CN106883159B - A kind of ultraviolet probe of Thiourea and its preparation and application - Google Patents
A kind of ultraviolet probe of Thiourea and its preparation and application Download PDFInfo
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- CN106883159B CN106883159B CN201710060437.8A CN201710060437A CN106883159B CN 106883159 B CN106883159 B CN 106883159B CN 201710060437 A CN201710060437 A CN 201710060437A CN 106883159 B CN106883159 B CN 106883159B
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- Prior art keywords
- probe
- ultraviolet
- lead ion
- thiourea
- concentration
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- 239000000523 sample Substances 0.000 title claims abstract description 99
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 title claims abstract description 59
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 6
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000002904 solvent Substances 0.000 claims abstract description 56
- 238000001514 detection method Methods 0.000 claims abstract description 33
- 238000002835 absorbance Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 13
- -1 plumbum ion Chemical class 0.000 claims abstract description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 64
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000004611 spectroscopical analysis Methods 0.000 claims description 2
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical group CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims 1
- QKFJKGMPGYROCL-UHFFFAOYSA-N phenyl isothiocyanate Chemical compound S=C=NC1=CC=CC=C1 QKFJKGMPGYROCL-UHFFFAOYSA-N 0.000 abstract description 14
- 229940117953 phenylisothiocyanate Drugs 0.000 abstract description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000870 ultraviolet spectroscopy Methods 0.000 abstract description 6
- 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 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 230000036571 hydration Effects 0.000 abstract description 2
- 238000006703 hydration reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 150000002500 ions Chemical class 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000012086 standard solution Substances 0.000 description 11
- 229910021645 metal ion Inorganic materials 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 8
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000000673 graphite furnace atomic absorption spectrometry Methods 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000985 reactive dye Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000008280 blood Substances 0.000 description 3
- 210000004369 blood Anatomy 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 206010027439 Metal poisoning Diseases 0.000 description 2
- 159000000009 barium salts Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001661 cadmium Chemical class 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 208000008127 lead poisoning Diseases 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 150000002730 mercury Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 108010024636 Glutathione Proteins 0.000 description 1
- 206010018910 Haemolysis Diseases 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 102000003960 Ligases Human genes 0.000 description 1
- 108090000364 Ligases Proteins 0.000 description 1
- ZIVOKOPGPJWHMY-UHFFFAOYSA-N NN(C(N)=O)S(O)(=O)=O Chemical group NN(C(N)=O)S(O)(=O)=O ZIVOKOPGPJWHMY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FNYLWPVRPXGIIP-UHFFFAOYSA-N Triamterene Chemical compound NC1=NC2=NC(N)=NC(N)=C2N=C1C1=CC=CC=C1 FNYLWPVRPXGIIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- UXHQMSUJQLPRAW-UHFFFAOYSA-N benzene;isothiocyanic acid Chemical compound N=C=S.C1=CC=CC=C1 UXHQMSUJQLPRAW-UHFFFAOYSA-N 0.000 description 1
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical class C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 210000000748 cardiovascular system Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001793 charged compounds Polymers 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003891 environmental analysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229960003180 glutathione Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000008588 hemolysis Effects 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 238000000120 microwave digestion Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 210000005227 renal system Anatomy 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide group Chemical group NNC(=O)N DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C337/00—Derivatives of thiocarbonic acids containing functional groups covered by groups C07C333/00 or C07C335/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C337/06—Compounds containing any of the groups, e.g. thiosemicarbazides
-
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
Abstract
The present invention relates to a kind of ultraviolet probes of Thiourea and its preparation and application, the structural formula of probe to be：Probe is obtained by phenyl isothiocyanate and hydration hydrazine reaction.The ultraviolet probe of Thiourea is used for the detection of lead ion：Probe solution is prepared, probe solution then is added in lead ion solution to be measured, after solvent constant volume, it stands, by ultraviolet visible spectrometry, detects the absorbance under 382nm wavelength, according to opposite UV intensity and plumbum ion concentration relationship, the content of lead ion in lead ion prepare liquid is determined.The ultraviolet probe of Thiourea is solid powder in the present invention, is easy to use storage, and it directly reacts gained by phenyl isothiocyanate and hydrazine hydrate, and synthetic method is simple, high income, at low cost, and application prospect is good.
