CN110563734A - 一种吩嗪***类化合物的合成及其识别汞离子和钴离子的应用 - Google Patents
一种吩嗪***类化合物的合成及其识别汞离子和钴离子的应用 Download PDFInfo
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- CN110563734A CN110563734A CN201910922215.1A CN201910922215A CN110563734A CN 110563734 A CN110563734 A CN 110563734A CN 201910922215 A CN201910922215 A CN 201910922215A CN 110563734 A CN110563734 A CN 110563734A
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- phenazine
- triazole
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- phta
- triazole compound
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- 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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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N2021/6417—Spectrofluorimetric devices
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6443—Fluorimetric titration
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- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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Abstract
本发明公开了一种吩嗪***1H‑[1,2,3]***[4,5‑b]吩嗪,是以二氨基吩嗪盐酸盐和NaNO2为原料,在酸性环境中反应而得。该吩嗪***可以作为荧光传感器同时在含水30%的体系中对Hg2+、Co2+进行双功能检测:即在吩嗪***的DMSO/H2O体系中加入12种常见的重金属阳离子,只有Hg2+的加入可使主体溶液的荧光变为亮黄色,且只有Co2+的加入可使主体溶液的荧光变为蓝绿色。滴定实验表明,该吩嗪***对Hg2+荧光响应的最低检测限为4.96×10‑7M,对Co2+荧光响应的最低检测限为3.33×10‑8M,因而对Hg2+、Co2+的检测具有很高的灵敏度。
Description
技术领域
本发明涉及一种吩嗪***类化合物的合成方法,尤其涉及一种吩嗪***1H-[1,2,3]*** [4,5-b] 吩嗪(PHTA)的合成方法;本发明同时涉及该吩嗪***类化合物在含水体系中双功能检测Hg2+和Co2+ 的应用,属于化学合成技术领域和离子检测领域。
背景技术
水体中的无机汞离子通过微生物的作用可以转变成剧毒的甲基汞,由食物链进人人体,引起汞中毒事件。慢性汞中毒可使人性格变得胆小怕羞、孤独、厌烦、消极抑郁、易激怒,有时行为怪僻,自觉口内有金属味,口腔黏膜充血、牙龈红肿、牙齿松动、牙龈或口颊黏膜出现色素沉着,亦可出现“汞毒性震颤”,手指、舌、眼睑震颤最为常见,严重时可蔓延至颊肌、上肢、下肢,并出现手指书写震颤。钴是维生素B12组成部分,反刍动物可以在肠道内将摄入的钴合成为维生素B12,已观察到无机钴对刺激红细胞生成有重要的作用。有种贫血用叶酸、铁、B12治疗皆无效,有人用大剂量的二氯化钴可治疗这类贫血。然而,这么大剂量钴反复应用可引起中毒。