CN106977487B - 一种用于检测肼的新型荧光探针及其应用 - Google Patents
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Abstract
本发明涉及一种用于检测肼的新型荧光探针及其应用,属于分析化学技术领域。本发明的荧光探针,在肼存在的环境下,其乙酰酯基水解为羟基,生成具有高荧光发射能力的荧光物质;所生成的荧光物质发射罗丹明衍生物染料的红色荧光(峰值约为630 nm)。另外,本发明的荧光探针只对肼有响应,而对Hcys、Na2S、Na2SO3、NO、H2O2、HClO4、GSH、NaNO2、VC等小分子没有响应。所以,本发明的荧光探针是对肼的特异性探针,基本不受其他小分子的干扰。通过荧光检测器检测加入本发明的荧光探针之后环境和细胞的荧光强度,从而确定确定肼在环境和细胞中的含量,从而实现肼的快速灵敏检测。因此,本发明的荧光探针能应用于环境和细胞内肼的检测评价。
Description
技术领域
本发明涉及一种用于检测肼的新型荧光探针及其应用,属于分析化学技术领域。
背景技术
肼(Hydrazine)是一种无色易挥发的液体,在水溶液中亦称作水合肼,具有强碱性。水合肼是一种重要的化工原料和中间体,它能够合成发泡剂,供热系统中的除氧剂;水合肼还是药物合成重要的原料,常备用来制备农药,抗癌药和降压药;肼还在纺织染料,摄影化学中右重要的作用;肼易燃易爆,也被用来作为火箭推进剂和染料。虽然肼有很多应用价值,但是肼也是具有一定的毒性,所以在肼的生产、运输、应用和后处理中不恰当的使用和操作都会带来肼的泄漏,从而对环境带来一定的污染。肼的水溶性较好,人体很容易通过水环境吸收肼,长时间的累积可能会对人体的多种器官如肝、肾和肺带来危害。除此之外,肼还具有致癌性。综上所述,测定环境和生物体内肼的含量具有十分重要的意义。
相比于传统的测定肼的气相色谱法和化学滴定法,荧光成像分析法具有灵敏度高、选择性好、操作简单等优点,并且在生物样本检测中不会对样品带来损伤,已广泛用于各种生物体内的小分子检测。因此开发新的具有高灵敏度、高选择性、光稳定性,能够实时快速检测肼的荧光探针具有重要的意义。
发明内容
针对现有技术的不足,本发明要解决的问题是提供一种新型检测肼的荧光探针及其应用。
一种用于检测肼的新型荧光探针,其化学结构通式如式()所示:
式()
本发明的荧光探针,在肼存在的环境下,其乙酰酯基水解为羟基,生成具有高荧光发射能力的荧光物质;也就是说本发明的荧光探针的乙酰酯基部分为肼的响应位点;所生成的荧光物质发射罗丹明衍生物染料的红色荧光(峰值约为630 nm)。另外,本发明的荧光探针只对肼有响应,而对Hcys、Na2S、Na2SO3、NO、H2O2、HClO4、GSH、NaNO2、VC等小分子没有响应。所以,本发明的荧光探针是对肼的特异性探针,基本不受其他小分子的干扰。通过荧光检测器检测加入本发明的荧光探针之后环境和细胞的荧光强度,从而确定确定肼在环境和细胞中的含量,从而实现肼的快速灵敏检测。因此,本发明的荧光探针能应用于环境和细胞内肼的检测评价。
本发明的荧光探针在应用于环境和细胞内肼的检测评价时的检测条件为:激发波长为560 nm,在590~700 nm之间进行荧光发射光谱的检测。
本发明的荧光探针应用于环境内肼的检测评价时的具体测定方法为:将待测样品加入到的荧光探针的乙醇水溶液中,测定溶液的荧光强度作为是否含有肼及肼浓度的评价指标。
本发明采用MTT比色法,通过分析活细胞在加入荧光探针之后的存活率,讨论荧光探针对细胞的毒性;然后进一步研究通过研究加入荧光探针后活细胞的荧光成像。实验证明本发明的荧光探针对活细胞没有毒性、且荧光成像清晰可以对活细胞内的肼进行快速检测。
将本发明所述荧光探针的乙醇水溶液注入细胞的培养基中进行培养,然后用PBS(磷酸盐缓冲溶液)冲洗培养细胞,再进行荧光成像;根据荧光成像结果判断是否含有肼。
