CN105057692A - Green synthesis method of gold nanoparticles - Google Patents
Green synthesis method of gold nanoparticles Download PDFInfo
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- CN105057692A CN105057692A CN201510477792.6A CN201510477792A CN105057692A CN 105057692 A CN105057692 A CN 105057692A CN 201510477792 A CN201510477792 A CN 201510477792A CN 105057692 A CN105057692 A CN 105057692A
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Abstract
The invention discloses a green synthesis method of gold nanoparticles and relates to a preparation method of gold nanoparticles. The green synthesis method of gold nanoparticles solves the technical problems that an existing chemical method for preparing the gold nanoparticles is prone to polluting the environment because too many chemical reagents exist, and a physical cost is high. The green synthesis method includes the steps that firstly, citrus fruits are cleaned, dried, juiced and then centrifuged, supernate is taken and diluted with deionized water by 1-10 times, and a juice solution is obtained; secondly, under the room temperature condition, a chloroauric acid solution is magnetically stirred for 2 min, then the juice solution is rapidly added, and stirring continues for 20 min when wine red happens, and a reaction ends; and then a gold nanoparticle solution is obtained and placed in a refrigerator at the temperature of 4 DEG C to be preserved. Pure natural citrus fruit juice is used for preparing the gold nanoparticles (AuNPs) in a green manner, no chemical reduction agents are added, and no chemical protective agents are added. The synthesis method is simple and fast, low in cost and small in pollution to the environment.
Description
Technical field
The present invention relates to a kind of preparation method of golden nanometer particle.
Background technology
Gold nano-material earns widespread respect because it has unique catalysis and optical property, and its preparation and application have become a study hotspot in current field of nanometer technology.Relative to traditional Physical and chemical method, the biological reducing method based on microorganism or plant occurred in recent years, have that cost is low, environmental protection, nano material stability advantages of higher, become the novel fabrication method that nm of gold material has development prospect.The method preparing gold nano-material is at present more, due to the difference of preparation technology, the particle diameter obtained, purity and the physicochemical properties had also different.Physical products obtained therefrom quality is high, but requires higher to instrument and equipment, and producing cost is expensive, and limited to the ability of regulation and control of gold nano grain pattern; Chemical method is versatile and flexible, can be used for the nanogold particle preparing different morphologies, but most chemical method needs to introduce more chemical reagent, may bring certain problem of environmental pollution.
Summary of the invention
The present invention will solve the existing chemical method preparing gold nano grain because of more chemical reagent and easily cause environmental pollution, technical problem that Physical cost is high; The invention provides the green synthesis method of golden nanometer particle.
In the present invention, the green synthesis method of golden nanometer particle carries out in the steps below: step one, by citrus fruit (i.e. Rutaceae citrus plant fruit) clean dry, squeeze the juice, then centrifugal, get supernatant, with deionized water dilution (1 ~ 10) times (by volume), obtain juice solution; Under step 2, room temperature condition, with. after magnetic stirring apparatus vigorous stirring chlorauric acid solution 2min, rapidly (add rapidly refer within short time as far as possible chlorauric acid solution is added) adds juice solution, occurs that claret continues to stir 20min and terminates reaction; Namely obtain solution of gold nanoparticles, preserve under being placed in refrigerator 4 DEG C of conditions.
Further restriction, carries out with 4000r/min rotating speed in step one.Citrus fruit described in step one is the one in orange, orange, lemon.The mass concentration of chlorauric acid solution described in step 2 is 1% (w/v, i.e. weight/volume).Described in step 2, chlorauric acid solution consumption is identical with the volume of the supernatant measured.
The present invention adopts the citrus fruit juices Green synthesis golden nanometer particle (AuNPs) of pure natural, does not add any chemical reducing agent, does not also add any chemical protective agent.Synthetic method of the present invention is simple and quick, with low cost, and environmental pollution is little.
The present invention utilizes orange, orange and lemon juice all successfully to prepare golden nanometer particle (AuNPs).Wherein, 1 ×, 5 × and AuNPs absworption peak prepared by 10 × fruit juice at about 530nm.The particle diameter utilizing laser fineness gage to record the AuNPs that 1 × orange, orange and lemon juice are prepared respectively is normal distribution, and average grain diameter is respectively 7.8 ± 0.4nm, 11.8 ± 0.5nm and 6.8 ± 0.3nm.