Description
Technical field
The invention belongs to probe and its preparation and application field, more particularly to the ultraviolet probe of a kind of Thiourea and its prepare and
Using.
Background technology
In heavy metal, the content highest of lead, therefore it is to the harm of human health also most serious.Lead passes through gasoline, painting
Material etc. enters environment, and lead there is strong toxic action to make blood if lead can inhibit haeme synthetase environment and human health
Red pigment biosynthesis block, hemoglobin level reduce；In addition lead poisoning can also cause safe limits to increase and be easy to haemolysis, make its longevity
Life shortens and anaemia occurs, and lead poisoning can also be to each system such as nervous system, digestive system, cardiovascular system, renal system
Damage is generated, human health is seriously endangered.Lead is even more serious to the harm of children, can lead to the dysnoesia of children.According to
It is investigating in recent years as a result, blood lead is more than children's ratio of 100 μ g/L 30% or so.Blood lead is higher than the children of 250 μ g/L
Ratio also 5% or so.Therefore, the detection of lead ion is an important content in environmental analysis.
The detection method of metal ion experienced from traditional analysis to instrument analytical method, from single detection means
The evolution being combined to multiple technologies.The Pb of EPA (Environmental Protection Agency) approvals2+There are three types of detection methods：Inductive coupling etc.
Gas ions mass spectrography (ICP-MS), detection are limited to 0.6ppb；Inductively coupled plasma atomic emission spectrometry (ICP-AES),
Detection is limited to 42ppb；And graphite furnace atomic absorption spectrometry (GFAAS), detection are limited to 0.7ppb.These methods can measure
The lead of underground water, surface water, drinking water, sewage, sludge and pedotheque dissolving, detection limit and linearly interval depend on sample base
Matter, instrument and equipment, and choose operating condition.There are four types of natural isotopes for lead, and ICP-MS visible detections are to three kinds therein
(206Pb, 207Pb and 208Pb), there are more interference such as isobar interference, abundance sensitivity to interfere for this method,
Press Polyatomic ion and physical disturbance.Usual ICP-AES measures Pb under 220.353nm wavelength2+When, can by Al, Cu,
The interference of Ni, Ti, Ce and Fe (δ=100ppm).Similar to ICP-MS, GFAAS can equally complete the direct analysis of sample.
GFAAS is reliable, susceptibility is high, but it needs to use additive and modifying agent in detection, for example, if sample needs hydrochloric acid to disappear
Solution, it can influence Pb2+At this moment the sensitivity of detection can be improved by adding Pd/Mg/H2 modifying agent.Although FDA, CPSC couple
Lead has higher limitation, but the detection method that they use is similar with EPA.
The sample size very little that above-mentioned detection method usually requires, but they are very sensitive, it is impossible to be used in Site Detection, and need
Want well-trained technical staff.The detection of special metal ion needs prolonged digestion process, and first, composite sample is necessary
It is mixed with water and/or nitric acid, suspended sample needs predigestion to handle.In general, GFAAS, ICP-AES and ICP-MS also need to carry out
Micro-wave digestion.Generally speaking, that EPA most approves in the analysis method of lead in environmental water sample is ICP-MS.The analysis sample of ICP-MS
Product prepare relatively easy, interference at least, and detection limit is minimum, and for these reasons, ICP-MS becomes above-mentioned detection method most
Whole standard.There are one prodigious limitations for the detection method of these regulatory agency's approveds：It is dfficult to apply to the real-time of metal ion
On-line monitoring.
Glutathione functionalization described in Chinese patent 201310029248.6 " a kind of fluorescent detection probe of lead ion "
Gold nanoclusters, by fluorescence detection method, for detecting the Pb in water body2+, and achieve high sensitivity and selectivity.It should
Method does not need large-scale instrument, it can be achieved that quickly detection in situ, detection limit is low, can be applied to more many condition and range, and grasp
Make simple low cost, agents useful for same and operating process have no toxic side effect.A kind of " the 1,8- naphthoyls of Chinese patent 201410156989.5
1,8- naphthalimide derivatives (6- [1- amino -3- (benzene described in application of the imine derivative as polyion spectral probe "
Base)-thiocarbamide] -2- normal-butyl benzisoquinoline -1,3- diketone) for detecting Pb2+、Fe3+、Hg2+.The probe extends 1,8- naphthalenes
The application range of imide derivative, detection dicyandiamide solution have developed to Aquo System from pure organic solvent, and the probe of acquisition has
Good selectivity, sensitivity and very strong anti-interference ability.
