CN114230574B - 一种n-芳基吡啶噻唑并噻唑-葫芦脲复合物及其制备方法和应用 - Google Patents
一种n-芳基吡啶噻唑并噻唑-葫芦脲复合物及其制备方法和应用 Download PDFInfo
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- CN114230574B CN114230574B CN202111567868.6A CN202111567868A CN114230574B CN 114230574 B CN114230574 B CN 114230574B CN 202111567868 A CN202111567868 A CN 202111567868A CN 114230574 B CN114230574 B CN 114230574B
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- cucurbituril
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- Plural Heterocyclic Compounds (AREA)
Abstract
本发明提出了一种N‑芳基吡啶噻唑并噻唑‑葫芦脲复合物的制备方法,包括将2,5‑二(4‑吡啶基)噻唑并噻唑溶于2,4‑二硝基氟苯加热、冷却,用正己烷洗涤并真空干燥得到Zincke盐;将Zincke盐和对氯苯胺加入乙醇和水混匀并加热回流,用乙醚清洗,将获得的粗产物在甲醇溶液中重结晶,获得N‑芳基吡啶噻唑并噻唑分子;将该分子和葫芦脲8分别用二甲基亚砜溶解后混合,配成储存液。本发明首次发现了噻唑并噻唑衍生物的类氧化物酶活性,并将该复合物与大环分子葫芦脲自组装,大大提升了N‑芳基吡啶噻唑并噻唑的光致氧化酶活性,构建一种具有优异光致类氧化酶活性的纳米复合物,在纳米酶生物治疗和传感中具有更好的应用前景。
Description
技术领域
本发明涉及纳米酶技术领域,尤其涉及一种N-芳基吡啶噻唑并噻唑-葫芦脲复合物及其制备方法和应用。
背景技术
纳米酶是一类具有类似天然酶催化活性和酶促反应动力学特征的纳米材料。相对于天然酶来说,纳米酶具有稳定性好,易于制备合成,酶活性可控可调等性能,在实际应用中日益受到大家的关注。开发高活性的类酶先导化合物是纳米酶研究领域的一个热点。
噻唑并噻唑衍生物是2017年首次发现的一类新型的有机分子,该类分子具有优异的光致变色、电化学催化活性,在电池领域引起了大家的关注。然而有关其在类酶活性研究方面尚未见报道。
发明内容
针对上述的技术问题,本发明提出一种N-芳基吡啶噻唑并噻唑-葫芦脲复合物及其制备方法,用以解决现有技术中尚无噻唑并噻唑衍生物在类酶活性方面的研究的问题。
为了达到上述目的,本发明的技术方案是这样实现的:
一种N-芳基吡啶噻唑并噻唑-葫芦脲复合物,所述N-芳基吡啶噻唑并噻唑-葫芦脲复合物的结构式为:
一种N-芳基吡啶噻唑并噻唑-葫芦脲复合物的制备方法,包括如下步骤:
S1.将2,5-二(4-吡啶基)噻唑并噻唑溶于2,4-二硝基氟苯加热、冷却,用正己烷洗涤三次,然后真空干燥得到Zincke盐;
S2.将步骤S1获得的Zincke盐和对氯苯胺置于烧瓶中,加入乙醇和水混匀,加热回流待反应完成后,用乙醚清洗,并将所获得的粗产物在甲醇溶液中重结晶,获得纯的草绿色N-芳基吡啶噻唑并噻唑分子;
S3.将步骤S2获得的N-芳基吡啶噻唑并噻唑分子和葫芦脲8分别用二甲基亚砜溶解,然后将两者的二甲基亚砜溶液混合,在搅拌条件下逐滴加入水溶液中配成N-芳基吡啶噻唑并噻唑-葫芦脲复合物的储存液。
进一步地,所述步骤S1中的2,5-二(4-吡啶基)噻唑并噻唑和2 ,4-二硝基氟苯的摩尔比为1:(42-85)。
进一步地,所述步骤S1中的2,5-二(4-吡啶基)噻唑并噻唑溶于2,4-二硝基氟苯中90℃加热48 h。
进一步地,所述步骤S2中Zincke盐和对氯苯胺的摩尔比为1:(2-4),乙醇和水的体积比为3:2。
进一步地,所述步骤S2中Zincke盐和对氯苯胺置于烧瓶中,加入20 mL的乙醇和水混匀,于100℃加热回流48 h。
