CN111484447A - 双吡啶基类配体及其制备方法、含双吡啶基类配体的钌超分子自组体及其制备方法和应用 - Google Patents

双吡啶基类配体及其制备方法、含双吡啶基类配体的钌超分子自组体及其制备方法和应用 Download PDF

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CN111484447A
CN111484447A CN202010360374.XA CN202010360374A CN111484447A CN 111484447 A CN111484447 A CN 111484447A CN 202010360374 A CN202010360374 A CN 202010360374A CN 111484447 A CN111484447 A CN 111484447A
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曹昌盛
史延慧
张立倩
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Abstract

本发明提供了一种新型的双吡啶基的双齿配体及其制备方法，其结构式如下式所示。本发明还提供了上述配体的钌超分子自组装体及其制备方法，包括：将制备的钌受体和双吡啶基配体置于容器中，加入等比例的甲醇和二氯甲烷混合溶剂，室温下搅拌一段时间，反应结束后将溶液旋干至一定体积然后缓慢加入乙醚，析出固体粉末即为含双吡啶基类配体的钌超分子自组体。该自组装体是一种新式的含钌自组装化合物，对癌肿瘤细胞系A549和HepG‑2具有良好的抑制效果。

Description

双吡啶基类配体及其制备方法、含双吡啶基类配体的钌超分 子自组体及其制备方法和应用
技术领域
本发明涉及有机合成和生物医药领域，具体涉及双吡啶基类配体及其制备方法、含双吡啶基类配体的钌超分子自组体及其制备方法和应用。
背景技术
癌症，尤其是一些恶性肿瘤，是科学家久攻不破的难点，目前，化疗是治疗癌症主要的有效措施之一。但是，临床上可供选择的化疗药物的数量非常有限，因此发现新的可以用于临床使用的化疗药物是目前癌症研究中的热点。
发明内容
本发明的目的之一在于提供一种新的双吡啶基类配体，其结构式如下式所示：
Figure BDA0002474774960000013
其中，R为n-C4H9O,n-C8H17O,n-C10H21O或n-C12H25O。
作为本发明的第二个方面，还提供了上述双吡啶基配体的制备方法，包括以下步骤：
S1：在碱存在和加热条件下，对二苯酚与正丁基溴、正辛基溴、正癸基溴或正十二基溴于有机溶剂中反应，反应结束后经后处理得下式所示产物b
Figure BDA0002474774960000011
其中，R为n-C4H9O,n-C8H17O,n-C10H21O或n-C12H25O；
S2：将产物b溶于有机溶剂中，缓慢滴加液溴，反应结束后经后处理得下式所示产物c；
Figure BDA0002474774960000012
其中，R为n-C4H9O,n-C8H17O,n-C10H21O或n-C12H25O；
S3：将产物c加入到史莱克瓶中，将史莱克瓶置于含丙酮的杜瓦瓶中，在双排管中加上液氮同时连接氮气将瓶中抽换气后，用针头加入重蒸的四氢呋喃，在含有丙酮的杜瓦瓶中逐步加入干冰搅拌，至反应温度降至一定温度，向混合溶液中缓慢滴加正丁基锂，滴加完毕回温至一定温度搅拌一段时间，继续升温至0℃，向溶液中滴加重蒸DMF，滴加结束后反应过夜；结束后经后处理得下式所示产物d
Figure BDA0002474774960000021
其中，R为n-C4H9O,n-C8H17O,n-C10H21O或n-C12H25O；
S4：将产物d和4-吡啶乙腈盐酸盐置于容器中，加入叔丁醇和THF并加热，搅拌，迅速加入叔丁醇钾、四丁基氢氧化铵继续反应一段时间后将混合溶液倒入酸化的甲醇溶液中，放置一段时间，析出固体即为所述双吡啶基配体。
进一步的，所述步骤S1中，所述对二苯酚与正丁基溴、正辛基溴、正癸基溴或正十二基溴的摩尔比为1:3。
作为本发明的第三个方面，还提供了含上述双吡啶基类配体的钌超分子自组体的制备方法，包括以下步骤：
S1：分别制备下式所示钌受体A1、A2和A3；
Figure BDA0002474774960000022
S2：将步骤S1制备钌受体中的一种和权利要求1所述双吡啶基配体中的一种置于容器中，加入等比例的甲醇和二氯甲烷混合溶剂，室温下搅拌一段时间，反应结束后将溶液旋干至一定体积然后缓慢加入乙醚，析出固体粉末即为含双吡啶基类配体的钌超分子自组体。
作为本发明的第四个方面还提供了由上述方法制备的含双吡啶基类配体的钌超分子自组体。
作为本发明的第五个方面，还提供了上述含双吡啶基类配体的钌超分子自组体在制备抗肿瘤药物中的应用。
与现有技术相比，本发明的有益效果：
本发明提供了一种双吡啶基配体，该类配体还具有一定的光谱性质，同时配体中连接长短不同碳链，是一种新型的双吡啶基的双齿配体；
