CN116731294A - 一种共轭聚合物生物催化材料及其制备方法和应用 - Google Patents
一种共轭聚合物生物催化材料及其制备方法和应用 Download PDFInfo
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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Abstract
本发明提供了一种共轭聚合物生物催化材料及其制备方法和应用,属于生物催化领域。本发明首次发现,与现有的小分子铁基生物催化剂酞菁铁(II)、酞菁、间‑四苯基卟啉氯化铁(III)、四氧化三铁、氯化血红素相比,本发明提供的共轭聚合物具有更优异的仿POD活性。本发明还发现,除了具有优异的仿POD活性外,本发明提供的共轭聚合物还具有优异的仿CAT、OXD、HPO和GPx活性。本发明提供的共轭聚合物的制备方法简单,适合大规模生产,在制备高效多功能仿酶催化剂中具有广阔的应用前景。
Description
本申请为专利申请号为“2022109892992”,申请日为“2022年08月17日”,发明名称为“一种共轭聚合物生物催化材料及其制备方法和应用”的分案申请。
技术领域
本发明属于生物催化领域,具体涉及一种共轭聚合物生物催化材料及其制备方法和应用。
背景技术
卟啉(porphyrins)是一类由四个吡咯环通过次甲基相连形成的共轭骨架大环化合物,其中心的氮原子与金属原子配位即成为金属卟啉配合物(metalloporphyrins)。天然卟啉及金属卟啉配合物广泛存在于动植物中,如血红素、叶绿素、维生素B12、细胞色素P-450,它们具有特殊的生理活性。由于天然卟啉及金属卟啉配合物分子具有刚柔性、电子缓冲性、光电磁性和高度的化学稳定性,早在20世纪30年代就有人从事卟啉化学的研究,现已广泛用作光导体、半导体、超导体、催化剂、抗癌药物、显色剂等。
天然卟啉及金属卟啉化合物虽然具有上述多种优异的性质,但批量生产困难。因此,设计出人工合成的卟啉和金属卟啉配合物具有重要意义。酞菁作为一种人工合成的卟啉衍生物,因具有诸多与卟啉相似的性质而也受到了广泛的关注。酞菁结构上和卟啉类似,酞菁和非过渡金属形成的配合物对肿瘤有光生物活性。20世纪80年代以来,已先后报道了一系列有关酞菁对体外培养人癌细胞光灭活作用和动物移植瘤光动力损伤作用的实验结果,其中锌酞菁已进入I期临床试验。
虽然目前在生物催化领域已有人工合成的小分子金属卟啉化合物应用于伤口愈合、抗肿瘤、抗炎等方面的报道,但是,一方面,这些小分子金属卟啉化合物在体内发挥治疗作用的机理尚未阐明;另一方面,这些小分子金属卟啉化合物的治疗效果还有待进一步提高。
发明内容
本发明的目的在于提供一种共轭聚合物生物催化材料及其制备方法和应用。
共轭聚合物是由一种或两种以上种重复结构单元通过共价键连接起来形成的具有共轭结构的高分子量化合物。
本发明提供了一种共轭聚合物材料,它是将式I或式II所示重复结构单元通过共价键连接形成的聚合物:
其中,M为金属原子。
进一步地,M为Fe。
进一步地,它是将式I所示重复结构单元通过共价键连接形成的聚合物,它是以卟啉基共轭聚合物和金属盐为原料反应得到的产物,卟啉基共轭聚合物是将式III所示重复结构单元通过共价键连接形成的聚合物:
进一步地,所述卟啉基共轭聚合物和金属盐的质量比为(1.0-2.0):1,优选为1.2:1;所述金属盐为铁盐,优选为Fe3+盐;所述反应的温度为100-140℃,优选为120℃,反应的时间为8-16h,优选为12h,反应的溶剂为有机溶剂,优选为二甲基甲酰胺。