进一步地,所述步骤S3中N-芳基吡啶噻唑并噻唑分子和葫芦脲8的摩尔比为1:1,储存液浓度为2 mM。
一种所述的N-芳基吡啶噻唑并噻唑-葫芦脲复合物作为光驱动的有机类氧化酶的应用,所述的N-芳基吡啶噻唑并噻唑-葫芦脲复合物的类氧化酶活性可通过控制光的开关来调控酶的活性。
进一步地,包括如下步骤:将N-芳基吡啶噻唑并噻唑-葫芦脲复合物和3, 3’, 5,5’-四甲基联苯二胺(TMB)置于HAc-NaAc缓冲溶液中,在氙灯照射后,在肉眼或者紫外可见分光光度计的检测下,明显观察到TMB的氧化产物(蓝色TMB);而在同样时间下,不光照上述体系只观察到很少量的蓝色TMB。
进一步地,所述N-芳基吡啶噻唑并噻唑-葫芦脲复合物的浓度为15 μM,TMB浓度为0.3 mM,HAc-NaAc缓冲溶液的pH为3.0,溶液总体积为2 mL,光照时间为5 min;所述的光源为可见光,波长范围为400-780 nm。
本发明的有益效果:
1.本发明基于N-芳基吡啶噻唑并噻唑分子的显著的可见光吸收和固有的光控性质,将其通过与与大环分子葫芦脲自组装,大大提升了N-芳基吡啶噻唑并噻唑的光致氧化酶活性,构建一种具有优光致氧化酶活性的纳米复合物;
2.本发明的复合物具有确定的化学组成,可以通过化学合成的方法制备,具有更加精准的可控性;
3.该复合物在紫外-可见光的照射下,可产生羟基自由基、超氧阴离子自由基,使TMB变色,同时基于产生的自由,可以有效快速杀死细菌;
4.该复合物的活性可以通过光的调控进行开关和活性大小调节,可以满足更多的使用场景需求;
5.该复合物具有类氧化酶活性,相对于目前大量的过氧化物类酶物质来说,该复合物的催化活性无需过氧化氢的辅助,在生物应用场景中,可以避免加入过氧化氢带来的背景干扰和生物机体损伤,在纳米酶生物治疗和传感中具有更好的应用前景。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为本发明的复合路线图;
图2为本发明的实施例1 的TTz-Cl2+-CB[8]和TTz-Cl2+在水溶液中的紫外可见光谱;
图3为本发明的实施例1 的TTz-Cl2+-CB[8]和TTz-Cl2+在水溶液中的荧光光谱;
图4为本发明的实施例1的TTz-Cl2+-CB[8]复合物在不同的摩尔比值TTz-Cl2+/ CB[8]的荧光光谱图;
图5为本发明的实施例1的TTz-Cl2+-CB[8]复合物在不同的摩尔比下制作的Job’s曲线;
图6为本发明的实施例1的TTz-Cl2+-CB[8]复合物的HR-MS图谱;
图7为本发明的实施例1的TTz-Cl2+,CB[8]和摩尔比值为1:1的TTz-Cl2+和CB[8]的1H NMR滴定图;
图8为本发明的实施例1 的TTz-Cl2+-CB[8]复合物的粒度分布图;
图9为本发明的实施例1 的TTz-Cl2+-CB[8]的TEM图谱;
图10为本发明在HAc-NaAc缓冲(100 mM, pH=3.0)体系中, 15 μL TTz-Cl2+-CB[8](2 mM)与100 μL TMB (6 mM) 在光照5 min后的紫外可见吸收光谱谱;
图11为本发明在HAc-NaAc缓冲(100 mM, pH=3.0)体系中,相同量的TTz-Cl2+-CB[8]、TTz-Cl2+、CB[8]在不同光照时间下的紫外可见吸收光谱;
图12为本发明在HAc-NaAc缓冲(100 mM, pH=3.0)体系中,15 μL TTz-Cl2+-CB[8](2 mM)与100 μL TMB (6 mM) 在空气中和N2氛围中光照5 min后的紫外可见吸收光谱;
图13为本发明在HAc-NaAc缓冲(100 mM, pH=3.0)体系中,15 μL TTz-Cl2+-CB[8](2 mM)与100 μL TMB (6 mM)在不同清除剂条件下的紫外可见吸收光谱;
图14为本发明的TTz-Cl2+-CB[8] 复合物在HAc-NaAc缓冲(100 mM, pH=3.0)体系中光电流测定;
图15为本发明的SOSG对TTz-Cl2+-CB[8]复合物在黑暗和光照条件下产生的1O2测定;
