CN114516836A - 一种荧光探针材料及其制备方法和检测硫化物的方法 - Google Patents
一种荧光探针材料及其制备方法和检测硫化物的方法 Download PDFInfo
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- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
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- C07D221/06—Ring systems of three rings
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- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
本发明材料和检测技术,公开了一种荧光探针,并将其用于检测硫化物,尤其是硫化氢。该探针基于以萘酰亚胺部分作为荧光团,2,4‑二硝基苯氧基部分通过光诱导电子转移(PET)效应作为猝灭基团。H2S作为亲核攻击试剂攻击探针,并断裂萘酰亚胺环和2,4‑二硝基苯基团之间的键,从而释放荧光团,系统出现明显的荧光增强和裸眼可视现象,从而实现对H2S的有效检测。本发明可在较短时间内(60s)实现对硫化物的快速响应,对硫化氢的最低检出限低至5μM,具有较高的灵敏性、较强的抗干扰能力、识别快速、检测结果准确,有效地实现硫化氢在0‑200μM范围的定量检测;检测过程简便,具有开发使用前景。
Description
技术领域
本发明涉及检测和材料领域,具体公开了一种荧光探针及检测硫化物的方法。
背景技术
硫化氢(H2S)已被公认为继一氧化氮(NO)和一氧化碳(CO)之后的第三种气体信号分子,具有臭鸡蛋气味。硫化氢(H2S)作为三大气体分子之一,与人体健康、植物生长和环境问题密切相关。就人类健康而言,细胞内H2S在消化系统、神经系统、心血管系统和泌尿系统的调节中起着重要作用。H2S浓度失衡会导致动脉和肺动脉高压、阿尔茨海默病、骨损伤、肝硬化等疾病。外源性H2S的重要性也在许多方面得到了承认。硫化氢(H2S)虽然是硫化物工业中重要的工业原料,但在工业过程中也是一种严重的有害物质。如,H2S会严重腐蚀金属设备此外,H2S也是红酒质量的指标之一,也是劣质葡萄酒的罪魁祸首。由于葡萄酒本身具有强烈的氧化还原作用,当H2S浓度为1.1μg/L或更高时,会破坏葡萄酒的香气成分。从而会对葡萄酒的风味产生负面影响。因此,开发快速、灵敏、专一检测硫化氢的方法在环境科学、生物科学、食品健康等领域具有重要的研究意义。目前,检测H2S的方法包括电化学方法、碘量法、亚甲基蓝法、色谱法、硫化物沉淀法等,这些技术不适用于复杂生物系统中H2S水平的无损和现场检测。光谱技术,如紫外光谱,荧光和近红外光谱因具有高灵敏度、高效率、高通量、可直接测量和不需要任何先进仪器等优点已经成为一个有吸引力和有前途的候选方法日益受到青睐。这些分析技术可以通过制备廉价的试剂盒实现在复杂的背景下的视觉识别,是最有潜力成为在广大农业地区域推广的快速分析技术。
近年来,应用于硫化氢检测的荧光/比色探针得到了一定的发展。然而,大多数探针只是专一的应用于生物成像,且都只是单一的荧光型探针或比色型探针。据我们所知,荧光法/比色法双模式检测硫化氢在食品、水和蒸汽中的应用鲜有报道,比色法简单、成本低、分析速度快,能实现裸眼识别的效果,同时荧光法浓度低、灵敏度高,两种模式同时启用,可增加检测的准确度和检测范围。因此,开发具有快速响应和高灵敏度的荧光法和比色法双重作用的新型荧光探针仍然是非常重要的。
发明内容
本发明旨在提供一种荧光探针材料、制备方法和应用,能够用于检测硫化氢。