进一步地,所述卟啉基共轭聚合物的制备方法包括以下步骤:将聚苯乙烯微球加入水中形成聚苯乙烯微球悬浮液,在聚苯乙烯微球悬浮液中加入乙酸混合均匀,然后加入对苯二甲醛和吡咯,反应,得到聚苯乙烯微球负载的卟啉聚合物;将聚苯乙烯微球负载的卟啉聚合物加入甲苯中,搅拌10-14小时,过滤,保留固体,得到卟啉基共轭聚合物;
优选地,所述聚苯乙烯微球悬浮液、苯二甲醛、吡咯的比例为(4-6)mL:(50-55)mg:(50-60)μL,优选为5mL:52.5mg:54μL;所述聚苯乙烯微球悬浮液中,聚苯乙烯微球的固含量为4wt.%-6wt.%,优选为5wt.%;所述反应是在三氟乙酸和硝基苯的存在下进行的;所述反应的温度为60-100℃,优选为80℃,时间为10-14小时,优选为12小时。
进一步地,它是将式II所示重复结构单元通过共价键连接形成的聚合物,它是以1,2,4,5-苯四甲腈和金属盐为原料反应得到的产物。
进一步地,所述1,2,4,5-苯四甲腈和金属盐的摩尔比为(1.5-3.5):1,优选为2.5:1;所述金属盐为铁盐,优选为Fe3+盐;所述反应的温度为160-200℃,优选为180℃,反应的时间为5-15min,优选为10min,反应的溶剂为有机溶剂,优选为乙二醇;
和/或,所述反应是在微波反应器中进行的,所述反应是在催化剂的存在下进行的,所述催化剂为有机碱,所述有机碱优选为1,8-二氮杂环(5,4,0)十一-7-烯。
本发明还提供了上述共轭聚合物材料在制备仿酶催化剂中的用途。
进一步地,所述酶为POD酶、CAT酶、OXD酶、HPO酶和/或GPx酶。
进一步地,所述仿酶催化剂为预防和/或治疗细菌感染的药物、加速伤口愈合的药物。
本发明提供了一类具有共轭网络结构的聚合物:Fe-PorBC和Fe-PcBC。本发明首次发现,与现有的小分子铁基生物催化剂酞菁铁(II)、酞菁、间-四苯基卟啉氯化铁(III)、四氧化三铁、氯化血红素相比,本发明提供的共轭聚合物Fe-PorBC和Fe-PcBC具有更加优异的仿POD活性。
Fe-PorBC在催化过程中所产生的自由基主要是·OH,而Fe-PcBC主要是·OH和O2·-。与Fe-PorBC相比,Fe-PcBC具有更好的仿POD活性、更好的催化动力学、更强的催化氧化能力。
本发明还发现,除了具有优异的仿POD活性外,本发明提供的共轭聚合物Fe-PorBC和Fe-PcBC还具有优异的仿CAT、OXD、HPO和GPx活性,可以作为高效多功能仿酶催化剂。其中,与Fe-PorBC相比,Fe-PcBC具有更佳的仿POD、CAT、OXD、HPO和GPx活性。
本发明提供的共轭聚合物的制备方法简单,适合大规模生产,在制备高效多功能仿酶催化剂中具有广阔的应用前景。
显然,根据本发明的上述内容,按照本领域的普通技术知识和惯用手段,在不脱离本发明上述基本技术思想前提下,还可以做出其它多种形式的修改、替换或变更。
以下通过实施例形式的具体实施方式,对本发明的上述内容再作进一步的详细说明。但不应将此理解为本发明上述主题的范围仅限于以下的实例。凡基于本发明上述内容所实现的技术均属于本发明的范围。
附图说明
图1.原子尺度下Fe-PorBC和Fe-PcBC的结构表征。(a)Fe-PorBC结构示意图;(b,c)Fe-PorBC的AC-HAADF-STEM图像;(d)Fe-PcBC结构示意图;(e,f)Fe-PcBC的AC-HAADF-STEM图像。
图2.(a)Fe-PorBC和(b)Fe-PcBC的13C NMR谱图;(c)Fe-PorBC和商用TPPFe的拉曼光谱;(d)Fe-PcBC和商用PcFe的拉曼光谱。
图3.Fe-PorBC和Fe-PcBC的催化动力学。(a)不同铁基生物催化剂的相对POD活性;(b)以H2O2和TMB为底物的Fe-PorBC和Fe-PcBC的Vmax和TON值。
