CN103558336A - Portable food safety inspection reagent as well as preparation method and application thereof - Google Patents
Portable food safety inspection reagent as well as preparation method and application thereof Download PDFInfo
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- CN103558336A CN103558336A CN201310511426.9A CN201310511426A CN103558336A CN 103558336 A CN103558336 A CN 103558336A CN 201310511426 A CN201310511426 A CN 201310511426A CN 103558336 A CN103558336 A CN 103558336A
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Abstract
The invention discloses a portable food safety inspection reagent as well as a preparation method and application thereof. The inspection reagent provided by the invention is a metal salt solution comprising a surface active agent and a reducing agent; the metal salt is gold salt, silver salt or a mixture of the gold salt and the silver salt; the gold salt, the silver salt, the surface active agent and the reducing agent are shown in the specification and the claims. The inspection reagent provided by the invention is added into a to-be-inspected water solution, and whether toxic substances exist in the to-be-inspected water solution is inspected through observing the color change or inspecting the ultraviolet absorption change. The inspection reagent provided by the invention is high in specificity and flexibility, simple and convenient to operate and high in inspection speed, can obtain intuitive and accurate inspection results, is low in inspection cost and less in investment, is portable without special instrument and equipment and professional personnel, and is easy to popularize and implement and high in practicability.
Description
Technical field
The present invention relates to analytical chemistry and food safety detection field, particularly a kind of portable food safety detection reagent and preparation method thereof and application.
Technical background
In recent years, China Duo Jia manufacturer is used " clenbuterol hydrochloride " as feed addictive, pasture." clenbuterol hydrochloride " is numerous in variety, comprises Dopamine hydrochloride, clenobuterol hydrochloride, Ractopamine, salbutamol, salbutamol sulfate, Cimaterol, bricalin, phenolethanolamine, bambuterol, hydrochloric acid Zilpaterol, clorprenaline hydrochloride, Mabuterol, western Boot sieve, bromine Boot sieve, tartrate Afromoterol and formoterol fumarate.In animal feeding-stuff, overdose adds " clenbuterol hydrochloride " can make livestock adipose tissue be converted into musculature.And people is edible, contain after the residual food of dopamine, often can not feel like oneself, with symptoms such as palpitaition, muscular tremor, n and V, heating shiver with colds, " clenbuterol hydrochloride " is larger to the patients' such as heart disease, diabetes, hypertension harm especially.
2008 there is food safety affair-dairy produce contamination accident together in China, and the cause of event is that the baby of many edible Sanlu milk powder suffers from kidney stone, has found industrial chemicals-melamine subsequently in its milk powder.Owing to there is defect in the assay method of protein content in food and feeds industry, melamine often by illegal retailer as food additives, to promote the content's index of protein in food and feeds detects, melamine is also called " extract of protein " by people.
On September 13rd, 2011, Chinese police loopful joint is cracked the case that edible oil is made and sold in especially big utilization " waste oil ".Waste oil, the rubbish silently trickling in municipal sewage system.The naughty waste oil person who has processes it, transforms into " edible oil " on dining table.The three-without-product of this being known as " waste oil ", its principal ingredient remains triglyceride, but than real edible oil many manyly cause a disease, carcinogenic toxicants, long-term edible may cause cancer, very harmful to human body.
At present, the detection method of guaranteeing food security has gas chromatography-mass spectrography (GC-MS), high performance liquid chromatography (HPLC), enzyme linked immunosorbent assay (ELISA) and liquid chromatography-mass spectrography/mass spectroscopy (HPLC-MS/MS) etc.But the instrument that above-mentioned detection method is relevant is expensive, heaviness Portable belt not, often has the defects such as sample preparation steps complexity during for food inspection.At present, shortage of funding, technology is immature or condition does not possess unit or the individual instrument and equipment of above-mentioned costliness that cannot adopt detect food, and the offender who manufactures poisoned food is at large.For guaranteeing consumer's health diet, must accomplish to detect food in real time, on the spot, guarantee the security of food.
Therefore, research and develop a kind of very sensitive, detection speed is fast, selectivity good and practical food in detection reagent and the analytical approach of poisonous and harmful substance very important.
Summary of the invention
The object of the present invention is to provide a kind of high selectivity, detect delicately portable detection reagent of poisonous and harmful substance in food and preparation method thereof.
