CN115178746B - Preparation method and application of gold nanoparticles for detecting mercury ions in cosmetic water - Google Patents
Preparation method and application of gold nanoparticles for detecting mercury ions in cosmetic water Download PDFInfo
- Publication number
- CN115178746B CN115178746B CN202210829982.XA CN202210829982A CN115178746B CN 115178746 B CN115178746 B CN 115178746B CN 202210829982 A CN202210829982 A CN 202210829982A CN 115178746 B CN115178746 B CN 115178746B
- Authority
- CN
- China
- Prior art keywords
- aqueous solution
- solution
- gold nanoparticle
- gold nanoparticles
- sulfadiazine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 84
- 239000010931 gold Substances 0.000 title claims abstract description 83
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 82
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 37
- -1 mercury ions Chemical class 0.000 title claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002537 cosmetic Substances 0.000 title abstract description 24
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229960004306 sulfadiazine Drugs 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 49
- 238000001514 detection method Methods 0.000 claims description 27
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 22
- 239000001509 sodium citrate Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000006210 lotion Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 2
- 239000012047 saturated solution Substances 0.000 claims 1
- 238000002211 ultraviolet spectrum Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 14
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 230000002776 aggregation Effects 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 7
- 125000000524 functional group Chemical group 0.000 abstract description 7
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000007246 mechanism Effects 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract 2
- 239000000523 sample Substances 0.000 description 26
- 239000003607 modifier Substances 0.000 description 13
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000012086 standard solution Substances 0.000 description 8
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 4
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002343 gold Chemical class 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 208000016285 Movement disease Diseases 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 206010062237 Renal impairment Diseases 0.000 description 1
- 230000002744 anti-aggregatory effect Effects 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 230000005977 kidney dysfunction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0545—Dispersions or suspensions of nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- G01N21/55—Specular reflectivity
- G01N21/552—Attenuated total reflection
- G01N21/553—Attenuated total reflection and using surface plasmons
- G01N21/554—Attenuated total reflection and using surface plasmons detecting the surface plasmon resonance of nanostructured metals, e.g. localised surface plasmon resonance
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Analytical Chemistry (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Pathology (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a preparation method and application of gold nanoparticles for detecting heavy metal mercury ions, and the technology can rapidly, qualitatively and quantitatively detect the content of mercury ions in cosmetic water. The technical method is based on an agglomeration mechanism, utilizes the strong hydrogen bond action formed by functional groups on sulfadiazine, can generate bonding action with mercury ions to cause agglomeration of gold nanoparticles, changes the color of a solution, causes the peak position and the absorption intensity of a plasmon resonance absorption peak on the surface of the gold nanoparticles to change, and can directly judge whether Hg is contained in a sample by naked eyes 2+ Ions; the concentration of mercury ions can be quantitatively detected by calculating the intensity change of the ultraviolet visible absorption peak. The technology has the advantages of simplicity in operation, low cost, wide application range and the like.
Description
Technical Field
The invention belongs to the field of nano material and ion detection, and in particular relates to a method for detecting Hg in cosmetic water 2+ A preparation method and application of gold nano particles.
