CN105717102A - 一种用三苯胺衍生物对Hg2+和CN-的高选择性识别的方法 - Google Patents
一种用三苯胺衍生物对Hg2+和CN-的高选择性识别的方法 Download PDFInfo
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- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 125000006617 triphenylamine group Chemical group 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000001514 detection method Methods 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims description 82
- 239000000523 sample Substances 0.000 claims description 29
- 238000000862 absorption spectrum Methods 0.000 claims description 24
- 239000003960 organic solvent Substances 0.000 claims description 20
- 150000001412 amines Chemical class 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000012360 testing method Methods 0.000 claims description 12
- 238000002189 fluorescence spectrum Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 230000003595 spectral effect Effects 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- ZYMCBJWUWHHVRX-UHFFFAOYSA-N (4-nitrophenyl)-phenylmethanone Chemical compound C1=CC([N+](=O)[O-])=CC=C1C(=O)C1=CC=CC=C1 ZYMCBJWUWHHVRX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- BGUWFUQJCDRPTL-UHFFFAOYSA-N pyridine-4-carbaldehyde Chemical compound O=CC1=CC=NC=C1 BGUWFUQJCDRPTL-UHFFFAOYSA-N 0.000 claims description 6
- 239000007850 fluorescent dye Substances 0.000 claims description 5
- 239000013067 intermediate product Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
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- 238000001953 recrystallisation Methods 0.000 claims description 4
- 238000002835 absorbance Methods 0.000 claims description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims 1
- 150000001450 anions Chemical class 0.000 abstract description 9
- 238000001228 spectrum Methods 0.000 abstract description 8
- 150000001768 cations Chemical class 0.000 abstract description 3