本发明的另一个目的在于提出一种基于荧光和/或比色双模式检测硫化氢的方法,以解决环境和食品中硫化氢的检测时长久、检测灵敏度低、检测范围窄、裸眼识别难等问题。
本发明是通过以下技术方案实现的。
一种荧光探针材料,为式I所示的化合物:
上述化合物的制备方法包括以下步骤:将化合物C2与2,4-二硝基氟苯在催化剂和保护气氛下,加热回流至反应完全。
优选的,所述催化剂为三乙胺;反应溶剂为DMF、乙腈或三氯甲烷。
C2与2,4-二硝基氟苯和催化剂的摩尔比为1:1-1.5:2-4,在本发明的一个优选实施例中,摩尔比为1:1.2:3。回流反应条件为:70-100℃下反应4-12小时,优选为75-90℃下反应6-8小时。
所述的化合物C2通过以下方法制备:化合物C1与4-羟基苯基硼酸及催化剂和碱在有机溶剂中回流反应。
C1与4-羟基苯基硼酸及催化剂和碱的摩尔比为1:1-2:0.02-0.1:5-12,优选为1:1.1-1.4:0.03-0.05:6-9。回流反应条件为:70-100℃下反应4-12小时,优选为75-90℃下反应6-8小时。
所述的化合物C1通过以下方法制备:4-溴-1,8-萘酸酐溶解于有机酸,加入丁胺,升温至100-120℃,回流搅拌反应4-16h,获得中间产物C1。
所述的有机酸为乙酸。
上述荧光探针材料,在400nm激发条件下,在458nm处有荧光发射强度;加入硫化氢后,在458nm处的荧光发射强度明显减弱,发生红移,在540nm处出现新峰,548nm处荧光增强。同时,在458nm处具有紫外吸收强度;加入硫化氢后,在360nm处的紫外吸收强度明显减弱,且发生红移,在450nm处有新的吸收峰出现。加入其他物质时,紫外吸收强度和荧光发射强度没有明显变化,说明该探针具有特异性,有较好的荧光专一选择性和抗干扰性,以及较好的紫外转移选择性。因此,上述荧光探针材料能够用于检测硫化物,或者用于制备检测硫化物的试剂。
所述的硫化物为硫化氢或者可溶性硫化盐,如硫化钠或硫化钾。
探针的工作原理是,以萘酰亚胺部分作为荧光团,2,4-二硝基苯氧基部分通过光诱导电子转移(PET)效应作为猝灭基团,通过荧光增强(荧光法)且裸眼识别(比色法)型探针检测硫化物,尤其是硫化氢。
由于硫化氢强的亲电性,硫化氢作为亲核攻击试剂进攻探针分子,导致断裂萘酰亚胺环和2,4-二硝基苯氧基团之间的键,释放出荧光信号,生成具有荧光的产物C2,系统出现明显的荧光增强和裸眼可视现象,从而实现对H2S的有效检测。随着硫化氢浓度的增加,检测液的颜色在可见光下从无色变为黄色最后为紫红色,在365nm紫外灯下,探针由很弱的蓝色荧光到明亮的黄绿色,实现裸眼识别硫化氢的效果。
基于上述荧光探针材料检测硫化物,可用荧光检测、紫外检测或可视化检测。上述荧光探针材料既可以定性,也可以定量检测硫化氢或硫化盐。
一种检测硫化物的方法,将上述荧光探针材料与待测样品混合,检测458nm-540nm处的荧光发射强度,即荧光检测的方法。若在400nm激发条件下,在458nm处的荧光发射强度明显减弱,发生红移,在540nm处出现新峰,548nm处荧光增强,则说明含有硫化物。
或者,将上述荧光探针材料与待测样品混合,检测紫外吸收强度(360-450nm处),即紫外检测的方法。若360nm的紫外吸收强度减弱,且发生红移,在450nm处有新的吸收峰出现,则说明含有硫化物。
或者,将上述荧光探针材料与待测样品混合,观察溶液颜色是否发生变化,即可视化检测的方法。若颜色从无色变成黄色,最后为紫红色,则说明含有硫化物。
将所述的荧光探针材料和待测样品分散于二甲基亚砜与水混合液后,检测其荧光强度或者紫外吸收度,或者用肉眼观察。优选的,所述二甲基亚砜与水的体积比为6-12:1,优选为8-10:1;在本发明一个优选方式中,为9:1。
