CN111087415B - 铕掺杂的有机框架材料及其制备方法与应用 - Google Patents
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Abstract
本发明公开了一种铕掺杂的有机框架材料及其制备方法与应用，该有机框架材料的化学式为C14H11N3O8Eu，其是以1,4‑双(咪唑‑1‑基)对苯二甲酸、2,6‑吡啶二羧酸、Eu(NO3)3·6H2O为原料，采用溶剂热法制得。本发明制备的有机框架材料对肿瘤细胞具有明显抑制作用，且对正常细胞毒性小，故有望发展成肿瘤治疗药物。
Description
技术领域
本发明属于药物化学领域，具体涉及一种铕掺杂的有机框架材料及其制备方法与应用。
背景技术
目前稀土金属有机框架材料（Ln-MOFs）因具有独特的光电磁、催化、热稳定性质和拓扑结构，具有广阔的应用前景而备受关注，在化学、合成、材料研究领域中都取得了相当巨大的进展，但应用于药学、生物、医学领域仍较少。
1,4-双(咪唑-1-基)对苯二甲酸(
，HBTA)，是一个新合成的氮杂环化合物，其具有一定的荧光活性，兼具氮杂环化合物和芳香多羧酸的优点，N、O配位点丰富。稀土（Ln3+）金属离子具有独特的4f电子层结构，较高的正电荷导致配位数多（8~12）、配位能力强、配位模式丰富，且通常具有特殊的光电磁性。本发明以新配体HBTA与稀土金属离子设计合成出一种铕掺杂的有机框架材料。
发明内容
本发明的目的在于提供一种铕掺杂的有机框架材料及其制备方法与应用。
为实现上述目的，本发明采用如下技术方案：
一种铕掺杂的有机框架材料，其化学式为C14H11N3O8Eu，分子量为501.23，为单斜晶系，C 2/c空间群，单胞参数为a=17.7353(5) 
，b=10.4300(4)
，c=16.7035(5) 
，α=γ=90°，β=91.996(3)°，V=3087.92(17)
，Z=8。
所述铕掺杂的有机框架材料的制备方法，是将1,4-双(咪唑-1-基)对苯二甲酸（HBTA）、2,6-吡啶二羧酸（2,6-pydc）、NaOH溶于甲醇溶液中，室温下搅拌30min后加入Eu(NO3)3·6H2O固体，混匀后置于聚四氟乙烯的不锈钢反应釜中，继续搅拌10min后于120℃恒温反应3天，再以10℃/h的速率降至室温，过滤后用蒸馏水冲洗得到白色块状晶体。
其中，所用HBTA、2,6-pydc、NaOH与Eu(NO3)3·6H2O的摩尔比为1:2:6:1。
所述甲醇溶液中甲醇与水的体积比为3:7。
所得的铕掺杂的有机框架材料具有癌细胞抑制活性，可用于制备肿瘤治疗药物。
本发明的显著优点在于：
1）本发明制备的铕掺杂的有机框架材料表现出较强的癌细胞抑制活性，有望制备成肿瘤治疗药物。
2）本发明合成方法简单、经济，为配位化合物的合成提供了新的思路。
附图说明
图1为所合成配合物的配位环境。
图2为所合成配合物的三维堆积结构图（b轴方向、H原子省略）。
图3为所合成配合物的拓扑结构图。
图4为所合成配合物的荧光光谱图（λex=340nm）。
具体实施方式
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
将HBTA(0.0298g，0.1 mmol)、2,6-pydc（0.0334g，0.2 mmol）、NaOH(0.0240g，0.6mmol)溶于10mL溶剂（去离子水:甲醇=7:3，v/v）中，在室温下搅拌30min后加入Eu（NO3）3·6H2O（0.0045g，0.1mmol)固体，混匀后置于聚四氟乙烯的不锈钢反应釜中继续搅拌10min，然后在120℃恒温反应3天后，以10℃/h的速率降至室温，过滤后用蒸馏水冲洗得到C14H11N3O8Eu的白色块状晶体。
单晶结构分析
在体视显微镜下，挑选出合适大小、规则外形且无缺角、裂纹等明显缺陷的晶体，置于白凡士林中洗涤去粘附于表面的物质，选择并截取粗细、长短合适的玻璃丝，然后用502快速胶水将挑选单晶粘附在玻璃丝顶端之上，使晶体尽可能地直立于玻璃丝的顶端。将玻璃丝的底端固定在载晶台上，在Rigaku 18KW R-AXIS RAPID Weissenberg IP衍射仪上收集衍射强度数据，采用石墨单色器过滤的Mo-Ka射线（λ=0.71073Å），设定收集参数及扫描程序，完成后对收集的衍射强度数据进行Lp因子的校正处理。晶体的衍射强度条件和晶体数据见表1。
表1 配合物单晶的晶体学数据表
单晶结构分析表明该晶体属于单斜晶系，中心对称，C 2/c空间群。配合物的配位环境如图1所示，图2为配合物的三维堆积图。从图中可以看出该配合物形成了类似蜂窝状的结构，晶胞相当致密。金属中心Eu（Ⅲ）分别配位了来自3个HBTA的一个N原子、一个O原子和一个羧基；2,6-吡啶二甲酸的N原子和两个羧基上各一个O原子与Eu（Ⅲ）形成三齿螯合结构；另外金属中心还配位两个水分子，总共形成8配位。Nd-O键长2.461(3) Å至2.796(3) Å，Nd-N键长为2.563(3) Å和2.590(3)，表明该配合物相当稳定牢固。
荧光活性测试