Background
Due to the rapid development of industry, heavy metal pollution in many parts of the world has exceeded regulatory limits, and this problem is becoming more and more interesting. Mercury is one of the most toxic elements on earth, a known environmental pollutant, and is typically released by coal-fired power plants, marine and volcanic emissions, gold mining, and solid waste incineration. The long residence time of mercury vapor in the atmosphere and its oxidation to soluble inorganic mercury (II) provide a means of contaminating large amounts of water and soil, etc. The natural components in cosmetics are extracted from plants, and heavy metals enriched in plants are inevitably remained in the plant extracts when plant essences are extracted. On the other hand, chemicalThe mercury ions in the cosmetics can generate the effects of whitening and lightening spots, and compared with the safe substances with the effects, the cosmetics have low price, so that partial illegal merchants can maliciously add heavy metal mercury ions into the cosmetics so as to achieve the effects of quickly whitening and lightening spots. The long-term use of the cosmetic containing mercury can lead mercury to permeate into the human body through the skin, and the heavy metals in the human body can be accumulated continuously. When mercury in a human body is accumulated to a certain content, huge damage is brought to the central nervous system of the human body, such as headache, dizziness, hypomnesis, movement disorder and other symptoms. Some of the mercury ions are transferred to the kidneys, which can cause kidney dysfunction. Therefore, each country has clear requirements for the amount of mercury ions contained in cosmetics. The related standard of China requires that the content of mercury element in cosmetics is not more than 1.0 mg.kg -1 。
To date, there are a number of methods for detecting heavy metal mercury ions, such as detection of Hg using cold vapor technology atomic absorption spectrometry (Anal.chem.2005, 77, 5124-5128), inductively coupled plasma atomic emission spectrometry (Anal.chem., 2008,80,7043-7050), inductively coupled plasma-mass spectrometry (Anal.at.Spectrom., 2009,24, 1414-1420), surface enhanced Raman scattering (Anal.chem.2013, 85, 3160-3165) fluorescence spectrometry (Anal.chem., 2013,85,8594-8600), and the like 2+ . Gao et al realized Hg based on aggregation mechanism 2+ Quick colorimetric detection of ions (chem. Commun,2014,50,6447; invention patent 201310091158.X,2013-03-26, china). Jin et al uses Hg 2+ The competition relationship between ions and Au NPs on 2-mercaptobenzothiazole realizes the anti-aggregation colorimetric detection of Hg 2+ Ion (Sensor actoat B-Chem,2016,233,233-229). Although these methods have excellent sensitivity, the detection procedure is complicated and costly. Developing sensitive and economical detection of trace Hg in cosmetic water 2+ Is necessary.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the cosmetic water Hg detection device which has the advantages of good stability, simple operation steps and capability of rapidly and accurately detecting Hg in the cosmetic water 2+ Gold nanoparticles and a preparation method thereof.
The technical scheme adopted for solving the technical problems is as follows:
a preparation method of gold nanoparticles for detecting heavy metal ions in cosmetic water adopts sodium citrate as a reducing agent to reduce trivalent gold into stable gold nanoparticles with uniform particles; adding the prepared gold nanoparticles into a modifier sulfadiazine to synthesize gold nanoparticles with the modifier; hg at a certain concentration 2+ The aqueous solution is added to the gold nanoparticle solution with the modifier, and the color of the solution changes from red to blue gray or grey. The gold nanoparticles reduced by sodium citrate are negatively charged, and the amino Yi Shidian in sulfadiazine is positively charged, so that the sulfadiazine is modified on the gold nanoparticles by combining electrostatic attraction and bonding. whereas-SO on sulfadiazine 2 The base and the pyridyl can also generate bonding effect with mercury ions to form gold nanoparticles with modifier, when the mercury ions are added into the aqueous solution of the gold nanoparticles with modifier, the mercury ions can generate bonding effect with functional groups on sulfadiazine molecules, so that a plurality of gold nanoparticles are connected, the gold nanoparticles are caused to agglomerate and macroscopically show a change in solution color, and Hg in the solution is realized 2+ Is detected rapidly by naked eyes. The change of aggregation state of gold nano particles causes the change of surface plasmon resonance absorption (SPR) of the gold nano particles, and the quantitative detection of mercury ions can be realized according to the change of the intensity and displacement of SPR absorption peaks.
Sulfadiazine (C) 10 H 10 N 4 O 2 S) has a structural formula as follows:
the invention provides a preparation method of gold nanoparticles, which specifically comprises the following steps:
adding a certain volume of chloroauric acid aqueous solution into a round bottom flask, adding water for dilution according to the volume ratio of 1:39, stirring and heating to boil, and rapidly adding sodium citrate (C 6 H 5 Na 3 O 7 ) Stirring the aqueous solution continuously for reaction for 15min, changing the color of the solution from yellow to wine red, standing and cooling to room temperature to obtain gold nanoparticle aqueous solution after sodium citrate reduction; then diluting the gold nanoparticle aqueous solution reduced by sodium citrate with deionized water according to the volume ratio of 1:1, measuring a certain volume of the diluted gold nanoparticle aqueous solution reduced by sodium citrate, adding a certain volume of saturated sulfadiazine aqueous solution, shaking uniformly, and reacting for a period of time to obtain a sulfadiazine modified gold nanoparticle aqueous solution, namely the gold nanoparticle;
the mercury ions are bivalent mercury ions;
the concentration of the chloroauric acid aqueous solution is 9-10 mM;
the mass fraction of the sodium citrate aqueous solution is 1%;
the pH range of the gold nanoparticle aqueous solution is 6.0-7.0;
the modifier solution is a saturated sulfadiazine water solution at room temperature;
the substances participating in the reaction are all analytically pure.