图4.Fe-PorBC和Fe-PcBC生成的活性氧种类。记录(a)·OH信号和(c)O2·-信号的EPR光谱;记录(b)·OH信号和(d)O2·-信号的荧光光谱。
图5.(a)Fe-PorBC和Fe-PcBC的MB降解试验;(b)在MB催化降解过程中TBA淬灭·OH,BQ淬灭O2·-;Fe-PorBC和Fe-PcBC在不同(c)pH条件和(d)温度下的POD活性,在pH 4.5下的吸光度定义为100%;***p<0.001。图6.Fe-PorBC和Fe-PcBC的多种模拟酶活性。(a)Fe-PorBC和Fe-PcBC催化生成O2的时间依赖过程;(b)Fe-PorBC和Fe-PcBC在HAc-NaAc缓冲液(0.1M,pH 4.5)中催化氧化TMB(oxTMB)的紫外-可见吸收光谱;(c)用于记录O2·-信号的EPR谱;(d)Fe-PorBC和Fe-PcBC在PBS缓冲液(pH5.8)中催化氧化CB的紫外-可见吸收光谱;(e)记录OCl-信号的荧光光谱;(f)Fe-PorBC和Fe-PcBC在PBS缓冲液(pH 7.4)下催化氧化DTNB的紫外-可见吸收光谱;(g)Fe-PorBC和Fe-PcBC催化降解DTNB的时间依赖性曲线;***p<0.001。
图7.Fe-PorBC合成路线示意图。
图8.Fe-PcBC合成路线示意图。
图9.Fe-PorBC(a,b)和Fe-PcBC(c,d)的SEM照片及尺寸分布。比例尺:1μm。
图10.Fe-PorBC的(a)TEM,(b)高分辨率TEM图像。
图11.Fe-PcBC的(a)TEM,(b)高分辨率TEM,(c,d)HAADF-STEM图像。
图12.Fe-PcBC,PcFe和Pc的(a)FT-IR光谱和(b)UV-vis光谱。
图13.Fe-PorBC和Fe-PcBC的典型XRD谱图。
具体实施方式
本发明所用原料与设备均为已知产品,通过购买市售产品所得。
实施例1:制备铁卟啉基生物催化剂Fe-PorBC
采用一锅法合成Fe-PorBC,合成路线示意图如图7所示。
1.合成卟啉基生物催化剂(PorBC)
1)合成单分散聚苯乙烯(PS)微球
参照文献(Shen,K.;Zhang,L.;Chen,X.;Liu,L.;Zhang,D.;Han,Y.;Chen,J.;Long,J.;Luque,R.;Li,Y.;et al.Ordered Macro-Microporous Metal-OrganicFramework Single Crystals.Science 2018,359,206-210.)记载的方法,制备单分散PS微球。制备方法如下:首先分别用12mL NaOH水溶液(浓度为10wt.%)和去离子水洗涤苯乙烯(39mL)除去稳定剂,然后将洗涤后的苯乙烯倒入含有300mL去离子水的三颈烧瓶中。向三颈烧瓶中加入1.5g聚乙烯吡咯烷酮(PVP),将混合溶液用氮气鼓泡15min,并在95℃的磁力搅拌下回流30min。最后,在三颈烧瓶中加入0.5g K2S2O8和50mL去离子水引发苯乙烯聚合。在此温度下持续搅拌24h(500r/min),得到固体含量为5wt.%的单分散PS微球的悬浮液。
2)以单分散PS微球为模板合成PS@Por
首先,将5mL固体含量为5wt.%的单分散PS微球的悬浮液与250mL冰乙酸超声混合30min形成均匀的悬浮液。然后,将52.5mg对苯二甲醛(BDA)和54μL吡咯加入悬浮液中超声30min,再加入1mL三氟乙酸(TFA)和5mL硝基苯(NBZ)分别作为催化剂和氧化剂,继续超声30min,然后将悬浮液在80℃下连续搅拌12h,反应结束后冷却至室温。最后将反应液过滤,滤饼用乙醇洗涤三次,60℃干燥24h,得到黑色的聚苯乙烯微球负载的卟啉聚合物,命名为PS@Por。
