CN106092977A - A kind of sensor detecting formaldehyde and preparation method thereof - Google Patents
A kind of sensor detecting formaldehyde and preparation method thereof Download PDFInfo
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- CN106092977A CN106092977A CN201610361248.XA CN201610361248A CN106092977A CN 106092977 A CN106092977 A CN 106092977A CN 201610361248 A CN201610361248 A CN 201610361248A CN 106092977 A CN106092977 A CN 106092977A
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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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- 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"
- G01N2021/6432—Quenching
Abstract
The present invention relates to chemical analysis detection field, particularly to a kind of sensor detecting formaldehyde and preparation method thereof.A kind of sensor detecting formaldehyde, chemical formula is (C15H10N3O2)2(C4H4N8S)Zn2.Sensor of the invention can realize the change PARA FORMALDEHYDE PRILLS(91,95) molecular of fluorescence intensity before and after PARA FORMALDEHYDE PRILLS(91,95) Molecular Adsorption and carry out that selectivity is qualitative and detection by quantitative, highly sensitive, has good application prospect.
Description
Technical field
The present invention relates to chemical analysis detection field, particularly to a kind of sensor detecting formaldehyde and preparation method thereof.
Background technology
Formaldehyde is a kind of colourless readily soluble irritative gas, can absorb through respiratory tract, can with biological cell protein bound,
It is the protoplasm material that a kind of toxicity is the strongest, is classified as one of carcinogen by international cancer institute, occupy hypertoxicity material control
The second of system.Formaldehyde is mainly manifested in heterosmia, stimulation, allergy, abnormal pulmonary function, liver function to the impact of health
The aspects such as exception and immunologic dysfunction.Formaldehyde pollution problem focuses primarily upon in room, textile and food at present.Room fills
Containing a large amount of Lauxites based on formaldehyde in the artificial boards such as plywood in exterior material and furniture, fibre board, particieboard,
All kinds of paint, coating all contain formaldehyde.Textile use in process of manufacture containing formaldehyde material whole as resin
Reason agent, to increase the elasticity of fabric, improves crapyness, also uses the cationic resin containing formaldehyde to improve dyefastness, causes
Formaldehyde in textile residue problem.It addition, because economic interests are ordered about, some lawless persons are with formaldehyde as food additive, such as water
Send out food add formaldehyde with coagulated protein anticorrosion, improve outward appearance, increase mouthfeel, in inebriant add formaldehyde prevent muddiness, increase
Transparency, these all can cause the severe contamination of food, damage health.In " Food Hygiene Law of the People's Republic of China "
Explicit stipulation forbids that formaldehyde is as food additive.As can be seen here, each angle during formaldehyde pollution problem has spread to life
Fall, serious threat health, the highest attention of people should be caused.Content of formaldehyde has become in current room, textile, food
One important safety index of pollution monitoring.
Summary of the invention
The technical problem to be solved is to provide the sensing of the detection formaldehyde with high selectivity and susceptiveness
Device.
Further object is that the preparation method that the sensor is provided.
A kind of sensor detecting formaldehyde, chemical formula is (C15H10N3O2)2(C4H4N8S)Zn2;Wherein, C15H10N3O2For 4'-
(4H-1,2,4-triazole-4-yls)-[1,1'-xenyl]-4-carboxylate radical, C4H6N8S is two ((1H-TETRAZOLE-5-base) methyl) sulfur
Alkane root, described sensor is rhombic system,PnnaSpace group, cell parameter isa=15.359 (2),b =12.854(5)
,c=13.735 (3),α =β =γ =90, V=2711.62 (6)3。
The preparation method of the sensor of above-mentioned detection formaldehyde is: by organic compound 4'-(4H-1,2,4-triazole-4-yl)-
[1,1'-xenyl]-4-carboxylic acid, 2,2'-sulfur are dissolved in the mixed solvent of water and acetonitrile for diethyl acyl cyanide, Hydrazoic acid,sodium salt and zinc nitrate
In the middle of, wherein water and acetonitrile volume ratio are 1:2, are stirred at room temperature formation mixed liquor A, then by described mixed liquor A in hydro-thermal
Under the conditions of react after 48 hours and obtain described sensor.
Further, (English is described 4'-(4H-1,2,4-triazole-4-yls)-[1,1'-xenyl]-4-carboxylic acid: 4'-
(4H-1,2,4-triazol-4-yl)-[1,1'-biphenyl]-4-carboxylic acid), 2,2'-sulfur for diethyl acyl cyanide,
The mol ratio of Hydrazoic acid,sodium salt and zinc nitrate is 1:1:2:1.