Furthermore, the invention also provides the application of the gold nano-particles, which is characterized in that the application of the gold nano-particles is that Hg in the cosmetic water can be detected 2+ The method specifically comprises the following steps:
the prepared gold nanoparticle aqueous solution is mixed with Hg with different concentrations 2+ Standard cards (figure 3) are manufactured according to different color changes, and the standard cards comprise cards of blank experiment results and are used for on-site naked eye colorimetric detection of samples to be detected in different environments.
The prepared aqueous solution of gold nano particles with modifier is mixed with Hg with different concentrations 2+ Then through ultraviolet visible absorption spectrum, the changes of peak position and intensity of plasma resonance absorption peak on the surface of the reacted gold nano particle are tested, ultraviolet visible absorption spectrum (figure 4) and standard curve (figure 5) are drawn, the ultraviolet visible absorption spectrum is used for detecting the sample to be detected in different environments, the test result is substituted into the standard curve, and comparison, calculation and judgment are carried outDetermination of the Presence of Hg in samples 2+ Or calculating Hg in the sample to be measured 2+ Thereby achieving a concentration of Hg in the sample 2+ Is used for quantitative detection of (a);
Hg 2+ the naked eye detection limit is 1.0 mug/mL;
Hg 2+ the detection limit of the ultraviolet-visible spectrum is 0.071 mug/mL;
the sample to be detected can be French elegance toning lotion, skin care spring toning lotion and Evian toning lotion.
In summary, the invention provides a gold nanoparticle, a preparation method thereof, and a technology for detecting mercury ions by using the prepared nanoparticle; the technical method is based on an agglomeration mechanism, and utilizes the bonding effect of partial functional groups on the modifier and mercury ions to cause gold nanoparticles to agglomerate, so that the color of a solution is changed to cause the peak position and absorption intensity of a plasma resonance absorption peak on the surface of the gold nanoparticles to be changed, therefore, the judgment is directly carried out by naked eyes or ultraviolet-visible spectrophotometry, and Hg in a sample can be realized 2+ Qualitative and quantitative detection of (a).
Compared with the prior art, the invention has the advantages that:
the invention provides gold nanoparticles, a preparation method thereof and Hg detection method 2+ The application technology of the method has the advantages of simple and convenient operation, low-cost and easily available raw materials, low cost, rapid detection, high sensitivity and strong selectivity, can implement on-site naked eye colorimetric detection, can be used for rapid detection of whether mercury ions in the toning lotion exceed standards, and has wide potential application value.
The modifier sulfadiazine used by the invention has the advantages of low toxicity, small dosage, environmental protection, specific space structure and configuration, and multiple coordination functional groups, and the functional groups of the sulfadiazine can form specific electrostatic attraction and specific bonding effect with gold nanoparticles and modify the gold nanoparticles, so that the gold nanoparticles have specific stability; and sulfadiazine can pass through its pyridine N, amino N or-SO 2 Forming quaternary chelate ring or six-membered chelate ring with mercury ion to aggregate gold nanometer particleCausing a color change.
In addition, pyridine N and amino NH on sulfadiazine 2 Imino NH, or-SO 2 The O can form a special hydrogen bond with or adjacent to the functional group of the modifier sulfadiazine, and the gold nanoparticles are aggregated and agglomerated. Other research works or techniques use 8-hydroxyquinoline, oxalate or 2-mercaptobenzothiazole and other organic ligands as modifiers and the like, and the organic ligand modifier sulfadiazine used by the invention has larger differences in spatial configuration, conformation and coordination functional groups, obviously different mechanisms of bonding mercury ions and causing aggregation of gold nanoparticles, different bonding directions and sizes of hydrogen bonds and coordination bonds, and obviously different stability of aggregated gold nanoparticles, so that the technical scheme formed by the invention has specific detection technical parameters and specific application scenes.
