CN102416482A - Nanogold solution and method for detecting Co<2+> by using same - Google Patents

Nanogold solution and method for detecting Co<2+> by using same Download PDF

Info

Publication number
CN102416482A
CN102416482A CN2011103639545A CN201110363954A CN102416482A CN 102416482 A CN102416482 A CN 102416482A CN 2011103639545 A CN2011103639545 A CN 2011103639545A CN 201110363954 A CN201110363954 A CN 201110363954A CN 102416482 A CN102416482 A CN 102416482A
Authority
CN
China
Prior art keywords
solution
gold
detection
nano gold
functionalized nano
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.)
Granted
Application number
CN2011103639545A
Other languages
Chinese (zh)
Other versions
CN102416482B (en
Inventor
冷玉敏
吴爱国
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Institute of Material Technology and Engineering of CAS
Original Assignee
Ningbo Institute of Material Technology and Engineering of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ningbo Institute of Material Technology and Engineering of CAS filed Critical Ningbo Institute of Material Technology and Engineering of CAS
Priority to CN201110363954.5A priority Critical patent/CN102416482B/en
Publication of CN102416482A publication Critical patent/CN102416482A/en
Application granted granted Critical
Publication of CN102416482B publication Critical patent/CN102416482B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)

Abstract

The invention discloses a nanogold solution and a method for detecting Co<2+> by using the same. The water soluble functional nanogold solution is prepared by using a gold salt as the resource of gold nanoparticles, a quaternary ammonium salt as a surfactant, ion clusters containing sulfur elements and carbon oxygen groups (O=C=O) as ligands, sodium borohydride, potassium borohydride or ascorbic acid as a reducing agent, and deionized water as a synthesis medium and by modifying the surface of the nanogold with the ion clusters containing sulfur elements and carbon oxygen groups (O=C=O) under the action of gold-sulfur bonds (Au-S). The nanogold solution has high speed, selectivity, sensitivity and practicality for detection of trace amount of Co<2+> in the water solution system, and therefore can be used in combination of a colorimetric process for detecting trace amount of Co<2+>; the detection concentration is lower than 8.5*10<-7>M; the detection threshold value may reach 5*10<-10>M; the detection speed is high, the selectivity is high, the cost is low, and the carrying is convenient; and the detection method has a bright application prospect in fields of environmental science, detection chemistry and analysis chemistry, and the like.