Invention content
Technical problem to be solved by the invention is to provide a kind of ultraviolet probe of Thiourea and its preparation and application, the present invention
The middle ultraviolet probe of Thiourea is solid powder, is easy to use storage, and it is directly reacted by phenyl isothiocyanate and hydrazine hydrate
Gained, synthetic method is simple, high income, at low cost, and application prospect is good.
A kind of ultraviolet probe of Thiourea of the present invention, the structural formula of the probe are：
A kind of preparation method of the ultraviolet probe of Thiourea of the present invention, including：
Hydrazine hydrate is added in solvent, stirs and be added dropwise to phenyl isothiocyanate at room temperature, under nitrogen atmosphere, 80-85
DEG C it is heated to reflux 3-5h, is cooled to room temperature after reaction；Purification, vacuum drying to get；Wherein hydrazine hydrate and isothiocyanic acid benzene
The molar ratio of ester is 1:1.
The solvent is acetonitrile.
Purification is specially：Suction filtration obtains solid and precipitates and washed with acetonitrile, is then purified with acetone recrystallization.
A kind of application of the ultraviolet probe of Thiourea of the present invention, the ultraviolet probe of Thiourea are used for the detection of lead ion, including：
Probe solution is prepared, probe solution then is added in lead ion solution to be measured, it is quiet after solvent constant volume
It sets, by ultravioletvisible spectroscopy, detects the absorbance under 382nm wavelength, closed according to opposite UV intensity and plumbum ion concentration
System, determines the content of lead ion in lead ion prepare liquid.
The probe solution a concentration of 0.8 × 10-4~1.2 × 10-4M。
Probe solution prepares specific：The ultraviolet probe of Thiourea is dissolved in solvent (DMF), using solvent constant volume, is visited
Needle storing solution pipettes probe storing solution in volumetric flask, using solvent (DMF) constant volume, obtains probe solution；Its middle probe is storeed
A concentration of the 0.9 × 10 of liquid-3M~1.1 × 10-3M。
The solvent of the probe PHT solution is n,N-Dimethylformamide (DMF), PHT-Pb after the constant volume2+System
Solvent is DMF/H2O(9/1,v/v)。
The time of repose is 1min~10min.
It is described to be with plumbum ion concentration relationship with respect to UV intensity：Y=1.21+0.85x, wherein y indicate relatively ultraviolet strong
Degree；X is the concentration of lead ion.
The ultraviolet probe of Thiourea is limited to 1.5 μM~2.5 μM to the detection of lead ion prepare liquid.
Opposite UV intensity determines that method includes with plumbum ion concentration relationship：
Lead salt is dissolved in solvent by step (1), using solvent constant volume, obtains lead ion storing solution；Pipette lead ion deposit
Liquid, using solvent constant volume, obtains the lead ion standard solution of various concentration in volumetric flask；Probe is dissolved in solvent, is utilized
Solvent constant volume obtains probe storing solution；
The probe solution obtained in step (1) is added in step (2) in lead ion standard solution, quiet using solvent constant volume
It sets, detects uv-visible absorption spectra, determine absorbance and the relationship of plumbum ion concentration；
Preferably, a concentration of 0.85 × 10 of the lead ion storing solution in the step (1)-2M~1.15 × 10-2M。
Preferably, " lead salt being dissolved in solvent respectively, using solvent constant volume, obtains lead ion in the step (1)
Storing solution；Lead ion storing solution is pipetted in volumetric flask, using solvent constant volume, obtains the lead ion standard solution of various concentration "
In solvent be deionized water, solvent in " probe being dissolved in solvent, using solvent constant volume, obtain probe storing solution " is N,
Dinethylformamide DMF.
Preferably, ranging from 0-50 μM of the lead ion standard solution of various concentration in the step (1).