钴对红细胞生成作用的机制是影响肾释放***,或者通过刺激胍循环。还观察到供给钴后可使血管扩张和脸色发红,动物实验结果显示,甲状腺素的合成可能需要钴,钴能拮抗碘缺乏产生的影响。钴元素能刺激人体骨髓的造血***,促使血红蛋白的合成及红细胞数目的增加。大多以组成维生素B12的形式参加体内的生理作用。钴刺激造血的机制为,钴元素可抑制细胞内呼吸酶,使组织细胞缺氧,反馈刺激红细胞生成素产生,进而促进骨髓造血。钴元素可促进脾脏释放红细胞,但经常注射钴制剂或暴露于过量的原始钴环境中,可引起钴中毒。因此能够在含水体系中检测Hg2+和Co2+具有重要的意义。
吩嗪及其衍生物最早的应用是染料,接着发现它们有生物活性,可以用作杀菌剂。近年来吩嗪在医药、农药、发色体、导体和电池材料等领域的应用越来越广泛。含氮杂环化合物有着独特的生物活性,毒性低,内吸性高,常被用作医药和农药的结构组成单元,在医药和农药合成方面起着重要的作用。其中***类化合物作为含氮杂环的重要组成部分,因其独特的结构特征而得到广泛的应用。然而,关于吩嗪***类化合物在离子检测方面的应用尚未见报道。
发明内容
本发明的目的是提供一种吩嗪***类化合物——吩嗪***1H-[1,2,3]*** [4,5-b] 吩嗪及其合成方法;
本发明的另一目的是提供该吩嗪***类化合物在含水体系中双功能检测Hg2+、Co2+的应用。
一、吩嗪***类化合物及其合成
吩嗪***1H-[1,2,3]*** [4,5-b] 吩嗪,标记为PHTA,结构式为:
吩嗪***1H-[1,2,3]*** [4,5-b] 吩嗪的合成:将二氨基吩嗪盐酸盐溶解于30~37%的稀盐酸,加入NaNO2和水,先在0~4℃下搅拌反应2~3h,再在100℃下搅拌反应2~3h;反应结束后抽滤,烘干,即得目标产物1H-[1,2,3]*** [4,5-b] 吩嗪(PHTA)。
二氨基吩嗪盐酸盐与NaNO2的摩尔比为1:10。
图1为上述合成的PHTA的部分核磁氢谱图,图2为PHTA的部分核磁碳谱图,图3为1H-[1,2,3]*** [4,5-b] 吩嗪(PHTA)的部分质谱图。可见吩嗪***1H-[1,2,3]*** [4,5-b] 吩嗪成功合成。
二、吩嗪***(PHTA)作为荧光传感器双功能检测Hg2+ 和Co2+
1、溶剂的选择
将主体PHTA用各种溶剂(THF、DMSO、DMF、MeCN、MeOH、EtOH、CHCl3、CCl4)配制成10ml,2×10-4mol/L的溶液,进行荧光扫描。结果发现,DMSO配制的主体溶液的荧光最强且溶解性最好,因此我们选择DMSO为溶剂(如图4)。
2、含水量的测定
将PHTA在25 ml的试管中配置成2×10-3mol/L的PHTA水溶液(DMSO);配置4×10-3mol/L的Hg2+和Co2+水溶液(H2O配置),用移液管取比色管中的PHTA稀释溶液0.5 ml,Hg2+和Co2+水溶液0.5 ml,分别将其配置成不同含水比的溶液(0,10%,20%,30%,40%,50%,60%,70%,80%,90%)的溶液并进行荧光扫描。结果发现,在含水30%时PHTA对Hg2+和Co2+的荧光强度最强(如图5,图6),因此,我们确定本次实验的溶剂为DMSO/H2O(7: 3,v/v)。
3、荧光检测Hg2+
将PHTA在25 ml的试管中配置成2×10-3mol/L的PHTA水溶液(DMSO),放置备用。配置4×10-3mol/L的Hg2+水溶液(用Hg(ClO4)2·3H2O,H2O配置),用移液管取比色管中的PHTA稀释溶液0.5 ml,Hg2+溶液0.5 ml,蒸馏水1 ml用DMSO定容至5 ml(此时主体PHTA溶液的浓度为2×10-4mol/L),摇晃使其反应均匀后将其溶液倒入石英比色皿中,进行荧光扫描。并用相同的方法加入,扫描Fe3+,Ag+,Ca2+,Cu2+,Co2+,Ni2+,Cd2+,Pb2+,Zn2+,Cr3+和 Mg2+离子的溶液。