Further, described hydrothermal temperature is 180 DEG C.
Wherein, 2,2'-sulfur are 2,2'-thiodiacetonitrile, under hydrothermal conditions, 2 for diethyl acyl cyanide English,
2'-sulfur utilizes for diethyl acyl cyanide and can generate two ((1H-TETRAZOLE-5-base) methyl) under the catalytic action of zinc ion and Hydrazoic acid,sodium salt
Sulfane, and can be with 4'-(4H-1,2,4-triazole-4-yls)-[1,1'-after the protonation of two ((1H-TETRAZOLE-5-base) methyl) sulfane
Xenyl]-4-carboxylic acid forms in situ a kind of coordination compound with zinc ion.And tetrazolium in two (4-(1H-TETRAZOLE-5-base) phenyl) sulfane
Ring has abundant nitrogen-atoms, and the special construction of this formation can make this sensor generation fluorescence by active adsorption formaldehyde molecule
Quenching.
There is advantages that
Sensor of the invention is easily prepared, and reaction in-situ, the sensor being synthesized can occur in the case of hydro-thermal
Chemical stability is good.Sensor of the invention has good fluorescent characteristic, rich in having lone pair electrons in tetrazole ring structure
Nitrogen-atoms, it is possible to achieve before and after PARA FORMALDEHYDE PRILLS(91,95) Molecular Adsorption the change PARA FORMALDEHYDE PRILLS(91,95) molecular of fluorescence intensity carry out selectivity qualitative and
Detection by quantitative, highly sensitive, there is good application prospect.
Accompanying drawing explanation
Fig. 1 is the fluorescence spectrum figure of sensor of the invention formaldehyde adsorption molecule.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention,
It it not limitation of the invention.
Embodiment 1
By 1mmol4'-(4H-1,2,4-triazole-4-yl)-[1,1'-xenyl]-4-carboxylic acid, 1mmol2,2'-sulfur for diacetyl
Nitrile, 2mmol Hydrazoic acid,sodium salt and 1mmol zinc nitrate are dissolved in the mixed solution of 5mL water and 10mL acetonitrile, stirring at normal temperature 30 points
Clock, is subsequently transferred in politef autoclave, places it in 180 DEG C of baking ovens anti-48 hours, afterwards with 5 DEG C/little
Shi Jiangzhi room temperature is filtrated to get sensor, and productivity 69.2%(is based on zinc).
Then the sensor of gained is carried out monocrystalline sign.
The X ray diffracting data of this sensor is to visit on diffractometer in Bruker Smart Apex CCD face, uses MoKαSpoke
Penetrating (λ=0.71073), collect and carry out Lp factor correction with ω scan mode, absorption correction uses SADABS program.With
Direct method solution structure, then obtains whole non-hydrogen atom coordinate by difference Fourier method, and obtains hydrogen atom with theoretical hydrogenation method
Position (C H 1.083), is modified structure with method of least square.Evaluation work uses SHELXTL program bag on PC
Complete.
Resolving after tested and understand, this sensor chemistry formula is (C15H10N3O2)2(C4H4N8S)Zn2;Wherein, C15H10N3O2For
4'-(4H-1,2,4-triazole-4-yls)-[1,1'-xenyl]-4-carboxylate radical, C4H6N8S is two ((1H-TETRAZOLE-5-base) methyl)
Sulfane root, described sensor is rhombic system,PnnaSpace group, cell parameter isa=15.359 (2),b =12.854(5)
,c=13.735 (3),α = β = γ=90, V=2711.62 (6)3, Z=2.
Embodiment 2
The sensor of gained in 0.001g embodiment 1 is pulverized last being dispersed in 10mL alcohol solvent, then add not
Carrying out fluorescence spectrum test with the formaldehyde of concentration, excitation wavelength is 330nm.Fluorescence spectrum figure is as it is shown in figure 1, we can from figure
To find out, along with the concentration of formaldehyde increases to 10mM from 0, fluorescence intensity is gradually lowered, and, if add is methanol and third
Not affecting sensor of the invention fluorescence intensity if this kind of material of ketone, its fluorescence intensity is similar when being 0mM with concentration substantially, because of
This can utilize the change PARA FORMALDEHYDE PRILLS(91,95) molecule of fluorescence intensity to carry out, and selectivity is qualitative and detection by quantitative.
Embodiment described above only have expressed embodiments of the present invention, therefore it describes more concrete and detailed, but can not be
And it is interpreted as the restriction to the scope of the claims of the present invention, as long as using the technical side that the form of equivalent or equivalent transformation is obtained
Case, all should fall within the scope and spirit of the invention.