Preferably, when " detection uv-visible absorption spectra " in the step (2), the absorbing wavelength that uses for
270-600nm。
Preferably, time of repose is 1~10min in the step (2).
Probe in the present invention is obtained by phenyl isothiocyanate and hydration hydrazine reaction, and thiocarbamide structure therein is because former containing N
Son and this two kinds of coordination atoms of S atom, the donor that can be used as electronics provides electronics pair and various metals ion coordination generates
The features such as metal chelate, realizes the distinguishing complex to heavy metal ion.
The present invention is using thiocarbamide as probe, by the increase of the ultraviolet absorptivity of thiocarbamide with lead ion solution concentration
Increase, the characteristic that absorbance remains unchanged after plumbum ion concentration reaches certain value, the lead ion in solution is carried out highly sensitive
Detection.The ultraviolet probe of the present invention contains sulfo-amino urea groups, has recognition reaction to lead ion.Its mechanism is：
Pb2+In identification process, Pb2+Pass through 1 with semicarbazide moiety:1 complexing is 5.8 × 10 than realizing coordination, complexation constant4~6.2 ×
104M-1.By ultravioletvisible spectroscopy, the content of lead ion is detected using the absorbance under 380~384nm wavelength.Dense
Degree is that the good range of linearity is presented within the scope of 2~10 μM, and linearly dependent coefficient is 0.989~0.991, detection limit 1.5~
2.5μM。
Advantageous effect
(1) the ultraviolet probe of Thiourea in the present invention has good selectivity to lead ion, in sewage disposal application not
Only facilitate and there is preferable using effect；
(2) the ultraviolet probe of Thiourea is solid powder in the present invention, is easy to use storage, and it is by phenyl isothiocyanate
Directly react gained with hydrazine hydrate, synthetic method is simple, high income, at low cost, and application prospect is good.
Description of the drawings
Fig. 1 is that the ultraviolet spectra variation after lead ion is added in ultraviolet probe in embodiment 3；In Fig. 1, abscissa is ultraviolet
Absorbing wavelength (nm), ordinate are absorbance；
Fig. 2 is ultraviolet probe PHT uv-visible absorption spectras and Pb in embodiment 42+Concentration relationship figure；In fig. 2,
Abscissa is UV absorption wavelength (nm), and ordinate is absorbance, and curve respectively represents the lead ion that various concentration is added in figure
Absorbance change curve (concentration be followed successively by 0 μM, 1 μM, 2 μM, 3 μM, 4 μM, 5 μM, 6 μM, 7 μM, 8 μM, 9 μM, 10 μM, 20 μM, 30
μM、40μM、50μM)；Wherein illustration is the scattergram that absorbance changes with plumbum ion concentration at 382nm.
Fig. 3 is 5 middle probe of embodiment with respect to UV absorption intensity A/A0And Pb2+Concentration linear relationship curve (λ=
382nm), in figure 3, abscissa is plumbum ion concentration, and ordinate is ratio (the wherein A of absorbance0It indicates to be added respectively with A
The absorbance of the front and back probe system surveyed of ion)；Wherein illustration is linear relation and its parameter list after fitting；
Fig. 4 is coexistent metallic ion in embodiment 6 to containing Pb2+Solution uv-visible absorption spectra influence.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
The synthesis of ultraviolet probe PHT：80% hydrazine hydrates of 1.2mL (19.8mmol) are taken to be added in 20mL acetonitriles, at room temperature
It stirs and 0.85mL (19.8mmol) phenyl isothiocyanate is slowly inwardly added dropwise.Under nitrogen atmosphere, 82 DEG C are heated to reflux 5h, reaction
After be cooled to room temperature；Suction filtration obtains solid and precipitates and washed with acetonitrile.Crude product, vacuum drying oven are purified with acetone recrystallization