图7为PHTA以及在PHTA加入其他的金属阳离子的荧光光谱图(λ ex=450nm)。由图7可以看出,主体PHTA自身在365 nm的紫外灯下发出微弱的黄色荧光。在加入Hg2+后其荧光迅速变为亮黄色(3s)。同时,在荧光发射光谱中也可以观察到:当激发波长为450 nm时,PHTA微弱的黄色荧光(发射波长530nm)且荧光强度最大为33a.u。当加入Hg2+后,荧光强度增加到237a.u,荧光强度大约增加了7倍。因此,该吩嗪***PHTA能够作为识别Hg2+的荧光传感器。
荧光滴定实验:用0~6.92当量的Hg2+对PHTA做荧光滴定,检测主体不同浓度的Hg2+对主体PHTA的荧光光谱特性的影响(图8)。结果发现,随着溶液中Hg2+浓度的增加,PHTA荧光强度逐渐增强,在加入到6.92当量的Hg2+之后荧光强度达到最大值,为245a.u,再进行滴加强度便不再变化。同时,我们根据荧光滴定曲线做出了发射波长为530nm的荧光滴定散点图(图8插图),根据此散点图用3σ/m法做出了荧光拟合曲线(图9),并且计算出了主体分子PHTA对Hg2+荧光响应的最低检测限为4.96×10-7M。
4、荧光检测Co2+
将PHTA在25 ml的试管中配置成2×10-3mol/L的PHTA水溶液(DMSO),放置备用。配置4×10-3mol/L的Co2+水溶液(用Co(ClO4)2•6H2O,H2O配置),用移液管取比色管中的PHTA稀释溶液0.5 ml,Co2+溶液0.5 ml,蒸馏水1 ml用DMSO定容至5 ml(此时主体PHTA溶液的浓度为2×10-4mol/L),摇晃使其反应均匀后将其溶液倒入石英比色皿中,进行荧光扫描。并用相同的方法加入,扫描Fe3+,Hg2+,Ag+,Ca2+,Cu2+,Ni2+,Cd2+,Pb2+,Zn2+, Cr3+和 Mg2+离子的溶液。
图9为PHTA以及在PHTA加入其他的金属阳离子的荧光光谱图(λ ex=450 nm)。由图可以看出,主体PHTA自身在365 nm的紫外灯下发出微弱的黄色荧光,在加入Co2+后其荧光迅速变为蓝绿色(3s)。同时,在荧光发射光谱中我们也可以观察到:当激发波长为450 nm时,PHTA微弱的黄色荧光(发射波长530nm)且荧光强度最大为33 a.u。当加入Co2+后,波长移动到497 nm处,且荧光强度增加到497a.u,荧光强度大约增加了15倍。因此,该吩嗪***PHTA能够作为识别Co2+的荧光传感器。
荧光滴定实验:用0~1.14当量的Co2+对PHTA做荧光滴定,检测主体不同浓度的Co2+对主体PHTA的荧光光谱特性的影响(图10)。结果发现,随着溶液中Co2+浓度的增加,PHTA荧光强度逐渐增强,在加入到1.14当量的Co2+之后荧光强度达到最大值,为498a.u,再进行滴加强度便不再变化。同时,我们根据荧光滴定曲线做出了发射波长为485nm的荧光滴定散点图(图10插图),根据此散点图用3σ/m法做出了荧光拟合曲线(图11),并且计算出了主体分子PHTA对Co2+荧光响应的最低检测限为3.33×10-8M。
5、荧光传感器PHTA识别Hg2+和 Co2+的机理
图12为PHTA滴加0.01当量、0.05当量、0.1当量、0.2当量、0.5当量、1.0当量、1.5当量、2.0当量和3.0当量Hg2+的部分核磁滴定氢谱图,由图12可以看出,通过在核磁滴定实验中滴加不同当量的Hg2+,***环中的活泼氢Hd逐渐消失,这说明加入Hg2+后***环上发生了去质子化作用。吩嗪环中的质子氢Ha没有发生移动,而Hb和Hc都向低场移动,这说明Hg2+的加入在吩嗪***PHTA的***环和邻近***环的苯环上作用。而且在PHTA和PHTA-Hg红外光谱图上也能清楚地看到-NH峰和苯环上的-CH峰都发生了变化。图13为PHTA与Hg2+的荧光工作曲线,可以看出,拐点在0.75处,证明PHTA和Hg2+ 是以2:5的络合比进行络合的。图14和图15为PHTA与Co2+的荧光工作曲线图,可以看到,在逐渐增大Co2+的含量时分别有两个拐点在出现在0.2和0.7处,说明PHTA和Co2+在Co2+含量小时是以4:1的络合比进行络合的,而当Co2+含量大时是以2:4的络合比进行络合的。图16为PHTA、PHTA-Hg和PHTA-Co的红外光谱图,发现-NH峰和苯环上的-CH峰发生变化,也就是说明PHTA和Co2+也在***环和邻近***环的苯环上作用。图17为PHTA的XRD谱图,图18为PHTA-Hg和PHTA-Co的XRD谱图,可以知道,在加入Hg2+后PHTA分子间距增大,说明有cation-π作用存在。通过比较PHTA和PHTA-Co的XRD谱图和红外光谱图发现,在加入Co2+后PHTA分子间距也增大,说明有也存在cation-π作用。