Drawings
FIG. 1 is a TEM image of gold nanoparticles modified with a sulfadiazine modifier according to example 4 of the present invention;
FIG. 2 Hg was added to example 6 of the present invention 2+ TEM image after gold nano particle agglomeration;
FIG. 3 different Hg 2+ Standard card of ion concentration;
FIG. 4 different Hg 2+ Ion concentration ultraviolet-visible absorption spectrum (concentration from 0-6 mug/mL);
FIG. 5 different Hg 2+ A standard curve drawn by ion concentration;
fig. 6 is a naked eye observation comparison chart of actual sample detection: (a) Blanc is a comparative solution, and # 1 is a labeled sample of the aqueous solution of the elegance cosmetic to which mercury ions were added (example 9); (b) Blank is a comparative solution, 2# is a standard sample of mercury ions added to the skin conditioning spring lotion solution (example 10), (c) Blank is a comparative solution, and 3# is a standard sample of mercury ions added to the cloud lotion solution (example 11).
Detailed Description
The invention is further described by the following specific examples, without limiting the scope of the invention.
Manufacturing a standard card:
adding 2.5mL of 9.5mM chloroauric acid solution into 97.5mL of deionized water, adding 5mL of 1% sodium citrate solution as a reducing agent under the conditions of stirring and heating to boiling, continuing to react for 15min, stopping adding, and cooling to room temperature to obtain sodium citrate reduced gold nanoparticle aqueous solution;
step (2) preparing a saturated sulfadiazine aqueous solution: dissolving 0.07g sulfadiazine in 100mL of water, stirring, ultrasonic treatment and dissolution; and then standing the solution until the solution is clear, and bottling for standby.
Step (3) preparing mercury ion standard solutions with different concentrations: a series of aqueous solutions of mercury ion concentrations were prepared with deionized water and 100 μg/mL of mercury ion standard solution, with final concentrations of 0, 0.25, 0.5, 0.75, 1, 1.25, 1.5, 1.75, 2, 2.5, 3, 4, and 5 μg/mL of standard solution in order.
Respectively taking 100 mu L of the saturated sulfadiazine aqueous solution prepared in the step (2), adding the saturated sulfadiazine aqueous solution into 800 mu L of the gold nanoparticle aqueous solution prepared in the step (1), shaking uniformly, waiting for three minutes, adding 100 mu L of the mercury ion standard solution with different concentrations prepared in the step (3), and standing for 5 minutes. Because the gold nanometer modified by sulfadiazine can have bonding effect with mercury ions to cause gold nanometer particles to agglomerate, the color of the mixed solution is macroscopically changed, and Hg is obtained 2+ Standard cards for ion concentration (fig. 3), including cards for blank test results.
Drawing a standard curve:
and respectively adding the mercury ion standard solutions with different concentrations into the prepared gold nanoparticle aqueous solution, standing for 5 minutes, measuring the peak position and the intensity of a surface plasmon resonance absorption peak of the gold nanoparticle in the wavelength range of 400-800 nm in each reaction solution (figure 4), and recording the ultraviolet-visible spectrum absorbance ratio at 655nm and 519 nm. The concentration of the standard sample is taken as the abscissa, and the absorbance ratio (A 655 nm/A 519 nm) as ordinate, a standard curve was prepared (fig. 5); obtaining Hg at the concentration of mercury ions ranging from 0 to 1.3 mug/mL through linear fitting 2+ Ion solution standard curveThe linear equation of the line is y=0.209811 x+0.08241, r 2 =0.9938。
Hg concentration was varied using standard card and standard curve 2+ Detecting, namely detecting the naked eye detection limit: hg of Hg 2+ 1.0 μg/mL; ultraviolet visible spectrum detection limit: hg of Hg 2+ 0.071 μg/mL; the calculation formula of the ultraviolet visible spectrum detection limit is K multiplied by SD/S, K=3, SD is standard deviation, and S is slope.