25 DEG C dry to obtain product, yield 47%.
FTIR(KBr):V=3221cm-1,3116cm-1(NH2):1192cm-1(C=S):1541cm-1(-NH-):
2061cm-1(- N=C=S)；HNMR(400MHz,DMSO,298K,δ/ppm):3.33(S,2H),7.16-7.55(m,ArH)
9.64-9.87(d,-NH)
Embodiment 2
The specific method of the ultraviolet probe in detecting lead ion of Thiourea：
Configuration 1 × 10-5The lead ion prepare liquid of M, the ultraviolet probe in detecting of Thiourea synthesized in Application Example 1 are therein
The method of lead ion, the specific steps are：
Step 1：The ultraviolet probe of Thiourea that embodiment 1 synthesizes is dissolved in solvent DMF, is held in 100mL using solvent DMF
Constant volume in measuring bottle obtains a concentration of 1.0 × 10-3The probe storing solution of M；
Step 2：Plumbi nitras is dissolved in solvent deionized water, using solvent deionized water in 100mL volumetric flasks constant volume,
Obtain a concentration of 1.0 × 10-2The lead ion storing solution of M；Pipette a concentration of 1.0 × 10-2The lead ion storing solution of M holds in 100mL
In measuring bottle, using solvent deionized water constant volume, a concentration of 1.0 × 10 are obtained-3The lead ion storing solution of M；Pipette a concentration of 1.0 ×
10-3The lead ion storing solution of M, using solvent deionized water constant volume, obtains a concentration of 1.0 × 10 in 100mL volumetric flasks-4M's
Lead ion standard solution；
Step 3：Pipette respectively 0mL, 0.1mL, 0.2mL, 0.3mL, 0.4mL, 0.5mL, 0.6mL, 0.7mL, 0.8mL,
0.9mL, 1mL a concentration of 1.0 × 10-4The probe storing solution obtained in 1mL steps 1 is added in the lead ion standard solution of M, and utilization is molten
Agent DMF constant volumes in 10ml volumetric flasks after standing 5min, by ultravioletvisible spectroscopy, detect the extinction under 382nm wavelength
Degree, result 1,1.153,1.37,1.468,1.463,1.59,1.733,1.802,1.95,1.978,2.025 determine opposite
Good linear relationship is presented with plumbum ion concentration in UV absorption intensity.
Step 4：Take 0.55mL lead ion prepare liquids, a concentration of 1.0 × 10-41mL steps are added in the lead ion standard solution of M
The probe storing solution obtained in 1, using solvent DMF, constant volume passes through ultraviolet-visible light after standing 5min in 10mL volumetric flasks
Spectrometry, detects the absorbance under 382nm wavelength, result 1.71, according to surveying opposite UV intensity and plumbum ion concentration relationship,
Determine that the content of lead ion in lead ion prepare liquid, result are 5.3 μM.
Embodiment 3
Selectivity of the PHT uv-visible absorption spectras to metal ion：
In volume ratio 9：1 DMF/H2In O systems, measures ultraviolet probe (PHT) and metal ion Pb is being added2+、Fe3+、Cd2 +、Zn2+、Mg2+、Cr3+、Ca2+、Ba2+、Sn2+、Na+、Mn2+、Hg2+Front and back uv-visible absorption spectra.
Step 1：The reactive dye fluorescence probe that embodiment 1 synthesizes is dissolved in solvent DMF, using solvent DMF in 100mL
Constant volume in volumetric flask obtains a concentration of 1.0 × 10-3The probe storing solution of M；
Step 2：Lead salt, molysite, cadmium salt, zinc salt, magnesium salts, chromic salts, calcium salt, barium salt, sodium salt, manganese salt, mercury salt are dissolved in molten
In agent deionized water, using solvent deionized water in 100mL volumetric flasks constant volume, obtain a concentration of 1.0 × 10-2Each metal of M
Ion stock liquid；
Step 3：1mL a concentration of 1.0 × 10 is pipetted respectively-2Each metal ion storing solution of M is added in 1mL steps 1 and obtains
Probe storing solution, using solvent DMF in 10mL volumetric flasks constant volume, stand 5min after, detect its ultraviolet-visible spectrum；
It is found through experiments that the uv-visible absorption spectra of PHT has good response to lead ion.Wherein, solvent：DMF/
H2O (9/1, v/v), concentration：10 μM (PHT), 100 μM (metal ions).