- 238000002211 ultraviolet spectrum Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 239000012488 sample solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 230000007423 decrease Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
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- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 206010002660 Anoxia Diseases 0.000 description 1
- 241000976983 Anoxia Species 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000007953 anoxia Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- KBYOBAICCHNMNJ-UHFFFAOYSA-L diperchloryloxymercury Chemical group [Hg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O KBYOBAICCHNMNJ-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
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- 238000004186 food analysis Methods 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 229960004580 glibenclamide Drugs 0.000 description 1
- ZNNLBTZKUZBEKO-UHFFFAOYSA-N glyburide Chemical compound COC1=CC=C(Cl)C=C1C(=O)NCCC1=CC=C(S(=O)(=O)NC(=O)NC2CCCCC2)C=C1 ZNNLBTZKUZBEKO-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000000968 intestinal effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 231100000636 lethal dose Toxicity 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000008194 pharmaceutical composition Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000003969 polarography Methods 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
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- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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Abstract
本发明涉及一种用三苯胺衍生物对Hg2+和CN?的高选择性识别的方法,属于阴、阳离子检测领域。该方法为将三苯胺衍生物L与待测溶液混合,当待测溶液颜色发生变化,则说明待测溶液中含有Hg2+或CN?,再通过紫外光谱或者荧光光谱结合标准方程y=A1*exp(x/t1)+y0,即可得知Hg2+、CN?的含量;本发明的方法能够在含水体系下高效、快速、高选择性和灵敏度的对Hg2+和CN?进行定性定量检测。
Description
技术领域
本发明涉及一种用三苯胺衍生物对Hg2+和CN-的高选择性识别的方法,属于阴、阳离子检测领域。
背景技术