Under normal temperature condition (25 DEG C), the AuNPs that orange, orange and lemon juice are prepared respectively, after 120h, activity is followed successively by 76%, 47% and 69%.Adopt catalysis p-nitrophenol hydrogenation as the probe reaction of the AuNPs catalytic activity of the juice preparation of the different fruit of assessment.Research shows, the AuNPs prepared by 3 kinds of fruit juice all has catalytic activity, and the catalytic activity of orange and the AuNPs prepared by lemon than orange juice preparation continue more of a specified duration.
With the golden nanometer particle of 1 × orange juice preparation for detecting the Detecting Pesticide of A sulfur phosphorus.Along with the raising of pesticide concentration, color is converted to purple from shallow claret gradually and becomes navy blue again, in explanation system, the activity of acetylcholinesterase is suppressed gradually, and the content of substrate increases the particle diameter causing golden nanometer particle gradually and increases gradually, occurs gathering in various degree.Uv-visible absorption spectroscopy presents the result similar to colorimetric directly perceived substantially.When the concentration of agricultural chemicals increases gradually, the peak value of wavelength 530nm place golden nanometer particle characteristic peak starts to decline; Meanwhile, in the scope of wavelength 650-780nm, there is new absworption peak.Result illustrates, the agricultural chemicals of variable concentrations can cause the gathering of golden nanometer particle in various degree, forms the golden nanometer particle of different-grain diameter size, and then causes the wavelength of golden nanometer particle characteristic absorption peak different.Selective experiment is carried out by adding 0.1mg/mL glucose, sucrose, maltose, sodium chloride, potassium chloride, magnesium sulfate, calcium chloride and zinc acetate, after reaction, color does not change, and illustrates and has material common in general food higher selective based on the Pesticides Testing system constructed by the golden nanometer particle of orange fruit juice synthesis.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture () of golden nanometer particle; (1 × orange juice solution)
Fig. 2 is the uv-visible absorption spectroscopy figure of orange juice preparation golden nanometer particle
,in Fig. 2,1 represents that dilution is 1 × juice solution, 2 represent that dilutions are 5 × juice solution, 3 represent that dilutions are 10 × juice solution, 4 represent mother liquors, 5 represent that dilutions are 15 × juice solution, 6 represent that dilutions are 20 × juice solution;
Fig. 3 is the grain size distribution of orange juice preparation golden nanometer particle;
Fig. 4 is the uv-visible absorption spectroscopy figure of orange juice preparation golden nanometer particle, in Fig. 4,1 represents that dilution is 1 × juice solution, 2 represent that dilutions are 5 × juice solution, 3 represent that dilutions are 10 × juice solution, 4 represent mother liquor, 5 represent that dilutions are 15 × juice solution, 6 represent that dilutions are 20 × juice solution;
Fig. 5 is the grain size distribution of orange juice preparation golden nanometer particle;
Fig. 6 is the uv-visible absorption spectroscopy figure that lemon juice prepares golden nanometer particle, in Fig. 6,1 represents that dilution is 1 × juice solution, 2 represent that dilutions are 5 × juice solution, 3 represent that dilutions are 10 × juice solution, 4 represent mother liquor, 5 represent that dilutions are 15 × juice solution, 6 represent that dilutions are 20 × juice solution;
Fig. 7 is the grain size distribution that lemon juice prepares golden nanometer particle;
Fig. 8 is the stability study figure of orange juice preparation golden nanometer particle;
Fig. 9 is the stability study figure of orange juice preparation golden nanometer particle;
Figure 10 is the stability study figure that lemon juice prepares golden nanometer particle;
Figure 11 is the gold nanoparticle catalyzed activity research figure of orange juice preparation;
Figure 12 is the gold nanoparticle catalyzed activity research figure of orange juice preparation;
Figure 13 is gold nanoparticle catalyzed activity research figure prepared by lemon juice;
Figure 14 is 4 sample uv-visible absorption spectroscopy figure, a in Figure 14---same volume golden nanometer particle system, b---contrast 2, c---contrast 1, d---contrast 3 (agricultural chemicals is A sulfur phosphorus), e---contrast 4 (agricultural chemicals is phosphamidon);
Figure 15 is the uv-visible absorption spectroscopy figure of agricultural chemicals that golden nanometer particle detects variable concentrations, and in Figure 15,1 to 10 is followed successively by: be 0,0.1 × 10 containing A sulfur phosphorus concentration
-4, 0.5 × 10
-4, 1.0 × 10
-4, 2.5 × 10
-4, 5.0 × 10
-4, 10 × 10
-4, 25 × 10
-4, 50 × 10
-4with 100 × 10
-4mg/mL, 1 is contrast;
Figure 16 is that golden nanometer particle detects containing A sulfur phosphorus concentration 0.1 × 10
-4the transmission electron microscope picture of the agricultural chemicals of mg/mL;
Figure 17 is that golden nanometer particle detects containing A sulfur phosphorus concentration 10 × 10
-4the transmission electron microscope picture of the agricultural chemicals of mg/mL;
Figure 18 is that golden nanometer particle detects containing A sulfur phosphorus concentration 100 × 10
-4the transmission electron microscope picture of the agricultural chemicals of mg/mL.