Embodiment 4
PHT uv-visible absorption spectras and Pb2+Concentration relationship：
The Pb of various concentration is added2+Afterwards, ultraviolet probe PHT is measured in DMF/H2The ultraviolet-visible of O (9/1, v/v) system
Abosrption spectrogram.Wherein, solvent：DMF/H2O (9/1, v/v), concentration：10 μM (PHT), Pb2+Equivalent is followed successively by from top to bottom
0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1.0、2.0、3.0、4.0、5.0。
Step 1：The reactive dye fluorescence probe that embodiment 1 synthesizes is dissolved in solvent DMF, using solvent DMF in 100mL
Constant volume in volumetric flask obtains a concentration of 1.0 × 10-3The probe storing solution of M；
Step 2：Plumbi nitras is dissolved in solvent deionized water, using solvent deionized water in 100ml volumetric flasks constant volume,
Obtain a concentration of 1.0 × 10-2The lead ion storing solution of M；Pipette a concentration of 1.0 × 10-2The lead ion storing solution of M holds in 100ml
In measuring bottle, using solvent deionized water constant volume, a concentration of 1.0 × 10 are obtained-3The lead ion storing solution of M；Pipette a concentration of 1.0 ×
10-3The lead ion storing solution of M, using solvent deionized water constant volume, obtains a concentration of 1.0 × 10 in 100mL volumetric flasks-4M's
Lead ion standard solution；
Step 3. pipette respectively 0mL, 0.1mL, 0.2mL, 0.3mL, 0.4mL, 0.5mL, 0.6mL, 0.7mL, 0.8mL,
0.9mL, 1mL a concentration of 1.0 × 10-4The probe storing solution obtained in 1mL steps 1 is added in the lead ion standard solution of M, and utilization is molten
Agent DMF constant volumes in 10mL volumetric flasks separately pipette 0.2mL, 0.3mL, 0.4mL, 0.5mL a concentration of 1.0 × 10-3The lead ion of M
Obtained probe storing solution in 1mL steps 1 is added in storing solution, using solvent DMF in 10mL volumetric flasks constant volume, stand 5min
Afterwards, by ultravioletvisible spectroscopy, the absorbance at 382nm is detected；
As addition Pb2+Concentration when reaching 2M, occur new absorption peak in 382nm, with Pb2+Concentration is continuously increased,
Its UV absorption intensity is also continuously increased, and preferable linear relationship is presented between 2~10 μM.
Embodiment 5
The measurement of standard curve and detection limit：
It is managed and is taken turns based on Stern-Volmer, measure probe (10 μM) solution in DMF/H2The in the mixed solvent of O (9/1) is to Pb2 +Range of linearity when being detected and minimum detection limit.
Step 1：The reactive dye fluorescence probe that embodiment 1 synthesizes is dissolved in solvent DMF, using solvent DMF in 100mL
Constant volume in volumetric flask obtains a concentration of 1.0 × 10-3The probe storing solution of M pipettes probe storing solution in 100mL volumetric flasks, profit
With solvent DMF in 100mL volumetric flasks constant volume, obtain a concentration of 1.0 × 10-4M probe solutions；
Step 2：Plumbi nitras is dissolved in solvent deionized water, using solvent deionized water in 100mL volumetric flasks constant volume,
Obtain a concentration of 1.0 × 10-2The lead ion storing solution of M；Pipette a concentration of 1.0 × 10-2The lead ion storing solution of M holds in 100mL
In measuring bottle, using solvent deionized water constant volume, a concentration of 1.0 × 10 are obtained-3The lead ion storing solution of M；Pipette a concentration of 1.0 ×
10-3The lead ion storing solution of M, using solvent deionized water constant volume, obtains a concentration of 1.0 × 10 in 100mL volumetric flasks-4M's
Lead ion standard solution；
Step 3. pipette respectively 0mL, 0.1mL, 0.2mL, 0.3mL, 0.4mL, 0.5mL, 0.6mL, 0.7mL, 0.8mL,
0.9mL, 1mL a concentration of 1.0 × 10-4The probe storing solution obtained in 1mL steps 1 is added in the lead ion standard solution of M, and utilization is molten
Agent DMF constant volumes in 10mL volumetric flasks after standing 5min, by ultravioletvisible spectroscopy, detect the absorbance at 382nm；
The concentration of lead ion increases to 1.0 × 10 from 0-5M is tested after standing 30min.Absorbance is very at 382nm for probe
It is low.With Pb2+Addition, absorbance constantly enhances, according to Stern-Volmer equations：
A/A0=1+KsvCq
Wherein A0Indicate the absorbance that the probe system surveyed before and after ion is added, K respectively with AsvIt is enhancing constant, CqFor
The concentration of ion.Probe system absorbance enhances degree and good linear relationship is presented with ion concentration, as shown in figure 4, passing through
Equation of linear regression, linearly dependent coefficient 0.990 are calculated, the range of linearity is that the practical detections of 2~10 μM of are limited to 2 μM.Above-mentioned meter
Calculating result can be seen that probe to Pb2+Show good detection sensitivity, Pb2+Identification process is simple.