Example 1
Adding 2.5mL of 9.5mM chloroauric acid aqueous solution into a round bottom flask, adding 97.5mL of deionized water, stirring and heating to boil, rapidly adding 5mL of 1% sodium citrate aqueous solution by mass fraction, reacting for 15 minutes, changing the color of the solution from pale yellow to wine red, obtaining a reaction mixture solution, standing and cooling to room temperature, obtaining gold nanoparticle aqueous solution after sodium citrate reduction, and placing into a refrigerator at 0-4 ℃ for standby.
Example 2
2mL of 10mM chloroauric acid aqueous solution is added into a round bottom flask, 98mL of deionized water is added, stirring and heating are carried out until boiling, 5mL of 1% sodium citrate aqueous solution with mass fraction is added rapidly, after reaction for 15 minutes, the color of the solution is changed from pale yellow to wine red, a reaction mixture solution is obtained, standing and cooling are carried out to room temperature, a gold nanoparticle aqueous solution after sodium citrate reduction is prepared, and the gold nanoparticle aqueous solution is put into a refrigerator at 0-4 ℃ for standby.
Example 3
3mL of 10mM chloroauric acid aqueous solution is added into a round bottom flask, 97mL of deionized water is added, stirring and heating are carried out until boiling, 5mL of 1% sodium citrate aqueous solution with mass fraction is added rapidly, after reaction for 15 minutes, the color of the solution is changed from pale yellow to wine red, a reaction mixture solution is obtained, standing and cooling are carried out to room temperature, a gold nanoparticle aqueous solution after sodium citrate reduction is prepared, and the gold nanoparticle aqueous solution is put into a refrigerator at 0-4 ℃ for standby.
Example 4
Diluting the gold nanoparticles reduced by the prepared sodium citrate with deionized water according to the volume ratio of 1:1, taking 800 mu L of the gold nanoparticles, adding 100 mu L of saturated sulfadiazine aqueous solution, shaking uniformly, and waiting for the reaction for three minutes to prepare a sulfadiazine modified gold nanoparticle aqueous solution, namely the gold nanoparticles, and observing the morphology of the gold nanoparticles by using a TEM (figure 1).
Example 5
Diluting the gold nanoparticles reduced by the prepared sodium citrate with deionized water according to the volume ratio of 1:1.5, taking 800 mu L of the gold nanoparticles, adding 100 mu L of saturated sulfadiazine aqueous solution, shaking uniformly, and waiting for the reaction for three minutes to prepare a sulfadiazine modified gold nanoparticle aqueous solution, namely the gold nanoparticles, and observing the morphology of the gold nanoparticles by using TEM.
Example 6
100 mu L of mercury ion standard solution with the concentration of 2.0 mu g/mL is added into 900 mu L of gold nanoparticle aqueous solution modified by sulfadiazine, the gold nanoparticles are uniformly shaken and stand for 5 minutes, the gold nanoparticles are agglomerated, the color of the solution is changed into blue gray, and the morphology of the gold nanoparticles is observed by TEM (figure 2).
Example 7
100 mu L of mercury ion standard solution with the concentration of 3.0 mu g/mL is added into 900 mu L of gold nanoparticle aqueous solution modified by sulfadiazine, the mixture is shaken uniformly and is kept stand for 5 minutes, the color of the solution becomes blue gray, and the morphology of the gold nanoparticle aqueous solution is observed by TEM.
Example 8
100 mu L of mercury ion standard solution with the concentration of 5.0 mu g/mL is added into 900 mu L of gold nanoparticle aqueous solution modified by sulfadiazine, the mixture is shaken uniformly and is kept stand for 5 minutes, the color of the solution becomes blue gray, and the morphology of the gold nanoparticle aqueous solution is observed by TEM.
Example 9
Hg in the elegance cosmetic water 2+ Detection of ions
(a) Taking 100 mu L of two actual sample elegance water solutions, wherein one of the two actual sample elegance water solutions is used as a comparison solution;
(b) Adding mercury ions into a practical sample, namely the elegance cosmetic water solution to serve as a standard adding sample, wherein the mercury content in the standard adding sample solution is just 1.0mg/kg of national standard;
(c) 900. Mu.L of the modified gold nanoparticle solution was added to each of the control solution and the labeled sample, and after five minutes of reaction, the color changes of the labeled sample and the control solution were compared (FIG. 6 (a)) and compared with a standard colorimetric card.