Claims (5)
1. the sensor detecting formaldehyde, it is characterised in that: chemical formula is (C15H10N3O2)2(C4H4N8S)Zn2;Wherein,
C15H10N3O2For 4'-(4H-1,2,4-triazole-4-yls)-[1,1'-xenyl]-4-carboxylate radical, C4H6N8S be two ((1H-TETRAZOLE-
5-yl) methyl) sulfane root.
A kind of sensing detecting formaldehyde the most according to claim 1, it is characterised in that described sensor is rhombic system,PnnaSpace group, cell parameter isa=15.359 (2),b=12.854 (5),c=13.735 (3),α = β = γ=
90, V=2711.62 (6)3。
3. the method for the sensor of the detection formaldehyde that one kind is prepared described in claim 1, it is characterised in that: by organic compound
4'-(4H-1,2,4-triazole-4-yl)-[1,1'-xenyl]-4-carboxylic acid, 2,2'-sulfur are for diethyl acyl cyanide, Hydrazoic acid,sodium salt and nitric acid
Zinc is dissolved in the middle of the mixed solvent of water and acetonitrile, and wherein water and acetonitrile volume ratio are 1:2, are stirred at room temperature formation mixed liquor A,
Then described sensor is obtained after described mixed liquor A being reacted 48 hours under hydrothermal conditions.
The preparation method of sensor the most according to claim 3, it is characterised in that: described 4'-(4H-1,2,4-triazole-4-
Base)-[1,1'-xenyl]-4-carboxylic acid, 2,2'-sulfur is 1:1:2:1 for the mol ratio of diethyl acyl cyanide, Hydrazoic acid,sodium salt and zinc nitrate.
The preparation method of sensor the most according to claim 3, it is characterised in that: described hydrothermal temperature is 180 DEG C.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012089969A1 (en) * | 2010-12-30 | 2012-07-05 | Centre National De La Recherche Scientifique - Cnrs | 3,6-functionalized 1,2,4,5-tetrazines, method for preparation, compositions comprising same and use in detecting organic pollutants |
CN104327042A (en) * | 2014-09-26 | 2015-02-04 | 郑州大学 | Formaldehyde quick detection reagent, preparation method and application thereof |
US20150323532A1 (en) * | 2014-05-08 | 2015-11-12 | Agilent Technologies, Inc. | Multiple epitope detection in an ffpe tissue section |
CN105372217A (en) * | 2015-11-17 | 2016-03-02 | 济南大学 | Formaldehyde fluorescent probe, and preparation method and application thereof |
CN105542756A (en) * | 2016-02-03 | 2016-05-04 | 浙江理工大学 | Fluorescent probe for detecting formaldehyde as well as preparation method and application of fluorescent probe |
-
2016
- 2016-05-27 CN CN201610361248.XA patent/CN106092977B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012089969A1 (en) * | 2010-12-30 | 2012-07-05 | Centre National De La Recherche Scientifique - Cnrs | 3,6-functionalized 1,2,4,5-tetrazines, method for preparation, compositions comprising same and use in detecting organic pollutants |
US20150323532A1 (en) * | 2014-05-08 | 2015-11-12 | Agilent Technologies, Inc. | Multiple epitope detection in an ffpe tissue section |
CN104327042A (en) * | 2014-09-26 | 2015-02-04 | 郑州大学 | Formaldehyde quick detection reagent, preparation method and application thereof |
CN105372217A (en) * | 2015-11-17 | 2016-03-02 | 济南大学 | Formaldehyde fluorescent probe, and preparation method and application thereof |
CN105542756A (en) * | 2016-02-03 | 2016-05-04 | 浙江理工大学 | Fluorescent probe for detecting formaldehyde as well as preparation method and application of fluorescent probe |
Non-Patent Citations (2)
Title |
---|
叶存玲等: "吖啶红动力学荧光法测定痕量甲醛", 《分析试验室》 * |
嵇正平等: "间苯三酚显色法测甲醛含量的研究", 《青海师专学报( 自然科学)》 * |
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Effective date of registration: 20190505 Address after: 528400 Zhongshan, Guangdong Torch Development Zone, 6 Xiang Hao Road, South Korea, 12 trading tower (1201 cards to 1208 cards) Applicant after: Zhongshan eternal Detection Technology Co., Ltd. Address before: No. 23, Wanjiang Road, Yingjiang District, Anqing, Anhui Province, Anhui Applicant before: Xu Weipeng |
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