A first aspect of the present invention, provides a kind of detection reagent, and described detection reagent is the metal salt solution that comprises surfactant and reductive agent, and described slaine is golden salt, silver salt or its potpourri;
Wherein, described golden salt is one or more the potpourri in chlorauride trihydrate, chlorauride tetrahydrate, aurous chloride, gold oxide, chloroformyl fund, gold bromide, (pyridine) gold trichloride, chlorine (dimethyl sulfuration) gold, chlorine (trimethyl-phosphine) gold, (dimethylphenylphosphine) chlorauride, chloro tri-tert phosphatization gold, dichloro (2-pyridine carboxylic acid) gold, dichloro (2-pyridine carboxylic acid) gold, chlorine (trimethyl-phosphine) gold, chlorine [three (o-tolyl) phosphine] gold, chlorine [three (2,4-di-tert-butyl-phenyl) phosphorous acid] gold, gold potassium chloride and sodium chloraurate;
Described silver salt is silver nitrate, silver acetate, silver acetate, actol, silver fluoride, silver perchlorate, silver sulfate, trifluoroacetic acid silver, fluoroform, silver selenide, silver telluride, sulfonic acid silver, trifluoroacetic acid is silver-colored, p-toluenesulfonic acid is silver-colored, hexafluoro-antimonic acid is silver-colored and silver tetrafluoroborate in one or more potpourri;
Described surfactant is neopelex, stearic acid, lecithin, fatty glyceride, sodium glycocholate, quarternary ammonium salt compound, polysorbate and fatty acid sorb one or more the potpourri in smooth;
Described reductive agent is one or more the potpourri in sodium borohydride, potassium borohydride, oxalic acid, lactic acid, dithiothreitol (DTT), oxammonium hydrochloride, ascorbic acid, D-araboascorbic acid, sodium ascorbate, sodium isoascorbate and Calcium Ascorbate.
In another preference, described metal salt solution is aqueous metal salt.
In another preference, described quarternary ammonium salt compound is selected from: cetyl trimethyl ammonium bromide, DHAB, myristyl dimethyl benzyl ammonium chloride, cetyldimethylethylambromide bromide ammonium, Cetyltrimethylammonium bromide, OTAC, DTAB, DTAC and dodecyl benzyl dimethyl ammonium chloride.
In another preference, the concentration of described golden salt, silver salt or its potpourri is 0.001mM-1mM.In another preference, the concentration of described golden salt, silver salt or its potpourri is 0.002mM-0.8mM, preferably, is 0.004mM-0.75mM.
In another preference, the concentration of described surfactant is 0.0001mM-1mM.In another preference, the concentration of described surfactant is 0.001mM – 0.8mM, is preferably 0.005mM-0.5mM.
In another preference, the concentration of described reductive agent is 0.5mM – 80mM.In another preference, the concentration of described reductive agent is 1mM-75mM.
Wherein, 1mM=1 * 10
-3mol/L, 1M=1mol/L.
A second aspect of the present invention, the preparation method of the detection reagent described in a kind of first aspect is provided, comprise and add surfactant and described reductive agent to form described detection reagent in metal salt solution step, wherein, described slaine, described surfactant and described reductive agent are as described in first aspect.
A third aspect of the present invention, provides a kind of detection method, said method comprising the steps of:
(a) get the detection reagent described in the first aspect of two parts of same volumes, and get identical with aqueous solution volume to be detected and not containing the water of toxicant solution as a comparison;
(b) by first part, detect reagent and mix mutually with comparative solution, form the first mixed liquor; By second part of detection reagent and aqueous solution to be detected, form the second mixed liquor; And in the first mixed liquor and the second mixed liquor, add respectively highly basic and Biological cross-linker, form respectively the 3rd mixed liquor and the 4th mixed liquor;
(c) take the 3rd mixed liquor is reference, and the uv absorption of observing the change color of the 4th mixed liquor or detecting the 4th mixed liquor changes determines whether aqueous solution to be detected exists noxious material;
Wherein, described highly basic is one or more the potpourri in NaOH, potassium hydroxide, choline, thallium hydroxide, strontium hydroxide;
Described Biological cross-linker is one or more the potpourri in Cys, glutaraldehyde, mercaptoacetic acid, acetic anhydride, 2 mercaptopropionic acid, diglycidyl ether, 3-mercaptopropionic acid, pungent two imidic acid methyl esters, sodium thioglycolate, calcium mercaptoacetate and thiosalicylic acid.
In another preference, described noxious material is one or more the combination in Dopamine hydrochloride, clenobuterol hydrochloride, Ractopamine, salbutamol, salbutamol sulfate, Cimaterol, bricalin, phenolethanolamine, bambuterol, hydrochloric acid Zilpaterol, clorprenaline hydrochloride, Mabuterol, western Boot sieve, bromine Boot sieve, tartrate Afromoterol, formoterol fumarate, melamine, tonyred, formalin, sulphur and copper sulphate.
A fourth aspect of the present invention, provides the application of the detection reagent described in a kind of first aspect, for detection of whether there being noxious material in food.