Example 10
Hg in skin care spring toning lotion 2+ Detection of ions
(a) Taking 100 mu L of two actual sample skin care spring cosmetic water solutions, wherein one of the two actual sample skin care spring cosmetic water solutions is used as a comparison solution;
(b) Adding mercury ions into an actual sample skin care spring cosmetic water solution to serve as a standard adding sample, wherein the mercury content in the standard adding sample solution is just 1.0mg/kg of national standard;
(c) 900. Mu.L of the modified gold nanoparticle solution was added to the control solution and the labeled sample, respectively, and after five minutes of reaction, the color changes of the labeled sample and the control solution were compared (FIG. 6 (b)), and compared with a standard colorimetric card.
Example 11
Hg in Egyptian toning lotion 2+ Detection of ions
(a) Taking two actual samples, namely 100 mu L of cloud cosmetic water solution, wherein one of the two actual samples is used as a comparison solution;
(b) Adding mercury ions into an actual sample according to the cloud cosmetic water solution to serve as a standard adding sample, so that the mercury content in the standard adding sample solution is just 1.0mg/kg of national standard;
(c) 900. Mu.L of the modified gold nanoparticle solution was added to each of the control solution and the labeled sample, and after five minutes of reaction, the color changes of the labeled sample and the control solution were compared (FIG. 6 (c)) and compared with a standard colorimetric card.
The foregoing embodiments have been described in some detail by way of illustration of the principles of the invention, and it is to be understood that this invention is not limited to the specific embodiments described herein, but is intended to cover modifications and improvements made within the spirit and scope of the invention.
Claims (3)
1. A method for preparing gold nanoparticles, comprising the steps of:
adding a certain volume of chloroauric acid aqueous solution into a round bottom flask, and adding a certain volume of deionized waterStirring and heating to boiling, and rapidly adding sodium citrate (C 6 H 5 Na 3 O 7 ) Continuously stirring and reacting for 15 minutes, standing and cooling to room temperature to prepare gold nanoparticle aqueous solution after sodium citrate reduction; diluting the prepared gold nanoparticle aqueous solution reduced by sodium citrate by one time with deionized water according to the volume ratio of 1:1, then measuring a certain volume of the diluted gold nanoparticle aqueous solution reduced by sodium citrate, and adding a certain volume of saturated sulfadiazine (C 10 H 10 N 4 O 2 S) shaking the aqueous solution uniformly, and reacting for a period of time to obtain gold nanoparticle aqueous solution modified by sulfadiazine, namely the gold nanoparticle;
the concentration of the chloroauric acid aqueous solution is 9-10 mM;
the mass fraction of the sodium citrate aqueous solution is 1%;
the saturated sulfadiazine water solution is a saturated solution at room temperature;
the substances participating in the reaction are all analytically pure.