Detailed description of the invention
Detailed description of the invention one: present embodiment take orange as raw material green syt golden nanometer particle, concrete grammar carries out in the steps below: step one, get orange 1, and clean and dry, fruit juice extractor is squeezed the juice, by fruit juice under 4000r/min condition, centrifugal 3min; Get supernatant, collect supernatant, get 10mL deionized water and dilute 1 times (1 ×), obtain juice solution.
Under step 2, room temperature condition, by 10mL chlorauric acid solution (1%, W/V) reaction utensil is placed in, after magnetic stirring apparatus vigorous agitation 2min, add rapidly the juice solution that step one obtains, occur the change of color immediately, occur that claret terminates reaction after continuing to stir 20min, namely obtain golden nanometer particle (AuNPs) solution, preserve under being placed in refrigerator 4 DEG C of conditions.
The domain size distribution of the golden nanometer particle utilizing laser fineness gage to record prepared by present embodiment method is shown in Fig. 3.As shown in Figure 3, gold nanometer particle grain size presents normal distribution, is mainly distributed within the scope of 7-9nm, and account for 79% of whole distribution system, average grain diameter reaches 7.8 ± 0.4nm.
Detailed description of the invention two: present embodiment and detailed description of the invention one unlike: in step one, supernatant deionized water is diluted 5 times.Other step is identical with detailed description of the invention one with parameter.
Detailed description of the invention three: present embodiment and detailed description of the invention one unlike: in step one, supernatant deionized water is diluted 10 times.Other step is identical with detailed description of the invention one with parameter.
Dilute 1 respectively by obtaining supernatant in detailed description of the invention one method step one ×, 5 ×, 10 ×, 15 × and 20 × prepare golden nanometer particle, the uv-visible absorption spectroscopy of described golden nanometer particle as shown in Figure 2, as shown in Figure 2, the golden nanometer particle of variable concentrations orange juice preparation has obvious absworption peak between wavelength 520-570nm, and peak value height is different.It can thus be appreciated that the golden nanometer particle prepared by the fruit juice of variable concentrations has obvious difference on particle diameter and content.Result shows, 1 ×, 5 × and golden nanometer particle absworption peak prepared by 10 × fruit juice at about 530nm, there is less particle diameter; Meanwhile, mother liquor (referring to supernatant), 15 × and 20 × the golden nanometer particle absworption peak prepared by fruit juice there is blue shift gradually, in the appearance of wavelength 570nm place, illustrate that gold particle particle diameter increases gradually.Judged the content of golden nanometer particle by the peak value of absworption peak, the content in system of the golden nanometer particle prepared by 1 × orange fruit juice is maximum, and the peak value of absworption peak reaches 0.46, far away higher than 15 × and 20 × the content of the golden nanometer particle prepared by fruit juice.Although ascorbic acid concentrations contained in mother liquor is the highest, but prepared golden nanometer particle particle size and content are not preponderated, likely because in mother liquor except containing abundant ascorbic acid, also has other many kinds of substance (as carbohydrate etc.), these large biological molecules cause the gathering of the gold kind of harsh one-tenth compared with Gao Shihui in concentration, thus increase the particle diameter of gold particle, also delay gold particle generation.
Detailed description of the invention four: present embodiment take orange as raw material green syt golden nanometer particle, concrete grammar carries out in the steps below: step one, get orange 1, and clean and dry, fruit juice extractor is squeezed the juice, by fruit juice under 4000r/min condition, centrifugal 3min; Get supernatant, collect supernatant, get 10mL deionized water and dilute 1 times, obtain juice solution.
Under step 2, room temperature condition, by 10mL chlorauric acid solution (1%, W/V) reaction utensil is placed in, after magnetic stirring apparatus vigorous agitation 2min, add rapidly the juice solution that step one obtains, occur the change of color immediately, occur that claret terminates reaction after continuing to stir 20min, namely obtain solution of gold nanoparticles, preserve under being placed in refrigerator 4 DEG C of conditions.