In another preference, described noxious material is one or more the combination in Dopamine hydrochloride, clenobuterol hydrochloride, Ractopamine, salbutamol, salbutamol sulfate, Cimaterol, bricalin, phenolethanolamine, bambuterol, hydrochloric acid Zilpaterol, clorprenaline hydrochloride, Mabuterol, western Boot sieve, bromine Boot sieve, tartrate Afromoterol, formoterol fumarate, melamine, tonyred, formalin, sulphur and copper sulphate.
Detection reagent of the present invention, high specificity, highly sensitive, easy and simple to handle, detection speed is fast; Testing result is directly perceived, accurate; Testing cost is low, small investment; Be easy to carry, do not need specialized instrument and equipment and professional, easily promotion and implementation, practical.
In should be understood that within the scope of the present invention, above-mentioned each technical characterictic of the present invention and can combining mutually between specifically described each technical characterictic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, at this, tire out and state no longer one by one.
Accompanying drawing explanation
In Fig. 1, A is detection reagent and the mixing of variable concentrations toxicant of embodiment 1, under alkali condition, and the UV-vis absorption spectra under the assistance of Biological cross-linker; In Fig. 1, B is absorptance (A
0/ A) with the change curve of toxicant concentration.
In Fig. 2, upper figure is colorimetric photo, and figure below is Uv-vis absorptance (A
0/ A) figure.
The Uv-vis absorption spectra that in Fig. 3, A is different time points, B is the ratio (A of Uv-vis minimum and obtained the maximum absorption
min/ A
max) with the graph of a relation of time.
Fig. 4 is while detecting variable concentrations toxicant, the particle diameter of the nano particle that employing dynamic light scattering (DLS) records.
Fig. 5 is transmission electron microscope picture (TEM) figure of the microscopic appearance of nano particle.
Embodiment
Present inventor, through extensive and deep research, surprisingly finds detection reagent and the method for objectionable impurities in a kind of food first.This detection reagent is the metal salt solution that comprises surfactant and reductive agent, and high specificity, highly sensitive, easy and simple to handle, detection speed is fast; Testing result is directly perceived, accurate; Testing cost is low; Do not need specialized instrument and equipment and professional, easily promotion and implementation.On this basis, completed the present invention.
Detect reagent
The present invention is directed to non-security food, provide a kind of quick, practical, cost is low, portable detection reagent, described detection reagent is the metal salt solution that comprises surfactant and reductive agent, described slaine is golden salt, silver salt or its potpourri.
The preparation method of detection reagent of the present invention, comprises step:
(i) provide golden salt solusion, silver salt solution or its mixed solution;
(ii) in step I) add surfactant and reductive agent in the solution that provides, obtain described detection reagent.
In a preference of the present invention, gold/silver salt is dissolved in deionized water, add surfactant, stir 10-60 minute, drip reductive agent, make detection reagent.
In the present invention, described golden salt is one or more the potpourri in chlorauride trihydrate, chlorauride tetrahydrate, aurous chloride, gold oxide, chloroformyl fund, gold bromide, (pyridine) gold trichloride, chlorine (dimethyl sulfuration) gold, chlorine (trimethyl-phosphine) gold, (dimethylphenylphosphine) chlorauride, chloro tri-tert phosphatization gold, dichloro (2-pyridine carboxylic acid) gold, dichloro (2-pyridine carboxylic acid) gold, chlorine (trimethyl-phosphine) gold, chlorine [three (o-tolyl) phosphine] gold, chlorine [three (2,4-di-tert-butyl-phenyl) phosphorous acid] gold, gold potassium chloride and sodium chloraurate.
Described silver salt is silver nitrate, silver acetate, silver acetate, actol, silver fluoride, silver perchlorate, silver sulfate, trifluoroacetic acid silver, fluoroform, silver selenide, silver telluride, sulfonic acid silver, trifluoroacetic acid is silver-colored, p-toluenesulfonic acid is silver-colored, hexafluoro-antimonic acid is silver-colored and silver tetrafluoroborate in one or more potpourri.
Described surfactant is neopelex, stearic acid, lecithin, fatty glyceride, sodium glycocholate, quarternary ammonium salt compound (cetyl trimethyl ammonium bromide (CTAB), DHAB, myristyl dimethyl benzyl ammonium chloride, cetyldimethylethylambromide bromide ammonium, Cetyltrimethylammonium bromide, OTAC, DTAB, DTAC and dodecyl benzyl dimethyl ammonium chloride), the potpourri of one or more during polysorbate and fatty acid sorb are smooth.
Described reductive agent is one or more the potpourri in sodium borohydride, potassium borohydride, oxalic acid, lactic acid, dithiothreitol (DTT), oxammonium hydrochloride, ascorbic acid, D-araboascorbic acid, sodium ascorbate, sodium isoascorbate and Calcium Ascorbate.
