CN106432354A - 一种席夫碱钯配合物及其制备方法和应用 - Google Patents
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- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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Abstract
本发明提供了一种席夫碱钯配合物及其制备方法和应用,配合物分子式为PdLCl或[Pd(C13H11N6S)Cl],其中HL为N',N″‑双(吡啶‑2‑亚甲胺基)硫脲。该配合物的制备是将钯盐的水溶液滴加到置于圆底烧瓶配体的甲醇溶液,室温下搅拌10‑12小时,过滤,得到橘黄色沉淀,产率可达80%。将沉淀用二甲基亚砜(DMSO)溶解,得到橘黄色晶体,为该席夫碱钯配合物与DMSO的共晶。通过半数抑制浓度(IC50)的测定证明这个化合物对蛋白酪氨酸磷酸酶(PTP1B和TCPTP)的活性有较好的抑制作用,可以作为蛋白酪氨酸磷酸酶(PTP1B和TCPTP)的抑制剂应用。
Description
技术领域
本发明涉及金属配合物,尤其涉及一种席夫碱钯配合物及其制备方法和应用。
背景技术
蛋白酪氨酸磷酸酶(PTPs)是能特异性水解磷酸化的酪氨酸残基上的磷酸根的一类酶。蛋白酪氨酸磷酸化是生物体内细胞信号转导的主要途径,它是由PTPs和蛋白酪氨酸激酶(PTKs)两类酶协同作用的可逆性动态平衡过程,其中PTPs催化酪氨酸去磷酸化,而PTKs则催化酪氨酸磷酸化。研究表明蛋白酪氨酸磷酸化水平的异常与糖尿病、肥胖、自身免疫性缺陷、白血病和癌症等疾病的发病有着密切的联系。目前人们发现的PTPs的种类已有107种,如PTP1B、TCPTP、SHP-1、SHP-2等。
PTP1B能够使胰岛素受体、胰岛素受体底物以及瘦素等去磷酸化,从而对胰岛素和瘦素的信号转导进行负调节。敲除PTP1B基因的小鼠对胰岛素的敏感性明显提高,而且小鼠的发育良好,癌症发病率也未见提高。因此,PTP1B抑制剂的筛选是开发新型抗糖尿病药物的重要途径。
TCPTP是一种胞内非受体型蛋白酪氨酸磷酸酶。TCPTP是一个控制炎症的关键基因,TCPTP基因敲除的小鼠会在三至五周内死亡,并且出现矮小、淋巴结肿大、淋巴细胞增殖和造血缺陷等症状,甚至引发心肌炎、关节炎、胃炎等。因此TCPTP对炎症的控制起着重要作用,通过抑制TCPTP的活性能够治疗一些炎症。
发明内容
本发明的目的在于提供一种席夫碱钯配合物及其制备方法,以及该配合物作为一种PTP1B和TCPTP活性抑制剂的应用。
本发明提供的一种席夫碱钯配合物,其分子式为[Pd(C13H11N6S)Cl],分子量为425.20,其配合物结构式为:
本发明提供的一种席夫碱钯配合物的制备方法,包括如下步骤:
(1)将PdCl2和NaCl按1:2的摩尔比溶解于水中形成Na2PdCl4溶液;
(2)将上述Na2PdCl4溶液滴加到等摩尔量的N',N”-双(吡啶-2-亚甲胺基)硫脲的甲醇溶液中,室温下搅拌10-12小时,过滤得橘黄色粉末;
(3)将粉末溶于DMSO中形成过饱和溶液,过滤,滤液在室温下缓慢挥发,两周后得到橘黄色块状晶体。
上述合成的反应方程式为:
PdCl2+2NaCl=Na2PdCl4 (1)
本发明制备的席夫碱钯配合物从DMSO结晶出来的晶体,属于单斜晶系的P-1空间群,晶胞参数:α=80.740(2)°,β=83.3970(19)°,γ=73.223(2)°。配合物中钯离子与配体的摩尔比为1:1,配体以三齿螯合配位到钯离子,同时钯离子与一个氯离子配位达到电中性。本发明配合物晶体是从DMSO中结晶,晶体含有一分子溶剂。
本发明的配合物是N',N”-双(吡啶-2-亚甲胺基)硫脲与金属钯离子在室温反应下得到的,只有一个钯离子进行配位,得到了一种新的钯配合物。该配合物的合成方法简单,生产成本较低,过程易控制,产率高。
本发明的配合物对蛋白酪氨酸磷酸酶(PTP1B和TCPTP)的活性有较好的抑制作用,其对PTP1B的半数抑制浓度(IC50)为1.86μM,对TCPTP的半数抑制浓度(IC50)为1.59μM,可以作为蛋白酪氨酸磷酸酶(PTP1B和TCPTP)的抑制剂应用。
附图说明
图1为本发明配合物与DMSO共结晶([Pd(C13H11N6S)Cl]·DMSO)的晶体结构图。
图2为本发明配合物[Pd(C13H11N6S)Cl]的电喷雾质谱图。
图3为本发明化合物[Pd(C13H11N6S)Cl]抑制PTP1B活性的IC50值测定曲线。
图4为本发明化合物[Pd(C13H11N6S)Cl]抑制TCPTP活性的IC50值测定曲线。
具体实施方式
下面结合附图和实施例,对本发明作进一步详细说明。
实施例1.本发明钯配合物[Pd(C13H11N6S)Cl]的制备及晶体培养方法。