附图说明
图1为1H-[1,2,3]*** [4,5-b] 吩嗪(PHTA)的部分核磁氢谱图。
图2为1H-[1,2,3]*** [4,5-b] 吩嗪(PHTA)的部分核磁碳谱图。
图3为1H-[1,2,3]*** [4,5-b] 吩嗪(PHTA)的部分质谱图。
图4为PHTA在不同溶剂下的荧光光谱图。
图5为在PHTA中分别加入2倍当量的Hg2+在不同含水比下的荧光强度柱状图。
图6为在PHTA中分别加入2倍当量的Co2+在不同含水比下的荧光强度柱状图。
图7为PHTA加入不同金属阳离子的荧光全扫描光谱(λ ex=450 nm)和在紫外灯照射下的溶液荧光变化图。
图8为在PHTA加入不同当量Hg2+的荧光滴定光谱曲线以及在560 nm处的荧光散点图。
图9为PHTA和Hg2+ 在560 nm处的荧光强度拟合曲线图。
图10为PHTA加入不同当量Co2+的荧光滴定光谱曲线以及在498 nm处的荧光散点图。
图11为PHTA和Co2+在498 nm处的荧光强度拟合曲线图。
图12为PHTA对于Hg2+的部分核磁滴定氢谱图。
图13为PHTA与Hg2+的荧光工作曲线图。
图14为PHTA和Co2+以4:1络合时荧光工作曲线图。
图15为PHTA和Co2+以2:4络合时荧光工作曲线图。
图16为PHTA、PHTA-Hg和PHTA-Co的红外光谱图。
图17为PHTA的XRD谱图。
图18为PHTA-Hg和PHTA-Co的XRD谱图。
具体实施方式
下面通过具体实施例对本发明1H-[1,2,3]*** [4,5-b] 吩嗪(PHTA)的合成,以及其在DMSO/H2O (7: 3, v/v)体系对Hg2+和Co2+双功能检测的方法作进一步说明。
实施例1:1H-[1,2,3]*** [4,5-b] 吩嗪(PHTA)的合成
(1)2-氨基吩嗪盐酸盐的合成:按文献【B. R.Yong, T. B.Wei, W. J.Qu, Q.Lin, Y.M.ZhangandH. Yao. New J. Chem., 2018,42, 14766-14771】合成;
(2)1H-[1,2,3]*** [4,5-b] 吩嗪(PHTA)的合成:取100mL圆底烧瓶将1mmol(0.2121g)2-氨基吩嗪盐酸盐中加入10mL 37%稀盐酸进行溶解,再加入10mmol (0.6899 g)NaNO2,30mL水,在0℃下搅拌反应3h,溶液为深棕色,且放出有味气体。之后将溶液升温至100℃搅拌反应3h,反应放出大量气体,且颜色变为深红色;待反应结束后抽滤,烘干,得到深褐色粉末即为目标产物PHTA。产率:94.6%。产物PHTA的表征数据为:1H NMR (600MHz,DMSO-d6) δ(ppm):16.60(s,1H),8.33-8.31(dd,1H),8.24-8.22 (d,1H), 8.05-8.04(m,2H), 8.03-7.99 (m,2H).13C NMR (DMSO-d6, 150 MHz), δ/ppm:143.29, 142.26,141.83, 133.62, 132.27, 130.71,129.79.ESI-MS C12H7N5+Hcalcd for 222.0774,found 222.0773。
PHTA的合成式如下:
。
实施例2、在DMSO/H2O (7: 3,v/v)体系对Hg2+和Co2+双功能荧光检测
在DMSO/H2O(7: 3,v/v)体系中加入12种常见的重金属阳离子Fe3+,Hg2+,Ag+,Ca2+,Cu2+,Co2+,Ni2+,Cd2+,Pb2+,Zn2+,Cr3+,Mg2+的水溶液,若溶液的荧光变为亮黄色,说明加入的Hg2+,若溶液的荧光变为蓝绿色,说明加入的是Co2+,否则加入的是其他金属阳离子。