本发明还提供了上述配体的钌超分子自组装体，该自组装体是一种新式的含钌自组装化合物，对癌肿瘤细胞系A549和HepG-2具有良好的抑制效果。
附图说明
图1为本发明实施例3中的配体L1-L4及钌组装体M1-M12的吸收光谱测试结果；
图2为本发明实施例4中的钌组装体的稳定性测试结果。
具体实施方式：
下面参照附图对本发明做进一步描述。
实施例1
双吡啶基类配体的结构：
Figure BDA0002474774960000031
R为n-C4H9O(L1),n-C8H17O(L2),n-C10H21O(L3),n-C12H25O(L4)
2、合成步骤如下：
Figure BDA0002474774960000041
配体L1的合成过程及表征：(1)按照当量比1:3的比例分别称取对二苯酚(25mmol，2.75g)和正丁基溴(75mmol，10.20g)于100mL梨形瓶中，加入分析纯的DMF 40mL，放入至冰浴中搅拌，再向混合溶液中加入碳酸钾(125mmol，15g)，然后加热到80℃继续搅拌反应12h。反应结束后，冷却至室温，加入水/DCM萃取三次，再用饱和食盐水洗涤三次，无水硫酸钠干燥，用旋转蒸发仪旋干溶剂，用冷甲醇重结晶，析出固体迅速抽滤，得白色片状晶体，真空干燥得4.03g产物b1，产率为72.6％。(2)称取获得的产物b1(18.5mmol，4.10g)于100mL茄形瓶中，加入50mL氯仿后在冰浴中搅拌，向混合溶液中缓慢滴加液溴(37mmol，5.91g)，结束后室温搅拌过夜。反应结束后，加入饱和硫代硫酸钠并用DCM萃取三次，饱和氯化钠溶液洗三次，无水硫酸钠干燥，旋干溶剂，在甲醇中重结晶，得白色粉末产物c1 5.68g，产率为81％。(3)称取产物c1(6.5mmol，2.47g)加入到100mL史莱克瓶中，将史莱克瓶置于含丙酮的杜瓦瓶中，在双排管中加上液氮同时连接氮气将瓶中抽换气三次后，用针头加入重蒸的四氢呋喃20mL，在含有丙酮的杜瓦瓶中逐步加入干冰搅拌，至反应温度降至-78℃时，向混合溶液中缓慢滴加正丁基锂，滴加完毕回温至-20℃中搅拌30min，继续升温至0℃，向溶液中滴加重蒸DMF，滴加结束后反应过夜。结束后加入水淬灭，DCM萃取，饱和氯化钠溶液洗三次，无水硫酸钠干燥，旋干溶剂，用甲醇中重结晶，真空线干燥得淡黄色晶体d1 1.14g，产率为63％。(4)称取上一步产物d1(1.5mmol，0.42g)和4-吡啶乙腈盐酸盐(2mmol，0.5g)于100mL梨形瓶中，加入8mL 叔丁醇，2mL的THF并加热到50℃，搅拌半小时后迅速加入叔丁醇钾(0.15mmol，0.017g)、四丁基氢氧化铵(0.15mmol，1mL)继续反应15min后将混合溶液倒入酸化的甲醇溶液中，放置5h析出橙色固体产物L1 0.53g，产率为73％。L1的表征为：1H NMR(400MHz,CDCl3):δ8.73(d,J＝6.4Hz,4H,Hα-Py),8.24(s,2H,Hvinyl),7.94(s,2H,Hphenyl),7.58(d,J＝6.0Hz,4H,Hβ-Py),4.16(t,J＝6.6Hz,4H,CH2),1.83-1.90(m,4H,CH2),1.50-1.57(m,4H,CH2),1.01(t,J＝7.4Hz,6H,CH3).13C NMR(100MHz,CDCl3):δ13.9,19.4,31.1,69.2,109.9,111.5,117.2,120.0,125.8,138.7,141.8,150.7,151.8.ESI-MS:m/z calcd for[L1+H]+:479.2447；found:478.2369.Elemental analysis:Calcd for C30H30N4O2:C,75.28；H,6.32；N,11.71.Found:C,74.43；H,6.50；N,10.59.
配体L2的合成过程同L1，其中只需要把第一步反应中的正丁基溴改成正辛基溴。得橙色粉末固体L2，产率为70％，表征为1H NMR(400MHz,CDCl3):δ8.75(d,J＝6.4Hz,4H,Hα-Py),8.32(s,2H,Hvinyl),7.96(s,2H,Hphenyl),7.72(d,J＝6.4Hz,4H,Hβ-Py),4.15(t,J＝6.4Hz,4H,CH2),1.85-1.92(m,4H,CH2),1.28-1.52(m,20H,CH2),0.87(t,J＝6.8Hz,6H,CH3).13C NMR(100MHz,CDCl3):δ14.2,22.8,26.3,29.2,29.4,29.4,31.9,69.7,109.6,111.6,117.1,120.5,126.0,139.6,143.3,149.4,152.2.ESI-MS:m/z calcd for[L2+H]+:590.3699；found:590.3621.Elemental analysis:Calcd for C38H46N4O2:C,77.25；H,7.85；N,9.48.Found:C,76.46；H,7.75；N,8.94.