Description

A kind of nano-Au solution and utilize this nano-Au solution to detect Co 2+Method
Technical field
The present invention relates to environmental science, check chemistry, analytical chemistry and chemistry field, particularly relate to a kind of cobalt ions (Co 2+) extreme quick colorimetric detecting and analysing delicately.
Background technology
Cobalt element is one of required basic trace element of humans and animals.As Cobastab 12Part, Co 2+Can promote the formation of hemoglobin cell.But, excessive Co 2+Get in the human or animal body toxigenicity.If the human or animal uses by Co for a long time 2+The water that pollutes, Co 2+Will produce toxic and side effect, make the human or animal suffer from various diseases,, blood vessel dilatation rubescent, heart rate quickening, anaemia, cardiomyopathy etc. like apocleisis, face.Therefore measure Co in the Environmental Water 2+It is very important that content seems.
At present, measure Co 2+The instrument and equipment of content has: electric coupling plasma emission spectrometer (ICP), Atomic Absorption (AAS) and atomic fluorescence absorption (AFS) etc.But above-mentioned instrument costs an arm and a leg, the equipment heaviness is not easy to carry, and is used to measure Co 2+Often there are defectives such as sample preparation steps is complicated, other ion interference is serious during content.At present, unit or individuality cash-starved, that technology is immature or condition does not possess can't adopt above-mentioned expensive instrument and equipment to detect Co 2+, cause pollution sources to enlarge or Co 2+The Environmental Water of content overproof is drunk.And above-mentioned instrument and equipment heaviness is not easy to carry, and can not be used for on-site real-time, testing environment water Co on the spot 2+Content.For fear of or reduce Co 2+To the pollution that environment water causes, guarantee human and animal's had rehemorrhage, must the unit of accomplishing or the individual can reach on the spot Co in the testing environment water in real time 2+Content.
Adopt cheap being easy to carry of colorimetric analysis method of reagent, can reach above-mentioned requirements.At present, colorimetric analysis has been applied to detecting the Co in the aqueous solution 2+Content.For example, the Li Haibing of the Central China Normal University professor function of use Nano Silver check and analysis Co of seminar 2+Content (referring to document: Appl.Mater.Interfaces, 2 (2010) 684), the colorimetric detection limit reaches 7 * 10 -6M (wherein M refers to mol/L) is higher than Co in China's regulation drinking water 2+The highest limit 8.5 * 10 of content -7M is (referring to national standard: National Standards of P.R.China (1993) GB/T 14848-93).
Therefore, research and development a kind ofly have the detection sensitivity height, detection speed is fast, selectivity good and practical testing environment water in Co 2+The method of content, and this method can reach and is lower than 8.5 * 10 -7The detection limit of M will especially have important use in environmental science, check chemistry and the analytical chemistry field and be worth in practical application.
Summary of the invention
Technical purpose of the present invention is to micro-Co in the above-mentioned detection water solution system 2+The state of the art, a kind of nano-Au solution is provided and utilizes this nano-Au solution to detect Co 2+Method, this method detects Co 2+Sensitivity high, it detects solubility can be lower than 8.5 * 10 -7M, its detectability even reach 5 * 10 -10M, and detection speed is fast, selectivity is good, with low cost, be easy to carry, and is a kind of detection method with broad prospect of application.
In order to realize above-mentioned technical purpose; The inventor is on long-term research practice basis; Go out a kind of functionalized nano gold solution in conjunction with a large amount of Experiment Preparation; This nano-Au solution is nano Au particle source with golden salt, and the ion cluster that will contain element sulphur and carbon oxygen groups (O=C=O) through golden sulfide linkage (Au-S) bunch is modified at that nm of gold is surperficial to be obtained.Concrete preparation method comprises the steps:
(1) being the golden nanometer particle source with golden salt, is surfactant with the quaternary ammonium salt, sodium borohydride (NaBH 4), potassium borohydride (KBH 4) or ascorbic acid (L-Ascorbic acid) get a certain amount of golden salting liquid for reducing agent, add surfactant, stir the back and add reducing agent, make the nm of gold mixed solution;
The molecular formula of described quaternary ammonium salt is CH 3(CH 2) mNX (CH 3) n(CH 2) p(C 6H 5) q, m=7～15 wherein, n=2 or 3, p=0 or 1, q=0 or 1, X=Cl, Br, I or F;
(2) in described nm of gold mixed solution, add and contain sulfydryl (SH) and carboxyl (compound soluble in water COOH); PH value with the mixed solution that obtains transfers to 5.0～11.0 then, obtains containing the nano-Au solution of the ion cluster bunch modification of element sulphur and carbon oxygen groups (O=C=O) after sealing is stirred.
Described golden salt includes but not limited to chlorauride (AuCl 3), aurous chloride (AuCl), gold chloride (HAuCl 4), three hydration gold chloride (HAuCl 43H 2O), four hydration gold chloride (HAuCl 44H 2O), two hydration potassium chloroaurate (KAuCl 42H 2O), two hydration sodium chloraurate (NaAuCl 42H 2O) one or more in.
Described surfactant comprises but is not limited to softex kw (CH 3(CH 2) 15NBr (CH 3) 3), DTAC (CH 3(CH 2) 11NCl (CH 3) 3) and dodecyl benzyl dimethyl ammonium chloride (CH 3(CH 2) 11NCl (CH 3) 2CH 2C 6H 5) in one or more.
The described compound that contains sulfydryl and carboxyl includes but not limited to TGA (HSCH 2CO 2H), 2 mercaptopropionic acid (HSCH 3CHCOOH), 3-mercaptopropionic acid (HSCH 2CH 2CO 2H), L-cysteine (HSCH 2CHNH 2CO 2H, sodium thioglycolate (HSCH 2COONa), calcium mercaptoacetate ((HSCH 2COO) 2Ca) and thiosalicylic acid (HSC 6H 4CO 2H) one or more in.
The described ion cluster that contains element sulphur and carbon oxygen groups (O=C=O) bunch includes but not limited to [SCH 2CO 2] 2-, [SCH 3CHCO 2] 2-, [SCH 2CH 2CO 2] 2-, [SCH 2CHNH 2CO 2] 2-[SC 6H 4CO 2] 2-
Functionalized nano gold solution provided by the invention is the golden nanometer particle source with golden salt; With the quaternary ammonium salt is surfactant; The ion cluster bunch that contains element sulphur and carbon oxygen groups (O=C=O) is part, and sodium borohydride, potassium borohydride or ascorbic acid are reducing agent, and deionized water is a synthetic medium; It is surperficial through golden sulfide linkage (Au-S) effect the ion cluster that contains element sulphur and carbon oxygen groups (O=C=O) bunch to be modified to nm of gold, obtains water miscible functionalized nano gold solution.This functionalized nano gold solution has the following advantages:
(1) simple and easy to do, the good reproducibility of method of modifying.Sulphur and gold dollar are plain to be mixed, and is prone to form golden sulfide linkage (Au-S), and this experiment and theoretical research data show that the corresponding wave number of golden sulfide linkage (Au-S) stretching vibration is 278.5cm -1It is surperficial that the formation of gold sulfide linkage (Au-S) makes the ion cluster contain element sulphur and carbon oxygen groups (O=C=O) bunch modify to nm of gold.The ion cluster bunch that contains element sulphur and carbon oxygen groups (O=C=O), in the process through golden sulfide linkage (Au-S) modified nano gold, the hydration particle diameter of nm of gold and nm of gold surface Zeta electric potential changed with the modification time.
(2) can with Co 2+Complexing rapidly, this complex reaction is accomplished in 1min.With ion cluster bunch [SCH 2CO 2] 2-The nm of gold and the Co that modify 2+Complexing is an example, the complexing product molecular configuration of the two, and the structural stability that theoretical modeling calculates is [3AuSCH 2CO 2+ Co] -Can know that from structural stability bunch [SCH of modification group on nm of gold surface is lured in the formation of cobalt oxygen key (Co-O) into 2CO 2] 2-With Co 2+Complexing rapidly causes monodispersed ion cluster bunch [SCH 2CO 2] 2-The nm of gold of modifying is reunited.The formation of cobalt oxygen key (Co-O) obtains testing the dual confirmation with the Theoretical Calculation infrared spectrum, and the stretching vibration of cobalt oxygen key (Co-O) is presented on 500cm -1About wave number.
(3) to Co 2+Selectivity good, competitive reaction is strong.Relative other ion or Co 2+During with other ion coexist, contain preferential the selection and Co of nm of gold of the ion cluster bunch modification of element sulphur and carbon oxygen groups (O=C=O) 2+Complexing makes this functionalized nano gold solution color change rapidly.Therefore, this functionalized nano gold solution can be used in fast detecting Co 2+
The invention allows for and utilize the above-mentioned functions nano-Au solution to detect Co 2+Method, this method utilize this functionalized nano gold can with Co 2+Rapidly complexing, to Co 2+The good and Co of selectivity 2+Cause the RESONANCE ABSORPTION of this functionalized nano gold surface plasma to change after the complexing; Make the color of this functionalized nano gold solution and the characteristic that UV, visible light absorption intensity, peak value change; Directly perhaps test the variation of its absorption intensity and peak value, can whether contain Co in the fast detecting solution system through ultraviolet-uisible spectrophotometer through the variation of perusal solution colour 2+Concrete detection method comprises the steps:
(1) prepares the nano-Au solution of the ion cluster bunch modification that contains element sulphur and carbon oxygen groups (O=C=O) according to the preparation method of functionalized nano gold solution provided by the invention;
(2) in the nano-Au solution that step (1) makes, measure out two parts of test sample that volume is identical; Preparation and the aqueous solution that do not contain cobalt ions identical with detection aqueous solution volume is solution as a comparison; A test sample is mixed with comparative solution mutually, form first mixed liquor,, form second mixed liquor another part test sample and aqueous solution to be detected;
(3) be reference with first mixed solution, observe the color of second mixed liquor and first mixed liquor,, have Co in the aqueous solution then to be detected if there is change color 2+,, do not have Co in the aqueous solution then to be detected if there is not change color 2+Perhaps, contrast UV, visible light absorption intensity, the peak value of second mixed liquor and first mixed liquor, change, have Co in the aqueous solution then to be detected as if its UV, visible light absorption intensity, peak value 2+,, do not have Co in the aqueous solution then to be detected if do not change 2+
As preferably, in described step (1), prepare the nano-Au solution of the ion cluster bunch modification that contains element sulphur and carbon oxygen groups (O=C=O) after, this nano-Au solution is dialysed.Find that according to experiment the nano-Au solution that can improve the ion cluster bunch modification that contains element sulphur and carbon oxygen groups (O=C=O) through dialysis largely detects Co 2+Sensitivity.
With existing disclosed detection water solution system Co 2+Method compare, the present invention has following advantage:
(1), synthesized water-soluble nano gold solution, and workable, the common laboratory completion of all having ready conditions with the ion cluster bunch modification that contains element sulphur and carbon oxygen groups (O=C=O) with simple experiment flow;
(2) nm of gold that contains the ion cluster bunch modification of element sulphur and carbon oxygen groups (O=C=O) can very sensitive, fast, optionally detect Co micro-in the aqueous solution 2+, have very strong practicality.
(3) have high sensitivity, this method detects Co 2+Sensitivity high, its detection limit can be lower than 8.5 * 10 -7M, even reach 5 * 10 -10M (0.03 μ g/L) is lower than the limit of detection 1.7 * 10 of electric coupling plasma emission spectrometer (ICP) -8M (1 μ g/L).
(4) have that detection speed is fast, selectivity good, with low cost, be easy to carry, so practicality is very strong, is used to detect Co in the actual environment water sample 2+Content, colorimetric detection result is: Co in the environmental water sample 2+Content is 2.0 * 10 -7M is lower than Co in China's regulation drinking water 2+The highest limit 8.5 * 10 of content -7M; In addition, can be used in fields such as environmental science, check chemistry and analytical chemistry, have important use and be worth.
Description of drawings
Fig. 1 is preparation technology's flow chart of functionalized nano gold solution of the present invention;
Fig. 2 (a) is the ion cluster bunch [SCH that the present invention contains element sulphur and carbon oxygen groups (O=C=O) 2CO 2] 2-The sketch map of modified nano gold reaches the stable geometric configuration that theoretical modeling obtains;
Fig. 2 (b) is at 250-700cm -1In the wave-number range, modified outcome [AuSCH 2CO 2] -Experiment with calculate the simulation INFRARED SPECTRUM;
Fig. 3 (a) is that the present invention contains in the ion cluster bunch modified nano gold process of element sulphur and carbon oxygen groups (O=C=O), and the hydration particle diameter of nm of gold is with modifying change of time;