In the present invention, in described detection reagent, the concentration of slaine is 0.001mM-1mM, is preferably 0.002mM-0.8mM, more preferably, is 0.004mM-0.75mM.Wherein, 1mM=1 * 10
-3mol/L, 1M=1mol/L.
In the present invention, in described detection reagent, the concentration of surfactant is 0.0001mM-1mM, is preferably 0.001mM – 0.8mM, is more preferably 0.005mM-0.5mM.
In the present invention, in described detection reagent, the concentration of reductive agent is 0.5mM – 80mM.In another preference, the concentration of described reductive agent is 1mM – 75mM.
Detection method
The present invention utilizes above-mentioned detection reagent, under alkali condition, and under the assistance of the Biological cross-linker that contains sulfydryl and carboxylic group, and the noxious material in can fast detecting food.In alkaline solution, noxious material will be covered in nm of gold/silver surface, add the material that contains sulfydryl and carboxyl, the nm of gold/silver that impels noxious material to cover is assembled fast, cause that the color of nm of gold/silver-colored solution and surface plasma body resonant vibration absorption change.Therefore, whether the variation by visual inspection solution colour or test the variation of its absorption intensity and peak value by UV-vis spectrophotometer, can contain noxious material in fast detecting food.
Detection method of the present invention comprises the steps:
(1) get the detection reagent of two parts of same volumes, and get with to detect aqueous solution volume identical but not containing the water of toxicant solution as a comparison;
(2) by first part, detect reagent and mix mutually with comparative solution, form the first mixed liquor; By second part of detection reagent and aqueous solution to be detected, form the second mixed liquor; And in the first mixed liquor and the second mixed liquor, add respectively highly basic and Biological cross-linker, form respectively the 3rd mixed liquor and the 4th mixed liquor;
(3) take the 3rd mixed liquor is reference, the uv absorption of observing the change color of the 4th mixed liquor or detecting the 4th mixed liquor change determine noxious material existence whether.
In another preference, add the strong base solution of 0.1M-8M, the ultimate density that makes the middle highly basic of solution is 2 * 10
-3m – 0.16M.
In another preference, add the Biological cross-linker of 0.1M-6M, the final concentration that makes Biological cross-linker in solution is 4 * 10
-3m – 0.24M.
Described highly basic is one or more the potpourri in NaOH, potassium hydroxide, choline, thallium hydroxide, strontium hydroxide.
Described Biological cross-linker is one or more the potpourri in Cys, glutaraldehyde, mercaptoacetic acid, acetic anhydride, 2 mercaptopropionic acid, diglycidyl ether, 3-mercaptopropionic acid, pungent two imidic acid methyl esters, sodium thioglycolate, calcium mercaptoacetate and thiosalicylic acid.
Noxious material in described food is one or more the combination in Dopamine hydrochloride, clenobuterol hydrochloride, Ractopamine, salbutamol, salbutamol sulfate, Cimaterol, bricalin, phenolethanolamine, bambuterol, hydrochloric acid Zilpaterol, clorprenaline hydrochloride, Mabuterol, western Boot sieve, bromine Boot sieve, tartrate Afromoterol, formoterol fumarate, melamine, tonyred, formalin, sulphur and copper sulphate.
In another preference, observe the color of the 4th mixed liquor, if there is change color (as color becomes grey from redness or yellow before), in detected sample, have toxicant, if there is not change color, in detected aqueous solution, there is not toxicant.
In another preference, contrast UV-vis absorption intensity, the peak value of the 4th mixed liquor and the 3rd mixed liquor, if its UV-vis absorption intensity, peak value change, in tested test sample, have toxicant, if occur, significantly do not change, in tested test sample, do not have toxicant.
The above-mentioned feature that the present invention mentions, or the feature that embodiment mentions can combination in any.All features that this case instructions discloses can with any composition forms use, each feature disclosing in instructions, can be replaced by any alternative characteristics of identical, impartial or similar object that provide.Therefore except there being special instruction, the feature disclosing is only the general example of equalization or similar features.
Usefulness of the present invention is:
(1) functional gold nanoparticles provided by the invention/silver-colored solution manufacturing method is simple and easy to do, reproducible, the common laboratory realization of all having ready conditions.
(2) functional gold nanoparticles of the present invention/silver-colored solution has very strong practicality, and using method is simple, can be used in food safety detection, environmental science, check chemistry and analytical chemistry field.
(3) functional gold nanoparticles/silver-colored solution can fast detecting go out toxicant, and only need 30 minutes detection time, far below the detection time (approximately needing 3 hours) of inductively coupled plasma emission spectrography (ICP-OES).