配体L3的合成同上，其中把第一步反应中的正丁基溴改成正癸基溴。得橙色粉末固体L3，产率为65％，表征为1H NMR(400MHz,CDCl3):δ8.75(s,4H,Hα-Py),8.29(s,2H,Hvinyl),7.95(s,2H,Hphenyl),7.68(d,J＝4.8Hz,4H,Hβ-Py),4.15(t,J＝6.4Hz,4H,CH2),1.84-1.91(m,4H,CH2),1.46-1.53(m,4H,CH2),1.2-1.42(m,24H,CH2),0.87(t,J＝6.6Hz,6H,CH3).13C NMR(100MHz,CDCl3):δ14.3,22.8,26.3,29.2,29.5,29.5,29.7,29.8,32.0,69.7,109.5,111.6,117.0,120.7,126.1,139.9,143.9,143.9,148.8,152.2.ESI-MS:m/z calcd for[L3+H]+:647.4325；found:647.4247.Elemental analysis:Calcd for C42H54N4O2:C,77.98；H,8.41；N,8.66.Found:C,75.63；H,11.36；N,5.29.
配体L4的合成同上，其中把第一步反应中的正丁基溴改成正十二基溴。得橙色粉末固体L4，产率为63％，表征为1H NMR(400MHz,CDCl3):δ8.75(s,4H,Hα-Py),8.29(s,2H,Hvinyl),7.95(s,2H,Hphenyl),7.68(d,J＝4.8Hz,4H,Hβ-Py),4.15(t,J＝6.4Hz,4H,CH2),1.84-1.91(m,4H,CH2),1.46-1.53(m,4H,CH2),1.25-1.42(m,32H,CH2),0.87(t,J＝6.6Hz,6H,CH3).13C NMR(100MHz,CDCl3):δ14.3,22.8,26.2,29.1,29.5,29.7,29.8,32.0,69.9,108.9,111.7,116.6,121.4,126.3,138.4,141.2,146.2,152.5.ESI-MS:m/z calcd for[L4+H]+:703.4951；found:703.4872.Elemental analysis:Calcd for C46H62N4O2:C,78.59；H,8.89；N,7.97.Found:C,78.09；H,8.95；N,7.20.
实施例2
钌自组装化合物M1-M12，通用结构如下：
Figure BDA0002474774960000051
其中上下的部分为配体，左右两边的部分为钌受体，其结构及合成过程如下：
Figure BDA0002474774960000061
钌受体A1的合成：称取双氯对伞花烃双钌(II)(0.5mmol，306.2mg)和草酸铵(0.5mmol，62.1g)溶于甲醇/氯仿＝1:1的30mL溶剂中，抽换氮气三次，回流6h后降至室温，旋干溶剂，用DCM溶解、过滤，再将滤液旋干。获得的黄色固体产物再与AgOTf进行离子交换，最终获得黄色固体粉末钌受体A1。
钌受体A2和A3的合成:分别按1:1的当量比称取苯醌(0.30mmol，42.0mg)、萘醌(0.24mmol，45.6mg)与相对应的双氯对伞花烃双钌(II)于100mL茄形瓶中，加入2当量的醋酸钠和25mL的乙醇搅拌回流24h。反应结束后冷却至室温，处理后，继续加入2当量的AgOTf进行阴离子的交换，最终分别获得深红色固体粉末A2和绿色固体粉末A3。
4、组装体M1-M12的合成及表征：
组装体M1的合成及表征：用千万分之一的电子天平准确称取钌受体A1(4mmol，3.4306mg)和配体L1(4mmol，1.9793mg)置于8mL催化小瓶子中，再加入6mL的甲醇和二氯甲烷的等比例的混合溶剂，在室温下搅拌24h。反应结束后，将溶液旋干至1mL后缓慢加入乙醚，溶液中逐渐析出固体粉末，用乙醚洗涤两次后干燥得橙色粉末，产率为82％，数据表征为1H NMR(400MHz,CD3OD):δ8.29(s,4H,Hvinyl),8.17(d,J＝6.0Hz,8H,Hα-Py),7.80(s,4H,Hphenyl),7.64(d,J＝6.2Hz,8H,Hβ-Py),5.95(d,J＝6.2Hz,8H,Hp-cymene),5.78(d,J＝6.0Hz,8H,Hp-cymene),4.22-4.06(m,8H,OCH2),2.89-2.82(m,4H,CH),2.24(s,12H,CH3),1.97-1.92(m,8H,CH2),1.58-1.52(m,8H,CH2),1.39(d,J＝6.8Hz,24H,CH(CH3)2),1.06(t,J＝7.4Hz,12H,CH3).13C NMR(100MHz,CD3OD):δ172.3(C＝O),154.5,153.2,145.7,141.9,127.2,123.0,121.9(q,J＝316.9Hz,CF3),117.5,112.8,109.4,103.9,98.9,83.5,83.1,70.8,32.5,32.1,22.5,20.3,18.1,14.3.ESI-MS:m/z calcd for[M1-4OTf]4+:518.87；found:518.85.Elemental analysis:Calcd for C108H116O24N8S4F12Ru4:C,48.57；H,4.38；N,4.20.Found:C,48.30；H,4.13；N,4.01.