Fig. 3 (b) is that the present invention contains in the ion cluster bunch modified nano gold process of element sulphur and carbon oxygen groups (O=C=O), and nm of gold surface Zeta electric potential is with modifying change of time;
Fig. 4 is that functionalized nano gold solution of the present invention detects 1 * 10 -6The Co of M 2+The time, corresponding uv-vis spectra variation diagram in the 30min before detection;
Fig. 5 calculates the ion cluster bunch [SCH that simulation obtains 2CO 2] 2-The nm of gold and the Co that modify 2+Structural stability [the 3AuSCH of complexing 2CO 2+ Co] -
Fig. 6 is that functionalized nano gold solution of the present invention detects different content Co 2+(mass percent is: the infrared spectrum of corresponding complexing product in the time of 0,0.09% and 0.11%), and compare analysis chart with the infrared spectrum of the complexing configuration that calculates simulation;
Fig. 7 be the present invention's ion cluster bunch modification of containing element sulphur and carbon oxygen groups (O=C=O) nm of gold transmission electron microscope with can spectrogram;
Fig. 8 is that functionalized nano gold solution detectable concentration of the present invention is 2 * 10 -5Corresponding uv-vis spectra when the alkali metal of M, alkaline-earth metal and transition metal ions;
Fig. 9 is the Co that functionalized nano gold of the present invention detects variable concentrations 2+The time corresponding colorimetric photo and uv-vis spectra.
The specific embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is described in further detail, it is pointed out that the following stated embodiment is intended to be convenient to understanding of the present invention, and it is not played any qualification effect.
The functionalized nano gold solution that present embodiment provides is the water-soluble nano gold solution that contains the ion cluster bunch modification of element sulphur and carbon oxygen groups (O=C=O); Its preparation technology's flow process is as shown in Figure 1; Be specially: get a certain amount of golden salting liquid, add quaternary cationics, for example softex kw, DTAC are or/and dodecyl benzyl dimethyl ammonium chloride; Dropwise add reducing agent after the stirring; For example sodium borohydride, potassium borohydride add then and contain sulfydryl (SH) and carboxyl (compound soluble in water COOH) or/and ascorbic acid continues to stir; For example TGA, 2 mercaptopropionic acid, 3-mercaptopropionic acid, L-cysteine, sodium thioglycolate, calcium mercaptoacetate are or/and thiosalicylic acid; Use NaOH (NaOH), potassium hydroxide (KOH) or/and hydrochloric acid (HCl) transfers to 5.0～11.0 with the pH value of solution, dialyse, just make the nano-Au solution of the ion cluster bunch modification that contains element sulphur and carbon oxygen groups (O=C=O).
The functionalized nano of above-mentioned preparation gold, its group of modification bunch modifies to the nm of gold surface by golden sulfide linkage (Au-S).With ion cluster bunch [SCH 2CO 2] 2-Modified nano gold is an example, and its modification characterizes with corresponding INFRARED SPECTRUM sees Fig. 2 respectively: (a) TGA (HSCH 2CO 2H) hydrolysis goes out ion cluster bunch [SCH in solution 2CO 2] 2-, the formation of golden sulfide linkage (Au-S) impels ion cluster bunch [SCH 2CO 2] 2-Modify to the nm of gold surface.(b) (wave-number range is 250-700cm to the far infrared spectrum of the Fourier transform of modified outcome and theoretical modeling calculating -1), the eigen vibration peak of the two coincide in the extreme.Experiment and Theoretical Calculation analogue data show: wave number 278.5cm -1The eigen vibration peak at place is golden sulfide linkage (Au-S) stretching vibration peak.
In the process of above-mentioned preparation functionalized nano gold solution, use dynamic light scattering (DLS) sign nm of gold hydration particle diameter and surperficial Zeta electric potential with the modification reaction change of time.Dynamic light scattering (DLS) has been proved the hydration particle diameter that can characterize nano particle in the solution well and the minor variations of Zeta electric potential; During interaction between molecular detection and nm of gold; Very responsive (Nano Lett.3 (2003) 935, J.Am.Chem.Soc.130 (2008) 2780, Angew.Chem.Int.Ed.48 (2009) 1; Chem.Commun.47 (2011) 4192, J.Immunol.Methods 349 (2009) 38).Contain in the ion cluster modified nano gold process of element sulphur and carbon oxygen groups (O=C=O); Nm of gold hydration particle diameter and surperficial Zeta electric potential are with the modification reaction change of time; See Fig. 3 (a) and (b) respectively, can find out: nm of gold hydration particle diameter increased with the modification reaction time; Electronegative because of modifying cluster, make adorned nm of gold surface Zeta electric potential increase and reduce with the modification reaction time.The modification reaction time is approximately 40min, and particle diameter of nm of gold hydration subsequently and surperficial Zeta electric potential increased and no longer change with the modification reaction time, reached dynamic equilibrium.This DLS characterization data shows: contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O), reaching dynamic equilibrium approximately needs 40min.
Experiment one:
With the water-soluble nano gold solution of the ion cluster bunch modification that contains element sulphur and carbon oxygen groups (O=C=O) of above-mentioned preparation with contain Co 2+Concentration is 1 * 10 -6The water-soluble liquid-phase mixing of M uses ultraviolet-visual spectrometer (Uv-vis) to detect the variation in the 30min before detection of corresponding uv-vis spectra, sees Fig. 4.From Fig. 4, find: detect in the 1min, the ultraviolet and visible absorption peak of this functionalized nano gold solution obviously reduces.Ratio (the A of the absorption value that the illustration from Fig. 4: characteristic absorption wavelength 462nm and 527nm are corresponding 462/ A 527) with the variation of detection time, can find out that the water-soluble nano gold solution of the ion cluster bunch modification that contains element sulphur and carbon oxygen groups (O=C=O) can fast detecting Co 2+, only need 1min detection time.
The water-soluble nano gold solution of the ion cluster bunch modification that contains element sulphur and carbon oxygen groups (O=C=O) of above-mentioned preparation can fast detecting Co 2+Principle Exploration, used theoretical modeling to calculate and the mode of Experimental Characterization binding analysis.With ion cluster bunch [SCH 2CO 2] 2-The nm of gold of modifying is used to detect Co 2+Research is example, calculates from theoretical modeling, and the inventor has found bunch [SCH of modification group on nm of gold surface 2CO 2] 2-, through cobalt oxygen key (Co-O) and Co 2+Structural stability [the 3AuSCH of complexing 2CO 2+ Co] -, like Fig. 5.The inventor uses Gauss's software simulation to calculate structural stability [3AuSCH 2CO 2+ Co] -Vibration frequency, corresponding infrared vibration spectrum is seen Fig. 6.It is reported from the Theoretical Calculation frequency number: cobalt oxygen key (Co-O) stretching vibration is presented on 500cm -1About wave number.Simultaneously, the inventor uses the water-soluble nano gold solution of the ion cluster bunch modification that contains element sulphur and carbon oxygen groups (O=C=O) to detect the Co of variable concentrations 2+(mass percent is: 0,0.09% and 0.11%), with mixed liquor freeze drying powdered, use Fourier transformation infrared spectrometer (FT-IR) to characterize its infrared vibration spectrum, see Fig. 5.Know from experimental data: with Co to be detected 2+The increase of concentration, 500cm -1Cobalt oxygen key (Co-O) stretching vibration peak has appearred about wave number.Coincideing of theoretical modeling calculating and experimental data explained that the water-soluble nano gold solution of the ion cluster bunch modification that contains element sulphur and carbon oxygen groups (O=C=O) can fast detecting cobalt ions (Co 2+) reason be: the ion cluster that contains element sulphur and carbon oxygen groups (O=C=O) of nm of gold finishing bunch, through cobalt oxygen complex bonds (Co-O) quick identification Co 2+, cause monodispersed functionalized nano golden hair to give birth to and reunite, see shown in Figure 7.Fig. 7 is transmission electron microscope and ability spectrogram: the dispersed nano gold that (a) contains the ion cluster bunch modification of element sulphur and carbon oxygen groups (O=C=O) for the present invention; (b) be Co 2+Lure the living reunion of (a) functionalized nano golden hair into.Variation has taken place in the color of this functionalized nano gold solution and uv-vis spectra simultaneously, sees Fig. 9.
Above-mentioned experiment and analysis show: the water-soluble nano gold solution of ion cluster bunch modification that contains element sulphur and carbon oxygen groups (O=C=O) is to Co 2+Can play metachromasia, i.e. Co fast 2+Can be by the nm of gold surface ligand, for example: [SCH 2CO 2] 2-, [SCH 3CHCO 2] 2-, [SCH 2CH 2CO 2] 2-, [SCH 2CHNH 2CO 2] 2-[SC 6H 4CO 2] 2-In carbon oxygen groups (O=C=O) quick identification, this effect causes that nm of gold is reunited and variable color, and (colorimetric detection is limit and reached 5 * 10 with very high sensitivity to have very strong selectivity -10M), thus this functional nano gold solution can be used in on-the-spot actual detected Co 2+For example, can be used for micro-Co in on-site real-time and the quick colorimetric detection Environmental Water on the spot 2+
Experiment two:
The water-soluble nano gold solution of the ion cluster bunch modification that contains element sulphur and carbon oxygen groups (O=C=O) of present embodiment preparation is used to detect 2 * 10 -5The Co of M 2+The time, its change color and the alkali metal ion (Li that detects with concentration +, Na +, K +), alkaline-earth metal ions (Mg 2+, Ca 2+, Sr 2+, Ba 2+), transition metal ions (Co 2+, Mn 2+, Fe 2+, Fe 3+, Al 3+, Ni 2+, Cu 2+, Zn 2+, Cd 2+, Cr 3+, Hg 2+, Pb 2+), do not comprise Co 2+The hybrid ionic (M of above-mentioned 18 metal ion species X-1 +=Li ++ Na ++ K ++ Mg 2++ Ca 2++ Sr 2++ Ba 2++ Mn 2++ Fe 2++ Fe 3++ Al 3++ Ni 2++ Cu 2++ Zn 2++ Cd 2++ Cr 3++ Hg 2++ Pb 2+) and comprise Co 2+Hybrid ionic (M at interior above-mentioned 19 metal ion species x +=M X-1 ++ Co 2+) compare discovery: the color of pure function nano-Au solution relatively, have only to detect to contain Co 2+Functionalized nano gold solution color variation has taken place.
Simultaneously, use ultraviolet-visual spectrometer (Uv-vis) to characterize this functionalized nano gold solution and detect the uv-vis spectra of above-mentioned metal ion and the uv-vis spectra of pure function nano-Au solution, and obtain the ratio (A/A of corresponding ultraviolet and visible absorption peak value 0), see shown in Figure 8.Shown in Figure 8 showing: detection contains 2 * 10 -5M Co 2+(comprise hybrid ionic M x +) UV, visible light absorption spectra and the ratio (A/A of absorption value of functionalized nano gold solution 0) obviously be different from the ratio (A of the UV, visible light absorption spectra and the absorption value of pure function nano-Au solution 0/ A 0); Detection contains the ratio (A/A with the UV, visible light absorption spectra of the functionalized nano gold solution of above-mentioned other ion of concentration and absorption value 0), the UV, visible light absorption spectra of relative pure function nano-Au solution and the ratio (A of absorption value 0/ A 0), change little.
Above-mentioned experiment shows that the water-soluble nano gold solution of the ion cluster bunch modification that contains element sulphur and carbon oxygen groups (O=C=O) of present embodiment preparation detects Co 2+Has good selectivity.
Experiment three:
Dispose the Co that comprises of equal volume 2+The aqueous solution to be measured, Co wherein 2+Concentration is respectively: 10 -4M, 10 -5M, 10 -6M, 10 -7M, 5 * 10 -8M, 10 -8M, 5 * 10 -9M, 10 -9M, 5 * 10 -10M and 0M; The water-soluble nano gold solution of the ion cluster bunch modification that contains element sulphur and carbon oxygen groups (O=C=O) of present embodiment preparation of measuring many parts of equivalent is as test sample; With every part of test sample respectively with each water-soluble liquid-phase mixing to be measured, the change color of each mixed solution is as shown in Figure 9.As can be seen from Figure 9, relative Co 2+Concentration is the color of the mixed solution of 0M, contains Co 2+Concentration is equal to or greater than 5 * 10 -10The color of the mixed solution of M all changes.Simultaneously, use ultraviolet-visual spectrometer (Uv-vis) to characterize the different Co of above-mentioned detection 2+The uv-vis spectra of the functionalized nano gold solution of concentration is found the increase with concentration of cobalt ions to be detected, and blue shift has taken place the characteristic absorption peak of corresponding uv-vis spectra.
Above-mentioned experiment shows: the water-soluble nano gold solution of the ion cluster bunch modification that contains element sulphur and carbon oxygen groups (O=C=O) of present embodiment preparation detects Co 2+Has very strong sensitivity.
Experiment four:
Application for the water-soluble nano gold solution of the ion cluster bunch modification that contains element sulphur and carbon oxygen groups (O=C=O) of investigating present embodiment preparation; The inventor gathers environmental water sample from Ningbo gold and the blowdown of new material limited company; Use electric coupling plasma emission spectrometer (ICP) check and analysis, testing result: the environmental water sample of collection contains Co 2+Concentration is 2 * 10 -7M.
Simultaneously, use deionized water preparation Co 2+Concentration is 2 * 10 -7The standard water sample of M.The functionalized nano gold solution of the equivalent that present embodiment is prepared is respectively with the standard water sample of the above-mentioned environmental water sample of equivalent, preparation and do not comprise Co 2+Deionized water mix Co promptly to be detected by 3: 1 volume ratios 2+Diluted 4 times of concentration, the concentration after the dilution is 5 * 10 -8M.Find after the colorimetric: with respect to not comprising Co 2+Mixed solution, contain identical Co 2+The environmental water sample of concentration and the color of standard liquid change, and this change color is very approaching.
Above-mentioned experiment shows: the water-soluble nano gold solution of the ion cluster bunch modification that contains element sulphur and carbon oxygen groups (O=C=O) of present embodiment preparation can be used in Co in the colorimetric detection Environmental Water 2+Content has very strong application.
Below in conjunction with specific embodiment to the preparation of the water-soluble nano gold solution of the ion cluster bunch modification that contains element sulphur and carbon oxygen groups (O=C=O) and to Co 2+Colorimetric detection further specifies.
Embodiment 1:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get the four hydration gold chloride (HAuCl of 5mL 5mM 44H 2O) solution adds the deionized water of 95mL and the softex kw (CH of 1.5mL 2M respectively 3(CH 2) 15NBr (CH 3) 3) solution, stir 2) min; Sodium borohydride (the NaBH that dropwise adds 1.5mL 0.1M then 4), continue to stir 20min, make the nm of gold mixed solution, be placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 50mL above-mentioned steps (1) prepares, stir, add the TGA (HSCH of 40 μ L simultaneously 2CO 2H), after mixing, NaOH (NaOH) or the hydrochloric acid (HCl) that uses 0.2M transfers to 5.0 with the pH value of mixed liquor, and the about 40min of sealing stirring then obtains containing the nano-Au solution of the ion cluster bunch modification of element sulphur and carbon oxygen groups (O=C=O).
Adopt following method to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and application test, specific as follows:
(1) the above-mentioned functionalized nano gold solution for preparing of dialysis
Bag filter be cut into suitable length (10～20cm), be placed on and contain 0.24M sodium acid carbonate (NaHCO 3) and 1M ethylenediamine tetra-acetic acid (EDTA) mixed solution in boil 10min.Naturally bag filter is thoroughly cleaned with deionized water in the cooling back, is placed in the 1mM ethylenediamine tetra-acetic acid (EDTA), and bag filter is boiled 10min.Guarantee that bag filter is immersed in the 1mM ethylenediamine tetra-acetic acid (EDTA) all the time, naturally cooling.
Thoroughly clean bag filter with deionized water; Pack into the functionalized nano gold solution of above-mentioned preparation puts it into then in the beaker that fills deionized water and dialyses, and feeds nitrogen in the dialysis procedure; Make the pure function nano-Au solution, be placed in 4 ℃ of refrigerators subsequent use after the sealing.
(2) the functionalized nano gold solution is to Co 2+The rapidity test that detects:
Measure the functionalized nano gold solution that obtains through step (1) dialysis of two parts of 3mL; 4 * 10 of a copy of it and 1mL -6M standard C o 2+Solution mixes, and obtains first mixed solution, the Co in first mixed solution 2+Diluted 4 times, concentration is 1 * 10 -6M; Another part mixes with the deionized water of 1mL, obtains second mixed solution.
With second mixed solution is reference, carries out colorimetric, finds that the color of two parts of mixed solutions is different;
Mix in the 30min of back, use 11 UV, visible light spectrums of UV, visible light spectrometer (Uv-vis) test, see Fig. 4, be the ratio (A of the corresponding absorption value of absorbing wavelength 462nm and 527nm 462/ A 527) with the curve that change detection time, see Fig. 4 illustration, find that this functionalized nano gold solution is to Co 2+Detection time only need 1min.
(3) the functionalized nano gold solution is to Co 2+Selectivity test:
Take by weighing alkali metal containing ion (Li +, Na +, K +), alkaline-earth metal ions (Mg 2+, Ca 2+, Sr 2+, Ba 2+), transition metal ions (Co 2+, Mn 2+, Fe 2+, Fe 3+, Al 3+, Ni 2+, Cu 2+, Zn 2+, Cd 2+, Cr 3+, Hg 2+, Pb 2+) chloride, be dissolved in the deionized water, compound concentration is 8 * 10 -5Above-mentioned 19 metal ion species of M, the hybrid ionic (M of 18 metal ion species X-1 +, do not contain Co 2+) and the hybrid ionic (M of 19 metal ion species x +=M X-1 ++ Co 2+) standard liquid.
Measure the functionalized nano gold solution that obtains through step (1) dialysis of two parts of 3mL; 8 * 10 of the above-mentioned preparation of a copy of it and 1mL -5The standard metal solion of M mixes, and obtains first mixed solution, diluted 4 times of the metal ion in first mixed solution, and concentration is 2 * 10 -6M; Another part mixes with the deionized water of 1mL, obtains second mixed solution.
With second mixed solution is reference, carries out colorimetric, and simultaneously, use ultraviolet-visual spectrometer (Uv-vis) characterizes the uv-vis spectra of this first mixed solution and second mixed solution, obtains the ratio (A/A of corresponding ultraviolet and visible absorption peak value 0), as shown in Figure 8, show that functionalized nano gold solution that present embodiment makes is to Co 2+Has good selectivity.
(4) the functionalized nano gold solution is to Co 2+Sensitivity test:
Take by weighing CoCL2 (CoCl 26H 2O), use deionized water preparation Co 2+Concentration is respectively 10 -4M, 10 -5M, 10 -6M, 10 -7M, 5 * 10 -8M, 10 -8M, 5 * 10 -9M, 10 -9M, 5 * 10 -10The standard C o of M and 0M 2+Solution.
With Co 2+Concentration is that the mixed solution of 0M is reference, carries out colorimetric, simultaneously, uses ultraviolet-visual spectrometer (Uv-vis) to characterize the functionalized nano gold solution and detects variable concentrations Co 2+Uv-vis spectra, as shown in Figure 9, the result shows that the functionalized nano gold that present embodiment makes detects Co 2+Have fabulous sensitivity, the colorimetric detection limit can reach 5 * 10 -10M.
(5) the functionalized nano gold solution detects Co 2+Application test:
The environment measuring center obtains Ningbo gold and new material limited company blowdown actual environment water sample from the Ningbo City, uses electric coupling plasma emission spectrometer (ICP) to carry out check and analysis, and testing result is: contain 2 * 10 in the environmental water sample -7The Co of M 2+
Use the deionized water preparation to contain 2 * 10 -7The Co of M 2+The standard water sample.
Measure the functionalized nano gold solution that obtains through step (1) dialysis of two parts of 3mL; A copy of it mixes with the above-mentioned environmental water sample of 1mL, obtains first mixed solution; Portion mixes with the above-mentioned standard water sample of 1mL, obtains second mixed solution; Portion mixes with the deionized water of 1mL in addition, obtains the 3rd mixed solution.Co in first mixed solution and second mixed solution 2+Concentration is diluted, is 5 * 10 -8M.
With the 3rd mixed solution is reference, carries out colorimetric, finds: contain identical cobalt ions (Co 2+) after the functionalized nano gold solution that made by present embodiment of environmental water sample and the standard water sample of concentration detected, change color was very approaching, explains that the functionalized nano gold that present embodiment makes can be applied to micro-Co in the testing environment water 2+Content.
Embodiment 2:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get the three hydration gold chloride (HAuCl of 5mL 5mM 43H 2O) solution adds the deionized water of 95mL and the softex kw (CH of 5mL 0.04M respectively 3(CH 2) 15NBr (CH 3) 3) solution, stir 15min; Potassium borohydride (the KBH that dropwise adds 2mL 0.1M then 4), continue to stir 20min, make the nm of gold mixed solution, be placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 100mL above-mentioned steps (1) prepares, stir, add the 3-mercaptopropionic acid (HSCH of 100 μ L simultaneously 2CH 2CO 2H), after mixing, the NaOH (NaOH) of use 0.2M or hydrochloric acid (HCl) transfer to 6.0 with the pH value of mixed liquor, and about 45min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 3:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get the gold chloride (HAuCl of 5mL 5mM 4) solution, add the deionized water of 95mL and the softex kw (CH of 1mL 0.5M respectively 3(CH 2) 15NBr (CH 3) 3) solution, stir 10min; Oil bath is heated to 80 ℃, dropwise adds the ascorbic acid (L-Ascorbic acid) of 50mL 1M then, continues heated and stirred 5min, and cooling makes the nm of gold mixed solution naturally, is placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 100mL above-mentioned steps (1) prepares, stir, add the L-cysteine (HSCH of 10mL92mM simultaneously 2CHNH 2CO 2H), after mixing, the potassium hydroxide (KOH) of use 0.2M and hydrochloric acid (HCl) transfer to 6.68 with the pH value of mixed liquor, and about 40min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 4:
In the present embodiment, functionalized nano gold mixed solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get the chlorauride (AuCl of 5mL 5mM 3) solution, add the deionized water of 95mL and the DTAC (CH of 3mL 0.05M respectively 3(CH 2) 11NCl (CH 3) 3) solution, stir 5min; Sodium borohydride (the NaBH that dropwise adds 1mL 0.2M then 4), continue to stir 10min, make the nm of gold mixed solution, be placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 100mL above-mentioned steps (1) prepares, stir, add the sodium thioglycolate (HSCH of 40mL80mM simultaneously 2COONa), after mixing, the NaOH (NaOH) of use 0.2M or hydrochloric acid (HCl) transfer to 7.4 with the pH value of mixed liquor, and about 50min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 5:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get the chlorauride (AuCl of 5mL 5mM 3) solution, add the deionized water of 95mL and the DTAC (CH of 15mL 5mM respectively 3(CH 2) 11NCl (CH 3) 3) solution, stir 25min; Potassium borohydride (the KBH that dropwise adds 5mL 0.1M then 4), continue to stir 20min, make the nm of gold mixed solution, be placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 90mL above-mentioned steps (1) prepares, stir, add the calcium mercaptoacetate ((HSCH of 10mL94mM simultaneously 2COO) 2Ca), after mixing, the potassium hydroxide (KOH) of use 0.2M or hydrochloric acid (HCl) transfer to 8.0 with the pH value of mixed liquor, and about 38min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 6:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get the chlorauride (AuCl of 5mL 5mM 3) solution, add the deionized water of 95mL and the DTAC (CH of 8mL 0.1M respectively 3(CH 2) 11NCl (CH 3) 3) solution, stir 10min; Oil bath is heated to 90 ℃, dropwise adds the ascorbic acid (L-Ascorbic acid) of 60mL 0.8M then, continues to stir 35min, and cooling makes the nm of gold mixed solution naturally, is placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 90mL above-mentioned steps (1) prepares, stir, add the thiosalicylic acid (HSC of 10mL50mM simultaneously 6H 4CO 2H), after mixing, the NaOH (NaOH) of use 0.2M or hydrochloric acid (HCl) transfer to 8.68 with the pH value of mixed liquor, and about 60min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 7:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get aurous chloride (AuCl) solution of 5mL 5mM, add the deionized water of 95mL and the DTAC (CH of 10mL 0.08M respectively 3(CH 2) 11NCl (CH 3) 3) solution, stir 26min; Oil bath is heated to 100 ℃, dropwise adds the ascorbic acid (L-Ascorbic acid) of 70mL 0.65M then, continues heated and stirred 30min, and cooling makes the nm of gold mixed solution naturally, is placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 80mL above-mentioned steps (1) prepares, stir, add the sodium thioglycolate (HSCH of 8mL15mM simultaneously 2COONa), after mixing, the potassium hydroxide (KOH) of use 0.2M or hydrochloric acid (HCl) transfer to 9.6 with the pH value of mixed liquor, and about 35min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 8:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get the gold chloride (HAuCl of 5mL 5mM 4) solution, add the deionized water of 95mL and the softex kw (CH of 6mL 0.3M respectively 3(CH 2) 15NBr (CH 3) 3) solution, stir 3min; Oil bath is heated to 80 ℃, dropwise adds the ascorbic acid (L-Ascorbic acid) of 5mL 10M then, continues heating and stirs 35min, and cooling makes the nm of gold mixed solution naturally, is placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 60mL above-mentioned steps (1) prepares, stir, add the L-cysteine (HSCH of 20mL1.5mM simultaneously 2CHNH 2CO 2H), after mixing, the NaOH (NaOH) of use 0.2M or hydrochloric acid (HCl) transfer to 9.4 with the pH value of mixed liquor, and about 40min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 9:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get the two hydration potassium chloroaurate (KAuCl of 5mL 5mM 42H 2O) solution adds the deionized