采用本发明的荧光探针,当硫化物例如硫化氢含量为0-50μM时,采用荧光法可以检测;当含量超过50μM时,可用比色法检测。因此,在硫化物含量不同是,采用上述荧光探针,分别采用荧光法和比色法,都可以实现检测。当硫化氢含量超过50μM时,肉眼可以观察到颜色变化:随着硫化氢浓度的增加,检测液的颜色在可见光下从无色变为黄色最后为紫红色,在365nm紫外灯下,探针NI-SH由很弱的蓝色荧光到明亮的黄绿色。
采用荧光法检测时,根据540nm/458nm处的荧光强度比,可以定量检测。
以360nm为激发波长,在荧光光谱仪上测定456nm和540nm处的荧光发射强度,以硫化氢的浓度为横坐标,以540nm/458nm处的荧光强度比为纵坐标,可得到硫化氢浓度的工作曲线,进行定性检测。
利用上述探针及检测方法,能够在较短时间内(60s)实现对硫化的快速响应,通过荧光法检测硫化氢的最低检出限为5×10-6mol/L,具有较高的灵敏性、较强的抗干扰能力、识别快速、检测结果准确。
本发明的有益效果在于:
(1)本发明基于亲核反应、探针的荧光“开-关”效应及紫外吸收特性建立了高灵敏度的双重模式的硫化氢的检测方法,并提供了一种新型的荧光探针,是一种增强型的探针。
相对于荧光淬灭型探针,荧光增强型探针具有较好的专一选择、抗干扰性和较高的灵敏度。
(2)本发明不仅可以通过肉眼对目标物硫化氢进行可视化鉴别,也可用比色法和荧光法对硫化氢进行定量检测,荧光法(0-50μM)和比色法(50-200μM或者更高)可相互补充,有效地实现半定量检测和在0-200μM范围的定量检测;能在短时间(60s)内实现对硫化的快速响应,对硫化氢的最低检出限低至5μM。双重模式的检测通过两种方法输出测定结果,减小了环境波动引起的误差,保证了测定结果的可靠性,更适合实际应用。
(3)本发明的探针易于制备,具有较高的灵敏性、较强的抗干扰能力,识别快速、检测结果准确,检测过程简便,可实现对实际样品中硫化氢的快速检测,可基于该探针制备廉价的试剂盒,具有良好的开发使用前景。
附图说明
图1为本发明的荧光探针NI-SH荧光选择性图,激发波长400nm;发射波长420nm;
图2为本发明的荧光探针NI-SH紫外选择性图;
图3为本发明的荧光探针NI-SH识别硫化氢的抗干扰性图,激发波长400nm,发射波长420nm;黑色柱为探针加入其他干扰性物质,灰色柱为探针加入硫化氢及其他干扰性物质;
图4为本发明的荧光探针NI-SH识别硫化氢的响应时间图,激发波长360nm;发射波长380nm;
图5为本发明的荧光探针NI-SH识别硫化氢的浓度滴定紫外吸收图;
图6为本发明的荧光探针NI-SH识别硫化氢的浓度滴定荧光图,激发波长360nm,发射波长380nm;
图7为本发明的荧光探针识别NI-SH识别硫化氢的工作曲线的绘制,激发波长360nm;发射波长380nm;
图8为本发明的荧光探针NI-SH识别硫化氢稳定性研究的图,激发波长360nm;发射波长380nm;(本图有两条线,下面的是探针本身,没有荧光,在长时间里探针稳定,上面的是加硫化氢后,荧光增强,且稳定,因为探针是比率型的,有双峰,所以是两个峰荧光的比值)
图9为本发明的荧光探针NI-SH识别硫化氢的机理图;
图10为本发明的荧光探针NI-SH识别硫化氢的机理验证高分辨质谱图。
具体实施方式
下面将结合本发明实施例,对本发明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。
本发明中制备荧光探针(以下称为NI-SH)的过程中所使用的化学试剂、溶剂、均购自探索试剂公司,金属离子等均购自阿拉丁试剂公司。在荧光探针NI-SH的确证和性能测试过程采用Bruker公司DTX-400型核磁共振谱仪,溶剂为氘代氯DMSO,以TMS为内标记录核磁共振氢谱和碳谱;采用Thermo公司的Q-Exactive HR-MS质谱仪记录高分辨质谱数据。采用英国爱丁堡FS-5荧光分析仪记录荧光光谱。
实施例1荧光探针NI-SH的制备
1、C1的制备