(4) functional gold nanoparticles/silver-colored solution can Sensitive Detection go out toxicant, take dopamine as example, and detectability reaches 3.3 * 10
-8m, lower than the detection limit 6 * 10 of having reported
-8m(Chem.Commun., 2011,47:1181-1183.).
(5) functional gold nanoparticles/silver-colored solution optionally detects the toxicant in food.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.The experimental technique of unreceipted actual conditions in the following example, conventionally according to normal condition as people such as Sambrook, molecular cloning: laboratory manual (New York:Cold Spring Harbor Laboratory Press, 1989) condition described in, or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise number percent and umber calculate by weight.
Unless otherwise defined, the familiar meaning of all specialties of using in literary composition and scientific words and one skilled in the art is identical.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The use that better implementation method described in literary composition and material only present a demonstration.
(1) detect the preparation of reagent
Under room temperature, get the four hydration chlorauric acid solutions of the 10mM of 5mL, join in the cetyl trimethyl ammonium bromide mixed solution of the deionized water of 95mL and the 3.5mM of 1mL, stir 5 minutes; Then dropwise add the sodium borohydride of the 0.1M of 1.5mL, continue to stir 20 minutes, make nano-Au solution and detect reagent, be placed in 4 ℃ of refrigerators standby.
(2) use the above-mentioned nano-Au solution making to detect Dopamine hydrochloride:
The nano-Au solution that measures the above-mentioned preparation of ten part of 80 μ L detects reagent, respectively with the deionized water (as blank) of 20 μ L, and 10 of 20 μ L
-9-10
-2m Dopamine hydrochloride (detected ultimate density) solution mixes, and then adds respectively the sodium hydrate aqueous solution of 10 μ L0.1M, obtains ten parts of mixed solutions.In ten parts of mixed solutions, add respectively again the mercaptoacetic acid (TGA) of 6 μ L0.1M, carry out colorimetric, visual inspection, along with Dopamine hydrochloride solution increases, increase gradually with the color distortion of blank, by pink to purple to grey, yellow, open hole detection is limited to 10
-7m.Adopt ultraviolet spectrometer (UVS) to detect, result is as shown in A in Fig. 1, with Dopamine hydrochloride concentration (detected toxicant concentration: 0,10
-9, 10
-8, 10
-7, 2 * 10
-7, 3 * 10
-7, 4 * 10
-7, 5 * 10
-7, 6 * 10
-7, 10
-6, 2 * 10
-6, 5 * 10
-6with 10
-5m) increase, corresponding UV-vis absorption spectrum generation red shift and absorption intensity weaken.According to the UV-vis absorption spectrum of A in Fig. 1, obtain the absorptance (A that nano-Au solution detects the Dopamine hydrochloride of reagent and its detection variable concentrations
0/ A), this absorptance, with the variation of Dopamine hydrochloride concentration, meets linear relationship, and the lowest detection that calculates Dopamine hydrochloride according to this linear relationship is limited to 3.3 * 10
-8m, as shown in B in Fig. 1.
For investigating nano-Au solution, detect reagent, could optionally detect sitotoxismus material (Dopamine hydrochloride), 80 μ L nano-Au solutions of preparation are detected to reagent and 20 μ L5 * 10
-4the common material containing in M food and Dopamine hydrochloride mix, and then add the highly basic of 10 μ L5mM, then add respectively the mercaptoacetic acid (TGA) of 6 μ L0.1M, mix, and place room temperature and observe its change color.The common material containing in the food of investigating comprises tyrosine (L-Tyrosine, L-Tyr), lactic acid (Lactate, Lac), uric acid (Uric Acid, UA), aspartic acid (L-Aspartic acid, L-Asp), oxalic acid (Oxalate, Oxa), histidine (Histidine, Hist), folic acid (Folic acid, Foli), lysine (Lysine, Lys), threonine (Threonine, Thr), glucose (Glucose, Gluc), Dopamine hydrochloride (Dopamine, DA), glycocoll (Glycine, Gly), forulic acid (Ferulic acid, Fer), urea (Urea), ascorbic acid (Ascorbic acid, AA), tryptophane (Tryptophan, Try), 5 kinds of kation (Zn
2+, K
+, Ca
2+, Na
+and NH
4 +) and 2 kinds of negative ion (Cl
-and CO
3 2-).Wherein, the ultimate density of detected material is 8 * 10
-5m.Colorimetric digital photograph is shown in the upper figure of Fig. 2, the corresponding UV-vis absorptance of each material (A
0/ A) see figure below of Fig. 2.Result shows that only Dopamine hydrochloride makes to detect liquid color generation significant change; Other material of being investigated and detect liquid and mix after, the color with the detection liquid (i.e. the mixed liquor of 80 μ L nano-Au solutions and 20 μ L deionized waters) of concentration does not have obvious difference relatively.According to corresponding UV-vis absorption spectra, by calculating, obtain A corresponding to above-mentioned detection material
0/ A value, is shown in figure below of Fig. 2, wherein, and A
0be respectively and detect liquid and with detection liquid and the mixed UV-vis absorption value of detection material of concentration with A.From figure below of Fig. 2, can find out: the histogram (A that Dopamine hydrochloride is corresponding
0/ A), and histogram corresponding to other material completely different.Visible: to detect liquid sitotoxismus material (Dopamine hydrochloride) is had to specific selectivity.