water of 95mL and the dodecyl benzyl dimethyl ammonium chloride (CH of 15mL 5mM respectively 3(CH 2) 11NCl (CH 3) 2CH 2C 6H 5) solution, stir 4min; Potassium borohydride (the KBH that dropwise adds 5mL 0.06M then 4), continue to stir 2min, make the nm of gold mixed solution, be placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 100mL above-mentioned steps (1) prepares, stir, add the calcium mercaptoacetate ((HSCH of 50mL1.5mM simultaneously 2COO) 2Ca), after mixing, the NaOH (NaOH) of use 0.2M or hydrochloric acid (HCl) transfer to 7.5 with the pH value of mixed liquor, and about 42min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 10:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get the two hydration sodium chloraurate (NaAuCl of 5mL 5mM 42H 2O) solution adds the deionized water of 95mL and the dodecyl benzyl dimethyl ammonium chloride (CH of 15mL 5mM respectively 3(CH 2) 11NCl (CH 3) 2CH 2C 6H 5) solution, stir 2min; Sodium borohydride (the NaBH that dropwise adds 2mL 0.3M then 4), continue to stir 10min, make the nm of gold mixed solution, be placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 90mL above-mentioned steps (1) prepares, stir, add the 3-mercaptopropionic acid (HSCH of 100 μ L simultaneously 2CH 2CO 2H), after mixing, the potassium hydroxide (KOH) of use 0.2M or hydrochloric acid (HCl) transfer to 10.8 with the pH value of mixed liquor, and about 45min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 11:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get the two hydration potassium chloroaurate (KAuCl of 5mL 5mM 42H 2O) solution adds the deionized water of 95mL and the dodecyl benzyl dimethyl ammonium chloride (CH of 0.5mL 5M respectively 3(CH 2) 11NCl (CH 3) 2CH 2C 6H 5) solution, stir 1min; Oil bath is heated to 70 ℃, dropwise adds the ascorbic acid (L-Ascorbic acid) of 10mL 5M then, continues heated and stirred 30min, and cooling makes the nm of gold mixed solution naturally, is placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 100mL above-mentioned steps (1) prepares, stir, add the 2 mercaptopropionic acid (HSCH of 90 μ L simultaneously 3CHCOOH), after mixing, the NaOH (NaOH) of use 0.2M or hydrochloric acid (HCl) transfer to 11.0 with the pH value of mixed liquor, and about 40min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 12:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get the gold chloride (HAuCl of 5mL 5mM 4) solution, add the deionized water of 95mL and the softex kw (CH of 1mL 0.2M respectively 3(CH 2) 15NBr (CH 3) 3) solution, stir 5min; Potassium borohydride (the KBH that dropwise adds 1.5mL 0.1M then 4), continue to stir 2min, make the nm of gold mixed solution, be placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 100mL above-mentioned steps (1) prepares, stir, add the calcium mercaptoacetate ((HSCH of 10mL5.0mM simultaneously 2COO) 2Ca), after mixing, the NaOH (NaOH) of use 0.2M or hydrochloric acid (HCl) transfer to 7.0 with the pH value of mixed liquor, and about 42min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 13:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get aurous chloride (AuCl) solution of 5mL 5mM, add the deionized water of 95mL and the DTAC (CH of 2mL 0.1M respectively 3(CH 2) 11NCl (CH 3) 3) solution, stir 5min; Oil bath is heated to 85 ℃, dropwise adds the ascorbic acid (L-Ascorbic acid) of 50mL 0.4M then, continues heated and stirred 3min, and cooling makes the nm of gold mixed solution naturally, is placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 90mL above-mentioned steps (1) prepares, stir, add the 2 mercaptopropionic acid (HSCH of 90 μ L simultaneously 3CHCOOH), after mixing, the potassium hydroxide (KOH) of use 0.2M or hydrochloric acid (HCl) transfer to 82 with the pH value of mixed liquor, and about 37min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 14:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get the two hydration potassium chloroaurate (KAuCl of 5mL 5mM 42H 2O) solution adds the deionized water of 95mL and the dodecyl benzyl dimethyl ammonium chloride (CH of 1mL 0.2M respectively 3(CH 2) 11NCl (CH 3) 2CH 2C 6H 5) solution, stir 5min; Potassium borohydride (the KBH that dropwise adds 10mL 0.02M then 4), continue to stir 2min, make the nm of gold mixed solution, be placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 100mL above-mentioned steps (1) prepares, stir, add the 3-mercaptopropionic acid (HSCH that adds 100 μ L simultaneously simultaneously 2CH 2CO 2H), after mixing, the NaOH (NaOH) of use 0.2M or hydrochloric acid (HCl) transfer to 10.25 with the pH value of mixed liquor, and about 40min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 15:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get the two hydration sodium chloraurate (NaAuCl of 5mL 5mM 42H 2O) solution adds the deionized water of 95mL and the DTAC (CH of 2mL 0.1M respectively 3(CH 2) 11NCl (CH 3) 3) solution, stir 5min; Oil bath is heated to 88 ℃, dropwise adds the ascorbic acid (L-Ascorbic acid) of 10mL 5M then, continues heated and stirred 10min, and cooling makes the nm of gold mixed solution naturally, is placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 90mL above-mentioned steps (1) prepares, stir, add the 2 mercaptopropionic acid (HSCH of 90 μ L simultaneously 3CHCOOH), after mixing, the NaOH (NaOH) of use 0.2M or hydrochloric acid (HCl) transfer to 8.5 with the pH value of mixed liquor, and about 41min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 16:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get the gold chloride (HAuCl of 5mL 5mM 4) solution, add the deionized water of 95mL and the softex kw (CH of 1mL 0.5M respectively 3(CH 2) 15NBr (CH 3) 3) solution, stir 2min; Sodium borohydride (the NaBH that dropwise adds 500 μ L 0.5M then 4), continue to stir 40min, make the nm of gold mixed solution, be placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 90mL above-mentioned steps (1) prepares, stir, add the 3-mercaptopropionic acid (HSCH of 90 μ L simultaneously 2CH 2CO 2H), after mixing, the potassium hydroxide (KOH) of use 0.2M or hydrochloric acid (HCl) transfer to 104 with the pH value of mixed liquor, and about 50min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 17:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get the two hydration potassium chloroaurate (KAuCl of 5mL 5mM 42H 2O) solution adds the deionized water of 95mL and the DTAC (CH of 90 μ L 2M respectively 3(CH 2) 11NCl (CH 3) 3) solution, stir 1min; Oil bath is heated to 78 ℃, dropwise adds the ascorbic acid (L-Ascorbic acid) of 1mL 1M then, continues heated and stirred 12min, and cooling makes the nm of gold mixed solution naturally, is placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 100mL above-mentioned steps (1) prepares, stir, add the L-cysteine (HSCH of 15mL1mM simultaneously 2CHNH 2CO 2H), after mixing, the NaOH (NaOH) of use 0.2M or hydrochloric acid (HCl) transfer to 10.82 with the pH value of mixed liquor, and about 39min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 18:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get the gold chloride (HAuCl of 5mL 5mM 4) solution, add the deionized water of 95mL and the DTAC (CH of 5mL 0.03M respectively 3(CH 2) 11NCl (CH 3) 3) solution, stir 8min; Potassium borohydride (the KBH that dropwise adds 3mL 0.08M then 4), continue to stir 10min, make the nm of gold mixed solution, be placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 100mL above-mentioned steps (1) prepares, stir, add the calcium mercaptoacetate ((HSCH of 40mL0.5mM simultaneously 2COO) 2Ca), after mixing, the NaOH (NaOH) of use 0.2M or hydrochloric acid (HCl) transfer to 7.6 with the pH value of mixed liquor, and about 60min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 19:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get aurous chloride (AuCl) solution of 5mL 5mM, add the deionized water of 95mL and the softex kw (CH of 2mL 0.1M respectively 3(CH 2) 15NBr (CH 3) 3) solution, stir 5min; Oil bath is heated to 87 ℃, dropwise adds the ascorbic acid (L-Ascorbic acid) of 50mL 0.6M then, continues heated and stirred 10min, and cooling makes the nm of gold mixed solution naturally, is placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 90mL above-mentioned steps (1) prepares, stir, add the L-cysteine (HSCH of 30mL0.15mM simultaneously 2CHNH 2CO 2H), after mixing, the NaOH (NaOH) of use 0.2M or hydrochloric acid (HCl) transfer to 6.6 with the pH value of mixed liquor, and about 41min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 20:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get the two hydration potassium chloroaurate (KAuCl of 5mL 5mM 42H 2O) solution adds the deionized water of 95mL and the DTAC (CH of 1mL 0.2M respectively 3(CH 2) 11NCl (CH 3) 3) solution, stir 60min; Potassium borohydride (the KBH that dropwise adds 10mL 0.02M then 4), continue to stir 15min, make the nm of gold mixed solution, be placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 60mL above-mentioned steps (1) prepares, stir, add the 2 mercaptopropionic acid (HSCH that adds 60 μ L simultaneously simultaneously 3CHCOOH), after mixing, the potassium hydroxide (KOH) of use 0.2M or hydrochloric acid (HCl) transfer to 10.5 with the pH value of mixed liquor, and about 40min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 21:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get aurous chloride (AuCl) solution of 5mL 5mM, add the deionized water of 95mL and the DTAC (CH of 10mL 0.01M respectively 3(CH 2) 11NCl (CH 3) 3) solution, stir 9min; Oil bath is heated to 86 ℃, dropwise adds the ascorbic acid (L-Ascorbic acid) of 100mL 0.05M then, continues heated and stirred 3min, and cooling makes the nm of gold mixed solution naturally, is placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 200mL above-mentioned steps (1) prepares, stir, add 200 μ L TGA (HSCH simultaneously 2CO 2H), after mixing, the NaOH (NaOH) of use 0.2M or hydrochloric acid (HCl) transfer to 9.9 with the pH value of mixed liquor, and about 40min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 22:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get aurous chloride (AuCl) solution of 5mL 5mM, add the deionized water of 95mL and the softex kw (CH of 10mL 0.06M respectively 3(CH 2) 15NBr (CH 3) 3) solution, stir 15min; Oil bath is heated to 83 ℃, dropwise adds the ascorbic acid (L-Ascorbic acid) of 10mL 0.9M then, continues heated and stirred 13min, and cooling makes the nm of gold mixed solution naturally, is placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 120mL above-mentioned steps (1) prepares, stir, add the L-cysteine (HSCH of 100mL0.1mM simultaneously 2CHNH 2CO 2H), after mixing, the potassium hydroxide (KOH) of use 0.2M or hydrochloric acid (HCl) transfer to 6.25 with the pH value of mixed liquor, and about 60min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 23:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get aurous chloride (AuCl) solution of 5mL 5mM, add the deionized water of 95mL and the DTAC (CH of 3mL 0.08M respectively 3(CH 2) 11NCl (CH 3) 3) solution, stir 5min; Oil bath is heated to 89 ℃, dropwise adds the ascorbic acid (L-Ascorbic acid) of 100mL 0.1M then, continues heated and stirred 3min, and cooling makes the nm of gold mixed solution naturally, is placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 150mL above-mentioned steps (1) prepares, stir, add the sodium thioglycolate (HSCH of 50mL2mM simultaneously 2COONa), after mixing, the NaOH (NaOH) of use 0.2M or hydrochloric acid (HCl) transfer to 5.5 with the pH value of mixed liquor, and about 47min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Embodiment 24:
In the present embodiment, the functionalized nano gold solution adopts following steps to prepare:
(1) preparation of nm of gold mixed solution
Under the room temperature, get the two hydration potassium chloroaurate (KAuCl of 5mL 5mM 42H 2O) solution adds the deionized water of 95mL and the softex kw (CH of 7mL 0.3M respectively 3(CH 2) 15NBr (CH 3) 3) solution, stir 10min; Potassium borohydride (the KBH that dropwise adds 10mL 0.07M then 4), continue to stir 6min, make the nm of gold mixed solution, be placed in 4 ℃ of refrigerators subsequent use.
(2) contain the ion cluster bunch modified nano gold of element sulphur and carbon oxygen groups (O=C=O)
Get the nm of gold mixed solution that 20mL above-mentioned steps (1) prepares, stir, add the TGA (HSCH that adds 20uL simultaneously simultaneously 2CO 2H), after mixing, the NaOH (NaOH) of use 0.2M or hydrochloric acid (HCl) transfer to 6.83 with the pH value of mixed liquor, and about 40min is stirred in sealing then, obtains the functionalized nano gold solution.
Adopt with embodiment 1 in identical method of testing to the above-mentioned functionalized nano gold solution for preparing to micro-Co in the water solution system 2+Detection rapidity, selectivity, sensitivity and practicality etc. test, obtain identical result with embodiment, show that the functionalized nano gold solution that present embodiment makes can detect micro-Co in the water solution system 2+, and have the rapidity of detection, selectivity, sensitivity and practicality, in environmental science, check chemistry and analytical chemistry field, have important use and be worth.
Above-described embodiment specifies technical scheme of the present invention; Be understood that the above is merely specific embodiment of the present invention; Be not limited to the present invention; The all any modifications in principle scope of the present invention, made and improvement etc. all should be included within protection scope of the present invention.

