CN108562563A - Application of the gold nano grain of citrazinic acid functionalization in detecting Cr3+ - Google Patents

Application of the gold nano grain of citrazinic acid functionalization in detecting Cr3+ Download PDF

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Publication number
CN108562563A
CN108562563A CN201810225012.2A CN201810225012A CN108562563A CN 108562563 A CN108562563 A CN 108562563A CN 201810225012 A CN201810225012 A CN 201810225012A CN 108562563 A CN108562563 A CN 108562563A
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gold nano
nano grain
citrazinic acid
gold
detection
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卢小泉
张雪红
李学梅
尚登辉
张守婷
陕多亮
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Northwest Normal University
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Northwest Normal University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/005Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/33Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18Metal complexes
    • C09K2211/188Metal complexes of other metals not provided for in one of the previous groups

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
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  • Optics & Photonics (AREA)
  • Materials Engineering (AREA)
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  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

The invention discloses the gold nano grains of citrazinic acid functionalization in detection Cr3+In application, the gold nano grain of the citrazinic acid functionalization can be used as fluorescence analysis detection Cr3+Fluorescence probe.The fluorescence probe is to Cr3+Specific good selectivity and anti-interference ability are, it can be achieved that Cr3+Visualization quickly detect.

Description

The gold nano grain of citrazinic acid functionalization is in detection Cr3+In application
Technical field
The present invention relates to a kind of gold nano grains of citrazinic acid functionalization in detection Cr3+In application.
Background technology
Nano material refers at least one-dimensional being in three dimensions in nanoscale range (1nm~100nm) or by him As basic unit constitute material.Since the 1970s comes out, since it has very unique physics, chemistry And the properties such as biology, and as research hotspot in recent years.
Gold nano grain be even more because its have 1000 times of extinction coefficient higher than general dye molecule (13nm Au NPs' Extinction coefficient is up to 2.7 × 108Mol/ (Lcm)), according to Beer-Lambert laws it is found that gold nano grain can reach Detection limit be far below dye molecule.Furthermore since gold nano grain system has different color changes under different conditions, Therefore gold nano grain occupies an important position in Visual retrieval.Since the Visual retrieval mechanism of gold nano grain is: Red is presented in monodisperse gold particle in the solution, and when detected material is added, gold nano grain is assembled, to make The plasmon coupling of intergranular changes, and red shift occurs for absorption peak, and the color of solution changes.Gold nano grain is in addition to tool Have outside above-mentioned optical characteristics, surface is easy to be chemically modified the extensive use for being also gold nano grain in analysis detects Provide convenient condition.Row such as gold nano grain surface can be realized by modifying small molecule, protein, polypeptide, DNA to not With specific detection of target substance, including small molecule, heavy metal ion, protein, nucleic acid, tumour cell and pathogen etc.. Visible detection method based on gold nano grain does not depend on any large-scale instrument, and solution colour variation can be used as reading letter Number, signal detection speed is fast, and material requested cost is more cheap, has been particularly suitable for quickly detection, Site Detection demand and item Part falls behind the region for not having large-scale instrument relatively.
Invention content
It is an object of the invention to the present situations according to above-mentioned background technology, provide a kind of gold nano of citrazinic acid functionalization Particle is in detection Cr3+In application.
In order to solve the above technical problem, the present invention provides the following technical solutions:
The gold nano grain of citrazinic acid functionalization is in detection Cr3+In application;Cr is detected using fluorescence analysis3+, In, the gold nano grain of the citrazinic acid functionalization is detection Cr3+Fluorescence probe.
Preferably, the fluorescence analysis is optical colorimetry.The gold nano grain of the citrazinic acid functionalization is equally Fluorescence probe be can be used as spectrophotometry Cr3+