Colorimetric and UV-vis absorption value are than (A
0/ A) comprehensive analytical proof: under alkali condition, and under the assistance of Biological cross-linker TGA, nano-Au solution detects reagent sitotoxismus material (Dopamine hydrochloride) is had to specific selectivity.
For characterizing nano-Au solution, detect reagent under alkali condition, and under the induction of the Biological cross-linker that contains sulfydryl and carboxyl, the quick induction to toxicant, detects reagent and 20 μ L5 * 10 by 80 μ L nano-Au solutions
-5the toxicant of M (Dopamine hydrochloride) mixes, and then adds the NaOH of 10 μ L0.1M and the Biological cross-linker TGA that 6 μ L0.1M contain sulfydryl and carboxyl.The ultimate density of detected toxicant (Dopamine hydrochloride) is 8.6 * 10
-6m, in above-mentioned substance hybrid reaction after 0,1,3,6,9,12,15,18,21,24,27,30 and 35 minute, the UV-vis spectrum of test mixing liquid (pH=8.0), its characterization information is shown in Fig. 3.From Fig. 3, A figure is known, detects liquid and 8.6 * 10
-6m toxicant (Dopamine hydrochloride) mixed in 35 minutes, and the intensity of its UV-vis absorption spectra weakens gradually.In Fig. 3, B figure is known, the ratio (A of the minimum of mixed liquor and obtained the maximum absorption
min/ A
max) with the increase in reaction time, present the trend of exponent increase, after 20 minutes, reach mobile equilibrium.The variation explanation of this UV-vis spectrum: detect liquid and fully react with Dopamine hydrochloride, approximately need 20 minutes, far below the detection time (approximately needing 3 hours) of inductively coupled plasma emission spectrography (ICP-OES).
Use dynamic light scattering (DLS) to detect when detecting reagent (80 μ L) and detect variable concentrations Dopamine hydrochloride (0,5.8 * 10 of 20 μ L
-7, 5.8 * 10
-6with 5.8 * 10
-2under the assistance of M) (in pH of mixed=8.0, and inducing reagent TGA(6 μ L0.1M)) time, the ultimate density of detected toxicant (Dopamine hydrochloride) is respectively 0,10
-7, 10
-6with 10
-2m, the particle diameter of nano particle in detection liquid, measurement data is shown in Fig. 4.Result shows, with the increase of detected Dopamine hydrochloride concentration, and the aggravation of the reunion degree of functional gold nanoparticles, it is large that its granularity becomes gradually.
In addition,, in detecting the process of Dopamine hydrochloride, use TEM to characterize the variation that detects the microscopic appearance of reagent.Nano-Au solution is detected to reagent (80 μ L) and 0,5.8 * 10 of 20 μ L
-6m(1 sample) and 5.8 * 10
-6m(2 sample) Dopamine hydrochloride mixes, and then adds the NaOH of 10 μ L0.1M, wherein, in No. 2 samples, add 6 μ L0.1M TGA, above-mentioned solution mixed after 10 minutes, centrifugal washing again, nano particle after centrifugal washing is dripped on carbon film, adopt TEM to characterize, result as shown in Figure 5.Wherein, left figure is the TEM figure of nano particle in detection reagent, and middle for being coated with the TEM figure of the nano particle of Dopamine hydrochloride, right figure is the TEM figure that Biological cross-linker is induced the reunion that is coated with Dopamine hydrochloride nano particle.Result shows, under alkali condition, Dopamine hydrochloride will cover nm of gold surface (in Fig. 5), and the nm of gold being covered by Dopamine hydrochloride reunite (Fig. 5 is right) will be further induced in the carboxyl of TGA and sulfydryl and nm of gold effect.
(1) detect the preparation of reagent
Under room temperature, get the liquor argenti nitratis ophthalmicus of 5mL10mM, add respectively the deionized water of 85mL and the neopelex solution of 5mL5mM, stir 20 minutes; Then dropwise add the sodium borohydride of 1mL0.2M, stir 30 minutes, make Nano silver solution, be placed in 4 ℃ of refrigerators standby.