称取0.0177g(0.1mmol)PdCl2和0.0116g(0.2mmol)NaCl溶解于5mL水中形成Na2PdCl4溶液,将上述Na2PdCl4溶液滴加到0.0284g(0.1mmol)的HL的10mL甲醇溶液中,室温下搅拌12小时,过滤得橘黄色粉末,分别用水、甲醇和乙醚各洗涤三次,真空干燥,得到发明钯配合物[Pd(C13H11N6S)Cl],产率80%。
配合物红外光谱特征吸收(cm-1):3247(N-H);1620(C=N);1083(N-N);882(C=S);453(Pd-N);439(Pd-S)。
配合物元素分析测定:[Pd(C13H11N6S)Cl]·2H2O·CH3OH,理论值:C 34.09,H2.67,N 17.04,S 6.50;实验值:C 34.07,H 2.56,N 17.39,S 6.84。
将干燥的粉末溶于适量DMSO中形成过饱和溶液,过滤,滤液在室温下缓慢挥发,两周后得到橘黄色块状晶体,晶体结构分析为[Pd(C13H11N6S)Cl]·C2H6OS,即配合物与DMSO共结晶。
实施例2.本发明钯配合物[Pd(C13H11N6S)Cl]·C2H6OS的晶体结构测定和结果。
在高倍显微镜下,挑选规则、透明的橘红色块状单晶颗粒,用X-ray晶体衍射方法测试。将所选晶体固定在Bruker APEX-II CCD面探衍射仪上,以石墨单色器Mo-Kα为辐射光源,收集样品对波长为的X-ray衍射数据。用SHELXL-2014/7程序包解得配合物的晶体结构。详细的晶体结构信息列于表1。
表1配合物与DMSO共结晶([Pd(C13H11N6S)Cl]·C2H6OS)晶胞及测量参数
实施例3.本发明钯配合物[Pd(C13H11N6S)Cl]的电喷雾质谱。
为了研究配合物在溶液中的存在形式,将适量的配合物固体粉末溶于甲醇中,振荡使其溶解达到饱和,并离心得到澄清透明溶液,上样至电喷雾质谱仪,采用电喷雾离子源,以正离子方式检测样品并记录质谱数据。图2是配合物的电喷雾质谱图。在电喷雾质谱图中能观察到配合物相应的分子离子峰。表2是配合物的正离子电喷雾质谱归属。结果表明,该结果与元素分析所得结果一致,表明配合物在溶液中以我们设计的结构形式稳定存在。
表2钯配合物[Pd(C13H11N6S)Cl](1)的正离子电喷雾质谱归属
实施例4.本发明钯配合物[Pd(C13H11N6S)Cl]对PTP1B和TCPTP抑制效果检测。
IC50测定原理:
六水合对硝基苯磷酸二钠盐(pNPP)在PTPs的催化作用下,可分解为黄色的对硝基苯酸(pNP),它在405mn处有很强的紫外吸收,终止反应后,通过酶标仪检测pNP的吸收值,然后进行分析可以得知作为催化剂的PTPs已经反应的量。
IC50值的意义:
IC50即半数抑制浓度,是引起酶活性下降至原酶活性一半时所需抑制剂的浓度,IC50值是用来评判抑制剂抑制能力大小的标准。其数值越低,表明抑制剂的抑制能力越强。
IC50的测定方法:
进行IC50值测定实验时,首先将抑制剂配制成10-3M的DMSO母液,然后稀释到一系列梯度的适宜浓度,用现配的缓冲溶液溶解PTPs使其浓度适宜,备用。抑制剂抑制PTPs的活性实验是在96孔板中进行,前三排加入83μL含酶的MOPS缓冲溶液(50mM NaCl,20mM MOPS,pH=7.2),最后一排加入不含酶的MOPS缓冲溶液作为对照。再以列为单位,依次加入10μL不同浓度梯度的抑制剂,置于37℃恒温水浴锅反应30分钟后,向上述溶液加入2μL pNPP(0.1M)来启动反应,15分钟后,用5μL(2M)NaOH终止反应,通过酶标仪测定底物的分解产物pNP在405nm处各孔的紫外吸收值。用Origin程序作图,拟合这些浓度梯度曲线从而求得IC50值。实验重复三次以上。
检测结果1:钯配合物[Pd(C13H11N6S)Cl]对PTP1B的半数抑制浓度(IC50)为:1.86μM(见图3)。
检测结果2:钯配合物[Pd(C13H11N6S)Cl]对TCPTP的半数抑制浓度(IC50)为:1.59μM(见图4)。
Claims (5)
1.一种席夫碱钯配合物,其特征在于,其结构式为:
2.根据权利要求1所述的一种席夫碱钯配合物的制备方法,其特征在于,包括如下步骤:
(1)将PdCl2和NaCl按1:2的摩尔比溶解于水中形成Na2PdCl4溶液;
(2)将上述Na2PdCl4溶液滴加到等摩尔量的N',N”-双(吡啶-2-亚甲胺基)硫脲的甲醇溶液中,室温下搅拌10-12小时,过滤得橘黄色粉末;
(3)将粉末溶于DMSO中形成过饱和溶液,过滤,滤液在室温下缓慢挥发,两周后得到橘黄色块状晶体。
3.如权利要求3所述的一种席夫碱钯配合物的制备方法,其特征在于,所述反应时间为12小时。
4.如权利要求1所述的一种席夫碱钯配合物作为PTP1B抑制剂的应用。
5.如权利要求1所述的一种席夫碱钯配合物作为TCPTP抑制剂的应用。
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