3)合成PorBC
将PS@Por加到50mL甲苯中超声分散30min,然后在60℃下连续搅拌12h,将反应液过滤,滤饼用乙醇洗涤,60℃干燥24h,得到空心球状的卟啉基生物催化剂,命名为PorBC。
2.合成Fe-PorBC
将10mg PorBC加到含有2mL二甲基甲酰胺(DMF)的小瓶中。随后,将FeCl3(8.1mg,0.05mM)加到溶液中超声10min,在120℃下连续搅拌12h。然后将产物过滤,滤饼分别用DMF、去离子水和乙醇洗涤三次,60℃真空干燥24h,得到空心球状的Fe-PorBC。
实施例2:制备铁酞菁基生物催化剂Fe-PcBC
通过快速微波加热工艺制备Fe-PcBC,合成路线示意图如图8所示。首先将1,2,4,5-苯四甲腈(89mg,0.5mM)和FeCl3(32.4mg,0.2mM)在10mL乙二醇中混合,将混合溶液超声10min,然后加入75μL的1,8-二氮杂环(5,4,0)十一-7-烯(DBU)作为催化剂。将整个体系放入微波反应器中,在180℃(320W)的环境下反应10min。反应结束后,过滤,滤饼分别用乙二醇、3%盐酸、去离子水和乙醇依次洗涤,60℃真空干燥过夜,得到Fe-PcBC。
以下通过实验例证明本发明的有益效果。
以下实验例采用的Fe-PorBC由实施例1制备,Fe-PcBC由实施例2制备;对照样品如表1所示,均为市售产品。
表1.对照样品信息
实验例1:生物催化剂的结构表征
1、实验方法
固体核磁共振波谱在Bruker AV400光谱仪上测量,工作在75.5MHz的13C。对Fe-PcBC和Fe-PorBC进行了13C交叉极化和魔角自旋光谱研究。采用Nicolet-560分光光度计(Nicol,US)对样品进行傅里叶变换红外光谱(FT-IR)分析,分析范围为4000-500cm-1,分辨率为2cm-1。拉曼光谱记录在Horiba Jobin Yvon LabRam HR800上,激发波长为633nm。紫外-可见(UV-vis)吸收光谱在波长为300~900nm的岛津V-2450上进行。扫描电子显微镜(SEM)图像由Apreo S HiVoc(Thermo Fisher Scientific,FEI)获得。透射电镜(TEM)图像和EDS测绘图像是通过Talos F200x TEM显微镜(FEI Ltd.,USA)在200kV下操作获得的。用BrukerD8聚焦x射线衍射仪在电压为40kV的铜辐射下观察了样品的晶相状态。样品在5~80的2θ范围内进行扫描。在JEOL-FA200 ESR分光光度计上进行ESR实验。荧光测量在日立F-4600荧光分光光度计上进行。
2、实验结果
表2.XPS测定的材料的原子比和Fe原子的重量比
表3.不同材料中C1s光谱的拟合结果
表4.不同材料中N1s光谱的拟合结果与相对N含量
表5.各样品Fe K-edge EXAFS曲线拟合参数(S02=0.90)
aN:配位数;bR:吸收体与后向散射原子之间的距离;cσ2:Debye-Waller因子;dΔE0:内电位校正。R factor:拟合度。e拟合范围:和/> f拟合范围:/>和/> g拟合范围:/>和
通过SEM观察发现(图9),本发明制备的Fe-PorBC和Fe-PcBC均为球形形貌,粒径分别为约220nm和141.7nm。TEM显示(图10和11),Fe-PorBC和Fe-PcBC具有无序的碳结构,没有Fe团簇或纳米颗粒,表明该聚合物为无定形结构且无金属原子聚集。AC-HAADF-STEM进一步观察到碳基底中有大量的小亮点,证明Fe-PorBC和Fe-PcBC中的Fe是单原子分散的,符合理论结构(图1a-f)。