The domain size distribution of the golden nanometer particle utilizing laser fineness gage to record prepared by present embodiment method is shown in Fig. 5.As shown in Figure 5, the domain size distribution of the golden nanometer particle in the preparation system of 1 × orange fruit juice also presents normal distribution, and average grain diameter is 11.8 ± 0.5nm, is mainly distributed within the scope of 9-12nm.Bigger than normal compared to the gold nanometer particle grain size prepared by orange fruit juice in proportion.
Detailed description of the invention five: present embodiment and detailed description of the invention four unlike: in step one, supernatant deionized water is diluted 5 times.Other step is identical with detailed description of the invention four with parameter.
Detailed description of the invention six: present embodiment and detailed description of the invention four unlike: in step one, supernatant deionized water is diluted 10 times.Other step is identical with detailed description of the invention four with parameter.
Dilute 1 respectively by obtaining supernatant in detailed description of the invention four method step 4 ×, 5 ×, 10 ×, 15 × and 20 × prepare golden nanometer particle, the uv-visible absorption spectroscopy of described golden nanometer particle as shown in Figure 4, as shown in Figure 4, the uv-visible absorption spectra of the golden nanometer particle prepared by orange fruit juice and the golden nanometer particle prepared by orange fruit juice basically identical.1 ×, 5 × and golden nanometer particle absworption peak prepared by 10 × fruit juice at about 540nm, bigger than normal compared to the gold nanometer particle grain size prepared by orange fruit juice.The content of the golden nanometer particle of the preparation system of 1 × fruit juice compared to same concentration orange fruit juice prepared by reduce, absorption peak only has about 0.32, and the poor-performing of orange fruit juice compared to orange juice preparation golden nanometer particle is described.
Detailed description of the invention seven: present embodiment take lemon as raw material green syt golden nanometer particle, concrete grammar carries out in the steps below: step one, get 1, lemon, and clean and dry, fruit juice extractor is squeezed the juice, by fruit juice under 4000r/min condition, centrifugal 3min; Get supernatant, collect supernatant, get 10mL deionized water and dilute 1 times, obtain juice solution.
Under step 2, room temperature condition, by 10mL chlorauric acid solution (1%, W/V) reaction utensil is placed in, after magnetic stirring apparatus vigorous agitation 2min, add rapidly the juice solution that step one obtains, occur the change of color immediately, occur that claret terminates reaction after continuing to stir 20min, namely obtain solution of gold nanoparticles, preserve under being placed in refrigerator 4 DEG C of conditions.
Detailed description of the invention eight: present embodiment and detailed description of the invention seven unlike: in step one, supernatant deionized water is diluted 5 times.Other step is identical with detailed description of the invention seven with parameter.
Detailed description of the invention nine: present embodiment and detailed description of the invention seven unlike: in step one, supernatant deionized water is diluted 10 times.Other step is identical with detailed description of the invention seven with parameter.
Dilute 1 respectively by obtaining supernatant in detailed description of the invention seven method step one ×, 5 ×, 10 ×, 15 × and 20 × prepare golden nanometer particle, the uv-visible absorption spectroscopy of described golden nanometer particle is as shown in Figure 6.Result shows, the overall distribution of the golden nanometer particle prepared by lemon juice is substantially the same with orange in orange.1 ×, 5 × and golden nanometer particle absworption peak prepared by 10 × fruit juice at about 530nm, in the preparation system of wherein 1 × fruit juice, the content of golden nanometer particle is the highest, and absorption peak reaches 0.47, a little more than the preparation system of orange and orange in proportion.The preparation system selecting 1 × lemon juice carries out Catalytic Activity Test.As can be known from Fig. 7, in the preparation system of 1 × lemon juice, the average grain diameter of golden nanometer particle is 6.8 ± 0.3nm, and particle diameter is mainly distributed within the scope of 5-8nm.
Adopt following experimental verification invention effect:
One, stability study
Stability study is carried out to the golden nanometer particle prepared by detailed description of the invention one, four and seven, choose the reactant liquor in 0h, 12h, 24h, 48h and 120h time interval respectively, join in cuvette, be placed in ultraviolet-visible spectrophotometer, the absorption spectrum of scanning golden nanometer particle, the change of comparative analysis spectrum, and then assessment stability; Result as seen in figs. 8-10.
As shown in Figure 8, under normal temperature condition (25 DEG C), the absworption peak peak value of the golden nanometer particle prepared by orange fruit juice declines gradually along with the prolongation in the time interval, initial spike is 0.63, after 12h, peak value drops to 0.57,0.48 is dropped to after dropping to 0.56,120h after 24h hour; After illustrating 5 days, golden nanometer particle remains good activity, and activity still maintains about 76%, can be applied to production practices.