Preferably, the preparation process of the gold nano grain of the citrazinic acid functionalization includes:By gold chloride and citrazinic acid sodium Mixed solution be heated to boiling, sodium citrate is then added, the gold nano grain of the citrazinic acid functionalization is obtained by the reaction.Its In, citrazinic acid sodium is the ligand of gold chloride, and sodium citrate is reducing agent.
Preferably, the molar ratio of the gold chloride and citrazinic acid sodium is 1:1~30:1.Mole of gold chloride and citrazinic acid sodium It is excessively more shallow or muddy than the too low or excessively high easy dispersion liquid color for making gold nano grain, the observation of color when visual colorimetric determination is influenced, Therefore, more preferably molar ratio is 10:1.
Preferably, the molar ratio of the gold chloride and sodium citrate is 1:1.5~1:8.
Description of the drawings
Attached drawing is used to provide further understanding of the present invention, and a part for constitution instruction, the reality with the present invention It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the transmission electron microscope figure of the Au NPs of the present invention.As seen from the figure, gold nano grain is in monodisperse type, Grain size is about 35nm.
Fig. 2 is the Au NPs+Cr of the present invention3+Transmission electron microscope figure.As seen from the figure, Cr is added3+Gold nano afterwards Coherent condition is presented in grain.
Fig. 3 is the ion selectivity test chart of the present invention.Uv absorption spectra, which can be seen that, is added Cr3+Gold nano Absorption peak of the particle at 525nm declines, and occurs new absorption peak at 700nm, and it is poly- that this also illustrates that gold nano grain occurs Collection.Block diagram is clearly seen that Cr3+It is highly selective, wherein photo also will become apparent from the variation of color.
Fig. 4 is the ion interference test chart of the present invention.As seen from the figure, other 18 kinds of ion pair Cr3+Detection do not produce Raw interference.
Fig. 5 is the sensitivity test figure of the present invention.
Specific implementation mode
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
Embodiment 1
1) preparation of gold nano grain (Au NPs):0.1mM 100mL gold chlorides and 0.1mM 100mL citrazinic acid sodium are mixed It closes in 250mL round-bottomed flasks, is heated to boiling in a water bath, 20mg sodium citrates (Na is added immediately3C6H5O7), solution by It is faint yellow to immediately become light gray, and baby pink is gradually become, stop heating after 20min, cooled to room temperature filters standby With the transmission electron microscope figure of Au NPs is as shown in Figure 1.
2) ion detection:Prepare 10mL 10-3mol·L-119 kinds of different metal cation (Na+、K+、Ag+、NH4 +、 Mg2+、Ca2+、Cu2+、Co2+、Mn2+、Cd2+、Ni2+、Hg2+、Pb2+、Zn2+、Fe2+、Al3+、Fe3+、Cr3+、Cr6+).Take a series of phases The above-mentioned Au NPs made of same volume sequentially add the above-mentioned different metal cations of 20 μ L, find only have in 1mL centrifuge tubes Added with Cr3+Solution colour change, and do not change added with the solution colour of other ions, as a result such as Fig. 3, Fig. 4 It is shown.Au NPs and Cr3+Transmission electron microscope figure in conjunction with after is as shown in Figure 2.
Comparison:The difference is that, be not added with ligand citrazinic acid sodium with the synthesis of above-mentioned Au NPs, above-mentioned most metals from Son can make obtained Au NPs that color change occur, and cannot achieve to Cr3+Selective recognition.
The citrazinic acid sodium of the present invention is obtained by the way that citrazinic acid to be dissolved in sodium hydroxide solution.
Embodiment 2
1) preparation of gold nano grain:0.3mM 100mL gold chlorides and 0.1mM 100mL citrazinic acid sodium are blended in It in 250mL round-bottomed flasks, is heated to boiling in a water bath, 20mg sodium citrates is added immediately, solution is immediately become by faint yellow Black then becomes red, muddy stain, stops heating after 20min, cooled to room temperature filters spare.
2) ion detection:Prepare 10mL 10-3mol·L-119 kinds of different metal cation (Na+、K+、Ag+、NH4 +、 Mg2+、Ca2+、Cu2+、Co2+、Mn2+、Cd2+、Ni2+、Hg2+、Pb2+、Zn2+、Fe2+、Al3+、Fe3+、Cr3+、Cr6+).Take a series of phases The above-mentioned Au NPs made of same volume sequentially add the different metal cations of 20 μ L in 1mL centrifuge tubes, find only added with Cr3+Solution grey is become from red immediately.And after crossing about 10min, added with Hg2+Solution colour slight change also has occurred, But its variation is less apparent.
Embodiment 3