Claims (7)

1. nano-Au solution, it is characterized in that: described nano-Au solution prepares with following step:
(1) being the golden nanometer particle source with golden salt, is surfactant with the quaternary ammonium salt, and sodium borohydride, potassium borohydride or ascorbic acid are reducing agent; Get a certain amount of golden salting liquid, add surfactant, stir the back and add reducing agent, make the nm of gold mixed solution;
The molecular formula of described quaternary ammonium salt is CH 3(CH 2) mNX (CH 3) n(CH 2) p(C 6H 5) q, m=7～15 wherein, n=2 or 3, p=0 or 1, q=0 or 1, X=Cl, Br, I or F;
(2) in described nm of gold mixed solution, add and contain sulfydryl (SH) and carboxyl (compound soluble in water COOH); PH value with the mixed solution that obtains transfers to 5.0～11.0 then, obtains containing the nano-Au solution of the ion cluster bunch modification of element sulphur and carbon oxygen groups (O=C=O) after sealing is stirred.
2. nano-Au solution according to claim 1 is characterized in that: described golden salt comprises one or more in chlorauride, aurous chloride, gold chloride, three hydration gold chlorides, four hydration gold chlorides, two hydration potassium chloroaurates, the two hydration sodium chloraurates.
3. nano-Au solution according to claim 1 is characterized in that: described surfactant comprises one or more in softex kw, DTAC and the dodecyl benzyl dimethyl ammonium chloride.
4. nano-Au solution according to claim 1 is characterized in that: the described compound that contains sulfydryl and carboxyl comprises one or more in TGA, 2 mercaptopropionic acid, 3-mercaptopropionic acid, L-cysteine, sodium thioglycolate, calcium mercaptoacetate and the thiosalicylic acid.
5. nano-Au solution according to claim 1 is characterized in that: the described ion cluster that contains element sulphur and carbon oxygen groups (O=C=O) bunch comprises [SCH 2CO 2] 2-, [SCH 3CHCO 2] 2-, [SCH 2CH 2CO 2] 2-, [SCH 2CHNH 2CO 2] 2-Or [SC 6H 4CO 2] 2-
6. one kind is utilized the described nano-Au solution of arbitrary claim in the claim 1 to 6 to detect Co 2+Method, it is characterized in that: comprise the steps:
(1) is test sample with the described nano-Au solution of arbitrary claim in the claim 1 to 6, measures two parts of test sample that volume is identical; Preparation and the aqueous solution that do not contain cobalt ions identical with detection aqueous solution volume is solution as a comparison; A test sample is mixed with comparative solution, form first mixed liquor,, form second mixed liquor another part test sample and aqueous solution to be detected;
(2) be reference with first mixed solution, observe the color of second mixed liquor and first mixed liquor,, have Co in the aqueous solution then to be detected if there is change color 2+,, do not have Co in the aqueous solution then to be detected if there is not change color 2+Perhaps, contrast UV, visible light absorption intensity, the peak value of second mixed liquor and first mixed liquor, change, have Co in the aqueous solution then to be detected as if its UV, visible light absorption intensity, peak value 2+,, do not have Co in the aqueous solution then to be detected if do not change 2+
7. detection Co according to claim 6 2+Method, it is characterized in that: the step in described claim 6 (1) is at first dialysed to described nano-Au solution before.
CN201110363954.5A 2011-11-16 2011-11-16 A kind of nano-Au solution and utilize this nano-Au solution to detect Co 2+method Active CN102416482B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201110363954.5A CN102416482B (en) 2011-11-16 2011-11-16 A kind of nano-Au solution and utilize this nano-Au solution to detect Co 2+method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201110363954.5A CN102416482B (en) 2011-11-16 2011-11-16 A kind of nano-Au solution and utilize this nano-Au solution to detect Co 2+method