组装体M2由配体L2与钌受体A1合成，步骤同上，得橙色固体粉末，产率为78％，数据表征为1H NMR(400MHz,CD3OD):δ8.29(s,4H,Hvinyl),8.16(d,J＝6.4Hz,8H,Hα-Py),7.80(s,4H,Hphenyl),7.64(d,J＝6.4Hz,8H,Hβ-Py),5.94(t,J＝5.2Hz,8H,Hp-cymene),5.78(t,J＝4.4Hz,8H,Hp-cymene),4.22-4.03(m,8H,OCH2),2.89-2.82(m,4H,CH),2.25(s,12H,CH3),1.98-1.93(m,8H,CH2),1.54-1.44,1.36-1.29(m,40H,CH2),1.39(d,J＝7.2Hz,24H,CH(CH3)2),0.94(t,J＝6.6Hz,12H,CH3).13C NMR(100MHz,CD3OD+DMSO-d6v/v＝5/1):δ172.2(C＝O),154.5,153.0,145.4,141.8,127.3,122.9,121.9(q,J＝318.1Hz,CF3),117.5,112.8,109.5,103.5,98.8,83.5,83.1,70.9,61.3,33.0,32.4,30.5,30.1,27.0,23.7,22.7,18.3,14.8.ESI-MS:m/z calcd for[M2-4OTf]4+:574.94；found:574.91.Elemental analysis:Calcd(％)for C124H148O24N8S4F12Ru4:C,51.44；H,5.15；N,3.87.Found:C,50.49；H,4.10；N,3.03.
组装体M3由配体L3与钌受体A1合成，步骤同上，得橙色固体粉末，产率为75％，数据表征为1H NMR(400MHz,CD3OD):δ8.29(s,4H,Hvinyl),8.16(d,J＝6.0Hz,8H,Hα-Py),7.80(s,4H,Hphenyl),7.64(d,J＝6.4Hz,8H,Hβ-Py),5.94(t,J＝5.2Hz,8H,Hp-cymene),5.78(t,J＝5.2Hz,8H,Hp-cymene),4.22-4.03(m,8H,OCH2),2.89-2.82(m,4H,CH),2.25(s,12H,CH3),1.99-1.93(m,8H,CH2),1.55-1.44,1.35-1.33(m,56H,CH2),1.39(d,J＝7.2Hz,24H,CH(CH3)2),0.93(t,J＝6.6Hz,12H,CH3).13C NMR(100MHz,CD3OD+DMSO-d6 v/v＝5/1):δ172.2(C＝O),154.5,153.1,145.5,141.8,127.1,122.9,121.9(q,J＝318.1Hz,CF3),117.5,112.8,109.5,103.5,98.9,83.5,83.1,71.0,33.1,32.4,30.9,30.8,30.6,30.5,30.2,27.0,23.8,22.6,18.2,14.7.ESI-MS:m/z calcd for[M3-4OTf]4+:602.98；found:602.95.Elemental analysis:calcd(％)for C132H164O24N8S4F12Ru4:C,52.72；H,5.50；N,3.73.Found:C,48.91；H,5.59；N,1.05.
组装体M4由配体L4与钌受体A1合成，步骤同上，得橙色固体粉末，产率为78％，数据表征为1H NMR(400MHz,CD3OD):δ8.27(s,4H,Hvinyl),8.14(d,J＝6.4Hz,8H,Hα-Py),7.78(s,4H,Hphenyl),7.63(d,J＝6.8Hz,8H,Hβ-Py),5.93(t,J＝5.4Hz,8H,Hp-cymene),5.77(t,J＝5.0Hz,8H,Hp-cymene),4.18-4.01(m,8H,OCH2),2.87-2.80(m,4H,CH),2.23(s,12H,CH3),1.98-1.91(m,8H,CH2),1.54-1.42,1.34-1.26(m,72H,CH2),1.37(d,J＝7.2Hz,24H,CH(CH3)2),0.90(t,J＝6.8Hz,12H,CH3).13C NMR(100MHz,CD3OD):δ172.3(C＝O),154.5,153.2,145.7,141.9,127.2,123.0,121.9(q,J＝317.2Hz,CF3),117.4,112.8,109.4,103.8,98.9,83.6,83.1,71.1,33.1,32.5,30.9,30.9,30.9,30.7,30.6,30.2,27.1,23.8,22.5,18.1,14.5.ESI-MS:m/z calcd for[M4-4OTf]4+:630.99；found:630.99.Elementalanalysis:calcd(％)for C140H180O24N8S4F12Ru4:C,53.90；H,5.82；N,3.59.Found:C,53.85；H,5.34；N,3.58.
