I)浓度为15μM时，光照条件下对金黄色葡萄球菌的杀菌率能达到97.4％，非光照条件下只能达到65.2％，浓度为20μM时光照条件下的杀菌率达到99.1％，非光照条件下只能达到84.5％；具体见图4。
实施例6聚合物(I)对白色念珠菌(真菌)的杀菌性能测试
1)、白色念珠菌的培养
取出一支50mL离心管，吸取10mL YPD液体培养基到50mL无菌离心管中，再加入10μL白色念珠菌的菌种，30℃下180rpm震荡培养10小时。
2)、对白色念珠菌的杀菌率测试
将在YPD液体培养基中培养10小时的白色念珠菌吸取2mL菌液进行离心(7100rpm,2min)，对白色念珠菌进行沉淀，将沉淀的白色念珠菌用1×PBS洗涤后离心沉淀，重复两次后，弃去上清液，将菌液重新悬浮于1×PBS中，调OD600为2.0。
取100μL菌液(OD600＝1.0)的白色念珠菌的菌液和一定量共轭聚合物(I)(最终浓度分别为5μM,10μM,20μM)于1.5mL离心管中，用无菌1×PBS将体积补充到500μL，并在暗处37℃下孵育20min，每个浓度各两组，分别为非光照和光照组，同时做空白组(不加聚合物)为参照。孵育结束后，非光照组稀释1×103倍后吸取100μL菌液均匀涂布于90mm YPD琼脂培养基，30℃培养24h后计数菌落形成单位。
光照组在25mW/cm2的400～1000nm白光下照射15min，其它操作与非光照组均相同。
3)、在聚合物(I)浓度为20μM时，光照条件下对白色念珠菌的杀菌率能达到96.1％，非光照条件下比光照条件下杀菌率略低，在94.7％左右；具体结果见图5。
实施例7聚合物(I)与大肠杆菌(Top10)的荧光成像
1)、大肠杆菌(Top10)的培养，方法同实施例4；
2)、聚合物(I)与大肠杆菌的荧光成像
将培养8h的大肠杆菌用1×PBS调OD600值为1.0。取少量菌液用1×PBS稀释1×103倍后，加入终浓度为5μM的聚合物(I)，37℃下转速180rpm震荡培养8h，取10μL混液于共聚焦激光扫描显微镜(CLSM)下成像。在CLSM下可以看到大肠杆菌Top10与聚合物(I)形成很好的复合体，见图6；
实施例8聚合物(I)与金黄色葡萄球菌(ATCC6358)的荧光成像
1)、金黄色葡萄球菌(ATCC6358)的培养，方法同实施例5；
2)、聚合物(I)与金黄色葡萄球菌的荧光成像
将培养8h的金黄色葡萄球菌用1×PBS调OD600值为1.0。取少量菌液用1×PBS稀释1×103倍后，加入终浓度为15μM的聚合物(I)，37℃下转速180rpm震荡培养8h，取10μL混液于共聚焦激光扫描显微镜(CLSM)下观察。在CLSM下可以看到金黄色葡萄球菌与聚合物(I)形成很好的复合体，见图7。
实施例9聚合物(I)与白色念珠菌(真菌)的荧光成像
1)、白色念珠菌的培养，方法同实施例6；
2)、聚合物(I)与白色念珠菌的荧光成像
将培养10h的白色念珠菌用1×PBS调OD600值为2.0。取少量菌液用1×PBS稀释1×103倍后，加入终浓度为20μM的聚合物CCP-BFT，30℃下转速180rpm震荡培养10h，取10μL混液于共聚焦激光扫描显微镜(CLSM)下观察。在CLSM下可以看到白色念珠菌与聚合物(I)形成很好的复合体，见图8。
Claims (5)
1.一种光动力杀菌聚合物，其特征在于结构式为：
2.如权利要求1所述的一种光动力杀菌聚合物的制备方法，其特征在于包括如下步骤：
1)、按摩尔比1∶10∶3.6，将2,5-二溴对苯二酚、1,12-二溴十二烷和碳酸钾加入丙酮中，再加入催化量的18-冠-6相转移催化剂，搅拌下加热回流反应5h后，得到1,4-二溴-2,5-二(12-溴十二烷氧基)苯；
2)、氮气保护下，按摩尔比1∶2.5∶6，将2,7-二溴芴、频哪醇硼酸酯和醋酸钾加入二氧六环中，再加入催化量的Pd(dppf)2Cl2，加热到110℃搅拌反应12h，得到2,7-二(4,4,5,5-四甲基-1,3,2-二氧杂硼酯)芴；
3)、氮气保护下，按摩尔比1∶2∶1，将1,4-二溴-2,5-二(12-溴十二烷氧基)苯、2,7-二(4,4,5,5-四甲基-1,3,2-二氧杂硼酯)芴和4,7-二(2-溴-5-噻吩基)-2,1,3-苯并噻二唑加入体积比为1∶5的碳酸钾水溶液和甲苯的混合液中，再加入催化量的Pd(PPh3)4，加热回流反应48h得中间体产物，经甲醇沉淀后所得中间体产物加入含有10倍当量三甲胺的三氯甲烷溶液中，40℃下搅拌反应48h，得到聚合物(I)。
3.如权利要求1所述的聚合物在制备光动力杀菌剂中的应用。
4.如权利要求3所述的聚合物在制备光动力杀菌剂中的应用，其特征在于，所述光动力杀菌剂的应用条件：光源为400～1000nm白光，照射时间为15min，照射强度为25mW/cm2。
5.如权利要求1所述的聚合物在生物荧光成像中的应用。
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