100mL圆底烧瓶中,将4-溴-1,8-萘酸酐(2.7g,7.22mmol)溶解在乙酸(30mL)中,用针管加入丁胺(4ml,7.22mmol)。逐将反应混合物升温至115度左右,当温度达到80度时,溶液由浑浊变澄清,在回流中搅拌6小时。待反应结束,冷却至室温后,有固体析出(棕色),将混合物过滤并在减压下干燥,得到棕色针状固体。即中间产物C1,产率为80%。
2、C2的制备
室温条件下,准确称量化合物C1(500mg,1.00mmol)、4-羟基苯基硼酸(249.12mg,1.2mmol)和四-(三苯基膦)钯(55mg,0.0407mmol)放置于100ml的反应瓶中,抽真空,插氮气球保护,加入15mL的DMF,加入K2CO3溶液(1.12g/5mL水),升温110度,加热回流,搅拌待固体化合物完全溶解。取反应液点板监测反应进行的程度,至反应物点消失或不再发生变化,停止加热,移出反应瓶,冷却反应液,冷却过程中,有黄绿色固体析出,进行减压抽滤,将粗产物进行硅胶层析柱提纯,洗脱剂为DCM,得到黄绿色固体C2,产率为50%。
3、探针NI-SH的制备
将反应物C2(240mg,1.0mmol),2,4-二硝基氟苯(193.98mg,1.2mmol)和三乙胺(152.39mg,3.0mmol)加入三口圆底烧瓶,加入15ml干燥的DMF(二甲基甲酰胺),用氮气保护,搅拌,加热回流6到8小时,温度升至80℃,点板监测反应,待反应结束,点板监测反应(PE:EA=5:1),待反应结束,冷却至室温,然后用水和二氯甲烷进行萃取,加入无水硫酸钠,进行抽滤,最后,旋蒸有机相,柱层析(PE:EA=18:1,10:1),得到纯黄白色固体,产率为43.22%。
核磁共振测定:1H NMR(400MHz,DMSO)δ8.94(d,J=2.7Hz,1H),8.54(ddd,J=18.6,8.4,3.3Hz,3H),8.31(d,J=8.4Hz,1H),7.94–7.81(m,2H),7.72(d,J=8.5Hz,2H),7.47(dd,J=25.2,8.9Hz,2H),4.15–4.00(m,2H),1.65(dt,J=14.7,7.4Hz,2H),1.44–1.32(m,2H),1.00–0.85(m,3H).13C NMR(101MHz,DMSO)δ163.92,163.70,155.03,154.65,145.35,142.32,140.25,132.63,131.34,130.89,130.13,129.85,128.65,128.09,123.02,122.39,122.05,120.89,120.55,55.32,40.66,40.45,40.24,40.03,39.83,39.62,39.41,30.14,20.25,14.17.高分辨质谱测定:HR-ESI-MS calcd for C30 H24 O8:512.14637,found512.14637[M];13C NMR(101MHz,DMSO)δ163.92,163.70,155.03,154.65,145.35,142.32,140.25,132.63,131.34,130.89,130.13,129.85,128.65,128.09,123.02,122.39,122.05,120.89,120.55,55.32,40.66,40.45,40.24,40.03,39.83,39.62,39.41,30.14,20.25,14.17.HR-ESI-MS calcd for C30 H24 O8:511.1380.14637,found 512.14637[M+H+];将上述得到的探针用荧光法和比色法双模式检测硫化氢。
实施例2荧光探针的选择性
配制DMSO:H2O=9:1(体积比)的混合液A,并用DMSO配制浓度为1mM的探针NI-SH溶液。
在干净的荧光比色皿中加入2mL溶液(DMSO:H2O=9:1),并加入探针NI-SH二甲基亚砜溶液使其浓度为20μM。