固体荧光实验在Edinburgh Instrument F900 荧光光谱仪上进行，光源为Xe灯，检测器为Red PMT，扫描3次，室温下测量固体的荧光发射光谱。
Eu作为最有前途的红色发光金属，目前已有大量报道发现Eu（Ⅲ）配合物在约615nm处的尖锐发射。对于该配合物，由图4可见，在340nm激发下，发射光谱显示出在589、615和696nm处的强烈谱带，分别对应于5D0→7FJ的特征跃迁（J=1,2,4）。此外，5D0→7F2跃迁的强度比5D0→7F1跃迁要强得多。该配合物荧光的CIE颜色坐标为（0.6452，0.3471），表明它是红色发光体的良好候选者，可以用作发光体和荧光标记，为后期研究提供了更多的可能性。
抗癌活性测试
PBS的制备：将药品（NaCl 8.5g， Na2HPO4•H2O 2.2g）溶于1L超纯水中，0.22μm滤膜过滤，经高压蒸汽灭菌锅灭菌，冷却后使用。
1640完全培养基的配制：向市售1640不完全培养基（500mL）中加入提前解冻的50mL胎牛血清和5mL双抗（100 U•ml-1青霉素、100 μg •ml-1链霉素），摇晃均匀，置于4℃冰箱保存。使用时，提前分装至50mL离心管。
MTT溶液的配制：称取0.025g MTT，用5mL0.01M的PBS缓冲液完全溶解，经0.22μm水性滤膜过滤，铝箔包封，现配现用。
测试方法：
1）细胞复苏与培养
液氮中里取出细胞冻存管，立即放入37℃温水浴中，轻摇使其尽快融化后，转移到离心管中，加入RPMI-1640培养基，用滴管吹打混匀后1200 r/min离心3min。弃上清，加入RPMI-1640培养基，吹打，使细胞悬浮均匀。转移到培养瓶，放入37℃、CO2培养箱静置孵育，次日用倒置显微镜观察细胞生长状况。取出培养箱里的细胞，弃培养基，加入适量PBS缓冲液漂洗细胞后弃掉。加入适量胰酶（以刚好盖住所有细胞最好），置37℃孵箱内孵育，不同细胞所需消化时间不同（通常2~5min）。倒置显微镜下观察消化细胞，若胞质回缩，细胞之间不再连接成片，表明此时细胞消化适度，立即加入适量培养基中止消化。将细胞从瓶壁上吹下，轻轻吹打混匀，离心，得到的细胞液分瓶培养，放到CO2孵箱内。一般1~2天传代一次。
）体外细胞毒性试验(MTT)
以细胞存活率为指标，取对数生长期的三种细胞（Hela、HepG2、NCM460）进行生长抑制试验。用含10%新生牛血清的1640培养液稀释成5×104个细胞/ml，以100 μL/孔接种于96孔培养板上，在37℃、5％CO2孵箱中培养24 h使其贴壁后，分别加入用完全培养基配制的配合物溶液200μL，使样品液的终浓度分别为1.56、3.13、6.25、12.5、25、50、100μg/ml，培养48h之后PBS洗涤3次后每孔加入5 mg/ml MTT溶液10μL和完全培养基100μL，继续培养4 h后弃去液体，每孔加入150μL DMSO，避光震荡20 min，用酶标仪于490 nm测定吸光度，计算得到细胞生长存活率。以药物浓度为横坐标，细胞存活率为纵坐标，绘制药物浓度-存活率曲线，并计算半数致死量（IC50），结果见表2。
表2 配合物对不同细胞的IC50
由表2可见，该配合物对Hela细胞、HepG2细胞均表现较好的抑制效果，而对正常细胞株NCM460表现出的毒性较小，因此有望应用于肿瘤的特异性治疗。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (5)
1.一种铕掺杂的有机框架材料，其特征在于：其化学式为C14H11N3O8Eu，分子量为501.23，为单斜晶系，C2/c空间群，单胞参数为a=17.7353(5)
，b=10.4300(4)
，c=16.7035(5) 
，α=γ=90°，β=91.996(3)°，V=3087.92(17)
，Z=8；
所述有机框架材料的金属中心Eu（Ⅲ）分别配位了来自3个1,4-双(咪唑-1-基)对苯二甲酸的一个N原子、一个O原子和一个羧基；2,6-吡啶二甲酸的N原子和两个羧基上各一个O原子与Eu（Ⅲ）形成三齿螯合结构；另外金属中心还配位两个水分子，总共形成8配位。
2.一种如权利要求1所述的铕掺杂的有机框架材料的制备方法，其特征在于：将1,4-双(咪唑-1-基)对苯二甲酸、2,6-吡啶二羧酸、NaOH溶于甲醇溶液中，室温下搅拌30min后加入Eu(NO3)3·6H2O固体，混匀后置于聚四氟乙烯的不锈钢反应釜中，继续搅拌10min后于120℃恒温反应3天，再以10℃/h的速率降至室温，过滤后用蒸馏水冲洗得到白色块状晶体。
3.根据权利要求2所述的铕掺杂的有机框架材料的制备方法，其特征在于：所用1,4-双(咪唑-1-基)对苯二甲酸、2,6-吡啶二羧酸、NaOH与Eu(NO3)3·6H2O的摩尔比为1:2:6:1。
4.根据权利要求2所述的铕掺杂的有机框架材料的制备方法，其特征在于：所述甲醇溶液中甲醇与水的体积比为3:7。
5.一种如权利要求1所述的铕掺杂的有机框架材料在制备肿瘤治疗药物中的应用。
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