The stability result of the golden nanometer particle prepared by orange fruit juice is shown in Fig. 9.After placement 12h and 24h, the absorption peak fall of system is basically identical, illustrates in a certain time interval, and orange fruit juice can maintain good stability.After 120h, the activity of system maintains 47%, and stability is a lot of with the golden nanometer particle phase ratio prepared by orange fruit juice.
As can be seen from Figure 10, the golden nanometer particle prepared by lemon juice is after 120h, and activity maintains 69%, and activity is higher.
In sum, golden nanometer particle stability prepared by three kinds of fruit juices is by weak order being by force: orange > lemon > orange, wherein the active sustainment rate of the stability of orange and the golden nanometer particle prepared by lemon after 5d is more than 60%, has a good application prospect.
Two, catalytic activity research
To the p-nitrophenyl phenol solution (2.5 × 10 of 25mL
-4m) in, add successively respectively various dose golden nanometer particle prepared by 3 kinds of fruit juice (0,1,2,3,4,5mL, system difference deionized water polishing) and the freshly prepared NaBH of 1mL
4(0.25M).Be placed in ultraviolet-visible spectrophotometer, the absorption spectrum of scanning reaction system, observe the absworption peak change at 400nm wavelength place.
Adopt catalysis p-nitrophenol hydrogenation as the probe reaction of the gold nanoparticle catalyzed activity of the juice preparation of the different fruit of assessment.Add golden nanometer particle in normal reaction system after, hydrogenation reaction is obviously aggravated, and the p-nitrophenol in system becomes para-aminophenol, and the peak value of the ultraviolet absorption peak originally at wavelength 400nm place is declined.As shown in Figure 11, along with the increase of the golden nanometer particle quantity prepared by orange fruit juice, the process of catalytic reaction there occurs obvious change.When adding the golden nanometer particle colloidal sol of 1mL, the extent of reaction is basically identical with the quantity not adding p-nitrophenol remaining in the system of golden nanometer particle; When adding 2mL aurosol, catalytic reaction starts to occur significant change, and larger decline appears in the absorption peak at wavelength 400nm place; When added aurosol is 4mL, also can't see obvious absworption peak at wavelength 400nm place, illustrate that reaction thoroughly completes under the catalysis of golden nanometer particle.As can be seen from Figure 12, the golden nanometer particle prepared by orange fruit juice also has obvious catalytic activity, and when adding 1mL, catalytic reaction just occurs obvious change, and p-nitrophenol absorption peak drops to 0.8 by 0.88; But when aurosol joins 5mL, wavelength 400nm place still has absworption peak, illustrate that reaction does not have catalysis complete, active still not as good as the golden nanometer particle prepared by orange fruit juice.The catalytic activity of the golden nanometer particle prepared by lemon juice is shown in Figure 13, and when the aurosol added is 4mL, absorption peak just disappears, and illustrate that reaction has been carried out completely, the golden nanometer particle of interpolation has good catalytic activity.In sum, much better than orange juice preparation of the catalytic activity of orange and the golden nanometer particle prepared by lemon, may be relevant with particle size.
Three, golden nanometer particle detects organophosphorus pesticide research
Acetylcholinesterase specific catalytic substrate acetylthiocholine iodide (ATChI) can be hydrolyzed to acetylthiocholine and acetic acid, the electric charge of acetylthiocholine and S key can both cause surface with the gathering of the golden nanometer particle of negative electrical charge, thus cause the change of whole system color (being to blue in theory by redness).But in time having machine phosphorus insecticide in system, the activity of acetylcholinesterase is suppressed and cannot the hydrolysis of catalytic substrate, enters the aggregation extent hindering golden nanometer particle.The difference of pesticide concentration, makes the downtrod degree of acetylcholinesterase different, and the color of final system is also just different, builds according to this principle with the Fast Determination of Pesticide Residue system of golden nanometer particle colorimetric probe for relying on.
First select acetylthiocholine iodide (ATChI) as reaction substrate, adopt the ATChI solution 100mL of deionized water configuration 10mM.In 5mLATChI solution, add 18mg silver nitrate powder, fully vibrate 10s, centrifugally after vertically leaving standstill 1min goes precipitation, gets supernatant (this step for removing I ion, because iodide ion can disturb evaluation of pesticides result).In supernatant, add 1mg sodium chloride again, fully vibrate 10s, and after vertically leaving standstill 1min, centrifugal going is precipitated, and gets supernatant (this step is for removing unnecessary Ag ion).Now contain ATCh in supernatant
+, can be used for ensuing chrominance response.