图16为本发明的TTz-Cl2+-CB[8] 在光照条件下发挥酶作用时产生的•OH, 1O2,O2 -•活性氧物质的EPR光谱一;
图17为本发明的TTz-Cl2+-CB[8] 在光照条件下发挥酶作用时产生的•OH, 1O2,O2 -•活性氧物质的EPR光谱二;
图18为本发明在HAc-NaAc缓冲(100 mM, pH=3.0)体系中,15 μLTTz-Cl2+-CB[8](2 mM)与100 μL TMB (6 mM) 及不同浓度的GSH(0-400 μM)光照5 min后,紫外可见吸收光谱的变化图一;
图19为本发明在HAc-NaAc缓冲(100 mM, pH=3.0)体系中,15 μLTTz-Cl2+-CB[8](2 mM)与100 μL TMB (6 mM) 及不同浓度的GSH(0-400 μM)光照5 min后,紫外可见吸收光谱的变化图二;
图20为本发明基于TTz-Cl2+-CB[8]和TMB构建的传感平台对GSH含量测定的选择性测试;
图21为本发明在HAc-NaAc缓冲(100 mM, pH=3.0)体系中,15 μMTTz-Cl2+-CB[8]在光照条件下的杀菌效果图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有付出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
一种N-芳基吡啶噻唑并噻唑-葫芦脲复合物的制备方法,包括如下步骤:
S1.根据发表在JACS上的文献《Thiazolothiazole Fluorophores ExhibitingStrong Fluorescence and Viologen-Like Reversible Electrochromism》报道,合成2,5-二(4-吡啶基)噻唑并噻唑,所述2,5-二(4-吡啶基)噻唑并噻唑作为中间体,将该中间体溶于2,4-二硝基氟苯中,且2,5-二(4-吡啶基)噻唑并噻唑和2 ,4-二硝基氟苯的摩尔比为1:(42-85),然后90℃加热48 h,冷却,用正己烷洗涤三次,真空干燥得到Zincke盐,即N-芳基或N-烷基吡啶盐;
S2.将步骤S1中获得的Zincke盐和对氯苯胺按照摩尔比为1:(2-4)置于圆底烧瓶中,加入20 mL的乙醇和水混匀,其中乙醇和水体积比为3:2,然后于100℃加热回流48 h,待反应完成后,用乙醚清洗,并将所获得的粗产物在甲醇溶液中重结晶,进而获得纯的草绿色N-芳基吡啶噻唑并噻唑分子;
S3.将步骤S2中获得的N-芳基吡啶噻唑并噻唑分子和购买的葫芦脲8分别用二甲基亚砜即DMSO溶解,然后将两者DMSO溶液混合,在搅拌条件下逐滴加入水溶液中配成N-芳基吡啶噻唑并噻唑-葫芦脲复合物的储存液。其中,N-芳基吡啶噻唑并噻唑分子和葫芦脲8的摩尔比为1:1,储存液浓度为2 mM。
实施例1,0.126g的Zincke盐,0.153g的对氯苯胺,12 mL的乙醇和8 mL的水置于100 mL的圆底烧瓶中。该反应混合物于100°C 回流48 h。待反应完成后待反应完成后,用乙醚清洗,并将所获得的粗产物在甲醇溶液中重结晶,进而获得纯的草绿色N-芳基吡啶盐(38.6 mg, 33.7% yield)。
1H NMR (600 MHz, D2O): δ 9.19 (d, J = 6.4 Hz, 4H), 8.75 (d, J = 6.6Hz, 4H), 7.73 (d, J = 2.8 Hz, 8H)。
0.126 g 的Zincke 盐, 0.0765 g的对氯苯胺,12 mL的乙醇和8 mL的水置于100mL的圆底烧瓶中。该反应混合物于100°C 回流48 h。待反应完成后待反应完成后,用乙醚清洗,并将所获得的粗产物在甲醇溶液中重结晶,进而获得纯的草绿色N-芳基吡啶噻唑并噻唑分子。
N-芳基吡啶噻唑并噻唑分子和葫芦脲8分别溶于1mL二甲基亚砜即 DMSO中,混合两者的DMSO溶液,在搅拌条件下,向水溶液逐滴加入混合的DMSO溶液,搅拌1 h后,制得N-芳基吡啶噻唑并噻唑-葫芦脲复合物的储存液。