利用固体13C NMR和拉曼光谱研究了共轭聚合物的化学结构。如图2a所示,13C NMR谱中136.5ppm的峰归属于C2、Cmeso、Cβ,119.1ppm的峰归属于Cα和C2,证实了铁卟啉基共轭聚合物的成功构建。13C NMR谱在164.5,132.4,114.9ppm处的三个峰则归因于铁酞菁基共轭聚合物网络中的酞菁大环(图2b)。此外,Fe-PorBC在1332cm-1处的拉曼光谱表现出典型的B1g模式,这是由卟啉分子的对称吡咯环振动引起的(图2c)。同样,Fe-PcBC的拉曼光谱也得到了酞菁分子面内振动的A1g、B1g和B2g模式的验证,分别为677、744、1456cm-1(图2d),表明两种共轭聚合物的成功合成。
FT-IR和UV-vis进一步研究了Fe-PcBC扩展的共轭结构。FT-IR光谱显示(图12左图),与PcFe小分子相比,Fe-PcBC的C-H在1118cm-1处的信号显著降低,表明苯环外围C-H的平面内弯曲振动减小,证实了酞菁单体发生聚合。UV-vis进一步发现Fe-PcBC的B带和Q带与PcFe相比有明显的红移,这表明Fe-PcBC通过苯环的连接生成了扩展的共轭结构(图12右图)。此外,XRD显示Fe-PcBC和Fe-PorBC都在26°左右出现了一个典型的共轭聚合物峰(图13),没有出现Fe或氧化铁的结晶峰,证明二者是不含金属单质的无定形结构,这也与STEM数据一致。
上述实验表明,本发明提供的Fe-PorBC和Fe-PcBC是具有共轭网络结构的共轭聚合物。
实验例2:生物催化剂仿过氧化物酶的性能测试和催化机理研究
1、实验方法
(1)仿过氧化物酶催化活性测试
以TMB为底物监测H2O2的分解,测定了生物催化剂的过氧化物酶活性。在1.926mL的醋酸-醋酸钠缓冲溶液(HAc-NaAc)(0.1M,pH 4.5)中加入生物催化剂(4mg/mL,25μL),H2O2(100mM,25μL)和TMB(41.6mM,24μL,溶于DMF),并充分混合。25℃孵育10min后,用酶标仪记录反应溶液在652nm处的吸光度。此外,通过检测生物催化剂在pH 2.5-10.5和25-90℃静置2h后在652nm处的吸光度来测定其pH稳定性和热稳定性。
(2)稳态动力学计算
稳态动力学测试在25℃进行,将2mL含生物催化剂(4mg/mL,25μL)、H2O2(100mM,25μL)和不同浓度TMB的HAc-NaAc缓冲溶液(0.1M,pH 4.5)混合,用酶标仪记录反应溶液在652nm处不同时间的吸光度。为了研究生物催化剂对H2O2的反应动力学,使用恒定浓度的TMB和不同浓度的H2O2作为底物。同样,生物催化剂对TMB的反应动力学也通过使用恒定浓度的H2O2和不同浓度的TMB为底物。将反应速率和底物浓度在Michaelis-Menten方程中拟合,计算动力学常数(Vmax和Km),Michaelis-Menten方程如下:
式中,V0为初始反应速率,Vmax为最大反应速率。其中,Vmax是在饱和底物条件下得到的。[S]为底物浓度。Km为米氏常数,表示初始反应速率达到其最大反应速率的一半时的底物浓度。
生物催化剂的催化活性定义如下:
Kcat=Vmax/[E0] (2-2)
式中,Kcat表示反应常数,其值为每个活性催化中心的最大转化底物量(TON)。E0为金属活性中心的摩尔浓度。
(3)活性氧自由基的检测
3.1)荧光探针测试