2. Gold nanoparticle, characterized in that it is prepared according to the preparation method of claim 1.
3. The use of the gold nanoparticle according to claim 1, wherein the gold nanoparticle can be used for rapid detection of mercury ions in a french-ripple lotion, a skin care lotion, an elvan lotion, a naked eye detection limit of 1.0 μg/mL, and an ultraviolet spectrum detection limit of 0.071 μg/mL.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210829982.XA CN115178746B (en) | 2022-07-13 | 2022-07-13 | Preparation method and application of gold nanoparticles for detecting mercury ions in cosmetic water |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210829982.XA CN115178746B (en) | 2022-07-13 | 2022-07-13 | Preparation method and application of gold nanoparticles for detecting mercury ions in cosmetic water |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115178746A CN115178746A (en) | 2022-10-14 |
CN115178746B true CN115178746B (en) | 2024-03-01 |
Family
ID=83519641
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210829982.XA Active CN115178746B (en) | 2022-07-13 | 2022-07-13 | Preparation method and application of gold nanoparticles for detecting mercury ions in cosmetic water |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115178746B (en) |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003035829A2 (en) * | 2001-10-09 | 2003-05-01 | Nanosphere, Inc. | Nanoparticles having oligonucleotides attached thereto and uses therefor |
CN102188383A (en) * | 2010-03-05 | 2011-09-21 | 国家纳米科学中心 | Amiopyrimidine-modified gold nano particles and preparation method and use thereof |
CN102374986A (en) * | 2010-08-13 | 2012-03-14 | 国家纳米科学中心 | Method for detecting mercury ions by using surface modified gold nano particles |
CN103901030A (en) * | 2014-04-11 | 2014-07-02 | 合肥工业大学 | Mercury ion colloidal gold colorimetric detection method and mercury ion detection kit |
CN105137086A (en) * | 2015-07-29 | 2015-12-09 | 中国农业大学 | Kit and test strip for detecting sulfonamides and use thereof |
CN107153059A (en) * | 2017-05-18 | 2017-09-12 | 中国工程物理研究院材料研究所 | A kind of preparation method of nanogold colorimetric sensor and its application in dimercurion detection |
CN107462579A (en) * | 2017-07-03 | 2017-12-12 | 北京欧凯纳斯科技有限公司 | A kind of kit and detection method for detecting mercury ion |
CN107917876A (en) * | 2017-10-16 | 2018-04-17 | 太原理工大学 | Antibiotic detection device and method based on nanogold aptamers structure |
CN108827897A (en) * | 2018-08-02 | 2018-11-16 | 盐城工学院 | The method for detecting mercury ion |
CN108941601A (en) * | 2018-07-25 | 2018-12-07 | 宁波大学 | A kind of gold nanoparticle and preparation method thereof |
CN110118769A (en) * | 2019-05-16 | 2019-08-13 | 宁波大学 | A kind of gold nanoparticle and preparation method thereof for detecting heavy metal ion |
CN110770572A (en) * | 2017-02-09 | 2020-02-07 | Essenlix公司 | Colorimetric assay |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013006947A1 (en) * | 2011-07-08 | 2013-01-17 | Covalon Technologies Inc. | Method for treating a surface with a coating comprising a therapeutic agent and device with treated surface |
-
2022
- 2022-07-13 CN CN202210829982.XA patent/CN115178746B/en active Active
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003035829A2 (en) * | 2001-10-09 | 2003-05-01 | Nanosphere, Inc. | Nanoparticles having oligonucleotides attached thereto and uses therefor |
CN102188383A (en) * | 2010-03-05 | 2011-09-21 | 国家纳米科学中心 | Amiopyrimidine-modified gold nano particles and preparation method and use thereof |
CN102374986A (en) * | 2010-08-13 | 2012-03-14 | 国家纳米科学中心 | Method for detecting mercury ions by using surface modified gold nano particles |
CN103901030A (en) * | 2014-04-11 | 2014-07-02 | 合肥工业大学 | Mercury ion colloidal gold colorimetric detection method and mercury ion detection kit |
CN105137086A (en) * | 2015-07-29 | 2015-12-09 | 中国农业大学 | Kit and test strip for detecting sulfonamides and use thereof |
CN110770572A (en) * | 2017-02-09 | 2020-02-07 | Essenlix公司 | Colorimetric assay |
CN107153059A (en) * | 2017-05-18 | 2017-09-12 | 中国工程物理研究院材料研究所 | A kind of preparation method of nanogold colorimetric sensor and its application in dimercurion detection |
CN107462579A (en) * | 2017-07-03 | 2017-12-12 | 北京欧凯纳斯科技有限公司 | A kind of kit and detection method for detecting mercury ion |
CN107917876A (en) * | 2017-10-16 | 2018-04-17 | 太原理工大学 | Antibiotic detection device and method based on nanogold aptamers structure |