Publications (2)

Publication Number Publication Date
CN102416482A true CN102416482A (en) 2012-04-18
CN102416482B CN102416482B (en) 2015-10-28

Family

ID=45941271

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110363954.5A Active CN102416482B (en) 2011-11-16 2011-11-16 A kind of nano-Au solution and utilize this nano-Au solution to detect Co 2+method

Country Status (1)

Country Link
CN (1) CN102416482B (en)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102706866A (en) * 2012-05-18 2012-10-03 中国科学院宁波材料技术与工程研究所 Detection reagent for rapidly detecting multiple single metal ions, preparation and application thereof
CN103454268A (en) * 2013-04-19 2013-12-18 南京工业大学 Reducing sugar quantitative detection method based on click reaction
CN103487430A (en) * 2013-08-29 2014-01-01 中国科学院宁波材料技术与工程研究所 Trivalent aluminum ion detection reagent and method
CN104400005A (en) * 2014-12-16 2015-03-11 湖南科技大学 Synthetic method of fluorescent gold nanocluster
CN104858448A (en) * 2015-05-11 2015-08-26 华南理工大学 Green synthesis method for nanogold in lignin solution
CN105445259A (en) * 2015-11-10 2016-03-30 宁波大学 Method for quickly detecting clenbuterol based on functionalized gold nanoparticles
CN106290195A (en) * 2016-08-30 2017-01-04 中南林业科技大学 Gold contracted payment nanometer colorimetric sensor preparation method and the method for detection cobalt ion thereof
CN106807952A (en) * 2015-12-01 2017-06-09 中国科学院大连化学物理研究所 One kind synthesis Au25The method and Au of nanosphere25Nanosphere
CN107098823A (en) * 2017-04-10 2017-08-29 中国科学院深圳先进技术研究院 Amino acid gold nano grain and its production and use
CN107583643A (en) * 2017-10-11 2018-01-16 深圳砺剑超能材料有限公司 The preparation method and noble metal catalyst of noble metal catalyst
CN108043195A (en) * 2017-11-13 2018-05-18 广州泓生物科技有限公司 A kind of nanogold gas purification liquid and preparation method and application
CN108274019A (en) * 2018-01-31 2018-07-13 华南理工大学 A kind of synthetic method of the luminous gold nanoparticle with surface plasmon absorption property
CN108698010A (en) * 2016-02-26 2018-10-23 Mida科技有限公司 Nano particle produces
CN108732151A (en) * 2018-05-31 2018-11-02 华南理工大学 There is the preparation of luminous gold nanoparticle and its rapid analysis and test method of highly sensitive optic response for volatile amine
CN108795409A (en) * 2017-04-28 2018-11-13 中国科学院苏州纳米技术与纳米仿生研究所 A kind of fluorescence gold nano cluster aggregation and preparation method thereof
CN109030476A (en) * 2018-07-20 2018-12-18 安徽原上草节能环保科技有限公司 Preparation method, detection paper tube and the detection method of detection paper tube for cobalt ions
CN113984751A (en) * 2021-10-29 2022-01-28 中南林业科技大学 Gold nano star colorimetric sensor and preparation method thereof and application of gold nano star colorimetric sensor in Co detection2+Method (2)
CN114177198A (en) * 2021-10-29 2022-03-15 广东粤港澳大湾区国家纳米科技创新研究院 Nano-gold antibacterial agent and preparation method and application thereof
CN114289729A (en) * 2021-12-31 2022-04-08 广东粤港澳大湾区国家纳米科技创新研究院 Thiol-modified nanogold colloidal fluid and preparation method and application thereof
CN114778461A (en) * 2022-04-22 2022-07-22 南通大学 Preparation method of intelligent gold nanoparticles and application of intelligent gold nanoparticles in beta-amyloid protein colorimetric analysis
CN116042213A (en) * 2023-01-18 2023-05-02 曲阜师范大学 Near infrared emission gold nanocluster, preparation method and application