Claims (7)
1.一种吩嗪***类化合物,其化学命名为1H-[1,2,3]*** [4,5-b] 吩嗪,其结构式为:
。
2.如权利要求1所述吩嗪***类化合物的合成方法,是将二氨基吩嗪盐酸盐溶解于稀盐酸中,加入NaNO2和水,先在0~4℃下搅拌反应2~3h,之后再在95~100℃下搅拌反应2~3h;反应结束后抽滤,烘干,即得目标产物1H-[1,2,3]*** [4,5-b] 吩嗪。
3.如权利要求1所述吩嗪***类化合物的合成方法,其特征在于:所述稀盐酸的浓度为30~37%。
4.如权利要求1所述吩嗪***类化合物的合成方法,其特征在于:二氨基吩嗪盐酸盐与NaNO2的摩尔比为1:10。
5.如权利要求1所述吩嗪***类化合物作为荧光传感器在检测Hg2+和Co2+的应用。
6.如权利要求1所述吩嗪***类化合物作为荧光传感器在检测Hg2+和Co2+的应用,其特征在于:在吩嗪***类化合物主体的DMSO/H2O 体系中,加入Fe3+,Hg2+,Ag+,Ca2+,Cu2+,Co2+,Ni2+,Cd2+,Pb2+,Zn2+,Cr3+,Mg2+的水溶液,只有Hg2+ 的加入可使主体溶液的荧光变为亮黄色,且只有Co2+的加入可使主体溶液的荧光变为蓝绿色。
7.如权利要求1所述吩嗪***类化合物作为荧光传感器在检测Hg2+和Co2+的应用,其特征在于:DMSO/H2O 体系中,H2O的体积百分数为20~50%。
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102887864A (zh) * | 2011-07-21 | 2013-01-23 | 上海三爱思试剂有限公司 | 一种苯并三氮唑的合成方法 |
CN108409675A (zh) * | 2017-12-22 | 2018-08-17 | 西北师范大学 | 2,3-二氨基吩嗪盐作为传感器在纯水中识别氰根离子的应用 |
CN109900654A (zh) * | 2019-04-08 | 2019-06-18 | 西北师范大学 | 水溶性吩嗪染料在识别和吸附去除水样中铜离子的应用 |
-
2019
- 2019-09-27 CN CN201910922215.1A patent/CN110563734B/zh not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102887864A (zh) * | 2011-07-21 | 2013-01-23 | 上海三爱思试剂有限公司 | 一种苯并三氮唑的合成方法 |
CN108409675A (zh) * | 2017-12-22 | 2018-08-17 | 西北师范大学 | 2,3-二氨基吩嗪盐作为传感器在纯水中识别氰根离子的应用 |
CN109900654A (zh) * | 2019-04-08 | 2019-06-18 | 西北师范大学 | 水溶性吩嗪染料在识别和吸附去除水样中铜离子的应用 |
Non-Patent Citations (3)
Title |
---|
O.A. RYAZANOVA ET AL.: "Absorption and fluorescent spectral studies of imidazophenazine derivatives", 《SPECTROCHIMICA ACTA PART A》 * |
O.A. RYAZANOVA ET AL.: "pH-Induced changes in electronic absorption and fluorescence spectra of phenazine derivatives", 《SPECTROCHIMICA ACTA PART A》 * |
雍碧蓉: "吩嗪衍生物的合成及其在纯水相中对离子的识别与吸附", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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