组装体M5由配体L1与钌受体A2合成，步骤同上，得暗红色固体粉末，产率为73％，数据表征为1H NMR(400MHz,CD3OD):δ8.34(d,J＝6.0Hz,8H,Hα-Py),8.21(s,4H,Hvinyl),7.82(s,4H,Hphenyl),7.67(d,J＝6.0Hz,8H,Hβ-Py),6.05(d,J＝6.4Hz,8H,Hp-cymene),5.83(d,J＝7.6Hz,12H,Hp-cymene,Hdobq),4.04(t,J＝6.8Hz,8H,OCH2),2.93-2.86(m,4H,CH),2.21(s,12H,CH3),1.84-1.77(m,8H,CH2),1.50-1.42(m,8H,CH2),1.37(d,J＝6.8Hz,24H,CH(CH3)2),0.98(t,J＝7.4Hz,12H,CH3).13C NMR(100MHz,CD3OD+DMSO-d6 v/v＝5/1):δ185.2(C＝0),154.7,153.0,145.7,127.2,123.3,122.0(q,J＝318.3Hz,CF3),117.6,113.1,109.9,105.0,102.8,100.2,85.0,83.2,70.5,61.3,32.4,32.0,22.8,20.2,18.5,14.5.ESI-MS:m/z calcd for[M5-4OTf]4+:543.88；found:543.87.Elemental analysis:calcd(％)forC116H120O24N8S4F12Ru4:C,50.28；H,4.37；N,4.04.
Found:C,47.52；H,3.93；N,3.83.
组装体M6由配体L2与钌受体A2合成，步骤同上，得暗红色固体粉末，产率为70％，数据表征为1H NMR(400MHz,CD3OD):δ8.35(d,J＝5.6Hz,8H,Hα-Py),8.26(s,4H,Hvinyl),7.81(s,4H,Hphenyl),7.71(d,J＝6.0Hz,8H,Hβ-Py),6.05(d,J＝6.0Hz,8H,Hp-cymene),5.83(d,J＝4.4Hz,12H,Hp-cymene,Hdobq),4.03(t,J＝6.6Hz,8H,OCH2),2.93-2.86(m,4H,CH),2.22(s,12H,CH3),1.81-1.74(m,8H,CH2),1.37(d,J＝6.8Hz,24H,CH(CH3)2),1.33-1.16(m,40H,CH2),0.80(t,J＝6.4Hz,12H,CH3).13C NMR(100MHz,CD3OD+DMSO-d6 v/v＝5/1):δ185.4(C＝O),154.7,153.2,146.1,142.5,130.0,127.3,123.4,121.9(q,J＝317.4Hz,CF3),117.4,113.2,109.9,105.2,102.8,100.1,84.9,83.3,70.9,32.9,32.6,30.3,29.9,27.0,23.7,22.6,18.3,14.6.ESI-MS:m/z calcd for[M6-4OTf]4+:599.93；found:599.92.Elementalanalysis:calcd(％)for C132H152O24N8S4F12Ru4:C,52.93；H,5.12；N,3.74.Found:C,53.28；H,4.87；N,3.54.
组装体M7由配体L3与钌受体A2合成，步骤同上，得暗红色固体粉末，产率为72％，数据表征为1H NMR(400MHz,CD3OD):δ8.37(d,J＝6.0Hz,8H,Hα-Py),8.28(s,4H,Hvinyl),7.83(s,4H,Hphenyl),7.73(d,J＝6.0Hz,8H,Hβ-Py),6.05(d,J＝6.0Hz,8H,Hp-cymene),5.83(d,J＝5.6Hz,12H,Hp-cymene,Hdobq),4.04(t,J＝6.8Hz,8H,OCH2),2.93-2.86(m,4H,CH),2.22(s,12H,CH3),1.81-1.74(m,8H,CH2),1.37(d,J＝6.8Hz,24H,CH(CH3)2),1.32-1.10(m,56H,CH2),0.83(t,J＝7.2Hz,12H,CH3).13C NMR(100MHz,CD3OD+DMSO-d6 v/v＝5/1):δ185.4(C＝O),154.7,153.1,146.0,142.6,127.3,123.4,121.9(q,J＝317.2Hz,CF3),117.4,113.1,110.0,105.2,102.8,100.1,84.9,83.3,70.9,33.1,32.5,30.6,30.5,30.5,30.2,29.8,27.0,23.8,22.7,18.3,14.7.ESI-MS:m/z calcd for[M7-4OTf]4+:627.98；found:627.95.Elemental analysis:calcd(％)for C140H168O24N8S4F12Ru4:C,54.11；H,5.45；N,3.61.Found:C,53.50；H,5.14；N,3.44.