Embodiment 6
Ultraviolet probe PHT detects Pb2+When anti-interference：
Environment coexisting ion related to biology is probed into PHT/Pb2+DMF/H2O(9:1) solution absorbance at 382nm
Influence.Wherein, solvent：DMF/H2O (9/1, v/v), concentration：10 μM (PHT), 100 μM of (Pb2+), 100 μM (other ions),
Black bar is that different metal ions are added in PHT, and gray bars are in PHT-Pb2+Different metal ions are added in system.
Step 1：The reactive dye fluorescence probe that embodiment 1 synthesizes is dissolved in solvent DMF, using solvent DMF in 100mL
Constant volume in volumetric flask obtains a concentration of 1.0 × 10-3The probe storing solution of M；
Step 2：Lead salt, molysite, cadmium salt, zinc salt, magnesium salts, chromic salts, calcium salt, barium salt, sodium salt, manganese salt, mercury salt are dissolved in molten
In agent deionized water, using solvent deionized water in 100mL volumetric flasks constant volume, obtain a concentration of 1.0 × 10-2Each metal of M
Ion stock liquid；
Step 3：Pipette 1ml a concentration of 1.0 × 10-2The probe storage obtained in 1mL steps 1 is added in the lead ion storing solution of M
Standby liquid, using solvent DMF, constant volume detects its ultraviolet-visible spectrum after standing 5min in 10ml volumetric flasks；
Step 4：Pipette 1mL a concentration of 1.0 × 10-2The probe storage obtained in 1mL steps 1 is added in the lead ion storing solution of M
Standby liquid, is separately separately added into 1mL a concentration of 1.0 × 10-2Each metal ion storing solution of M, using solvent DMF in 10ml volumetric flasks
Constant volume detects its ultraviolet-visible spectrum after standing 5min；
It can be seen that Hg2+、Sn2+Keep absorbance slightly reduction outer, other ions influence it less, therefore, purple
Outer probe PHT has good anti-interference.
Claims (6)
1. a kind of application of the ultraviolet probe of Thiourea, it is characterised in that：The ultraviolet probe of Thiourea is used for the detection of lead ion, packet
It includes：
Prepare probe solution, be then added probe solution in lead ion solution to be measured, after constant volume, stand, by it is ultraviolet-can
Light-exposed spectrometry, the absorbance detected under 382nm wavelength determine lead ion according to opposite UV intensity and plumbum ion concentration relationship
The content of lead ion in prepare liquid；
The structural formula of the wherein described probe is：
2. a kind of application of the ultraviolet probe of Thiourea according to claim 1, it is characterised in that：The probe solution concentration
It is 0.8 × 10-4~1.2 × 10-4M。
3. a kind of application of the ultraviolet probe of Thiourea according to claim 1, it is characterised in that：The probe solution it is molten
Agent is n,N-Dimethylformamide DMF, and it is 9 that the solvent of system, which is volume ratio, after the constant volume:1 DMF/H2O。
4. a kind of application of the ultraviolet probe of Thiourea according to claim 1, it is characterised in that：The time of repose is 1
~10min.
5. a kind of application of the ultraviolet probe of Thiourea according to claim 1, it is characterised in that：Opposite UV intensity and lead
Ion concentration relationship is：Y=1.21+0.85x, wherein y indicate opposite UV intensity；X is the concentration of lead ion.
6. a kind of application of the ultraviolet probe of Thiourea according to claim 1, it is characterised in that：The ultraviolet probe pair of Thiourea
The detection of lead ion prepare liquid is limited to 1.5~2.5 μM.
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