汞是一种严重危害人体健康的重金属,有机汞沉积在脑、肝和其他器官中,产生慢性中毒,损害肾、脑、胃和肠道,甚至引起死亡。氰化物是合成树脂、医药、农药、杀虫剂、化肥等的重要原料。但氰化物是剧毒物质,对人的致死量极微,除了直接误服外,其蒸汽和粉尘也能通过呼吸道或消化道进入人体,甚至能渗入皮肤,与体内细胞色素氧化酶中的三价铁结合,从而使细胞不能利用氧,失去了传递氧的作用,使机体缺氧,从而引起中毒甚至死亡。因此,研究微量Hg2+和CN-的测定方法在环境监测和食品分析中相当重要。
现有的Hg2+和CN-的检测方法有原子发射光谱法(M.Gavrilov,M.Skocic,M.Burger,S.Bukvic,S.Djenize,Line broadening in the neutral and ionizedmercury spectra,New Astron.17(2012)624–628.),极谱分析法(H.Mandil,A.A.Sakur,S.Alulu,Differential pulse polarographic analysis of glyburide in pure formand pharmaceutical formulations,Asian J.Chem.24(2012)2980–2984.),X-射线荧光分析法(M.Alcalde-Molina,J.Ruiz-Jiménez,M.D.Luque de Castro,Automateddetermination of mercury and arsenic in extracts from ancient paper byintegration of solid-phase extraction and energy dispersive X-ray,Anal.Chim.Acta 652(2009)148–153.),红外光谱法(A.Chandrasoma,A.A.A.Hamid,A.E.Bruce,M.R.M.Bruce,C.P.Tripp,An infrared spectroscopic based method formercury(II)detection in aqueous solutions,Anal.Chim.Acta 728(2012)57–63.),但这些检测方法因有检测仪器昂贵,检测试样较多,检测时间较长,只能单一检测等缺点而不便广泛使用。
发明内容
本发明的目的是提供一种用三苯胺衍生物对Hg2+和CN-的高选择性识别的方法,该方法能够在含水体系下高效、快速、高选择性和高灵敏度的对Hg2+和CN-进行定性定量检测。
本发明的目的是通过下述技术方案实现的。
一种用三苯胺衍生物L对Hg2+和CN-的高选择性识别的方法:将三苯胺衍生物L与待测溶液混合,当待测溶液颜色发生变化,则说明待测溶液中含有Hg2+或CN-;
一种用三苯胺衍生物L对Hg2+和CN-的高选择性识别的方法,具体步骤如下:
步骤一、用有机溶剂将制得的三苯胺衍生物L配置成已知浓度的溶液,得到溶液A;
步骤二、将Hg2+和CN-分别加入到步骤一中所用的有机溶剂中,分别配置成不同浓度的Hg2+、CN-溶液;再将Hg2+的有机溶液与步骤一制备的溶液A混合,得到溶液B;将CN-的有机溶液与步骤一制备的溶液A混合,得到溶液C;Hg2+、CN-与三苯胺衍生物的摩尔比分别为1,2,4,5,10,15,20,25,30,35,40,50,100;
步骤三、分别测定步骤二所得不同混合溶液的紫外吸收光谱,将测得的紫外吸收光谱吸光度的变化与Hg2+、CN-浓度确定对应关系,即得到利用紫外吸收光谱定量检测Hg2+、CN-的标准方程y=A1*exp(x/t1)+y0,其中y为所测的含Hg2+、CN-荧光探针最大吸收波长处对应的紫外吸光度,x为样品中Hg2+、CN-的含量(单位:10-5M),对Hg2+,A1=0.22088,t1=-14.08706,y0=0.33903;CN-,A1=0.59857,t1=-14.12962,y0=0.10514;
步骤四、将含有Hg2+、CN-的待测样品加入到有机溶剂中,配制成溶液;然后加入到步骤一的溶液A中,测定紫外吸收光谱强度,根据紫外吸收光谱强度的变化和步骤三所得的标准函数确定其中Hg2+、CN-的含量。
所述紫外吸收光谱可用荧光光谱代替;
一种用三苯胺衍生物L对Hg2+和CN-的高选择性识别的方法,具体步骤如下:
步骤一、用有机溶剂将制得的三苯胺衍生物L配置成已知浓度的溶液,得到溶液A;
步骤二、将Hg2+和CN-分别加入到步骤一中所用的有机溶剂中,分别配置成不同浓度的Hg2+、CN-溶液;再将Hg2+的有机溶液与步骤一制备的溶液A混合,得到溶液B;将CN-的有机溶液与步骤一制备的溶液A混合,得到溶液C;Hg2+、CN-与三苯胺衍生物的摩尔比分别为1,2,4,5,10,15,20,25,30,35,40,50,100;