(2) use the Nano silver solution of above-mentioned preparation to detect melamine
Get 30 μ L variable concentrations (10
-9-10
-2m) the detection reagent mix of melamine and 1380 μ L, then adds the Cys of 30 μ L5M KOH solution and 60 μ L0.1M, mixes.
Adopt method of testing in the same manner as in Example 1 to test and characterize to the silver-colored solution of the above-mentioned functionalized nano preparing and for detection of melamine, result is as follows:
1. under alkali condition, and under the induction of Cys, when this detects reagent detection melamine, with the increase of melamine concentration, corresponding UV-vis absorption spectrum generation red shift and absorption intensity weaken, and its theoretical detectability that calculates can reach 10
-8m, this detection is very sensitive.
2. this detects reagent, under alkali condition, and under the induction of Cys, the detection of melamine is had to very strong selectivity (common elements relatively containing in food).
3. this detection reagent can fast detecting go out melamine in 30 minutes, and its detection time is far below the detection time (about 3 hours) of ICP-OES.
Embodiment 3
(1) detect the preparation of reagent
Under room temperature, the trifluoroacetic acid silver of 5mL0.25mM and the four hydration chlorauric acid solutions of 5mL0.25mM are mixed, add respectively the deionized water of 190mL and the DTAC of 20mL0.1mM, stir 30 minutes; Then add fast 60mL65mM oxammonium hydrochloride, stir 30 minutes, make nanometer gold silver mixed solution, be placed in 4 ℃ of refrigerators standby.
(2) use the nanometer gold silver solution of above-mentioned preparation to detect formalin
Get 0.5mL variable concentrations (10
-9-10
-2m) formalin mixes with the functionalized nano gold and silver solution of 1mL, then adds the thiosalicylic acid of 2mL0.8M choline and 1mL0.2mM, mixes.
Adopt method of testing in the same manner as in Example 1 to test and characterize to the above-mentioned functionalized nano gold and silver solution preparing and for detection of formalin.Result is as follows:
1. at alkali condition and under thiosalicylic acid auxiliary, when detecting reagent and detecting formalin, with the increase of formalin concentration, corresponding UV-vis absorption spectrum generation red shift and absorption intensity weaken, and its theoretical detectability that calculates can reach 10
-10m, this detection is very sensitive.
2. detect reagent, under alkali condition, and under thiosalicylic acid auxiliary, the detection of formalin is had to very strong selectivity (common elements relatively containing in food).
3. this detection reagent can fast detecting go out formalin in 30 minutes, and its detection time is far below the detection time (about 3 hours) of ICP-OES.
Embodiment 4
(1) detect the preparation of reagent
Under room temperature, get the actol solution of 5mL1mM, add respectively the deionized water of 95mL and the OTAC solution of 5mL5mM, stir 20 minutes; Then dropwise add the lactic acid of 1mL0.2M, be heated to 60 ℃, stir 30 minutes simultaneously, make Nano silver solution, be placed in 4 ℃ of refrigerators standby.
(2) use the Nano silver solution of above-mentioned preparation to detect sulphur
Get 30 μ L variable concentrations (10
-9-10
-2m) the detection reagent mix of sulphur and 1380 μ L, then adds the 3-mercaptopropionic acid of 30 μ L0.1M strontium hydroxide solutions and 30 μ L0.5M, mixes.
Adopt method of testing in the same manner as in Example 1 to test and characterize to the silver-colored solution of the above-mentioned functionalized nano preparing and for detection of sulphur, result is as follows:
1. under alkali condition, and under the induction of 3-mercaptopropionic acid, when this detects reagent detection sulphur, with the increase of sulphur concentration, corresponding UV-vis absorption spectrum generation red shift and absorption intensity weaken, and its theoretical detectability that calculates can reach 10
-8m, this detection is very sensitive.
2. this detects reagent, under alkali condition, and under the induction of 3-mercaptopropionic acid, the detection of sulphur is had to very strong selectivity (common elements relatively containing in food).
3. this detection reagent can fast detecting go out sulphur in 20 minutes, and its detection time is far below the detection time (about 3 hours) of ICP-OES.