用荧光光谱仪考察了探针NI-SH对硫化氢(H2S)在混合溶液A中的选择性。如图1所示,在400nm处激发条件下是,单独的探针NI-SH(20μM)在混合溶液A中在458nm处有荧光发射强度。当加硫化氢(H2S)(40μM)后,在458nm处的荧光发射强度明显减弱,发生红移,在540nm处出现新峰,548nm处荧光增强,但是加入其它物质(100μM)时,溶液体系的荧光发射强度与单独探针体系的荧光发射强度相比没有明显变化,即在540nm处没有新峰出现,如图1所示。
以上实验结果表明,探针NI-SH对硫化氢(H2S)在混合溶液A中具有较好的荧光专一选择性。
实施例3荧光探针的抗干扰性
配制DMSO:H2O=9:1的混合液A,并用DMSO配制浓度为1mM的探针NI-SH溶液。在18个干净的荧光比色皿中,分别加入2mL的混合溶液A和40μL的探针NI-SH二甲基亚砜溶液,再分别加入5个摩尔当量(相对于探针)的H2S和5个摩尔当量的其他分析物(Probe,GSH,L-cys,L-Val,L-Ary,L-His,L-Thre,L-Phe,K+,Ca2+,Na+,Mg2+,H2O2,ClO-,I-,Br-,HSO3 -,SO3 2-),在荧光光谱仪上检测,绘制不同分析物对应的F540nm/F458nm荧光强度的柱状图,得到荧光发射柱状图如图3所示。
经实验证明,探针对硫化氢(H2S)在混合溶液A中的识别不受上述其他分析物的干扰,具有较好的抗干扰性。
实施例4荧光探针的紫外专一选择性
配制DMSO:H2O=9:1的混合液A,并用DMSO配制浓度为1mM的探针NI-SH溶液。
在干净的紫外比色皿中加入2mL溶液(DMSO:H2O=9:1)并加入40μL探针NI-SH二甲基亚砜溶液使其浓度达到20μM,在紫外-可见分光光度计上测试,随着硫化氢溶液的加入,硫化氢使得溶液体系在360nm处的紫外吸收减弱,出现红移,在460nm处出现新吸收峰。
同时出现了肉眼可见的变化:随着硫化氢浓度的增加,检测液的颜色在可见光下从无色变为黄色最后为紫红色;在365nm紫外灯下,探针NI-SH由很弱的蓝色荧光到明亮的黄绿色。
用紫外-可见分光光度计考察了探针NI-SH对硫化氢(H2S)在混合溶液A中的选择性。如图3所示,单独的探针NI-SH(20μM)在混合溶液A中在458nm处具有紫外吸收强度,当加入硫化氢(H2S)(5eq.)后,在360nm处的紫外吸收强度明显减弱,且发生红移,在450nm处有新峰出现,但是加入其它物质(100μM)时,溶液体系的紫外吸收强度与单独探针体系的紫外吸收强度相比没有明显变化,如图2所示,并且,溶液的颜色也没有变化。
以上实验结果表明,探针NI-SH对硫化氢(H2S)在混合溶液A中具有较好的紫外专一选择性。
实施例5荧光探针的对硫化氢的响应时间
配制DMSO:H2O=9:1的混合液A,并用DMSO配制浓度为1mM的探针NI-SH溶液。
在比色皿中加入2000μL的混合溶液A和40μL的探针NI-SH二甲基亚砜溶液,再加入硫化氢(H2S)(30μM)后,用荧光光谱仪考察了探针NI-SH对硫化氢的响应时间。探针NI-SH可以在15min内实现对硫化氢的检测,如图4所示。
经实验证明,探针NI-SH在DMSO:H2O=9:1(v:v)混合液中能较快的实现对硫化氢的快速检测。
实施例6探针识别硫化氢的浓度滴定
配制DMSO:H2O=9:1的混合液A,并用DMSO配制浓度为1mM的探针NI-SH溶液。在干净的紫外比色皿中加入2mL溶液(DMSO:H2O=9:1)并加入40μL探针NI-SH二甲基亚砜溶液使其浓度达到20μM。
用蒸馏水配制0.005mol/L浓度的九水硫化钠溶液,用紫外-可见分光光度计考察了探针NI-SH对硫化氢(H2S)逐渐加入九水硫化钠溶液的体积分别为0,4μL,6μL,8μL,10μL,12μL,14μL,16μL,18μL,20μL(浓度从0-50μM),随着九水硫化钠浓度的增加,在368nm处的紫外吸收强度明显减弱,且发生红移,在450nm处有新峰出现,且逐渐增强。如附图5所示。