步骤三、分别测定步骤二所得不同混合溶液的荧光发射光谱,将测得的荧光发射光谱的变化与Hg2+、CN-浓度确定对应关系,即得到利用荧光发射光谱定量检测Hg2+、CN-的标准方程y=A1*exp(x/t1)+y0,其中y为所测的含Hg2+、CN-荧光探针最大发射波长处对应的荧光强度,x为样品中Hg2+、CN-的含量(单位:10-5M),对Hg2+,A1=131.54158,t1=-9.03647,y0=11.68292;CN-,A1=58.6775,t1=-10.74649,y0=7.41541;
步骤四、将含有Hg2+、CN-的待测样品加入到有机溶剂中,配制成溶液;然后加入到步骤一的溶液A中,测定荧光发射光谱强度,根据荧光发射光谱强度的变化和步骤五所得的标准函数确定其中Hg2+、CN-的含量。
所述的有机溶剂为N,N-二甲基甲酰胺(DMF)。
所述三苯胺衍生物L的结构式如下:
所述三苯胺衍生物L的制备方法,具体步骤如下:
步骤一、将N',N”,N”'-三(4-硝基苯基)胺与水合肼按摩尔比为1:3~1:5加入到容器中,加入无水乙醇做溶剂、钯碳(Pb/C)做催化剂,所述催化剂与水合肼的摩尔比为3:1~5:1;反应在80~100℃下、搅拌反应完全,过滤得淡黄色晶体中间产物N',N”,N”'-三(4-氨基苯基)胺。
步骤二、将步骤一制得的N',N”,N”'-三(4-氨基苯基)胺与4-吡啶甲醛按摩尔比为1:3~1:5加入容器中,加入无水乙醇做溶剂,通氮气排走空气后,在80~100℃下、搅拌直至反应完全,过滤出固体物质,用二氯甲烷重结晶,得棕红色晶体目标产物,即三苯胺衍生物L。
有益效果
1、本发明的一种用三苯胺衍生物对Hg2+和CN-的高选择性识别的方法,制备该种化学传感器的方法。
2、本发明的一种用三苯胺衍生物对Hg2+和CN-的高选择性识别的方法,简单、容易操作,反应条件温和,所得产物产率很高。通过使用紫外吸收光谱和荧光发射光谱实现了对Hg2+、CN-的快速检测,具备灵敏度高,选择性好,成本低,便捷等特点。
3、本发明的一种用三苯胺衍生物对Hg2+和CN-的高选择性识别的方法,以N',N”,N”'-三(4-硝基苯基)胺和4-吡啶甲醛为原料,通过二步反应制备了最终产物,反应条件温和,反应后处理简单,所得产物产率较高。
附图说明
图1是本发明中合成三苯胺衍生物L的核磁氢谱图;
图2为本发明实施例1中三苯胺衍生物L对几种不同阴离子的紫外吸收谱图;
图3为本发明实施例1中三苯胺衍生物L对几种不同阴离子的荧光发射谱图;
图4为本发明实施例1中三苯胺衍生物L随CN-加入摩尔比的紫外吸收谱图;
图5为本发明实施例1中三苯胺衍生物L随CN-加入摩尔比的荧光发射谱图;
图6为本发明实施例1中三苯胺衍生物L421nm处随CN-加入摩尔比的紫外吸收谱图;
图7为本发明实施例1中三苯胺衍生物L550nm处随CN-加入摩尔比的荧光发射光谱图;
图8为本发明实施例1中三苯胺衍生物L对几种不同阳离子的紫外吸收谱图;
图9为本发明实施例1中三苯胺衍生物L对几种不同阳离子的荧光发射谱图;
图10为本发明实施例1中三苯胺衍生物L随Hg2+加入摩尔比的紫外吸收谱图;
图11为本发明实施例1中三苯胺衍生物L随Hg2+加入摩尔比的荧光发射谱图;
图12为本发明实施例1中三苯胺衍生物L422nm处随Hg2+加入摩尔比的紫外吸收谱图。
图13为本发明实施例1中三苯胺衍生物L580nm处随Hg2+加入摩尔比的荧光发射光谱图。
具体实施方式
下面结合实例与附图将探针分子的制备以及传感器溶液的配制进行阐述。
实施例1
三苯胺衍生物L的制备
将1gN',N”,N”'-三(4-硝基苯基)胺与10ml水合肼加入到容器中,加入30ml无水乙醇做溶剂,加入300mg的Pb/C做催化剂,反应在80℃、40r/min的搅拌速度下反应10小时,过滤得淡黄色晶体中间产物N',N”,N”'-三(4-氨基苯基)胺。将190mgN',N”,N”'-三(4-氨基苯基)胺与210μl 4-吡啶甲醛按加入容器中,加入30ml无水乙醇做溶剂,通氮气一段时间排走空气后,反应在80℃下、40r/min的搅拌速度下反应12小时,过滤出固体物质,用二氯甲烷重结晶,得棕红色晶体目标产物,得率98%。通过核磁共振波谱仪和质谱仪表征得到晶体产物的核磁氢谱(如图1所示)和质谱数据如下:1H-NMR(CDCl3,400MHz,ppm)δ:8.75(d,6H),8.44(s,3H),7.65(d,6H),7.12(d,6H),7.02(d,6H)。MS(MALDI-TOF):calcd.for C36N7H27,557.0;found,557.2。