以TA为荧光探针(λex=315nm,λem=440nm)检测生物催化剂催化H2O2分解产生的·OH。在1.5mL HAc-NaAc缓冲溶液(0.1M,pH 4.5)中加入生物催化剂(4mg/mL,30μL),4mMNaTA(NaOH和TA的反应物)和60mM H2O2,然后将混合溶液在37℃孵育12h,用荧光光谱仪测定反应溶液的荧光光谱。以HE为荧光探针(λex=470nm,λem=624nm)检测生物催化剂催化H2O2分解产生的O2·-。首先将生物催化剂的HAc-NaAc缓冲溶液(pH 4.5,100μg/mL,1.5mL)与H2O2(100mM,1.5μL)混合,在37℃孵育30min。然后加入HE-乙醇溶液(1mg/mL,1.5mL),继续孵育30min后用荧光光谱仪测定反应溶液的荧光光谱。
3.2)EPR测试
以DMPO为自旋捕获剂检测生物催化剂催化H2O2分解产生的·OH。在0.5mL HAc-NaAc缓冲溶液(0.1M,pH 4.5)中加入生物催化剂(4mg/mL,50μL)和H2O2(10M,10μL),混合均匀后加入10μL DMPO。在25℃孵育10min后,用毛细管吸取反应溶液进行EPR测试。用DMSO替代HAc-NaAc缓冲溶液,以DMPO为捕获剂对产生的O2·-以相同的步骤进行检测。
2、实验结果
表6.不同铁基生物催化剂的相对POD活性
注:Fe content(wt%)表示铁的质量分数,Intensity of oxTMB表示氧化TMB的强度,Normalized intensity of oxTMB表示归一化后的氧化TMB的强度(即相同Fe含量下的强度),Relative intensity ratio(%)表示相对强度占比。
表7.以H2O2为底物的仿POD催化活性动力学比较
注:Km为Michaelis常数,Vmax为最大反应速度,V0为初始反应速度。[E0]为金属活性位点的摩尔浓度,通过改变底物浓度来拟合得到Michaelis-Menten图。转化数(TON)为每个活性催化中心的最大转化底物量,Kcat为催化常数。Kcat/Km值表示催化效率。
表8.以TMB为底物的仿POD催化活性动力学比较
首先采用TMB显色反应评价了Fe-PorBC和Fe-PcBC的POD性能。如图3a和表6所示,在Fe含量相同的情况下,Fe-PorBC和Fe-PcBC催化产生的oxTMB吸光度最高,表明二者的催化活性比其他小分子铁基催化剂更好。此外,Fe-PcBC具有比Fe-PorBC更高的吸光度,表明Fe-PcBC具有更好的POD性能。稳态动力学测试结果表明(图3b,表7和表8),对于底物H2O2,Fe-PcBC的Vmax(88.2)是Fe-PorBC(52.4)的约1.7倍。对于底物TMB,Fe-PcBC的Vmax(130.0)是Fe-PorBC(9.06)的约13.5倍。Fe-PcBC的TON值(H2O2 27.0,TMB 39.8)高于Fe-PorBC(H2O218.5,TMB 3.19),Km值(H2O2 0.106,TMB 0.165)远低于Fe-PorBC(H2O2 10.6,TMB 1.2)。也就是说,Fe-PcBC的催化速率更快,底物转换速率更快,且对底物的亲和力更好,最终导致其催化效率(Kcat/Km)极高,远高于Fe-PorBC(H2O2 146倍,TMB 90倍)。
为了阐明Fe-PorBC和Fe-PcBC的催化机理,利用EPR光谱和荧光探针来探究催化过程中产生的ROS。如图4a所示,DMPO/·OH加合物的特征峰信号强度明显为1:2:2:1,说明Fe-PorBC和Fe-PcBC在催化H2O2分解过程中都产生了·OH。TA作为·OH特异性荧光探针检测发现二者均生成了·OH,Fe-PorBC比Fe-PcBC的荧光强度略高,表明Fe-PorBC产生的·OH更多(图4b)。此外,EPR分析表明,当用DMSO替换反应溶液后,Fe-PcBC的信号强度为1:1:1:1:1(图4c),这是典型的DMPO/O2·-加合物的特征峰,说明Fe-PcBC在催化H2O2分解过程中也产生了O2·-。进一步通过特异性探针HE捕获了O2·-中间体(图4e),结果显示Fe-PcBC组在623nm的吸光度更高,表明Fe-PcBC能够产生更多的O2·-,这与EPR结果一致。