1) preparation of gold nano grain:0.3mM 100mL gold chlorides and 0.05mM 100mL citrazinic acid sodium are blended in It in 250mL round-bottomed flasks, is heated to boiling in a water bath, 20mg sodium citrates is added immediately, solution is immediately become by faint yellow Black then becomes red, muddy stain, stops heating after 20min, cooled to room temperature filters spare.
2) ion detection:Prepare 10mL 10-3mol·L-119 kinds of different metal cation (Na+、K+、Ag+、NH4 +、 Mg2+、Ca2+、Cu2+、Co2+、Mn2+、Cd2+、Ni2+、Hg2+、Pb2+、Zn2+、Fe2+、Al3+、Fe3+、Cr3+、Cr6+).Take a series of phases The above-mentioned Au NPs made of same volume sequentially add the different metal cations of 20 μ L in 1mL centrifuge tubes, find only added with Cr3+Solution grey is become from red immediately.After crossing about 10min, variation is not observed added with the solution colour of other ions.
Embodiment 4
1) preparation of gold nano grain:0.3mM 100mL gold chlorides and 0.01mM 100mL citrazinic acid sodium are blended in It in 250mL round-bottomed flasks, is heated to boiling in a water bath, 26mg sodium citrates is added immediately, solution is immediately become by faint yellow Black then becomes baby pink, bright, stops heating after 20min, and cooled to room temperature filters spare.
2) ion detection:Prepare 10mL 10-3mol·L-119 kinds of different metal cation (Na+、K+、Ag+、NH4 +、 Mg2+、Ca2+、Cu2+、Co2+、Mn2+、Cd2+、Ni2+、Hg2+、Pb2+、Zn2+、Fe2+、Al3+、Fe3+、Cr3+、Cr6+).Take a series of phases The above-mentioned Au NPs made of same volume sequentially add the different metal cations of 20 μ L in 1mL centrifuge tubes, find only added with Cr3+Solution grey is become from baby pink immediately.After crossing about 10min, the solution face for adding other metal ions is not observed Color changes.
Embodiment 5
1) preparation of gold nano grain:0.3mM 100mL gold chlorides and 0.03mM 100mL citrazinic acid sodium are blended in It in 250mL round-bottomed flasks, is heated to boiling in a water bath, 26mg sodium citrates is added immediately, solution is immediately become by faint yellow Black then becomes pink, bright, stops heating after 20min, and cooled to room temperature filters spare.
2) ion detection:Prepare 10mL 10-3mol·L-119 kinds of different metal cation (Na+、K+、Ag+、NH4 +、 Mg2+、Ca2+、Cu2+、Co2+、Mn2+、Cd2+、Ni2+、Hg2+、Pb2+、Zn2+、Fe2+、Al3+、Fe3+、Cr3+、Cr6+).Take a series of phases The above-mentioned Au NPs made of same volume sequentially add the different metal cations of 20 μ L in 1mL centrifuge tubes, find only added with Cr3+Solution grey is become from pink immediately, solution colour variation zone is shown clearly.After crossing about 10min, it is not observed and adds it The solution colour of its metal ion changes.
Embodiment 6
1) preparation of gold nano grain:0.5mM 100mL gold chlorides and 0.05mM 100mL citrazinic acid sodium are blended in (10 in 250mL round-bottomed flasks:1) it, is heated to boiling in a water bath, 26mg sodium citrates is added immediately, solution is by faint yellow vertical Become black, then become red, color is deeper, stops heating after 20min, and cooled to room temperature filters spare.
2) ion detection:Prepare 10mL 10-3mol·L-119 kinds of different metal cation (Na+、K+、Ag+、NH4 +、 Mg2+、Ca2+、Cu2+、Co2+、Mn2+、Cd2+、Ni2+、Hg2+、Pb2+、Zn2+、Fe2+、Al3+、Fe3+、Cr3+、Cr6+).Take a series of phases The above-mentioned Au NPs made of same volume sequentially add the different metal cations of 20 μ L in 1mL centrifuge tubes, find only added with Cr3+Solution grey is become from red immediately.After crossing about 10min, it is not observed plus the solution colour of other metal ions is sent out Changing.
3) a series of Cr of various concentrations is prepared3+Solution, successively from low concentration to high concentration be added dropwise Cr3+, while in purple The variation tendency that its ultraviolet absorpting spectrum is observed under external spectrum, when collection of illustrative plates is not when changing or varying less, stopping is dripped Add, obtains a figures in Fig. 5;Then two peak values and concentration are done into curve and obtains b figures;Then pass through fitting in the range of linearity Curve is schemed to c.It can be seen that with Cr3+Concentration is incremented by, and absorption peak continuously decreases at 525nm, and the suction at 700nm Peak is received to gradually increase.B, c figure are it can be seen that the linear correlation having had in the range of linearity, detection sensitivity reach 9nM.
Concentration unit mol/L of the present invention indicates that corresponding nM indicates nmol/L with M, μM expression μm ol/L, mM expression mmol/L。
Finally it should be noted that:The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features. All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention's Within protection domain.