本发明的荧光探针的制备方法:
式(Ⅱ)化合物 、乙酸酐用有机溶剂溶解后,在三乙胺存在的条件下进行反应,然后将所得固体进行柱层析纯化得到棕红色的产物,即可;层析纯化所用洗脱液V(DCM):V(MeOH)=50:1;
式(Ⅱ)
上述制备方法,优选的,所用溶剂为二氯甲烷。
上述制备方法,优选的,式(Ⅱ)化合物、酸酐、三乙胺和二氯甲烷的用量比为1mmol:2 mmol :2.2 mmol: 5 mL;反应时间为4小时。
上述制备方法,所述式(Ⅱ)化合物的制备方法:4-二乙氨基酮酸和1-6萘酚以浓硫酸为溶剂,于90℃回流;然后将反应液冷却至-5~0℃,加入高氯酸使其析出沉淀,抽滤、烘干及过层析柱纯化,纯化所用洗脱液V(DCM):V(MeOH)=10:1。
式(Ⅱ)合成路线:
。
本发明中,μM是指μmol/L;mM是指mmol/L;DCM即为二氯甲烷,MeOH即为甲醇。
本发明的有益效果为:
本发明所述的检测肼的荧光探针可经化学合成获得,合成工艺简单易行,原料廉价易得,制备成本低,易于推广。
本发明所述的检测细肼的荧光探针具有高特异性,在进行相应肼检测过程中基本不受其他组分的干扰,可用于环境和活细胞内肼的实时测定,具有广阔的应用前景。
本发明所述的检测肼的荧光探针灵敏度高,具有良好的荧光发射光谱特性(590~700 nm),可以实现对环境和活细胞中的肼快速准确检测的目的。
附图说明
图1是本发明荧光探针的1H NMR图谱;
图2是本发明荧光探针在不同浓度肼条件下的荧光光谱;
图3是本发明荧光探针与不同物质反应后的荧光光谱;
图4是本发明荧光探针在活细胞中的成像应用;
图2中,从下向上肼的浓度依次为:0μM-5μM -10μM -15μM -20μM -25μM -30μM -35μM -40μM -45μM -50μM -55μM -60μM -65μM -70μM -75μM -80μM -85μM -90μM -95μM-100μM -105μM -110μM -115μM -120μM -125μM -130μM -135μM -140μM -145μM -150μM;
图4中,a图:只加10 μM探针的细胞明场照片;b图:只加10 μM探针的细胞红色通道荧光照片;c图:a图和b图的叠加照片;d图:加入10 μM探针和100 μM肼的细胞明场照片;e图:加入10 μM探针和100 μM肼的细胞红色通道荧光照片;f图:d图和e图的叠加照片。
具体实施方式
下面结合实施例和附图对本发明做进一步说明,但本发明保护内容不仅限于此。
实施例1:本发明所述检测癌细胞内肼的荧光探针的制备
取50ml 圆底烧瓶将313mg、1mmol的4-二乙氨基酮酸(化合物1,CAS: 5809-23-4,)及160mg、 1mmol的1-6萘酚( 化合物2,CAS: 59335-81-8, )加入到瓶中,加入4mL浓硫酸做溶剂,于90℃回流6 h。等待反应液冷却至室温,将烧瓶放入低温环境(-5~0℃)缓慢滴加高氯酸使其析出沉淀,抽滤、烘干及过柱子纯化,洗脱液极性(V(DCM):V(MeOH)=10:1)得到红色固体产品即为式(Ⅱ)化合物,产率58%。
将式(Ⅱ)所示的化合物 (1 mmol)、乙酸酐(2 mmol)、三乙胺(2.2 mmol)和二氯甲烷 ( 5 mL) 加入到50 mL的单口烧瓶中,室温搅拌4小时,旋干。将所得固体进行柱层析纯化(V(DCM):V(MeOH)=50:1),得到棕红色的产物即为本发明所述检测肼的荧光探针,产率54%;其1H NMR图谱见图1。
实施例2:本发明所述荧光探针在不同肼浓度下的荧光光谱