本发明利用MB降解实验进一步探究了Fe-PorBC和Fe-PcBC的催化氧化能力。如图5a所示,与Fe-PorBC(13.5%)相比,Fe-PcBC在30min后对MB的催化降解率达到了74.8%,远高于Fe-PorBC,显示出了Fe-PcBC优异的催化氧化性能。为了研究Fe-PcBC产生的·OH和O2·-的相对含量,分别采用叔丁醇(TBA)和对苯醌(BQ)作为·OH和O2·-的清除剂。如图5b所示,无论加入TBA还是BQ,oxTMB的吸光度都迅速下降,说明·OH和O2·-中间产物在Fe-PcBC的ROS生成过程中都发挥着重要作用。其中,BQ对吸光度的影响较大,表明Fe-PcBC产生的ROS主要是O2·-。
此外,本发明还研究了pH和温度对POD活性的影响,如图5c、d所示,Fe-PorBC和Fe-PcBC在pH=4时表现出最佳的POD活性,并在较宽的温度范围内保持了高的催化活性,显示出Fe-PorBC和Fe-PcBC的在苛刻环境下的催化稳定性。
上述结果表明,在Fe含量相同的情况下,与现有的铁基生物催化剂Fe3O4、TPPFe、Hemin、PcFe相比,本发明提供的共轭聚合物Fe-PorBC和Fe-PcBC具有更优异的POD活性。另外,与Fe-PorBC相比,Fe-PcBC具有更好的POD活性、更好的催化动力学、更强的催化氧化能力。
实验例3:生物催化剂多酶活性的性能测试
1、实验方法
(1)仿氧化酶(OXD)活性测试
以TMB为底物研究材料的OXD活性。在1.951mL的HAc-NaAc缓冲溶液(0.1M,pH 4.5)中加入材料(4mg/mL,25μL)和TMB(41.6mM,24μL,溶于DMF),并充分混合。25℃孵育10min后,用酶标仪记录反应溶液在652nm处的吸光度。通入氧气、空气、氮气比较仿OXD活性。
(2)仿过氧化氢酶(CAT)活性测试
为考察材料分解H2O2的能力,在20mL的HAc-NaAc缓冲溶液(0.1M,pH 4.5)中加入材料(10mg/mL,20μL)和H2O2(10M,200μL),用溶解氧仪测试不同时间点的氧气产量。
(3)仿卤过氧化物酶(HPO)活性测试
次氯酸盐离子(ClO-)可和CB特异性结合,从而将蓝色的CB氧化成粉红色,使得CB的紫外吸光度从640nm降低,而在520nm处上升,在大约540nm处呈等同点。在1.84mL CB的PBS溶液(0.1M,pH 5.8,CB的终浓度为200μM)中加入材料(4mg/mL,150μL)和H2O2(100mM,10μL)。25℃孵育30min后,用酶标仪记录反应溶液在640nm和520nm处的吸光度。
以APF为荧光探针(λex=485nm,λem=514nm)检测材料催化反应中产生的OCl-。在100μL的材料溶液(0.1M,pH 5.8,材料的终浓度为300μg/mL)中加入H2O2(100mM,10μL)和APF(0.5mM,2μL)。25℃孵育30min后,用荧光酶标仪检测在514nm处的吸光度。
(4)仿谷胱甘肽过氧化物酶(GPx)活性测试
5,5’-二硫双(2-硝基苯甲酸)(DTNB)是一种巯基指示剂。其二硫键断裂后产生2-硝基-5-硫代苯甲酸,在408nm处的特征吸光度随着时间的推移而降低。在2mL PBS(0.1M,pH7.4)中加入材料(4mg/mL,25μL)和5mM GSH,然后加入DTNB(3mg/mL,30μL)监测不同时间点的紫外吸收光谱的变化。
2、实验结果