Claims (7)

1. the gold nano grain of citrazinic acid functionalization is in detection Cr3+In application.
2. application according to claim 1, it is characterised in that:Cr is detected using fluorescence analysis3+, wherein the lemon piperazine The gold nano grain of acid functionalization is detection Cr3+Fluorescence probe.
3. application according to claim 2, it is characterised in that:The fluorescence analysis is optical colorimetry.
4. application according to claim 1, it is characterised in that:The preparation of the gold nano grain of the citrazinic acid functionalization Journey includes:The mixed solution of gold chloride and citrazinic acid sodium is heated to boiling, sodium citrate is then added, the lemon is obtained by the reaction The gold nano grain of piperazine acid functionalization.
5. application according to claim 4, it is characterised in that:The molar ratio of the gold chloride and citrazinic acid sodium is 1:1~ 30:1。
6. application according to claim 4, it is characterised in that:The molar ratio of the gold chloride and citrazinic acid sodium is 10:1.
7. application according to claim 4, it is characterised in that:The molar ratio of the gold chloride and sodium citrate is 1:1.5 ~1:8.
CN201810225012.2A 2018-03-19 2018-03-19 Application of the gold nano grain of citrazinic acid functionalization in detecting Cr3+ Pending CN108562563A (en)

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Publication number Priority date Publication date Assignee Title
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CN102944551A (en) * 2012-10-16 2013-02-27 中国科学院宁波材料技术与工程研究所 Detection method of Cd2+
WO2013159185A1 (en) * 2012-04-24 2013-10-31 University Health Network Porphyrin-lipid stabilized nanoparticles for surface enhanced raman scattering based imaging
CN103852467A (en) * 2014-03-13 2014-06-11 哈尔滨师范大学 Chromium ion colorimetric detection probe and application method thereof
CN105372222A (en) * 2014-08-22 2016-03-02 中国科学院生态环境研究中心 Detection method of divalent heavy metal

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CN102507454A (en) * 2011-10-31 2012-06-20 中国科学院宁波材料技术与工程研究所 Method for detecting trivalent chromium ions
WO2013159185A1 (en) * 2012-04-24 2013-10-31 University Health Network Porphyrin-lipid stabilized nanoparticles for surface enhanced raman scattering based imaging
CN102944551A (en) * 2012-10-16 2013-02-27 中国科学院宁波材料技术与工程研究所 Detection method of Cd2+
CN103852467A (en) * 2014-03-13 2014-06-11 哈尔滨师范大学 Chromium ion colorimetric detection probe and application method thereof
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Application publication date: 20180921