All documents of mentioning in the present invention are all quoted as a reference in this application, just as each piece of document, are quoted as a reference separately.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned instruction content of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. detect a reagent, it is characterized in that, described detection reagent is the metal salt solution that comprises surfactant and reductive agent, and described slaine is golden salt, silver salt or its potpourri;
Wherein, described golden salt is one or more the potpourri in chlorauride trihydrate, chlorauride tetrahydrate, aurous chloride, gold oxide, chloroformyl fund, gold bromide, (pyridine) gold trichloride, chlorine (dimethyl sulfuration) gold, chlorine (trimethyl-phosphine) gold, (dimethylphenylphosphine) chlorauride, chloro tri-tert phosphatization gold, dichloro (2-pyridine carboxylic acid) gold, dichloro (2-pyridine carboxylic acid) gold, chlorine (trimethyl-phosphine) gold, chlorine [three (o-tolyl) phosphine] gold, chlorine [three (2,4-di-tert-butyl-phenyl) phosphorous acid] gold, gold potassium chloride and sodium chloraurate;
Described silver salt is silver nitrate, silver acetate, silver acetate, actol, silver fluoride, silver perchlorate, silver sulfate, trifluoroacetic acid silver, fluoroform, silver selenide, silver telluride, sulfonic acid silver, trifluoroacetic acid is silver-colored, p-toluenesulfonic acid is silver-colored, hexafluoro-antimonic acid is silver-colored and silver tetrafluoroborate in one or more potpourri;
Described surfactant is neopelex, stearic acid, lecithin, fatty glyceride, sodium glycocholate, quarternary ammonium salt compound, polysorbate and fatty acid sorb one or more the potpourri in smooth;
Described reductive agent is one or more the potpourri in sodium borohydride, potassium borohydride, oxalic acid, lactic acid, dithiothreitol (DTT), oxammonium hydrochloride, ascorbic acid, D-araboascorbic acid, sodium ascorbate, sodium isoascorbate and Calcium Ascorbate.
2. the detection reagent as described in right 1, it is characterized in that, described quarternary ammonium salt compound is selected from: cetyl trimethyl ammonium bromide, DHAB, myristyl dimethyl benzyl ammonium chloride, cetyldimethylethylambromide bromide ammonium, Cetyltrimethylammonium bromide, OTAC, DTAB, DTAC and dodecyl benzyl dimethyl ammonium chloride.
3. the detection reagent as described in right 1, is characterized in that, the concentration of described golden salt, silver salt or its potpourri is 0.001mM-1mM.
4. the detection reagent as described in right 1, is characterized in that, the concentration of described surfactant is 0.0001mM-1mM.
5. the detection reagent as described in right 1, is characterized in that, the concentration of described reductive agent is 0.5mM – 80mM.
6. the preparation method of the detection reagent as described in right 1, it is characterized in that, described method comprises adds surfactant and described reductive agent to form described detection reagent in metal salt solution step, wherein, described slaine, described surfactant and described reductive agent are as claimed in claim 1.
7. a detection method, is characterized in that, said method comprising the steps of:
(a) get the detection reagent claimed in claim 1 of two parts of same volumes, and get identical with aqueous solution volume to be detected and not containing the water of toxicant solution as a comparison;
(b) by first part, detect reagent and mix mutually with comparative solution, form the first mixed liquor; By second part of detection reagent and aqueous solution to be detected, form the second mixed liquor; And in the first mixed liquor and the second mixed liquor, add respectively highly basic and Biological cross-linker, form respectively the 3rd mixed liquor and the 4th mixed liquor;
(c) take the 3rd mixed liquor is reference, and the uv absorption of observing the change color of the 4th mixed liquor or detecting the 4th mixed liquor changes determines whether aqueous solution to be detected exists noxious material;
Wherein, described highly basic is one or more the potpourri in NaOH, potassium hydroxide, choline, thallium hydroxide, strontium hydroxide;
Described Biological cross-linker is one or more the potpourri in Cys, glutaraldehyde, mercaptoacetic acid, acetic anhydride, 2 mercaptopropionic acid, diglycidyl ether, 3-mercaptopropionic acid, pungent two imidic acid methyl esters, sodium thioglycolate, calcium mercaptoacetate and thiosalicylic acid.
8. detection method as claimed in claim 7, it is characterized in that, described noxious material is one or more the combination in Dopamine hydrochloride, clenobuterol hydrochloride, Ractopamine, salbutamol, salbutamol sulfate, Cimaterol, bricalin, phenolethanolamine, bambuterol, hydrochloric acid Zilpaterol, clorprenaline hydrochloride, Mabuterol, western Boot sieve, bromine Boot sieve, tartrate Afromoterol, formoterol fumarate, melamine, tonyred, formalin, sulphur and copper sulphate.
9. the application of detection reagent as claimed in claim 1, is characterized in that, for detection of whether there being noxious material in food.
10. application as claimed in claim 9, it is characterized in that, described noxious material is one or more the combination in Dopamine hydrochloride, clenobuterol hydrochloride, Ractopamine, salbutamol, salbutamol sulfate, Cimaterol, bricalin, phenolethanolamine, bambuterol, hydrochloric acid Zilpaterol, clorprenaline hydrochloride, Mabuterol, western Boot sieve, bromine Boot sieve, tartrate Afromoterol, formoterol fumarate, melamine, tonyred, formalin, sulphur and copper sulphate.
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