在不同的催化条件下,酶对不同的底物能表现出各种各样的催化活性,这被称为多酶活性。在验证了Fe-PorBC和Fe-PcBC具有仿POD活性后,本发明还研究了二者的仿CAT、OXD、HPO和GPx的性能。如图6a所示,当用于CAT酶催化反应时,Fe-PcBC在5min的氧气产量达到了22.07mg/L,是Fe-PorBC(3.72mg/L)的5.9倍,表现出了良好的H2O2分解能力。此外,在O2作为底物的情况下,Fe-PcBC的oxTMB在652nm处的吸光度更高,表明其OXD活性远优于Fe-PorBC(图6b),反应中产生的O2·-也被EPR检测到(图6c)。HPO酶可催化H2O2氧化卤化物生成ClO-,从而被CB和APF特异性识别。从图6d可以看出,相比Fe-PorBC,Fe-PcBC的CB紫外吸收光谱在640nm处迅速下降,表明产生了更多的ClO-。此外,APF也探测到Fe-PorBC和Fe-PcBC产生的ClO-,较高的荧光强度也证明了Fe-PcBC具有更好的仿HPO活性(图6e)。GPx酶可通过氧化还原反应将自由基清除剂还原型谷胱甘肽(GSH)转化为氧化型谷胱甘肽(GSSG),因此采用DTNB作为巯基指示剂研究了Fe-PorBC和Fe-PcBC的仿GPx活性。如图6f,g所示,在30min的反应时间内,Fe-PcBC表现出了77.34%的高GSH消耗率,而Fe-PorBC只有8.4%的GSH消耗,说明Fe-PcBC具有更好的仿GPx活性。
上述结果表明,本发明提供的共轭聚合物Fe-PorBC和Fe-PcBC除了具有优异的仿POD活性外,还具有优异的仿CAT、OXD、HPO和GPx活性,可以作为高效多功能仿酶催化剂。另外,与Fe-PorBC相比,Fe-PcBC具有更佳的仿POD、CAT、OXD、HPO和GPx活性。
综上,本发明提供了一种共轭聚合物生物催化材料及其制备方法和应用,属于生物催化领域。本发明首次发现,与现有的小分子铁基生物催化剂Fe3O4、TPPFe、Hemin、PcFe相比,本发明提供的共轭聚合物具有更优异的仿POD活性。本发明还发现,除了具有优异的仿POD活性外,本发明提供的共轭聚合物还具有优异的仿POD、CAT、OXD、HPO和GPx活性。本发明提供的共轭聚合物的制备方法简单,适合大规模生产,在制备高效多功能仿酶催化剂中具有广阔的应用前景。
Claims (7)
1.一种共轭聚合物材料,其特征在于:它是将式II所示重复结构单元通过共价键连接形成的聚合物:
其中,M为金属原子。
2.根据权利要求1所述的共轭聚合物材料,其特征在于:M为Fe。
3.根据权利要求1或2所述的共轭聚合物材料,其特征在于:它是以1,2,4,5-苯四甲腈和金属盐为原料反应得到的产物。
4.根据权利要求3所述的共轭聚合物材料,其特征在于:所述1,2,4,5-苯四甲腈和金属盐的摩尔比为(1.5-3.5):1,优选为2.5:1;所述金属盐为铁盐,优选为Fe3+盐;所述反应的温度为160-200℃,优选为180℃,反应的时间为5-15min,优选为10min,反应的溶剂为有机溶剂,优选为乙二醇;
和/或,所述反应是在微波反应器中进行的,所述反应是在催化剂的存在下进行的,所述催化剂为有机碱,所述有机碱优选为1,8-二氮杂环(5,4,0)十一-7-烯。
5.权利要求1-4任一项所述共轭聚合物材料在制备仿酶催化剂中的用途。
6.根据权利要求5所述的用途,其特征在于:所述酶为POD酶、CAT酶、OXD酶、HPO酶和/或GPx酶。
7.根据权利要求5或6所述的用途,其特征在于:所述仿酶催化剂为预防和/或治疗细菌感染的药物、加速伤口愈合的药物。
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