1.如图2和图3所示,TTz-Cl2+-CB[8]和TTz-Cl2+在水中的吸收和荧光发射光谱:
将制得浓度为2 mM的N-芳基吡啶噻唑并噻唑-葫芦脲复合物水溶液和DMSO溶解的浓度为2 mM TTz-Cl2+分别取15 μL加入2 mL的水溶液中,混匀后,分别在紫外可见分光光度计和荧光分光光度计测其吸收和发射光谱。图2和3表明TTz-Cl2+和CB[8]确实发生了相互作用,形成了N-芳基吡啶噻唑并噻唑-葫芦脲复合物。
2. TTz-Cl2+-CB[8] 复合物的表征。
Job’s曲线:保持TTz-Cl2+和CB[8]的总摩尔浓度为20 μM,制备不同摩尔比值10:0,9:1, 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, 2.5:7.5, 1.5:8.5, 0.5:9.5 (n/10-n) 的TTz-Cl2+/ CB[8]水溶液。放置半小时后,上述溶液的荧光光谱被记录。荧光光谱中荧光强度的最大值被采用。Job’s曲线的x轴是TTz-Cl2+/(CB[8]+ TTz-Cl2+)的摩尔比值,y轴是通过F=F10*n/10-Fn计算的荧光强度值。(F10是单独TTz-Cl2+ (20 μM)的荧光值,n是TTz-Cl2+的摩尔比,Fn代表TTz-Cl2+/CB[8]在n/(10-n)摩尔比的荧光强度值。图4和图5表明TTz-Cl2+/CB[8]的摩尔比值为1:1。
高分辨质谱:将上述摩尔比为1:1的TTz-Cl2+和CB[8]水溶液用于高分辨质谱的测定。图6中出现m/z为923.1976的峰,从而进一步表明1:1型TTz-Cl2+-CB[8] 复合物的生成。
1H NMR滴定实验:将浓度为50 μM的TTz-Cl2+,CB[8],以及1:1加入的TTz-Cl2+和CB[8]重水溶液,用于1H NMR的测定。图7中1:1加入TTz-Cl2+和CB[8] 的重水溶液与单独的TTz-Cl2+和CB[8]在芳香区氢的化学位移相比,1:1加入的TTz-Cl2+和CB[8]所展现出的氢谱发生了明显的裂分,表明TTz-Cl2+和CB[8]之间发生了相互作用。
结构的确定:从制得浓度为2 mM的N-芳基吡啶噻唑并噻唑-葫芦脲复合物水溶液取15 μL加入2 mL的水溶液中,混匀后,取出一定量,将其滴在铜网上,干燥后,用于TEM成像。剩余溶液用于水合半径的测定。图8和9分别为TTz-Cl2+和CB[8]组装后形成复合物的半径大小和具体形态,进一步表明TTz-Cl2+/CB[8] =1:1形成了首尾相连的TTz-Cl2+-CB[8]复合物。
3.如图10和图11所示,TTz-Cl2+-CB[8]在光照(不同时间)和非光照条件下的吸收光谱:
配制pH = 3.0的HAc-NaAc (100 mM)缓冲溶液;称取一定质量的TMB,用DMSO溶解,准确配制6 mM的TMB溶液。向离心管中加入15 μL TTz-Cl2+-CB[8],100 μL TMB,200 μL pH= 3.0的HAc-NaAc (100 mM)缓冲溶液,加入超纯水直至总体积为2 mL。氙灯光照(400-780nm)5 min 后,该体系的吸收在紫外可见分光光度计上被记录。图10表明该TTz-Cl2+-CB[8]可能具有光驱动类氧化酶活性。此外,向离心管中分别加入15 μL TTz-Cl2+-CB[8]、TTz-Cl2 +、CB[8],100 μL TMB,200 μL pH = 3.0的HAc-NaAc (100 mM)缓冲溶液,加入超纯水直至总体积为2 mL。氙灯光照(400-780 nm)不同时间后,3个体系的吸收在紫外可见分光光度计上被记录。图11进一步表明图10中TTz-Cl2+-CB[8]和TMB体系中发挥作用的是N-芳基吡啶噻唑并噻唑分子与葫芦脲自组装形成的复合物。
4.如图12~图17所示,TTz-Cl2+-CB[8]作为一种光驱动类氧化酶的进一步验证:
向离心管中加入15 μL TTz-Cl2+-CB[8]+,100 μL TMB,200 μL pH = 3.0的HAc-NaAc (100 mM)缓冲溶液,加入超纯水直至总体及为2 mL。待该体系通氮气5 min后,置于氙灯下光照(400-780 nm)5 min,然后该体系的吸收在紫外可见吸收光谱上被记录。另外一个,同TTz-Cl2+-CB[8]和TMB在光照条件下的吸收光谱操作一样。图12表明氧气在TTz-Cl2+-CB[8]发生催化作用时充当不可或缺的角色,侧面证明了TTz-Cl2+-CB[8]具有光驱动类氧化酶活性。之后,向离心管中加入15 μL TTz-Cl2+-CB[8]+,100 μL TMB,200 μL pH = 3.0的HAc-NaAc (100 mM)缓冲溶液和不同种类活性氧的清除剂,最后加入超纯水直至总体积为2mL。氙灯光照5 min后,在紫外可见分光光度计上记录其吸收光谱。图13表明TTz-Cl2+-CB[8]在光照条件下可催化氧气产生h+,•OH, 1O2, O2 -•活性氧物质。为了防止高浓度清除剂所来的误差,我们接下来对上述确定的活性氧种类进行再一次验证。h+的测定。光电流测量是用传统的三电极系统进行的。ITO电极作为工作电极,饱和Ag/AgCl作为参比电极,铂丝分别作为对电极。在进行光电流测量之前,将20 μL 2 mM的TTz-Cl2+-CB[8]+滴在ITO电极上三次,室温下干燥ITO电极。将TTz-Cl2+-CB[8]复合物修饰的ITO电极浸入100 mM NaAc-HAc缓冲液(pH 3.0)中。随后,在可见光下检测光电流响应。图14光电流实验数据表明,在光照条件下电子和空穴的有效结合和分离,进而证明h+的产生。
产生的•OH, 1O2, O2 -•活性氧物质可以通过电子顺磁共振光谱进一步鉴定。在本次工作中捕获剂5,5-二甲基-1-吡咯啉-N-氧化物(DMPO)和四甲基哌啶(TEMP)被采用,分别用于•OH, O2 -•和1O2的捕获。反应液总体积为2.0 mL,由TTz-Cl2+-CB[8] (15 μL, 2 mM)、DMPO(200 μL,100 mM)/乙醇(200 μL)、pH 3.0 HAc-NaAc缓冲液(200 μL, 0.1M)、TMB (100 μL,6 mM)和1485 μL超纯水组成。在室温下用氙灯照射试样5 min后,然后在Bruker EMX-10/12EPR光谱仪上进行自旋捕获电子顺磁共振(EPR)实验。图16和17清晰地出现了TEMP- 1O2 加合物(1:1:1),DMPO-OH加合物(1:2:2:1)和1:1:1:1的DMPO- O2 -•加合物(1:1:1:1)峰的出现,再次证明该体系中•OH, 1O2, O2 -•活性氧物质的存在。EPR光谱中,由于1O2在黑暗条件下与•OH, O2 -•的峰有些许出入,因此我们采用单线态氧荧光探针(SOSG)来测定黑暗条件下是否有1O2产生。TTz-Cl2+-CB[8] (15 μL, 2 mM)、SOSG (4 μL )、pH 3.0 HAc-NaAc缓冲液(200 μL, 0.1M)和μL超纯水组成的体系在光照前后测定其荧光光谱(激发:488 nm,发射:525 nm)。图15中在黑暗和光照条件下的荧光光谱和图16中EPR光谱的结果能够很好的吻合,表明1O2在黑暗和光照条件下均可产生,但光照条件下产生的更多。
综上所述,通过一系列除氧实验,自由基清除实验,光电流测量,EPR光谱,荧光光谱等实验手段,我们充分证明了TTz-Cl2+-CB[8]复合物可作为一种光驱动类氧化酶,并且在酶发挥作用的过程中产生的活性氧物质为h+,•OH, 1O2, O2 -•。
5.如图18~图20所示,基于TTz-Cl2+-CB[8] 光驱动类氧化酶活性进行GSH测定:
GSH的测定:在含有15 µM TTz-Cl2+-CB[8],0.3 mM TMB的HAc-NaAc缓冲(100 mM,pH = 3.0)体系中,加入不同浓度的谷胱甘肽,然后该体系用超纯水稀释至2 mL。在氙灯下光照5min后,进行紫外可见吸收光谱测量。GSH具有强的还原性,可与氧化型TMB发生反应或者与TMB一同竞争光照产生的ROS,从而致使氧化型的TMB减少,基于反应过程中体系吸收光谱的变化,构建GSH的比色检测。TMB图18和图19表明TTz-Cl2+-CB[8]的光驱动类氧化酶活性随着谷胱甘肽浓度的增加而逐渐降低,并且由TTz-Cl2+-CB[8]和TMB构建的传感体系可用于谷胱甘肽的检测,范围为0.03-30 μM检测限为5.16nΜ。