Respectively to the sterilized water adding 3mL in 5mL centrifuge tube, 0.1mLATCh
+solution, 0.1mL add 0.5mL aurosol stoste after fully not reacting 10min containing the buffer solution of enzyme, record color change (sample 1).
Respectively to the sterilized water adding 3mL in 5mL centrifuge tube, the ATCh of 0.1mL
+after acetylcholinesterase buffer solution (2U/mL) the abundant reaction 10min of solution and 0.1mL, add 0.5mL aurosol stoste, record color change (sample 2).
Respectively to the sterilized water adding 1mL in 5mL centrifuge tube, after 2mL A sulfur phosphorus solution liquid (0.01mg/mL) and 0.1mL acetylcholinesterase buffer solution (2U/mL) fully react 10min, then add 0.1mLATCh
+solution.After 10min, add 0.5mL aurosol stoste, record color change (sample 3).
Respectively to the sterilized water adding 1mL in 5mL centrifuge tube, after 2mL phosphorus ammonium working solution (0.01mg/mL) and 0.1mL acetylcholinesterase buffer solution (2U/mL) fully react 10min, then add 0.1mLATCh
+solution.After 10min, add 0.5mL aurosol stoste, record color change (sample 4).
The sterilized water of 2.5mL is added respectively, the phosphamidon solution (0,0.1 × 10 of 5mL variable concentrations in centrifuge tube
-4, 0.5 × 10
-4, 1.0 × 10
-4, 2.5 × 10
-4, 5.0 × 10
-4, 10 × 10
-4, 25 × 10
-4, 50 × 10
-4with 100 × 10
-4and 0.5mL acetylcholinesterase buffer solution (2U/mL) fully after reaction 10min, then add 0.5mLATCh mg/mL)
+solution.After 10min, after adding 2mL aurosol stoste, record the change of each concentration-response liquid color.Ultraviolet-visible spectrophotometer is adopted to scan the change of the absorption spectrum of different Colorimetric System.
In this experiment, acetylcholinesterase specific catalytic substrate acetylthiocholine iodide (ATChI) can be hydrolyzed to acetylthiocholine and acetic acid.When in system specific remove iodide ion after (part research thinks that iodide ion can with agricultural chemicals in conjunction with Interference Detection system), the positive charge that substrate surface is enriched can cause surface with the gathering of the golden nanometer particle of negative electrical charge, there is plasma resonance, thus cause the change of whole system color (being to blue in theory by redness).But in time having machine phosphorus insecticide in system, the activity of acetylcholinesterase is suppressed and cannot the hydrolysis of catalytic substrate, and thereupon, substrate can be combined the aggregation extent entering and improve golden nanometer particle with golden nanometer particle.The difference of pesticide concentration, makes the downtrod degree of acetylcholinesterase different, and the color of final system is also just different, builds according to this principle with the Fast Determination of Pesticide Residue system of golden nanometer particle colorimetric probe for relying on.
In order to explore the principle of golden nanometer particle 90 organophosphorus pesticide, according to design setting colorimetric preliminary experiment, wherein using A sulfur phosphorus as the model of organophosphorus pesticide, adopting orange fruit juice (1 ×) to prepare golden nanometer particle and participating in reaction.
Design four experiment contrasts.Wherein, contrast in 1 containing substrate A TCh
+and golden nanometer particle, and there is no acetylcholinesterase.This contrast is purple, and what original golden nanometer particle presented is claret, and assembling appears in declaratives golden nanometer particle under this system, causes the increase of particle diameter, the change of color.In contrast 2, containing substrate and enzyme liquid, add golden nanometer particle again after reaction a period of time, system color is substantially constant, presents light claret.Illustrate that the particle diameter of golden nanometer particle does not become large, reason is because most of substrate, by acetylcholinesterase institute catalytic decomposition, fails the adsorpting aggregation caused between electric charge.In contrast 3, containing A sulfur phosphorus and enzyme liquid in system, add substrate after reaction a period of time, then add golden nanometer particle after reacting a period of time.In contrast 4, system is substantially identical with contrast 3, just A sulfur phosphorus is replaced by phosphorus ammonium.Have contrast 3 and 4 Colorimetric results known, after adding agricultural chemicals, system color has claret to transfer lavender to, illustrates after adding agricultural chemicals, and the activity of acetylcholinesterase is suppressed, cannot normal catalytic substrate A TCh
+hydrolysis, makes substrate keep some, causes the gathering of golden nanometer particle.