本专利采用肼溶解在水溶液中供应肼。预先准备30份5mL的 5μM的探针缓冲溶液(乙醇的体积含量为5%);分别加入肼使得探针缓冲溶液中肼依次为0μM、5μM 、10μM 、15μM、20μM 、25μM 、30μM 、35μM 、40μM 、45μM 、50μM 、55μM 、60μM 、65μM 、70μM 、75μM 、80μM、85μM 、90μM 、95μM 、100μM 、105μM 、110μM 、115μM 、120μM 、125μM 、130μM 、135μM 、140μM 、145μM 、150μM。然后进行荧光检测(Ex = 560 nm);计算各体系中荧光强度;通过分析630 nm处的荧光强度与肼浓度的关系,评估该探针对肼的响应性能(见图2)。图2表明,随着肼浓度的增大,溶液的荧光强度逐渐增强。
实施例3:荧光探针与不同物质反应后的荧光光谱
预先准备10份5mL的 5μM的探针缓冲溶液(含5%乙醇,pH = 7.4),然后分别向该体系中依次加入50μL浓度为200μM的肼、Hcys、Na2S、Na2SO3、NO、H2O2、HClO4、Cys、GSH、NaNO2、VC等小分子的PBS溶液。然后进行荧光检测(λEx = 580 nm);计算各体系中荧光强度;评估该不同物质对荧光探针溶液的干扰性(见图3)。从图中看出,只有当探针溶液中加入肼时,能够使溶液产生显著的荧光;而当探针溶液中加入Hcys、Na2S、Na2SO3、NO、H2O2、HClO4、GSH、NaNO2、VC等小分子时,溶液荧光基本没有变化;这表示该探针只对肼有响应,而基本不受其他小分子的干扰。
实施例4:荧光探针在活细胞中的成像应用
将癌细胞HeLa细胞放在培养基(培养基中DMEM培养液和胎牛血清的体积比为9:1)中,放置于条件为37℃、5% (体积分数)CO2和20% (体积分数)O2的培养箱中培养24 -48h。加入本发明所述荧光探针的乙醇溶液(荧光探针浓度为5 μM,含5%(体积分数)乙醇,pH =7.4),注入含有HeLa细胞的培养基中,继续在培养箱中培养30 min,PBS (磷酸盐缓冲溶液)冲洗培养细胞3次。加入肼,使得培养基中肼的浓度为25 μM,继续培养30 min。之后用PBS冲洗培养细胞3次,进行荧光成像。
结果见图4:从a、b和c图中看出,只加入探针时,细胞无红色荧光;从d、e和f图中看出, 加入探针之后,再加入100 μ 肼,细胞有明显的红色荧光产生,这表示该探针可用于检测癌细胞中的肼。
Claims (5)
1.一种用于检测肼的荧光探针,其特征在于,其化学结构通式如式(I)所示:
。
2.一种权利要求1所述的荧光探针的制备方法,其特征在于,
式(Ⅱ)化合物 、乙酸酐用有机溶剂溶解后,在三乙胺存在的条件下进行反应,然后将所得固体进行柱层析纯化得到棕红色的产物,即可;层析纯化所用洗脱液VDCM:VMeOH=50:1;。
3.根据权利要求2所述的制备方法,其特征在于,所用溶剂为二氯甲烷。
4.根据权利要求2或3所述的制备方法,其特征在于,式(Ⅱ)化合物、酸酐、三乙胺和二氯甲烷的用量比为1mmol:2 mmol :2.2 mmol: 5 mL;反应时间为4小时。
5.根据权利要求4所述的制备方法,其特征在于,所述式(Ⅱ)化合物的制备方法:4-二乙氨基酮酸和1-6萘酚以浓硫酸为溶剂,于90℃回流;然后将反应液冷却至-5~0℃,加入高氯酸使其析出沉淀,抽滤、烘干及过层析柱纯化,纯化所用洗脱液VDCM:VMeOH=10:1。
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CN114113045A (zh) * | 2020-08-31 | 2022-03-01 | 湖南超亟检测技术有限责任公司 | 一种新型近红外水合肼荧光检测试剂及其应用 |
CN112625033B (zh) * | 2020-12-21 | 2022-03-22 | 青岛科技大学 | 一种检测胺类化合物气体的荧光探针 |
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