选择性实验:在含有15 µM TTz-Cl2+-CB[8],0.3 mM TMB的HAc-NaAc 缓冲(100mM,pH = 3.0)体系中,加入200 µL的分析物:丝氨酸,谷氨酸,精氨酸,赖氨酸,缬氨酸,亮氨酸,组氨酸,天冬氨酸,酪氨酸,抗坏血酸,半胱氨酸,然后该混合物用超纯水稀释至2 mL,接着在氙灯下光照5 min,进行紫外可见吸收光谱测量。同时,对不同分析物在652nm处的吸收值进行处理。图20实验结果表明,其它种类的氨基酸,阳离子和阴离子对该催化体系产生的干扰可以被忽略,这表明该TTz-Cl2+-CB[8]和TMB构成的光催化体系对GSH具有高的选择性。
6.如图21所示,TTz-Cl2+-CB[8]的抗菌作用:
TTz-Cl2+-CB[8]具有光致氧化酶活性,在光照条件下,产生自由基,基于自由基的的强氧化作用,可以抑制细菌的生长。在含有15µMTTz-Cl2+-CB[8]的HAc-NaAc缓冲(100 mM,pH =3.0)体系中,加入100 µL的金黄色葡萄球菌,然后该混合物用超纯水稀释至2 mL。在氙灯下光照5min后,稀释一定倍数,取100 µL涂板,将涂抹过的平板在37oC培养箱中培养17 h后计数。细菌的生长状况和细菌生存率如图21所示,表明:TTz-Cl2+-CB在光照的情况下,具有强烈的抑菌效果;在15µM TTz-Cl2+-CB[8]浓度条件下,光照5min即可杀灭所有的细菌,展现了优异的抑菌性能,表明该复合物在抑菌领域研究和应用的巨大前景。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
2.一种权利要求1所述的N-芳基吡啶噻唑并噻唑-葫芦脲复合物的制备方法,其特征在于,包括如下步骤:
S1.将2,5-二(4-吡啶基)噻唑并噻唑溶于2,4-二硝基氟苯加热、冷却,用正己烷洗涤,然后真空干燥得到Zincke盐;
S2.将步骤S1获得的Zincke盐和对氯苯胺置于烧瓶中,加入乙醇和水混匀,加热回流待反应完成后,用乙醚清洗,并将所获得的粗产物在甲醇溶液中重结晶,获得N-芳基吡啶噻唑并噻唑分子;
S3.将步骤S2获得的N-芳基吡啶噻唑并噻唑分子和葫芦脲8分别用二甲基亚砜溶解,然后将两者的二甲基亚砜溶液混合,在搅拌条件下逐滴加入水溶液中配成N-芳基吡啶噻唑并噻唑-葫芦脲复合物的储存液。
3.根据权利要求2所述的N-芳基吡啶噻唑并噻唑-葫芦脲复合物的制备方法,其特征在于,所述步骤S1中的2,5-二(4-吡啶基)噻唑并噻唑和2 ,4-二硝基氟苯的摩尔比为1:(42-85)。
4.根据权利要求2所述的N-芳基吡啶噻唑并噻唑-葫芦脲复合物的制备方法,其特征在于,所述步骤S1中的2,5-二(4-吡啶基)噻唑并噻唑溶于2,4-二硝基氟苯中90℃加热48 h。
5.根据权利要求2~4任一项所述的N-芳基吡啶噻唑并噻唑-葫芦脲复合物的制备方法,其特征在于,所述步骤S2中Zincke盐和对氯苯胺的摩尔比为1:(2-4),乙醇和水的体积比为3:2。
6.根据权利要求5所述的N-芳基吡啶噻唑并噻唑-葫芦脲复合物的制备方法,其特征在于,所述步骤S2中Zincke盐和对氯苯胺置于烧瓶中,加入20 mL的乙醇和水混匀,于100℃加热回流48 h。
7.根据权利要求2~4和6任一项所述的N-芳基吡啶噻唑并噻唑-葫芦脲复合物的制备方法,其特征在于,所述步骤S3中N-芳基吡啶噻唑并噻唑分子和葫芦脲8的摩尔比为1:1,储存液浓度为2 mM。
8.一种如权利要求1所述的N-芳基吡啶噻唑并噻唑-葫芦脲复合物的应用,其特征在于,所述的N-芳基吡啶噻唑并噻唑-葫芦脲复合物用于制备可作为光驱动的有机类氧化酶,且所述的N-芳基吡啶噻唑并噻唑-葫芦脲复合物的类氧化酶活性可通过控制光的开关来调控酶的活性。