传感器溶液的配制
将三苯胺衍生物L加入到溶剂中配制成浓度为1×10-5mol/L的溶液,溶剂为DMF。
Hg2+、CN-的紫外光谱选择性实例
在配置好的三苯胺衍生物溶液中,分别单独加入以下不同种阴离子:F-、Cl-、Br-、I-、Aco-、CN-、和H2PO4 -,所加入的量均为三苯胺衍生物摩尔量的20倍,在800-200nm波长范围内对以上7种溶液进行紫外吸收光谱测试。从紫外吸收光谱图中能够明显看出,只有含CN-的样品溶液在421nm处出现强度较低的新峰,而在504nm处的峰明显增强(如图2所示),而含有其他常见阴离子的样品表现出非常弱的紫外变化;
同样,在配置好的三苯胺衍生物溶液中,分别单独加入以下不同种阳离子:Ba2+、Mg2+、Zn2+、Cu2+、Ca2+、Hg2+、Ag+、Pb2+、Co2+、Ni2+和Cd2+,所加入的量均为三苯胺衍生物摩尔量的20倍,在700-200nm波长范围内对以上11种溶液进行紫外吸收光谱测试。从紫外吸收光谱图中能够明显看出,只有含Hg2+的样品溶液在422nm处出现强度较低的新峰,而在496nm处的峰明显增强(如图8所示),而含有其他常见阴离子的样品表现出非常弱的紫外变化由此,可以判断出本发明所制备的探针对Hg2+有很好的选择性。
Hg2+、CN-的荧光光谱选择性实例
在配置好的三苯胺衍生物溶液中,分别单独加入以下不同种阴离子:F-、Cl-、Br-、I-、Aco-、CN-、和H2PO4 -,所加入的量均为三苯胺衍生物摩尔量的20倍,在500-900nm波长范围内对以上7种溶液进行紫外吸收光谱测试。从荧光发射光谱图中能够明显看出,只有含CN-的样品溶液在550nm处峰的强度呈现明显的下降现象(如图3所示),属于荧光淬灭,而含有其他常见阴离子的样品表现出非常弱的荧光强度变化,由此,可以判断出本发明所制备的探针对CN-有很好的选择性。;
同样,在配置好的三苯胺衍生物溶液中,分别单独加入以下不同种阳离子:Ba2+、Mg2+、Zn2+、Cu2+、Ca2+、Hg2+、Ag+、Pb2+、Co2+、Ni2+和Cd2+,所加入的量均为三苯胺衍生物摩尔量的20倍,在465-850nm波长范围内对以上11种溶液进行紫外吸收光谱测试。从紫外吸收光谱图中能够明显看出,只有含Hg2+的样品溶液在580nm处峰的强度呈现明显的下降现象(如图9所示),属于荧光淬灭,而含有其他常见阴离子的样品表现出非常弱的荧光强度变化,由此,可以判断出本发明所制备的探针对Hg2+有很好的选择性。
实施例2
三苯胺衍生物L的制备
将1.5gN',N”,N”'-三(4-硝基苯基)胺与15ml水合肼加入到容器中,加入45ml无水乙醇做溶剂,加入450mg的Pb/C做催化剂,反应在80℃、40r/min的搅拌速度下反应10小时,过滤得淡黄色晶体中间产物N',N”,N”'-三(4-氨基苯基)胺。将100mgN',N”,N”'-三(4-氨基苯基)胺与100μl 4-吡啶甲醛按加入容器中,加入15ml无水乙醇做溶剂,通氮气一段时间排走空气后,反应在80℃下、40r/min的搅拌速度下反应10小时,过滤出固体物质,用二氯甲烷重结晶,得棕红色晶体目标产物,得率90%。通过核磁共振波谱仪和质谱仪表征得到晶体产物的核磁氢谱(如图1所示)和质谱数据如下:1H-NMR(CDCl3,400MHz,ppm)δ:8.75(d,6H),8.44(s,3H),7.65(d,6H),7.12(d,6H),7.02(d,6H)。MS(MALDI-TOF):calcd.for C36N7H27,557.0;found,557.2。
Hg2+和CN-紫外光谱的定量检测实例
步骤一、用有机溶剂将制得的三苯胺衍生物L配置成已知浓度的溶液,得到溶液A;
步骤二、将Hg2+和CN-分别加入到步骤一中所用的有机溶剂中,分别配置成不同浓度的Hg2+、CN-溶液;再将Hg2+的有机溶液与步骤一制备的溶液A混合,得到溶液B;将CN-的有机溶液与步骤一制备的溶液A混合,得到溶液C;Hg2+、CN-与三苯胺衍生物的摩尔比分别为1,2,4,5,10,15,20,25,30,35,40,50,100;