同样的方法进行荧光检测,激发波长360nm,发射波长380nm;荧光图如图6所示。
结果显示,荧光强度及紫外吸收强度随硫化氢浓度变化,可进行定量检测。
实施例7工作曲线的绘制
配制DMSO:H2O=9:1的混合液A,并用DMSO配制浓度为1mM的探针NI-SH溶液。用蒸馏水配制0.005mol/L浓度的九水硫酸钠溶液,把2000μL的混合溶液A和40μL的探针NI-SH二甲基亚砜溶液加到干净的荧光比色皿中,逐渐加入九水硫酸钠溶液的体积分别为0,4μL,6μL,8μL,10μL,12μL,14μL,16μL,18μL,20μL同时以360nm为激发波长,在荧光光谱仪上测定荧光发射强度,以硫化氢的浓度为横坐标,以F540nm/F458nm处的荧光强度比为纵坐标,得到硫化氢浓度的工作曲线,线性回归方程为:F540nm/F458nm=4666.25323C+9336.41706,C的单位为μmol/L,结果如图7所示,有良好的线性。
如图8所示,单独的探针在激发波长360nm、发射波长380nm下,F540nm/F458nm处的荧光强度比不随时间发生变化;而加入硫化氢后,F540nm/F458nm处的荧光强度比逐渐增加,说明该荧光探针识别硫化氢的稳定性好。图8有两条线,下面的是探针本身,没有荧光,在长时间里探针稳定,上面的是加硫化氢后,荧光增强,且稳定,因为探针是比率型的,有双峰,所以是两个峰荧光的比值。
荧光探针NI-SH识别硫化氢的原理如图9,由于硫化氢具有很强的亲电性,硫化氢进攻探针分子,导致断裂萘酰亚胺环和2,4-二硝基苯氧基团之间的键,释放出荧光信号,生成具有荧光的产物C2。化合物C2与荧光探针NI-SH的荧光和紫外特性及颜色不同,因此通过该探针可以检测硫化氢。经过硫化氢处理后的化合物高分辨质谱图如图10所示,显示为C2。
实施例8检测限考察
良好的检出限是检验一个探针分子是否具有应用价值的标准之一。
配制DMSO:H2O=9:1的混合液A,并用DMSO配制浓度为1mM的探针NI-SH溶液。把2000μL的混合溶液A和40μL的探针NI-SH二甲基亚砜溶液加到干净的荧光比色皿中,测定其对不同浓度的硫化氢的响应强度,随着硫化氢浓度的增加,体系荧光发射强度在535nm处不断增强,研究发现溶液荧光发射强度在硫化氢浓度线性范围为1.5×10-5—3.5×10-5mol/L(R2=0.956),经计算(3σ/k)得出该探针分子对硫化氢的检出限为5.0×10-5mol/L,如图7所示。
Claims (10)
3.根据权利要求2所述的制备方法,其特征在于,所述催化剂为三乙胺;反应溶剂为DMF、乙腈或三氯甲烷。
6.权利要求1所述荧光探针材料在检测硫化物或者制备检测硫化物的试剂方面的应用。
7.根据权利要求6所述的应用,其特征在于,检测硫化物的方法包括荧光检测、紫外检测、和可视化检测。
8.一种检测硫化物的方法,其特征在于,步骤包括:将权利要求1所述荧光探针材料与待测样品混合,检测458nm-540nm处的荧光发射强度;或者,
将权利要求1所述荧光探针材料与待测样品混合,用紫外法检测其360-450nm波长下的吸收度;或者,
将权利要求1所述荧光探针材料与待测样品混合,观察溶液颜色是否发生变化。
9.根据权利要求8所述的方法,其特征在于,所述的荧光探针材料和待测样品分散于二甲基亚砜与水混合液后,检测其荧光强度或者紫外吸收度,或者用肉眼观察。
10.根据权利要求8或9所述的方法,其特征在于,采用荧光法检测时,根据540nm/458nm处的荧光强度比进行定量检测。
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