9.根据权利要求8所述的N-芳基吡啶噻唑并噻唑-葫芦脲复合物的应用,其特征在于,包括如下步骤:将N-芳基吡啶噻唑并噻唑-葫芦脲复合物和3, 3’, 5, 5’-四甲基联苯二胺置于HAc-NaAc缓冲溶液中,在氙灯照射后,在肉眼或者紫外可见分光光度计的检测下,明显观察到TMB的氧化产物。
10.根据权利要求9所述的N-芳基吡啶噻唑并噻唑-葫芦脲复合物的应用,其特征在于,所述N-芳基吡啶噻唑并噻唑-葫芦脲复合物的浓度为15 μM,TMB浓度为0.3 mM,HAc-NaAc缓冲溶液的pH为3.0,溶液总体积为2 mL,光照时间为5 min;所述的紫外可见分光,波长范围为400-780 nm。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107383031A (zh) * | 2017-08-04 | 2017-11-24 | 厦门大学 | 一类氨基葫芦脲及其制备方法 |
CN110759926A (zh) * | 2019-11-06 | 2020-02-07 | 南开大学 | 基于水溶性的苯基吡啶衍生物-葫芦脲超分子假轮烷组装体及在细胞磷光成像的应用 |
CN112409388A (zh) * | 2020-11-28 | 2021-02-26 | 昆明理工大学 | 一类开环葫芦脲柱芳烃双主体化合物及其制备方法和应用 |
CN113563351A (zh) * | 2021-07-13 | 2021-10-29 | 昆明理工大学 | 一类水溶性开环葫芦脲荧光探针及其应用 |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107383031A (zh) * | 2017-08-04 | 2017-11-24 | 厦门大学 | 一类氨基葫芦脲及其制备方法 |
CN110759926A (zh) * | 2019-11-06 | 2020-02-07 | 南开大学 | 基于水溶性的苯基吡啶衍生物-葫芦脲超分子假轮烷组装体及在细胞磷光成像的应用 |
CN112409388A (zh) * | 2020-11-28 | 2021-02-26 | 昆明理工大学 | 一类开环葫芦脲柱芳烃双主体化合物及其制备方法和应用 |
CN113563351A (zh) * | 2021-07-13 | 2021-10-29 | 昆明理工大学 | 一类水溶性开环葫芦脲荧光探针及其应用 |
Non-Patent Citations (4)
Title |
---|
Color-tunable luminescent materials via a CB[8]-based supramolecular assembly strategy;Wei-Hanf Jin et al.;《Mater. Chem. Front.》;20210121;第5卷;第2347-2352页 * |
Four Keggin-based compounds constructed by a series of pyridine derivatives: synthesis, and electrochemical, photocatalytic and fluorescence sensing properties;Hai-chen Mou t al.;《New J. Chem.》;20200808;第44卷;第15122-15130页 * |
Humidity- and Temperature-Tunable Multicolor Luminescence of Cucurbit[8]uril-Based Supramolecular Assembly;Tao Jiang et al.;《ACS Applied Materials & Interfaces》;20190327;第11卷;第14309-14407页 * |
基于葫芦脲超分子作用的研究方法;张先廷;《化工技术与开发》;20140930;第43卷(第9期);第26-29页 * |
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