Detecting the colorimetric mechanism of agricultural chemicals in order to accurately inquire into golden nanometer particle further, adopting ultraviolet-visible spectrophotometer to characterize the characteristic absorption peak of golden nanometer particle in four contrasts, and then judging the result that chrominance response builds, seeing Figure 14.The structure result of colorimetric method shows, compared to same volume and the golden nanometer particle system of same concentrations, the system of contrast 2 is substantially identical with it, illustrate when only there is substrate and enzyme liquid in system, product after enzymolysis does not affect the particle diameter of golden nanometer particle, does not cause golden nanometer particle significantly to assemble.Meanwhile, contrast 1,3 and 4 can both cause the increase of the particle diameter of golden nanometer particle, makes absworption peak generation blue shift, occurs another obvious absworption peak at wavelength 630nm place.And then illustrate, substrate can cause the gathering of golden nanometer particle, and particle diameter increases.Result illustrates, system Pesticides concentration is higher, and golden nanometer particle gathering situation is more serious, and particle diameter is then larger.According to colour developing degree and the contrast difference of preliminary experiment, design the higher detection architecture of the reasonable detection sensitivity of peak value for detecting organophosphorus pesticide A sulfur phosphorus.
Colorimetric probe method detects residues of pesticides
According to the colorimetric principle tentatively probed into out in preliminary experiment, utilize the Colorimetric System redesigned to detect the agricultural chemicals of variable concentrations, contrast (golden nanometer particle of same concentrations, without other reactive materials), containing A sulfur phosphorus concentration 100 × 10
-4, 50 × 10
-4, 25 × 10
-4, 10 × 10
-4, 5.0 × 10
-4, 2.5 × 10
-4, 1.0 × 10
-4, 0.5 × 10
-4, 0.1 × 10
-4color comparison is carried out with 0mg/mL, along with the raising of pesticide concentration, color is converted to purple from shallow claret gradually and becomes navy blue again, in explanation system, the activity of acetylcholinesterase is suppressed gradually, the content of substrate increases the particle diameter causing golden nanometer particle gradually and increases gradually, occurs gathering in various degree.Be 100 × 10 at A sulfur phosphorus pesticide concentration
-4in the Colorimetric System of mg/mL, even there is precipitation in golden nanometer particle.Be 0 and 0.1 × 10 at A sulfur phosphorus pesticide concentration
-4in the Colorimetric System of mg/mL, integral color does not almost have difference with contrasting.When A sulfur phosphorus pesticide concentration is 0.5 × 10
-4during mg/mL, system color starts to occur lavender, presents distinct Colorimetric results.
Adopt uv-visible absorption spectroscopy to characterize the colorimetric detection result of variable concentrations agricultural chemicals, prove the change procedure of gold nanometer particle grain size further.As shown in Figure 1, uv-visible absorption spectroscopy presents the result similar to colorimetric directly perceived substantially.When the concentration of agricultural chemicals increases gradually, the peak value of wavelength 530nm place golden nanometer particle characteristic peak starts to decline; Meanwhile, in the scope of wavelength 650-780nm, there is new absworption peak.Result illustrates, the agricultural chemicals of variable concentrations can cause the gathering of golden nanometer particle in various degree, forms the golden nanometer particle of different-grain diameter size, and then causes the wavelength of golden nanometer particle characteristic absorption peak different.Wherein, be 0 and 0.1 × 10 at A sulfur phosphorus pesticide concentration
-4the peak value of the absworption peak of the system of mg/mL occurs significantly declining compared to the peak value of contrast, but color change not obvious in Colorimetric System.Composition graphs 3-8 analyzes, and may be because slight gathering appears in golden nanometer particle, cause peak value to decline, but does not have again new absworption peak to produce, so do not occur changing intuitively in color.
In Figure 15, Control is contrast; Be followed successively by from 1 to 10: be 0,0.1 × 10 containing A sulfur phosphorus concentration
-4, 0.5 × 10
-4, 1.0 × 10
-4, 2.5 × 10
-4, 5.0 × 10
-4, 10 × 10
-4, 25 × 10
-4, 50 × 10
-4with 100 × 10
-4mg/mL.
Adopt transmission electron microscope characterize further variable concentrations agricultural chemicals colorimetric detection system (select three individual system, respectively containing A sulfur phosphorus concentration be 0.1 × 10
-4, 10 × 10
-4with 100 × 10
-4mg/mL) in, the accumulation process of golden nanometer particle, the results are shown in Figure shown in 16-18.