步骤三、分别测定步骤二所得不同混合溶液的紫外吸收光谱,将测得的紫外吸收光谱吸光度的变化与Hg2+(如图10所示)、CN-(如图4所示)浓度确定对应关系,即得到利用紫外吸收光谱定量检测Hg2+、CN-的标准方程y=A1*exp(x/t1)+y0,其中y为所测的含Hg2+、CN-荧光探针最大吸收波长处对应的紫外吸光度,x为样品中Hg2+、CN-的含量(单位:10-5M),对Hg2 +,A1=0.242088,t1=-14.08706,y0=0.33903(如图12所示);CN-,A1=0.59857,t1=-14.12962,y0=0.10514(如图6所示);
步骤四、将含有Hg2+、CN-的待测样品加入到有机溶剂中,配制成溶液;然后加入到步骤一的溶液A中,测定紫外吸收光谱强度,根据紫外吸收光谱强度的变化和步骤三所得的标准函数确定其中Hg2+、CN-的含量。
实施例3
三苯胺衍生物L的制备
将2.0gN',N”,N”'-三(4-硝基苯基)胺与18ml水合肼加入到容器中,加入45ml无水乙醇做溶剂,加入500mg的Pb/C做催化剂,反应在80℃、40r/min的搅拌速度下反应13小时,过滤得淡黄色晶体中间产物N',N”,N”'-三(4-氨基苯基)胺。将1.0gN',N”,N”'-三(4-氨基苯基)胺与1.1ml 4-吡啶甲醛按加入容器中,加入50ml无水乙醇做溶剂,通氮气一段时间排走空气后,反应在80℃下、40r/min的搅拌速度下反应15小时,过滤出固体物质,用二氯甲烷重结晶,得棕红色晶体目标产物,得率84%。通过核磁共振波谱仪和质谱仪表征得到晶体产物的核磁氢谱(如图1所示)和质谱数据如下:1H-NMR(CDCl3,400MHz,ppm)δ:8.75(d,6H),8.44(s,3H),7.65(d,6H),7.12(d,6H),7.02(d,6H)。MS(MALDI-TOF):calcd.for C36N7H27,557.0;found,557.2。
Hg2+和CN-荧光光谱的定量检测实例
步骤一、用有机溶剂将制得的三苯胺衍生物L配置成已知浓度的溶液,得到溶液A;
步骤二、将Hg2+和CN-分别加入到步骤一中所用的有机溶剂中,分别配置成不同浓度的Hg2+、CN-溶液;再将Hg2+的有机溶液与步骤一制备的溶液A混合,得到溶液B;将CN-的有机溶液与步骤一制备的溶液A混合,得到溶液C;Hg2+、CN-与三苯胺衍生物的摩尔比分别为1,2,4,5,10,15,20,25,30,35,40,50,100;
步骤三、分别测定步骤二所得不同混合溶液的荧光发射光谱,将测得的荧光发射光谱的变化与Hg2+(如图11所示)、CN-(如图5所示)浓度确定对应关系,即得到利用荧光发射光谱定量检测Hg2+、CN-的标准方程y=A1*exp(x/t1)+y0,其中y为所测的含Hg2+、CN-荧光探针最大发射波长处对应的荧光强度,x为样品中Hg2+、CN-的含量(单位:10-5M),对Hg2+,A1=131.54158,t1=-9.03647(如图13所示),y0=11.68292;CN-,A1=58.6775,t1=-10.74649,y0=7.41541(如图7所示);
步骤四、将含有Hg2+、CN-的待测样品加入到有机溶剂中,配制成溶液;然后加入到步骤一的溶液A中,测定荧光发射光谱强度,根据荧光发射光谱强度的变化和步骤五所得的标准函数确定其中Hg2+、CN-的含量。
实施例4
为验证本发明Hg2+、CN-的检测方法的准确性和可靠性,采用人工配制含Hg2+、CN-的试样,Hg2+、CN-的含量分别为10-5,2×10-5,4×10-5,10-4,1.5×10-4,在充分搅拌均匀后采集紫外吸收光谱,采用本发明检测方法分别对上述试样的Hg2+、CN-含量进行检测,其检测结果如下表所示。
表一:试样使用三苯胺衍生物L对Hg2+的定量识别检测
试样 | 1 | 2 | 3 | 4 | 5 |
理论含量 | 10-5 | 2×10-5 | 4×10-5 | 10-4 | 1.5×10-4 |
检测含量 | 0.97×10-5 | 2.02×10-5 | 3.98×10-5 | 1.02×10-4 | 1.48×10-4 |
表二:试样使用三苯胺衍生物L对CN-的定量识别检测
试样 | 1 | 2 | 3 | 4 | 5 |
理论含量 | 10-5 | 2×10-5 | 4×10-5 | 10-4 | 1.5×10-4 |
检测含量 | 0.98×10-5 | 1.97×10-5 | 4.02×10-5 | 1.02×10-4 | 1.48×10-4 |
由表一至表二所示的结果可知,采用本发明方法对Hg2+、CN-含量的实际检测值与制作试样时加入的含量值,即理论含量基本相同,具有较小的误差范围。
所述Hg2+盐为高氯酸汞
所述CN-盐为四丁基氰化胺
综合试验数据表明,本发明使用三苯胺衍生物L对Hg2+、CN-进行定性、定量检测方法的有益效果是采用成本较低的设备进行检测,测量速度快,操作简单、方便,测量结果准确、可靠、重复性好。
Claims (5)
1.一种用三苯胺衍生物L对Hg2+和CN-的高选择性识别的方法:其特征在于:将三苯胺衍生物L与待测溶液混合,当待测溶液颜色发生变化,则说明待测溶液中含有Hg2+或CN-;
所述三苯胺衍生物L的结构式如下:
2.一种用三苯胺衍生物L对Hg2+和CN-的高选择性识别的方法,其特征在于:具体步骤如下:
步骤一、用有机溶剂将制得的三苯胺衍生物L配置成已知浓度的溶液,得到溶液A;
步骤二、将Hg2+和CN-分别加入到步骤一中所用的有机溶剂中,分别配置成不同浓度的Hg2+、CN-溶液;再将Hg2+的有机溶液与步骤一制备的溶液A混合,得到溶液B;将CN-的有机溶液与步骤一制备的溶液A混合,得到溶液C;Hg2+、CN-与三苯胺衍生物的摩尔比分别为1,2,4,5,10,15,20,25,30,35,40,50,100;
步骤三、分别测定步骤二所得不同混合溶液的紫外吸收光谱,将测得的紫外吸收光谱吸光度的变化与Hg2+、CN-浓度确定对应关系,即得到利用紫外吸收光谱定量检测Hg2+、CN-的标准方程y=A1*exp(x/t1)+y0,其中y为所测的含Hg2+、CN-荧光探针最大吸收波长处对应的紫外吸光度,x为样品中Hg2+、CN-的含量(单位:10-5M),对Hg2+,A1=0.22088,t1=-14.08706,y0=0.33903;CN-,A1=0.59857,t1=-14.12962,y0=0.10514;
步骤四、将含有Hg2+、CN-的待测样品加入到有机溶剂中,配制成溶液;然后加入到步骤一的溶液A中,测定紫外吸收光谱强度,根据紫外吸收光谱强度的变化和步骤三所得的标准函数确定其中Hg2+、CN-的含量。
3.一种用三苯胺衍生物L对Hg2+和CN-的高选择性识别的方法,具体步骤如下:
步骤一、用有机溶剂将制得的三苯胺衍生物L配置成已知浓度的溶液,得到溶液A;
步骤二、将Hg2+和CN-分别加入到步骤一中所用的有机溶剂中,分别配置成不同浓度的Hg2+、CN-溶液;再将Hg2+的有机溶液与步骤一制备的溶液A混合,得到溶液B;将CN-的有机溶液与步骤一制备的溶液A混合,得到溶液C;Hg2+、CN-与三苯胺衍生物的摩尔比分别为1,2,4,5,10,15,20,25,30,35,40,50,100;
步骤三、分别测定步骤二所得不同混合溶液的荧光发射光谱,将测得的荧光发射光谱的变化与Hg2+、CN-浓度确定对应关系,即得到利用荧光发射光谱定量检测Hg2+、CN-的标准方程y=A1*exp(x/t1)+y0,其中y为所测的含Hg2+、CN-荧光探针最大发射波长处对应的荧光强度,x为样品中Hg2+、CN-的含量(单位:10-5M),对Hg2+,A1=131.54158,t1=-9.03647,y0=11.68292;CN-,A1=58.6775,t1=-10.74649,y0=7.41541;
步骤四、将含有Hg2+、CN-的待测样品加入到有机溶剂中,配制成溶液;然后加入到步骤一的溶液A中,测定荧光发射光谱强度,根据荧光发射光谱强度的变化和步骤五所得的标准函数确定其中Hg2+、CN-的含量。
4.如权利要求2或3所述的一种用三苯胺衍生物L对Hg2+和CN-的高选择性识别的方法,其特征在于:所述的有机溶剂为N,N-二甲基甲酰胺。
5.如权利要求1所述的一种用三苯胺衍生物L对Hg2+和CN-的高选择性识别的方法,其特征在于:所述三苯胺衍生物L的制备方法,具体步骤如下:
步骤一、将N',N”,N″′-三(4-硝基苯基)胺与水合肼按摩尔比为1:3~1:5加入到容器中,加入无水乙醇做溶剂、钯碳(Pb/C)做催化剂,所述催化剂与水合肼的摩尔比为3:1~5:1;反应在80~100℃下、搅拌反应完全,过滤得淡黄色晶体中间产物N',N”,N″′-三(4-氨基苯基)胺;
步骤二、将步骤一制得的N',N”,N″′-三(4-氨基苯基)胺与4-吡啶甲醛按摩尔比为1:3~1:5加入容器中,加入无水乙醇做溶剂,通氮气排走空气后,在80~100℃下、搅拌直至反应完全,过滤出固体物质,用二氯甲烷重结晶,得棕红色晶体目标产物,即三苯胺衍生物L。
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