组装体M8由配体L4与钌受体A2合成，步骤同上，得暗红色固体粉末，产率为69％，数据表征为1H NMR(400MHz,CD3OD):δ8.38(d,J＝6.4Hz,8H,Hα-Py),8.30(s,4H,Hvinyl),7.84(s,4H,Hphenyl),7.73(d,J＝6.4Hz,8H,Hβ-Py),6.05(d,J＝6.0Hz,8H,Hp-cymene),5.82(d,J＝6.0Hz,12H,Hp-cymene,Hdobq),4.04(t,J＝6.6Hz,8H,OCH2),2.93-2.86(m,4H,CH),2.21(s,12H,CH3),1.82-1.75(m,8H,CH2),1.37(d,J＝7.2Hz,24H,CH(CH3)2),1.34-1.08(m,72H,CH2),0.86(t,J＝7.2Hz,12H,CH3).13C NMR(100MHz,CD3OD+DMSO-d6 v/v＝5/1):δ185.4(C＝O),154.7,153.1,145.9,142.6,127.3,123.4,121.9(q,J＝316.0Hz,CF3),117.4,113.1,110.1,105.2,102.9,100.1,84.9,83.3,70.8,33.1,32.5,30.9,30.7,30.6,30.5,30.1,29.8,27.0,23.8,22.7,18.3,14.7.ESI-MS:m/z calcd for[M8-4OTf]4+:656.00；found:656.00.Elemental analysis:calcd(％)for C148H184O24N8S4F12Ru4:C,55.21；H,5.76；N,3.48.Found:C,55.11；H,5.28；N,3.17.
组装体M9的合成及表征：用千万分之一的电子天平准确称取钌受体A3(4mmol，3.8274mg)和配体L1(4mmol，1.9793mg)置于8mL催化小瓶子中，再加入6mL的二氯甲烷和乙腈的混合溶剂，在室温下搅拌24h。反应结束后，将溶液旋干至1mL后缓慢加入乙醚逐渐析出固体粉末，用乙醚洗涤两次后干燥得绿色粉末，产率为71％，数据表征为1H NMR(400MHz,DMSO-d6):δ8.48(d,J＝6.4Hz,8H,Hα-Py),8.24(s,4H,Hvinyl),7.75(d,J＝6.4Hz,8H,Hβ-Py),7.57(s,4H,Hphenyl),7.25(s,8H,Hdonq),5.97(d,J＝6.4Hz,8H,Hp-cymene),5.76(d,J＝6.4Hz,8H,Hp-cymene),3.90(t,J＝6.8Hz,8H,OCH2),2.81-2.74(m,4H,CH),2.05(s,12H,CH3),1.60-1.53(m,8H,CH2),1.26(d,J＝6.8Hz,24H,CH(CH3)2),1.23-1.16(m,8H,CH2),0.73(t,J＝7.4Hz,12H,CH3).13C NMR(100MHz,DMSO-d6):δ170.5(C＝O),152.4,150.8,143.3,141.9,137.4,125.9,122.1,120.7(q,J＝320.2Hz,CF3),116.2,112.6,111.1,109.8,102.5,99.5,84.5,82.4,68.7,30.1,24.0,21.9,18.4,16.6,13.4.ESI-MS:m/z calcd for[M9-2OTf]2+:1286.72；found:1286.57.Elemental analysis:calcd(％)for C124H124O24N8S4F12Ru4:C,51.88；H,4.35；N,3.90.Found:C,48.10；H,3.74；N,4.25.
组装体M10由配体L2与钌受体A3合成，步骤同上，得绿色固体粉末，产率为71％，数据表征为1H NMR(400MHz,CD3OD):δ8.53(d,J＝6.4Hz,8H,Hα-Py),8.28(s,4H,Hvinyl),7.78(s,4H,Hphenyl),7.71(d,J＝6.8Hz,8H,Hβ-Py),7.26(s,8H,Hdonq),5.86(d,J＝6.0Hz,8H,Hp-cymene),5.64(d,J＝6.0Hz,8H,Hp-cymene),4.00(t,J＝6.6Hz,8H,OCH2),2.88-2.81(m,4H,CH),2.12(s,12H,CH3),1.72-1.66(m,8H,CH2),1.34(d,J＝6.8Hz,24H,CH(CH3)2),1.30-1.22,1.10-0.85(m,40H,CH2),0.53(t,J＝6.8Hz,12H,CH3).13C NMR(100MHz,CD3OD+DMSO-d6v/v＝5/1):δ172.2(C＝O),153.8,152.8,145.5,142.8,138.7,127.4,123.3,122.0(q,J＝318.9Hz,CF3),117.5,113.5,112.8,110.6,104.6,100.9,85.8,84.1,70.7,32.5,31.8,30.0,29.9,26.9,23.4,22.8,17.7,14.7.ESI-MS:m/z calcd for[M10-2OTf]2+:1398.85；found:1398.62.Elemental analysis:calcd(％)for C140H156O24N8S4F12Ru4:C,54.32；H,5.08；N,3.62.Found:C,52.38；H,4.57；N,3.41.
组装体M11由配体L3与钌受体A3合成，步骤同上，得绿色固体粉末，产率为71％，数据表征为1H NMR(400MHz,CD3OD):δ8.55(d,J＝6.0Hz,8H,Hα-Py),8.34(s,4H,Hvinyl),7.83(s,4H,Hphenyl),7.72(d,J＝6.4Hz,8H,Hβ-Py),7.27(s,8H,Hdonq),5.87(d,J＝6.0Hz,8H,Hp-cymene),5.64(d,J＝6.4Hz,8H,Hp-cymene),4.03(t,J＝6.2Hz,8H,OCH2),2.88-2.81(m,4H,CH),2.12(s,12H,CH3),1.76-1.69(m,8H,CH2),1.34(d,J＝7.2Hz,24H,CH(CH3)2),1.31-1.03,0.85-0.66(m,56H,CH2),0.59(t,J＝7.4Hz,12H,CH3).13C NMR(100MHz,CD3OD+DMSO-d6v/v＝5/1):δ172.3(C＝O),153.8,152.8,145.4,142.3,138.6,127.3,123.2,122.0(q,J＝318.5Hz,CF3),117.4,113.3,112.8,110.2,104.7,100.9,85.7,84.1,70.7,32.9,31.8,30.1,29.7,29.4,26.9,23.6,22.8,21.4,17.7,14.9.ESI-MS:m/z calcd for[M11-2OTf]2+:1454.90；found:1454.68.Elemental analysis:calcd(％)for C148H172O24N8S4F12Ru4:C,55.42；H,5.40；N,3.49.Found:C,52.73；H,4.21；N,2.57.
组装体M12由配体L4与钌受体A3合成，步骤同上，得绿色固体粉末，产率为68％，数据表征为1H NMR(400MHz,CD3OD):δ8.57(d,J＝6.0Hz,8H,Hα-Py),8.36(s,4H,Hvinyl),7.87(s,4H,Hphenyl),7.72(d,J＝6.4Hz,8H,Hβ-Py),7.27(s,8H,Hdonq),5.87(d,J＝6.4Hz,8H,Hp-cymene),5.64(d,J＝6.0Hz,8H,Hp-cymene),4.05(t,J＝6.2Hz,8H,OCH2),2.88-2.81(m,4H,CH),2.12(s,12H,CH3),1.77-1.71(m,8H,CH2),1.34(d,J＝6.8Hz,24H,CH(CH3)2),1.26-1.20,1.10-1.03,0.87-0.73,0.57-0.49(m,72H,CH2),0.75(t,J＝7.4Hz,12H,CH3).13C NMR(100MHz,CD3OD+DMSO-d6 v/v＝5/1):δ172.3(C＝O),153.9,152.9,145.2,142.0,138.7,127.2,123.1,122.1(q,J＝319.0Hz,CF3),117.4,113.2,112.8,110.1,104.6,100.9,85.8,84.1,70.7,33.0,31.8,30.6,30.4,30.3,30.0,30.0,29.6,29.3,26.9,23.7,22.9,17.7,15.0.ESI-MS:m/z calcd for[M12-3OTf]3+:957.67；found:957.61.Elemental analysis:calcd(％)for C156H188O24N8S4F12Ru4:C,56.44；H,5.71；N,3.38.Found:C,55.26；H,5.11；N,3.40.
实施例3光谱性质测试
用1901紫外分光光度计在25℃下用1cm的比色皿在200-700nm范围内测得吸光度的值，研究了配体L1-L4于室温下在甲醇溶液(1.0×10-5M)中的电子吸收特性。从图1中可以看出配体L1的吸收光谱在336和431nm处显示出强谱带；配体L2的吸收波长在337和433nm；配体L3的吸收波长在339和434nm；配体L4的吸收波长在333和437nm。这些吸收带可能是由于配体中的大共轭体系产生的分子内/分子间π→π*跃迁，苯环上的烷基链的链长对紫外吸收光谱的吸收峰的位移影响不大，峰位大致有3-6nm的变化。
金属环M1-M12紫外光谱中高的吸收带在对应的单个配体L1-L4光谱中也可以观察到，并且在组装之后的吸收峰的位置也发生了变化，且吸光度增加了0.2-0.4左右，进一步辅证了金属环的结构的形成。这些吸收带可能是由配体中大共轭体系产生的分子内/分子间π→π*跃迁导致的。同时，金属对配体的电荷转移(MLCT)也促进了这些吸收带的形成。与单一配体相比，组装后矩形M1-M12的吸光度显著提高。化合物M9给出了两个强的吸收带，相对于供体L1红移分别为14nm和19nm。在其他的组装体中也观察到类似的红移(4-22nm)，这与供体L1-L4的吸收相对应。
实施例4稳定性测试
取适量配合物固体粉末溶解于4.5mL的氘代DMSO溶剂中，通过布鲁克AV400光谱仪和日本电子JNM-ECZ400S光谱仪测得化合物在0h，12h和24h时的氢谱。记录时间为0h,12h,24h的谱图如图2所示，从1H NMR中可以看出，配合物在氘代DMSO中24小时后的峰的位置和峰型都没有改变，说明其结构并未发生改变，该类组装体是稳定的，并不会随着时间的改变而分解。可以作为药物用于下一步细胞毒性及其他生物实验的测试。
实施例5细胞毒性测试
所有细胞均在10％FBS胎牛血清和1％青霉素链霉素组成的DMEM培养基，放置于37℃的5％CO2培养箱中培养备用。培养的细胞经胰酶消化后分离，1/3细胞继续在新的培养基中培养传代，2/3细胞用于铺板备用。将MTT(3-(4，5-二甲基噻唑-2)-2，5-二苯基四氮唑溴盐)溶于磷酸盐缓冲液(PBS，pH＝7.2)后，用0.22μM微孔滤膜过滤，得MTT溶液(5mg/mL)。制备10mg/mL所有化合物的二甲基亚砜溶液，在-20℃条件下保存备用。
MTT实验法的检测原理是活细胞中琥珀酸脱氢酶将MTT还原为水不溶性蓝紫色结晶甲臜，然后用DMSO溶解甲臜，测溶液的吸光度来确定活细胞数。96孔培养板中的细胞置于培养箱中培养24h后拿出，加入浓度为0.10-50.00μM的化合物，继续培养24h。其中光动力学疗法[92]是在加入化合物12h(24h)后，再用光照(400-700nm，50mw/cm-2)5min，然后继续培养12h(24h)。用含0.5％DMSO的培养基培养的细胞设置为空白对照组。药物处理后，用PBS缓冲液清洗细胞，向96孔板中每孔加入配好的20μL MTT溶液。染色4h后，在培养基中加入DMSO(每孔100μL)溶解甲臜晶体。在波长为560nm或670nm处，用酶标仪测得溶液的吸光度。根据吸光度计算化合物的半抑制浓度的IC50值，每个实验平行3次。
实验测得结果如下表1所示：
可以看出，对于A549癌细胞，组装体M11和M12的抗癌效果都比顺铂和紫杉醇更优。组装体M9，M11和M12在A549癌细胞中半抑制效果比阿霉素更好。可以看出组装之后的化合物的抗癌活性是更高于组装之前的单个供体和受体，可能是因为大分子化合物更易积累在癌细胞中。
表1癌细胞抑制测试结果
Figure BDA0002474774960000121

Claims (6)

1.双吡啶基配体，其特征在于，其结构式如下式所示：
Figure FDA0002474774950000011
其中，R为n-C4H9O,n-C8H17O,n-C10H21O或n-C12H25O。
2.权利要求1中所述双吡啶基配体的制备方法，其特征在于，包括以下步骤：
S1：在碱存在和加热条件下，对二苯酚与正丁基溴、正辛基溴、正癸基溴或正十二基溴于有机溶剂中反应，反应结束后经后处理得下式所示产物b
Figure FDA0002474774950000012
其中，R为n-C4H9O,n-C8H17O,n-C10H21O或n-C12H25O；
S2：将产物b溶于有机溶剂中，缓慢滴加液溴，反应结束后经后处理得下式所示产物c；
Figure FDA0002474774950000013
其中，R为n-C4H9O,n-C8H17O,n-C10H21O或n-C12H25O；
S3：将产物c加入到史莱克瓶中，将史莱克瓶置于含丙酮的杜瓦瓶中，在双排管中加上液氮同时连接氮气将瓶中抽换气后，用针头加入重蒸的四氢呋喃，在含有丙酮的杜瓦瓶中逐步加入干冰搅拌，至反应温度降至一定温度，向混合溶液中缓慢滴加正丁基锂，滴加完毕回温至一定温度搅拌一段时间，继续升温至0℃，向溶液中滴加重蒸DMF，滴加结束后反应过夜；结束后经后处理得下式所示产物d
Figure FDA0002474774950000014
其中，R为n-C4H9O,n-C8H17O,n-C10H21O或n-C12H25O；
S4：将产物d和4-吡啶乙腈盐酸盐置于容器中，加入叔丁醇和THF并加热，搅拌，迅速加入叔丁醇钾、四丁基氢氧化铵继续反应一段时间后将混合溶液倒入酸化的甲醇溶液中，放置一段时间，析出固体即为所述双吡啶基配体。
3.根据权利要求2所述的制备方法，其特征在于，所述步骤S1中，所述对二苯酚与正丁基溴、正辛基溴、正癸基溴或正十二基溴的摩尔比为1:3。
4.含双吡啶基类配体的钌超分子自组体的制备方法，其特征在于，包括以下步骤：
S1：分别制备下式所示钌受体A1、A2和A3；
Figure FDA0002474774950000021
S2：将步骤S1制备钌受体中的一种和权利要求1所述双吡啶基配体中的一种置于容器中，加入等比例的甲醇和二氯甲烷混合溶剂，室温下搅拌一段时间，反应结束后将溶液旋干至一定体积然后缓慢加入乙醚，析出固体粉末即为含双吡啶基类配体的钌超分子自组体。
5.由权利要求4所述方法制备的含双吡啶基类配体的钌超分子自组体。
6.权利要求5中所述含双吡啶基类配体的钌超分子自组体在制备抗肿瘤药物中的应用。
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