From Figure 16-18, select three Colorimetric System containing variable concentrations A sulfur phosphorus to participate in morphology characterization, the aggregation extent of golden nanometer particle presents obvious difference.When containing 0.1 × 10 in system
-4a sulfur phosphorus time, golden nanometer particle compared to the system (see Fig. 5) of not adding agricultural chemicals to each other distance reduce, but obvious gathering could not be caused.When containing 10 × 10 in system
-4during the A sulfur phosphorus of mg/mL, surface with the golden nanometer particle of negative electrical charge by the substrate A TCh of surface with positive charge
+attract together, and then present clustering phenomena.And when containing 100 × 10 in system
-4during the A sulfur phosphorus of mg/mL, the gathering situation aggravation of golden nanometer particle, the phenomenon even having occurred hardening into piece, forms large-size particles, occurs precipitation.This result is substantially corresponding with the result of chrominance response before and uv-visible absorption spectroscopy.
In sum, the residual system that the colorimetric probe method of assembling based on golden nanometer particle detects agricultural chemicals has good using value.At present, China is 0.1mg/kg about the standard of the maximum residue limit of agricultural chemicals A sulfur phosphorus.According to the result in literary composition, the detectability of this experimental system, well below this standard, can be used for detecting the residual of A sulfur phosphorus in food.
Four, selective enumeration method research
Respectively to the sterilized water adding 2.5mL in system, 5mL concentration is glucose, sucrose, citric acid, maltose, the Na of A sulfur phosphorus (0.01mg/mL) 10 times
+, K
+, Mg
2+, Ca
2+and Zn
2solution (not containing A sulfur phosphorus in system), then add 0.5mL acetylcholinesterase buffer solution (2U/mL) abundant reaction 10min in system after, then add 0.5mLATCh
+solution; After 10min, add 2mL aurosol stoste.Compared with adding the A sulfur phosphorus system of 0.01mg/mL, the color change that in record food, Common materials causes, and then examine the anti-interference of this detection architecture.
An important indicator of colorimetric detection system detects selective exactly, i.e. anti-interference.Often have the material of other kind in reality sample, moieties can Interference Detection system to a certain extent.This research application detects the residues of pesticides in food, so for the Common materials in food, designs this partial content.Select the system containing 0.01mg/mL A sulfur phosphorus agricultural chemicals as reference, add material common in 9 kinds of food and be used as selective research, be respectively carbohydrate: glucose, sucrose, citric acid and maltose; Metal ion class: Na
+, K
+, Mg
2+, Ca
2+and Zn
2+; The concentration of often kind of interfering material is 10 times of A sulfur phosphorus concentration, i.e. 0.1mg/mL.The system color of adding 0.01mg/mL A sulfur phosphorus is still navy blue and has slight precipitation; Meanwhile, in the detection architecture of each interpolation 0.1mg/mL glucose, sucrose, maltose, sodium chloride, potassium chloride, magnesium sulfate, calcium chloride and zinc acetate, after reaction, color does not change, and illustrates that these materials fail the activity of acetylcholine esterase inhibition to weaken the concentration of substrate in system.But when adding citric acid in reaction system, reaction color changes, and changes purple into by claret.Occur that the reason of this phenomenon may be because citric acid have impact on the activity of acetylcholinesterase, thus cause concentration of substrate in system higher, caused the gathering of golden nanometer particle.
In sum, have higher selective to material common in general food based on the detection of organic phosphorus pesticide system constructed by golden nanometer particle colorimetric probe method.
Claims (5)
1. the green synthesis method of golden nanometer particle, is characterized in that the green synthesis method of golden nanometer particle carries out in the steps below:
Step one, citrus fruit cleaned and dries, squeeze the juice, then centrifugal, get supernatant, by volume dilute (1 ~ 10) doubly by deionized water, obtain juice solution;
Step 2, at ambient temperature, add juice solution rapidly with after magnetic stirring apparatus vigorous stirring chlorauric acid solution 2min, claret to appear continues to stir 20min and terminates reaction; Namely solution of gold nanoparticles is obtained.
2. the green synthesis method of golden nanometer particle according to claim 1, is characterized in that carrying out with 4000r/min rotating speed in step one.
3. the green synthesis method of golden nanometer particle according to claim 1, is characterized in that citrus fruit described in step one is orange, orange or lemon.
4. the green synthesis method of golden nanometer particle according to claim 2, is characterized in that the mass concentration of chlorauric acid solution described in step 2 is 1% (w/v).
5. the green synthesis method of golden nanometer particle according to claim 1, is characterized in that described in step 2, chlorauric acid solution consumption is identical with the volume of the supernatant measured.
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