CN108941601A (en) * | 2018-07-25 | 2018-12-07 | 宁波大学 | A kind of gold nanoparticle and preparation method thereof |
CN108827897A (en) * | 2018-08-02 | 2018-11-16 | 盐城工学院 | The method for detecting mercury ion |
CN110118769A (en) * | 2019-05-16 | 2019-08-13 | 宁波大学 | A kind of gold nanoparticle and preparation method thereof for detecting heavy metal ion |
Non-Patent Citations (2)
Title |
---|
Au NPs-enhanced surface plasmon resonance for sensitive detection of mercury(II) ions;Li Wang等;《Biosensors and Bioelectronics》;第25卷;第2622–2626页 * |
Study of the nucleation and growth of antibiotic labeled Au NPs and blue luminescent Au8 quantum clusters for Hg2+ ion sensing, cellular imaging and antibacterial applications;Puneet Khandelwal;《Nanoscale》;第7卷;第19985–20002页 * |
Also Published As
Publication number | Publication date |
---|---|
CN115178746A (en) | 2022-10-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Firdaus et al. | Colorimetric detection of mercury (II) ion in aqueous solution using silver nanoparticles | |
Yan et al. | Fluorescent sensor arrays for metal ions detection: A review | |
Zhuang et al. | A ratiometric fluorescent probe based on sulfur quantum dots and calcium ion for sensitive and visual detection of doxycycline in food | |
Jiang et al. | Zincon-immobilized silica-coated magnetic Fe3O4 nanoparticles for solid-phase extraction and determination of trace lead in natural and drinking waters by graphite furnace atomic absorption spectrometry | |
Adlnasab et al. | A preconcentration procedure for determination of ultra-trace mercury (II) in environmental samples employing continuous-flow cold vapor atomic absorption spectrometry | |
Kassem et al. | Spectrophotometric determination of iron in environmental and food samples using solid phase extraction | |
CN110118769B (en) | Gold nanoparticles for detecting heavy metal ions and preparation method thereof | |
Zhang et al. | Optical sensors for inorganic arsenic detection | |
Rastogi et al. | Selective colorimetric/visual detection of Al3+ in ground water using ascorbic acid capped gold nanoparticles | |
Liu et al. | Development of Eu-based metal-organic frameworks (MOFs) for luminescence sensing and entrapping of arsenate ion | |
Luo et al. | Preparation of nitrogen-doped carbon quantum dots and its application as a fluorescent probe for Cr (VI) ion detection | |
Zhang et al. | Dual-emitting metal–organic frameworks for ratiometric fluorescence detection of fluoride and Al3+ in sequence | |
Zhou et al. | Cysteine-rich protein-templated silver nanoclusters as a fluorometric probe for mercury (II) detection | |
Liu et al. | Resonance Rayleigh-scattering method for the determination of sildenafil citrate in a pharmaceutical formulation using Evans blue | |
CN110954526A (en) | Rapid detection method for trace mercury ions | |
Peng et al. | Ratiometric fluorescent sensor based on metal–organic framework for selective and sensitive detection of CO32– | |
Yang et al. | The reactivity study of peptide A3-capped gold and silver nanoparticles with heavy metal ions | |
Li et al. | Selective and cyclic detection of Cr 3+ using poly (methylacrylic acid) monolayer protected gold nanoparticles | |
CN115178746B (en) | Preparation method and application of gold nanoparticles for detecting mercury ions in cosmetic water | |
Lv et al. | Robust, reliable and quantitative sensing of aqueous arsenic species by Surface-enhanced Raman Spectroscopy: The crucial role of surface silver ions for good analytical practice | |
CN103487430A (en) | Trivalent aluminum ion detection reagent and method | |
Yu et al. | Quantitative determination of airborne redox-active compounds based on heating-induced reduction of gold nanoparticles | |
Bai et al. | Visual detection of barium ions using tiopronin functionalised gold nanoparticles | |
He et al. | Preparation of biomass water‐soluble carbon quantum dots and their application in Cr (VI) ions detection | |
Bai et al. | Rapid, sensitive and selective detection of pymetrozine using gold nanoparticles as colourimetric probes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right | ||
TR01 | Transfer of patent right |
Effective date of registration: 20240310 Address after: 401329 No. 99, Xinfeng Avenue, Jinfeng Town, Gaoxin District, Jiulongpo District, Chongqing Patentee after: Chongqing Science City Intellectual Property Operation Center Co.,Ltd. Country or region after: China Address before: 315211, Fenghua Road, Jiangbei District, Zhejiang, Ningbo 818 Patentee before: Ningbo University Country or region before: China |