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101268946A (en) * 2008-04-30 2008-09-24 东北师范大学 Method for latency fingerprint appearance of surface functionalization nano-gold particle
CN101881734A (en) * 2010-06-07 2010-11-10 中国科学院宁波材料技术与工程研究所 Detection method of metal ions
WO2011104497A1 (en) * 2010-02-24 2011-09-01 University Of Exeter Method for the preparation of a novel nanoparticle conjugate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101268946A (en) * 2008-04-30 2008-09-24 东北师范大学 Method for latency fingerprint appearance of surface functionalization nano-gold particle
WO2011104497A1 (en) * 2010-02-24 2011-09-01 University Of Exeter Method for the preparation of a novel nanoparticle conjugate
CN101881734A (en) * 2010-06-07 2010-11-10 中国科学院宁波材料技术与工程研究所 Detection method of metal ions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王慧娟等: "金纳米颗粒制备及其光学特性研究", 《传感技术学报》, vol. 24, no. 1, 31 January 2011 (2011-01-31), pages 14 - 17 *

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102706866B (en) * 2012-05-18 2014-12-03 中国科学院宁波材料技术与工程研究所 Detection reagent for rapidly detecting multiple single metal ions, preparation and application thereof
CN102706866A (en) * 2012-05-18 2012-10-03 中国科学院宁波材料技术与工程研究所 Detection reagent for rapidly detecting multiple single metal ions, preparation and application thereof
CN103454268A (en) * 2013-04-19 2013-12-18 南京工业大学 Reducing sugar quantitative detection method based on click reaction
CN103454268B (en) * 2013-04-19 2016-02-24 南京工业大学 Reducing sugar quantitative detection method based on click reaction
CN103487430B (en) * 2013-08-29 2018-08-14 中国科学院宁波材料技术与工程研究所 A kind of trivalent aluminium ion detection reagent and detection method
CN103487430A (en) * 2013-08-29 2014-01-01 中国科学院宁波材料技术与工程研究所 Trivalent aluminum ion detection reagent and method
CN104400005A (en) * 2014-12-16 2015-03-11 湖南科技大学 Synthetic method of fluorescent gold nanocluster
CN104858448A (en) * 2015-05-11 2015-08-26 华南理工大学 Green synthesis method for nanogold in lignin solution
CN105445259A (en) * 2015-11-10 2016-03-30 宁波大学 Method for quickly detecting clenbuterol based on functionalized gold nanoparticles
CN106807952A (en) * 2015-12-01 2017-06-09 中国科学院大连化学物理研究所 One kind synthesis Au25The method and Au of nanosphere25Nanosphere
CN106807952B (en) * 2015-12-01 2019-05-07 中国科学院大连化学物理研究所 A kind of synthesis Au25The method and Au of nanosphere25Nanosphere
CN108698010B (en) * 2016-02-26 2021-08-17 Mida科技有限公司 Nanoparticle production
CN108698010A (en) * 2016-02-26 2018-10-23 Mida科技有限公司 Nano particle produces
CN106290195A (en) * 2016-08-30 2017-01-04 中南林业科技大学 Gold contracted payment nanometer colorimetric sensor preparation method and the method for detection cobalt ion thereof
CN107098823A (en) * 2017-04-10 2017-08-29 中国科学院深圳先进技术研究院 Amino acid gold nano grain and its production and use
CN108795409B (en) * 2017-04-28 2020-09-01 中国科学院苏州纳米技术与纳米仿生研究所 Fluorescent gold nanocluster aggregate and preparation method thereof
CN108795409A (en) * 2017-04-28 2018-11-13 中国科学院苏州纳米技术与纳米仿生研究所 A kind of fluorescence gold nano cluster aggregation and preparation method thereof
CN107583643A (en) * 2017-10-11 2018-01-16 深圳砺剑超能材料有限公司 The preparation method and noble metal catalyst of noble metal catalyst
CN108043195A (en) * 2017-11-13 2018-05-18 广州泓生物科技有限公司 A kind of nanogold gas purification liquid and preparation method and application
CN108274019A (en) * 2018-01-31 2018-07-13 华南理工大学 A kind of synthetic method of the luminous gold nanoparticle with surface plasmon absorption property
CN108732151A (en) * 2018-05-31 2018-11-02 华南理工大学 There is the preparation of luminous gold nanoparticle and its rapid analysis and test method of highly sensitive optic response for volatile amine
CN109030476A (en) * 2018-07-20 2018-12-18 安徽原上草节能环保科技有限公司 Preparation method, detection paper tube and the detection method of detection paper tube for cobalt ions
CN109030476B (en) * 2018-07-20 2020-09-01 安徽原上草节能环保科技有限公司 Preparation method of detection paper tube for cobalt ions, detection paper tube and detection method
CN113984751A (en) * 2021-10-29 2022-01-28 中南林业科技大学 Gold nano star colorimetric sensor and preparation method thereof and application of gold nano star colorimetric sensor in Co detection2+Method (2)
CN114177198A (en) * 2021-10-29 2022-03-15 广东粤港澳大湾区国家纳米科技创新研究院 Nano-gold antibacterial agent and preparation method and application thereof
CN113984751B (en) * 2021-10-29 2024-05-03 中南林业科技大学 Gold nano star colorimetric sensor, preparation method thereof and Co detection method2+Is a method of (2)
CN114289729A (en) * 2021-12-31 2022-04-08 广东粤港澳大湾区国家纳米科技创新研究院 Thiol-modified nanogold colloidal fluid and preparation method and application thereof
CN114289729B (en) * 2021-12-31 2023-04-25 广东粤港澳大湾区国家纳米科技创新研究院 Thiol-modified nano gold colloid liquid and preparation method and application thereof
CN114778461A (en) * 2022-04-22 2022-07-22 南通大学 Preparation method of intelligent gold nanoparticles and application of intelligent gold nanoparticles in beta-amyloid protein colorimetric analysis
CN116042213A (en) * 2023-01-18 2023-05-02 曲阜师范大学 Near infrared emission gold nanocluster, preparation method and application
CN116042213B (en) * 2023-01-18 2024-03-01 曲阜师范大学 Near infrared emission gold nanocluster, preparation method and application

Also Published As

Publication number Publication date
CN102416482B (en) 2015-10-28

Similar Documents

Publication Publication Date Title
CN102416482A (en) Nanogold solution and method for detecting Co&lt;2+&gt; by using same
Li et al. Glutathione-stabilized silver nanoparticles as colorimetric sensor for Ni2+ ion
Zhou et al. Selective and sensitive colorimetric sensor of mercury (II) based on gold nanoparticles and 4-mercaptophenylboronic acid
Yi et al. Smartphone-based ratiometric fluorescent definable system for phosphate by merged metal− organic frameworks
CN101936905B (en) Mercury ion detection reagent and detection method
CN103837519B (en) Surface enhanced raman spectroscopy measures the method for Polychlorinated Biphenyls
CN106596651B (en) A kind of molybdenum disulfide/hydroxide nanoparticle composite material and preparation method and application
CN107141491B (en) Method for detecting atmospheric pollutants SO by using fluorescent test paper2And derivatives thereof
Yang et al. Carbon dots-embedded zinc-based metal-organic framework as a dual-emitting platform for metal cation detection
CN105140018A (en) Preparation method for magnetic macromolecule nanoball
CN106290186B (en) A kind of doping porous carbon Nano silver grain visualizing rapid mercury detection ion
Li et al. Ratiometric fluorescence for sensitive detection of phosphate species based on mixed lanthanide metal organic framework
Yang et al. Fluorosurfactant-capped gold nanoparticles-based label-free colorimetric assay for Au3+ with tunable dynamic range via a redox strategy
Cui et al. New strategy for fabricating Cd (II) sensing electrochemical interface based on enhanced adsorption followed by redox processes: Ferro-cerium oxide nanocomposite as an example
Peng et al. Ratiometric fluorescent sensor based on metal–organic framework for selective and sensitive detection of CO32–
Ahmed et al. SPR based gold nano-probe as optical sensor for cysteine detection via plasmonic enhancement in the presence of Cr3+
Xie et al. Sensitive colorimetric detection of Pb2+ by geometric field amplification and surface plasmon resonance visualization
Wang et al. Silver nanosol RRS aptamer assay of trace glyphosate based on gold-doped polystyrene nanocatalytic amplification
CN106520126B (en) Mercury ion probe and its synthetic method based on Doped ions luminous mechanism and application
CN113059175B (en) Preparation method of Au @ Ag @ AgCl nanoparticles and application of Au @ Ag @ AgCl nanoparticles in ammonia gas colorimetric detection
Qu et al. Sensitive determination of catechol using a glassy carbon electrode modified with L-cysteine and ZnS: Ni/ZnS quantum dots
CN104181154B (en) Formaldehyde detection agent and method
CN110776523B (en) Ultra-stable three-dimensional luminous zinc (II) metal organic framework material and preparation method and application thereof
Chen et al. Quantitative determination of proteins at nanogram levels by the resonance light-scattering technique with composite nanoparticles of CdS/PAA
CN103728255B (en) A kind ofly measure the method that one end on nano grain surface is the difunctional Small molecular soda acid dissociation constant of sulfydryl

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant