CN102962471A - Glucose responsive gold nanoparticle and preparation method and application thereof - Google Patents
Glucose responsive gold nanoparticle and preparation method and application thereof Download PDFInfo
- Publication number
- CN102962471A CN102962471A CN2012104527236A CN201210452723A CN102962471A CN 102962471 A CN102962471 A CN 102962471A CN 2012104527236 A CN2012104527236 A CN 2012104527236A CN 201210452723 A CN201210452723 A CN 201210452723A CN 102962471 A CN102962471 A CN 102962471A
- Authority
- CN
- China
- Prior art keywords
- solution
- acryloyl
- isopropylacrylamide
- nanometer particle
- boric acid
- 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
Links
Images
Landscapes
- Medicinal Preparation (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a glucose responsive gold nanoparticle and a preparation method and an application thereof. The method adopts the reversible addition-fragmentation chain transfer polymerization method to prepare isopropyl acrylamide-acrylyl sulfourea amino phenylboronic acid copolymer that which is modified to the surface of the gold nanoparticle to obtain the gold nanoparticle covered by the copolymer. The gold nanoparticle obtained through the method in disclosed by the invention can generate response with the glucose molecule in a solution; the developing system dispersed by the gold nanoparticle is driven through by the glucose molecule to change the colour of the gold nanoparticle solution at high temperature, so as to realize visual identification and detection for the glucose. The method in disclosed by the invention can be widely used for the field of nanometre bioanalysis.
Description
Technical field
The present invention relates to a kind of glucose responding golden nanometer particle and its preparation method and application, belong to chemistry and material science.
Background technology
The concentration of glucose is the important clinical diagnosis indexs of diabetes in blood and the urine.According to the data of the World Health Organization (WHO), there was the puzzlement that is subject to diabetes above 1.5 hundred million people in the whole world in 2004, and to the year two thousand thirty, this numeral will rise to 3.66 hundred million.Through years of researches, developed multiple glucose detection method.Because existing method mostly realizes based on redox reaction, so the reducing substances that may exist in the body fluid (such as the ascorbic acid in the urine etc.) very likely testing result is produced and disturb.Thereby developing new glucose method for quick still has very important meaning for the treatment of diabetes monitoring.
In recent years, the develop rapidly of nanometer technology is chemistry, the original position of biological information, real-time, the dynamic and highly sensitive approach that provides new that obtains in the life system.If connect specific acceptor at nano-material surface, can cause behind target substance in the medium and the receptor acting that the nano-material surface state changes, and cause material that the signal intensity (such as spectrum, electrochemistry, dispersiveness etc.) that easily detects occurs, can realize target substance is produced identification and sensing.Wherein, golden nanometer particle has obtained studying widely and using because of its unique optical property.As the metal nanoparticle that a class has surface plasma body resonant vibration (SPR) effect, the color of solution of gold nanoparticles can be along with particle dispersion and the degree generation significant change of assembling.The above characteristic of golden nanometer particle, the visual detection technique that has highly sensitive, high selectivity, the characteristics such as quick for exploitation provides good platform.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of glucose responding golden nanometer particle and preparation method thereof for above-mentioned prior art, has realized the half-quantitative detection to glucose molecule in the aqueous solution.
The present invention solves the problems of the technologies described above the technical scheme that adopts: the glucose responding golden nanometer particle is characterized in that including the product that is obtained by following reactions steps:
1) preparation of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer:
With N-isopropylacrylamide, acryloyl ghiourea group aminobenzene boric acid, dithio benzyl benzoate and initator azodiisobutyronitrile in molar ratio 190～170:30～10:2:1 join in the schlenk pipe, adding volume ratio is 1 of 3:1～5:1,4-dioxane/methanol solvate dissolves, adopt freeze-thaw pump round-robin method degassed at least 3 times, reacted 15～25 hours under 60～80 ℃ of oil baths, add chloroform and stop polymerisation, product precipitates with a large amount of n-hexanes, precipitation is dissolved in chloroform, with the n-hexane precipitation, repeat 3～4 times again, the product vacuum drying is spent the night, obtain the light orange powder, room temperature is placed for subsequent use;
2) preparation of the golden nanometer particle of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel:
At first take by weighing the N-isopropylacrylamide of 5～20 mg step 1) gained-acryloyl ghiourea group aminobenzene boric acid copolymer powder, be dissolved in 0.5～2 mL methyl alcohol, the mass body volume concentrations that adds 10～30 μ L is the methanol solution of the sodium borohydride of 5～10 mg/mL, again it is joined in the solution of gold nanoparticles of 30nmol/L natrium citricum parcel of 5～20 mL, 1～5 ℃ was reacted 36～60 hours, with products therefrom Amicon super filter tube purifying, 0.1 M pH 9.0 sodium carbonate buffers washing 3 times, be dissolved at last CBS, 4 ℃ of placements are for subsequent use, namely obtain the glucose responding solution of gold nanoparticles.
Press such scheme, the preparation method of the golden nanometer particle of described natrium citricum parcel is:
1 g gold chloride powder is dissolved in the 100 mL ultra-pure waters, obtain 1% gold chloride liquid storage, 1 mL gold chloride liquid storage is joined in the 100 mL ultra-pure waters, stir and be heated to and boil, add rapidly the 1 mol/L citric acid three sodium solution of 1 mL, solution reddens after a few minutes, continued to add thermal agitation 15 minutes, be cooled to room temperature, 4 ℃ of placements are for subsequent use, obtain the solution of gold nanoparticles of natrium citricum parcel.
Press such scheme, described N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer has the general structure of following formula (I):
Wherein x is that 3～6, y is 20～30, and its molecular weight is 3000～5000.
Press such scheme, preferred x is that 4, y is 22 in described N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer, and its molecular weight is 3500.
The preparation method of described glucose responding golden nanometer particle is characterized in that: include following steps:
1) preparation of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer:
With N-isopropylacrylamide, acryloyl ghiourea group aminobenzene boric acid, dithio benzyl benzoate and initator azodiisobutyronitrile in molar ratio 190～170:30～10:2:1 join in the schlenk pipe, adding volume ratio is 1 of 3:1～5:1,4-dioxane/methanol solvate dissolves, adopt freeze-thaw pump round-robin method degassed at least 3 times, reacted 15～25 hours under 60～80 ℃ of oil baths, add chloroform and stop polymerisation, product precipitates with a large amount of n-hexanes, precipitation is dissolved in chloroform, with the n-hexane precipitation, repeat 3～4 times again, the product vacuum drying is spent the night, obtain the light orange powder, room temperature is placed for subsequent use;
2) preparation of the golden nanometer particle of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel:
At first take by weighing the N-isopropylacrylamide of 5～20 mg step 1) gained-acryloyl ghiourea group aminobenzene boric acid copolymer powder, be dissolved in 0.5～2 mL methyl alcohol, the mass body volume concentrations that adds 10～30 μ L is the methanol solution of the sodium borohydride of 5～10 mg/mL, again it is joined in the solution of gold nanoparticles of 30nmol/L natrium citricum parcel of 5～20 mL, 1～5 ℃ was reacted 36～60 hours, with products therefrom Amicon super filter tube purifying, 0.1 M pH 9.0 sodium carbonate buffers washing 3 times, be dissolved at last CBS, 4 ℃ of placements are for subsequent use, namely obtain the glucose responding solution of gold nanoparticles.
Press such scheme, the preparation method of the golden nanometer particle of described natrium citricum parcel is:
1 g gold chloride powder is dissolved in the 100 mL ultra-pure waters, obtain 1% gold chloride liquid storage, 1 mL gold chloride liquid storage is joined in the 100 mL ultra-pure waters, stir and be heated to and boil, add rapidly the 1 mol/L citric acid three sodium solution of 1 mL, solution reddens after a few minutes, continued to add thermal agitation 15 minutes, be cooled to room temperature, 4 ℃ of placements are for subsequent use, obtain the solution of gold nanoparticles of natrium citricum parcel.
Described glucose responding golden nanometer particle is in the application as the material of the concentration range by visually observing to detect glucose.
The golden nanometer particle of natrium citricum parcel of the present invention is to make by the natrium citricum reducing process in the aqueous solution; The method for preparing the glucose responding golden nanometer particle of the present invention is to adopt above-mentioned N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer to modify the golden nanometer particle of natrium citricum parcel, its surface is wrapped up by copolymer molecule, specifically golden nanometer particle and N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer can be reacted in solvent, sulphur atom in the copolymer is combined with gold atom by coordination, be wrapped in the golden nanometer particle surface, described solvent is the mixed solvent of water and methyl alcohol.
In one embodiment of the invention, N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer is dissolved in methyl alcohol, again with the aqueous solution of golden nanometer particle, gained solution with the super filter tube of molecular cut off (MWCO) 100 KDa at 4000 rcf(RCFs) ultrafiltration 4 times under the condition, each 10 minutes, be dissolved in ultra-pure water, obtain the golden nanometer particle of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel.
The copolymer molecule of the surface parcel of the golden nanometer particle of this N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel can produce response to the glucose molecule in the solution specifically, causes that the solution of gold nanoparticles color changes under the high temperature.For example, in the embodiment of the invention this kind golden nanometer particle is dissolved in the glucose solution of a series of variable concentrations, through the process of hatching of simply heating, the color of the solution can produce variation in various degree.Fig. 2 be the golden nanometer particle (20 nM) of polymer wrapped in containing the sodium carbonate cushioning liquid (CBS) of different glucose through 37 ℃ of ultraviolet-visible spectrogram and pictures after hatching.When not containing glucose molecule in the solution, to assemble through the golden nanometer particle of hatching, solution colour is purple.And when the concentration of glucose in solutions rose gradually, solution colour reddened gradually; When concentration rises to 0.5 mM when above, under solution colour and the room temperature among the blank CBS state of golden nanometer particle identical, also no longer change even concentration of glucose continues to increase.
The golden nanometer particle of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel is based on a kind of special target molecule to the visual response process of glucose and drives that mechanism that particle disperses realizes.The golden nanometer particle of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel is in the state of dispersion at the beginning, and because the temperature response characteristics of surface aggregate thing layer, the golden nanometer particle of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel is hatched lower can generation the gathering at high temperature, follows simultaneously obvious change color.And when having a certain amount of glucose molecule in the solution, because glucose molecule and polymer interact, the formation of hydrogen bond in the polymer and the conformation of polymer have been affected, therefore can't reunite after the golden nanometer particle of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel is hatched through high temperature, solution colour also remains unchanged.
The present invention adopts a kind of semi-quantitative analysis method that the concentration range of glucose in solutions is detected: with 220 μ L, 110 μ L, 55 μ L, 20 μ L, 10 μ L, 5 μ L sample solutions drop to respectively among the CBS of golden nanometer particle that 1 mL contains 20 nM polymer wrappeds, are about to sample and have diluted respectively 5,10,20,50,100,200 times, hatched 5 minutes for 37 ℃, observe solution colour and change.When solution colour has occured in 5,10,20,50,100,200 times of dilutions by red to purple change color, so in the sample content of glucose be respectively 5～10,10-25,25-50,50-100,100 mM.Provide in the table 1 and adopted the present invention to detect the result of glucose content in the urine.The inventive method is expected to be widely used in the nano-bioanalysis field.
Beneficial effect of the present invention is: the golden nanometer particle of polymer wrapped is a kind of process of dominating of disperseing to the response of glucose, the polymeric layer that is testing molecule and particle surface interacts, stoped golden nanometer particle that the spontaneous gathering that the polymer temperature response property causes at high temperature occurs, so that golden nanometer particle continues to keep dispersity.Only need sample to be tested with different volumes join in the solution of gold nanoparticles of polymer wrapped of equal volume, through hatching of short time, it is interval that the variation by solution colour can obtain the concentration of sample glucose.The leading mechanism of this dispersion has been avoided the interference that golden nanometer particle generation non-specific aggregation may cause in the complex environment effectively, is more applicable for the actual sample analysis.
Description of drawings
Fig. 1 is the transmission electron microscope picture of the golden nanometer particle of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel;
Fig. 2 be the golden nanometer particle of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel in containing the CBS of different glucose through 37 ℃ of ultraviolet-visible spectrogram and images after hatching 5 minutes, the concentration of glucose is followed successively by: (1) blank; (2) 0.01 mM; (3) 0.1 mM; (4) 0.5 mM; (5) 1 mM; (6) 5 mM; (7) 10 mM.
The specific embodiment
Following examples further specify content of the present invention, but should not be construed as limitation of the present invention.Without departing from the spirit and substance of the case in the present invention, modification or replacement to the inventive method, step or condition are done all belong to scope of the present invention.If do not specialize, the conventional means that used technological means is well known to those skilled in the art among the embodiment.
This example is modified golden nanometer particle, and is showed that it to the response process of glucose molecule, is elaborated to method by employing N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer:
(1) golden nanometer particle (AuNPs) is synthetic: 1 g gold chloride powder is dissolved in the 100 mL ultra-pure waters, obtains 1% gold chloride liquid storage.1 mL gold chloride liquid storage is joined in the 100 mL ultra-pure waters, stir and be heated to and boil.Add rapidly the citric acid three sodium solution (1 mmol) of 1 mL, solution reddens after a few minutes.Continued the heating stir about 15 minutes, and be cooled to room temperature, 4 ℃ of placements are for subsequent use, obtain the solution of gold nanoparticles of natrium citricum parcel.
(2) acryloyl ghiourea group aminobenzene boric acid is synthetic: take by weighing 0.727 g potassium rhodanide, be dissolved in 15 mL anhydrous propanones, add 0.678 g acryloyl chloride (7.5 mmol), stirring reaction spends the night under the room temperature.With reacting liquid filtering, the extracting yellow supernatant is for subsequent use.Take by weighing 1.0 g 3-aminobenzene borate hydrochlorates (5.77 mmol) and be dissolved in 40 mL acetone/water solvents (v/v 1:1), add 0.484 g sodium acid carbonate (5.77 mmol), stirred 10 minutes, and dropwise added subsequently the yellow supernatant of previous step preparation, stirring reaction is 24 hours under the room temperature.Reactant liquor ethyl acetate extraction 3 times, collected organic layer, anhydrous sodium sulfate drying spends the night.After the filtration solvent is steamed, the crude product purification by silica gel column chromatography that obtains, leacheate are methylene chloride-methanol (15:1), and the product that obtains is white powder, and it is for subsequent use that productive rate is about 50%, 4 ℃ of placement.
(3) N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid Synthesis of copolymer: 6 mL phenyl-magnesium-bromides (0.05 mol) are joined in the 50 mL anhydrous tetrahydro furans, stir, be heated to 40 ℃, slowly add 10 mL carbon disulfide, solution becomes dark-brown.Slowly add subsequently 10 mL toluene bromides, and temperature is risen to 50 ℃, reacted 24 hours.150 mL frozen water are joined in the reactant liquor, with 200 mL ethyl acetate extractions.With the organic layer that obtains respectively water, saturated NaCl solution wash for several times, anhydrous sodium sulfate drying spends the night.After the filtration solvent is steamed, the crude product purification by silica gel column chromatography that obtains, leacheate are carrene-benzinum (1:5), obtain RAFT chain-transferring agent dithio benzyl benzoate (BDTB), are red oily liquids, and productive rate is about 60%.
N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer adopts the RAFT legal system standby.With N-isopropylacrylamide (NIPAAm), acryloyl ghiourea group aminobenzene boric acid (ATPBA), dithio benzyl benzoate (BDTB) and initator azodiisobutyronitrile in molar ratio 170:30:2:1 join in the schlenk pipe, add Isosorbide-5-Nitrae-dioxane/methanol solvate (4:1 volume ratio) dissolving.Adopt freeze-thaw pump round-robin method degassed at least 3 times, reaction is 20 hours under 70 ℃ of oil baths.Add a certain amount of chloroform and stop polymerisation, product precipitates with a large amount of n-hexanes.Precipitation is dissolved in chloroform, and the n-hexane precipitation repeats 3-4 time.The product vacuum drying is spent the night, obtain the light orange powder, room temperature is placed for subsequent use;
Described N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer has the structural formula of following formula (I):
（I）
Wherein x is that 4, y is 22, and its molecular weight is 3500;
(4) preparation of the golden nanometer particle of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel: the golden nanometer particle of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel forms by the ligand exchange legal system is standby.At first take by weighing 10 mg N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer powder, be dissolved in 1 mL methyl alcohol, the methanol solution (10 mg/mL) that adds 20 μ L sodium borohydrides, it is joined in the solution of gold nanoparticles of 10 mL 30nmol/L natrium citricums parcel, 4 ℃ were reacted 48 hours again.With product Amicon super filter tube (MWCO:100 kDa) purifying, 0.1 M pH 9.0 sodium carbonate buffers (CBS) are washed 3 times, be dissolved at last CBS, 4 ℃ of placements are for subsequent use, obtain the solution of gold nanoparticles (being the glucose responding golden nanometer particle) of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel.As shown in Figure 1, can find out that the golden nanometer particle of copolymer parcel is better dispersed in solution, can be clear that the golden nanometer particle surface wrapped up one layer of polymeric simultaneously.
(5) golden nanometer particle of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel is to the visual identification of glucose: the solution of gold nanoparticles of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel is joined in the sodium carbonate buffer (CBS) that contains glucose molecule, hatch after 5 minutes for 37 ℃ and observe.As shown in Figure 2, when not containing glucose molecule in the solution, assemble through the golden nanometer particle of hatching, the surface plasma resonance peak appears at 541 nm places, and the peak type is wider, and solution colour is purple.And when the concentration of glucose in solutions rose gradually, the half-peak breadth at golden nanometer particle SPR peak narrowed down gradually, and blue shift also occurs in the peak position, and solution colour reddens gradually; When concentration rises to 0.5 mM when above, the position at solution colour and SPR peak and shape with room temperature under among the blank CBS state of golden nanometer particle identical, do not changing even concentration of glucose continues to increase yet.
(6) with 220 μ L, 110 μ L, 55 μ L, 20 μ L, 10 μ L, 5 μ L urine samples drop to respectively among the CBS of golden nanometer particle that 1 mL contains 20 nM polymer wrappeds, be about to urine sample and diluted respectively 5,10,20,50,100,200 times, hatched 5 minutes for 37 ℃, observe solution colour, determine the concentration range of glucose in the urine, when solution colour 5,10,20,50,100, occured by red change color to purple in 200 times of dilutions, the content of glucose is respectively 5-10 in the sample so, 10-25,25-50,50-100,100 mM.
Table 1 is the testing result of concentration of glucose in the urine.All urine specimens all come from hospital; The glucose in urine Test paper is ten test paper of Siemens Multistix 10 SG urine.
This example is modified golden nanometer particle, and is showed that it to the response process of glucose molecule, is elaborated to method by employing N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer:
(1) golden nanometer particle (AuNPs) is synthetic: 1 g gold chloride powder is dissolved in the 100 mL ultra-pure waters, obtains 1% gold chloride liquid storage.1 mL gold chloride liquid storage is joined in the 100 mL ultra-pure waters, stir and be heated to and boil.Add rapidly the citric acid three sodium solution (1 mmol) of 1 mL, solution reddens after a few minutes.Continued the heating stir about 15 minutes, and be cooled to room temperature, 4 ℃ of placements are for subsequent use, obtain the solution of gold nanoparticles of natrium citricum parcel.
(2) acryloyl ghiourea group aminobenzene boric acid is synthetic: take by weighing 0.727 g potassium rhodanide, be dissolved in 15 mL anhydrous propanones, add 0.678 g acryloyl chloride (7.5 mmol), stirring reaction spends the night under the room temperature.With reacting liquid filtering, the extracting yellow supernatant is for subsequent use.Take by weighing 1.0 g 3-aminobenzene borate hydrochlorates (5.77 mmol) and be dissolved in 40 mL acetone/water solvents (v/v 1:1), add 0.484 g sodium acid carbonate (5.77 mmol), stirred 10 minutes, and dropwise added subsequently the yellow supernatant of previous step preparation, stirring reaction is 24 hours under the room temperature.Reactant liquor ethyl acetate extraction 3 times, collected organic layer, anhydrous sodium sulfate drying spends the night.After the filtration solvent is steamed, the crude product purification by silica gel column chromatography that obtains, leacheate are methylene chloride-methanol (15:1), and the product that obtains is white powder, and it is for subsequent use that productive rate is about 50%, 4 ℃ of placement.
(3) N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid Synthesis of copolymer: 6 mL phenyl-magnesium-bromides (0.05 mol) are joined in the 50 mL anhydrous tetrahydro furans, stir, be heated to 40 ℃, slowly add 10 mL carbon disulfide, solution becomes dark-brown.Slowly add subsequently 10 mL toluene bromides, and temperature is risen to 50 ℃, reacted 24 hours.150 mL frozen water are joined in the reactant liquor, with 200 mL ethyl acetate extractions.With the organic layer that obtains respectively water, saturated NaCl solution wash for several times, anhydrous sodium sulfate drying spends the night.After the filtration solvent is steamed, the crude product purification by silica gel column chromatography that obtains, leacheate are carrene-benzinum (1:5), obtain RAFT chain-transferring agent dithio benzyl benzoate (BDTB), are red oily liquids, and productive rate is about 60%.
N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer adopts the RAFT legal system standby.With N-isopropylacrylamide (NIPAAm), acryloyl ghiourea group aminobenzene boric acid (ATPBA), dithio benzyl benzoate (BDTB) and initator azodiisobutyronitrile in molar ratio 180:20:2:1 join in the schlenk pipe, add Isosorbide-5-Nitrae-dioxane/methanol solvate (3:1 volume ratio) dissolving.Adopt freeze-thaw pump round-robin method degassed at least 3 times, reaction is 25 hours under 65 ℃ of oil baths.Add a certain amount of chloroform and stop polymerisation, product precipitates with a large amount of n-hexanes.Precipitation is dissolved in chloroform, and the n-hexane precipitation repeats 3-4 time.The product vacuum drying is spent the night, obtain the light orange powder, room temperature is placed for subsequent use.
(4) preparation of the golden nanometer particle of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel: the golden nanometer particle of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel forms by the ligand exchange legal system is standby.At first take by weighing 10 mg N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer powder, be dissolved in 1.5 mL methyl alcohol, the methanol solution (10 mg/mL) that adds 30 μ L sodium borohydrides, again it is joined in the solution of gold nanoparticles of 30nmol/L natrium citricum parcel of 10 mL 4 ℃ of reactions 60 hours.With product Amicon super filter tube (MWCO:100 kDa) purifying, 0.1 M pH 9.0 sodium carbonate buffers (CBS) are washed 3 times, be dissolved at last CBS, 4 ℃ of placements are for subsequent use, obtain the solution of gold nanoparticles of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel.
(1) golden nanometer particle (AuNPs) is synthetic: 1 g gold chloride powder is dissolved in the 100 mL ultra-pure waters, obtains 1% gold chloride liquid storage.1 mL gold chloride liquid storage is joined in the 100 mL ultra-pure waters, stir and be heated to and boil.Add rapidly the citric acid three sodium solution (1 mmol) of 1 mL, solution reddens after a few minutes.Continued the heating stir about 15 minutes, and be cooled to room temperature, 4 ℃ of placements are for subsequent use, obtain the solution of gold nanoparticles of natrium citricum parcel.
(2) acryloyl ghiourea group aminobenzene boric acid is synthetic: take by weighing 0.727 g potassium rhodanide, be dissolved in 15 mL anhydrous propanones, add 0.678 g acryloyl chloride (7.5 mmol), stirring reaction spends the night under the room temperature.With reacting liquid filtering, the extracting yellow supernatant is for subsequent use.Take by weighing 1.0 g 3-aminobenzene borate hydrochlorates (5.77 mmol) and be dissolved in 40 mL acetone/water solvents (v/v 1:1), add 0.484 g sodium acid carbonate (5.77 mmol), stirred 10 minutes, and dropwise added subsequently the yellow supernatant of previous step preparation, stirring reaction is 24 hours under the room temperature.Reactant liquor ethyl acetate extraction 3 times, collected organic layer, anhydrous sodium sulfate drying spends the night.After the filtration solvent is steamed, the crude product purification by silica gel column chromatography that obtains, leacheate are methylene chloride-methanol (15:1), and the product that obtains is white powder, and productive rate is about 50%.4 ℃ of placements are for subsequent use.
(3) N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid Synthesis of copolymer: 6 mL phenyl-magnesium-bromides (0.05 mol) are joined in the 50 mL anhydrous tetrahydro furans, stir, be heated to 40 ℃, slowly add 10 mL carbon disulfide, solution becomes dark-brown.Slowly add subsequently 10 mL toluene bromides, and temperature is risen to 50 ℃, reacted 24 hours.150 mL frozen water are joined in the reactant liquor, with 200 mL ethyl acetate extractions.With the organic layer that obtains respectively water, saturated NaCl solution wash for several times, anhydrous sodium sulfate drying spends the night.After the filtration solvent is steamed, the crude product purification by silica gel column chromatography that obtains, leacheate are carrene-benzinum (1:5), obtain RAFT chain-transferring agent dithio benzyl benzoate (BDTB), are red oily liquids, and productive rate is about 60%.
N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer adopts the RAFT legal system standby.With N-isopropylacrylamide (NIPAAm), acryloyl ghiourea group aminobenzene boric acid (ATPBA), dithio benzyl benzoate (BDTB) and initator azodiisobutyronitrile in molar ratio 190:10:2:1 join in the schlenk pipe, add Isosorbide-5-Nitrae-dioxane/methanol solvate (5:1 volume ratio) dissolving.Adopt freeze-thaw pump round-robin method degassed at least 3 times, reaction is 15 hours under 80 ℃ of oil baths.Add a certain amount of chloroform and stop polymerisation, product precipitates with a large amount of n-hexanes.Precipitation is dissolved in chloroform, and the n-hexane precipitation repeats 3-4 time.The product vacuum drying is spent the night, obtain the light orange powder, room temperature is placed for subsequent use.
(4) preparation of the golden nanometer particle of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel: the golden nanometer particle of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel forms by the ligand exchange legal system is standby.At first take by weighing 10 mg N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer powder, be dissolved in 0.5 mL methyl alcohol, the methanol solution (10 mg/mL) that adds 10 μ L sodium borohydrides, it is joined in the solution of gold nanoparticles of 5 mL 30nmol/L natrium citricums parcel, 4 ℃ were reacted 36 hours again.With product Amicon super filter tube (MWCO:100 kDa) purifying, 0.1 M pH 9.0 sodium carbonate buffers (CBS) are washed 3 times, be dissolved at last CBS, 4 ℃ of placements are for subsequent use, obtain the solution of gold nanoparticles of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel.
Claims (7)
1. glucose responding golden nanometer particle is characterized in that including the product that is obtained by following reactions steps:
1) preparation of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer:
With N-isopropylacrylamide, acryloyl ghiourea group aminobenzene boric acid, dithio benzyl benzoate and initator azodiisobutyronitrile in molar ratio 190～170:30～10:2:1 join in the schlenk pipe, adding volume ratio is 1 of 3:1～5:1,4-dioxane/methanol solvate dissolves, adopt freeze-thaw pump round-robin method degassed at least 3 times, reacted 15～25 hours under 60～80 ℃ of oil baths, add chloroform and stop polymerisation, product precipitates with a large amount of n-hexanes, precipitation is dissolved in chloroform, with the n-hexane precipitation, repeat 3～4 times again, the product vacuum drying is spent the night, obtain the light orange powder, room temperature is placed for subsequent use;
2) preparation of the golden nanometer particle of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel:
At first take by weighing the N-isopropylacrylamide of 5～20 mg step 1) gained-acryloyl ghiourea group aminobenzene boric acid copolymer powder, be dissolved in 0.5～2 mL methyl alcohol, the mass body volume concentrations that adds 10～30 μ L is the methanol solution of the sodium borohydride of 5～10 mg/mL, again it is joined in the solution of gold nanoparticles of 30nmol/L natrium citricum parcel of 5～20 mL, 1～5 ℃ was reacted 36～60 hours, with products therefrom Amicon super filter tube purifying, 0.1 M pH 9.0 sodium carbonate buffers washing 3 times, be dissolved at last CBS, 4 ℃ of placements are for subsequent use, namely obtain the glucose responding solution of gold nanoparticles.
2. by glucose responding golden nanometer particle claimed in claim 1, it is characterized in that: the preparation method of the golden nanometer particle of described natrium citricum parcel is:
1 g gold chloride powder is dissolved in the 100 mL ultra-pure waters, obtain 1% gold chloride liquid storage, 1 mL gold chloride liquid storage is joined in the 100 mL ultra-pure waters, stir and be heated to and boil, add rapidly the 1 mol/L citric acid three sodium solution of 1 mL, solution reddens after a few minutes, continued to add thermal agitation 15 minutes, be cooled to room temperature, 4 ℃ of placements are for subsequent use, obtain the solution of gold nanoparticles of natrium citricum parcel.
3. by glucose responding golden nanometer particle claimed in claim 1, it is characterized in that: described N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer has the general structure of following formula (I):
Wherein x is that 3～6, y is 20～30, and its molecular weight is 3000～5000.
4. by glucose responding golden nanometer particle claimed in claim 3, it is characterized in that: x is that 4, y is 22 in described N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer, and its molecular weight is 3500.
5. the preparation method of glucose responding golden nanometer particle claimed in claim 1 is characterized in that: include following steps:
1) preparation of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer:
With N-isopropylacrylamide, acryloyl ghiourea group aminobenzene boric acid, dithio benzyl benzoate and initator azodiisobutyronitrile in molar ratio 190～170:30～10:2:1 join in the schlenk pipe, adding volume ratio is 1 of 3:1～5:1,4-dioxane/methanol solvate dissolves, adopt freeze-thaw pump round-robin method degassed at least 3 times, reacted 15～25 hours under 60～80 ℃ of oil baths, add chloroform and stop polymerisation, product precipitates with a large amount of n-hexanes, precipitation is dissolved in chloroform, with the n-hexane precipitation, repeat 3～4 times again, the product vacuum drying is spent the night, obtain the light orange powder, room temperature is placed for subsequent use;
2) preparation of the golden nanometer particle of N-isopropylacrylamide-acryloyl ghiourea group aminobenzene boric acid copolymer parcel:
At first take by weighing the N-isopropylacrylamide of 5～20 mg step 1) gained-acryloyl ghiourea group aminobenzene boric acid copolymer powder, be dissolved in 0.5～2 mL methyl alcohol, the mass body volume concentrations that adds 10～30 μ L is the methanol solution of the sodium borohydride of 5～10 mg/mL, again it is joined in the solution of gold nanoparticles of 30nmol/L natrium citricum parcel of 5～20 mL, 1～5 ℃ was reacted 36～60 hours, with products therefrom Amicon super filter tube purifying, 0.1 M pH 9.0 sodium carbonate buffers washing 3 times, be dissolved at last CBS, 4 ℃ of placements are for subsequent use, namely obtain the glucose responding solution of gold nanoparticles.
6. by the preparation method of glucose responding golden nanometer particle claimed in claim 5, it is characterized in that: the preparation method of the golden nanometer particle of described natrium citricum parcel is:
1 g gold chloride powder is dissolved in the 100 mL ultra-pure waters, obtain 1% gold chloride liquid storage, 1 mL gold chloride liquid storage is joined in the 100 mL ultra-pure waters, stir and be heated to and boil, add rapidly the 1 mol/L citric acid three sodium solution of 1 mL, solution reddens after a few minutes, continued to add thermal agitation 15 minutes, be cooled to room temperature, 4 ℃ of placements are for subsequent use, obtain the solution of gold nanoparticles of natrium citricum parcel.
7. glucose responding golden nanometer particle claimed in claim 1 is in the application as the material of the concentration range by visually observing to detect glucose.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210452723.6A CN102962471B (en) | 2012-11-13 | 2012-11-13 | Glucose responsive gold nanoparticle and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210452723.6A CN102962471B (en) | 2012-11-13 | 2012-11-13 | Glucose responsive gold nanoparticle and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102962471A true CN102962471A (en) | 2013-03-13 |
| CN102962471B CN102962471B (en) | 2014-10-01 |
Family
ID=47793064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210452723.6A Expired - Fee Related CN102962471B (en) | 2012-11-13 | 2012-11-13 | Glucose responsive gold nanoparticle and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102962471B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448333A (en) * | 2014-12-11 | 2015-03-25 | 湖南科技大学 | Preparation method and product of dual-sensitive polymer hybrid nanoparticle |
| CN104625045A (en) * | 2015-01-26 | 2015-05-20 | 华东师范大学 | Ultra-small gold nanometer particle and synthetic method thereof |
| CN104826119A (en) * | 2015-04-16 | 2015-08-12 | 厦门大学 | Preparation method of pH and glucose dual-sensitive mesoporous silica@polymer drug carrier |
| CN105136784A (en) * | 2015-07-27 | 2015-12-09 | 济南大学 | Preparation method and application of saccharide sensor based on colorimetric analysis |
| CN106770867A (en) * | 2016-11-18 | 2017-05-31 | 武汉理工大学 | A kind of method for being enriched with detection phosphorylated protein |
| CN108489869A (en) * | 2018-04-10 | 2018-09-04 | 吉林工程技术师范学院 | A kind of kit and its application changing detection glucose in urine exception based on contact angle |
| CN109622985A (en) * | 2018-12-11 | 2019-04-16 | 有研亿金新材料有限公司 | A kind of preparation method of high decentrality submicron grade bronze |
| CN111658668A (en) * | 2019-03-07 | 2020-09-15 | 国家纳米科学中心 | Functional antibacterial combined medicine and application |
| CN115351288A (en) * | 2022-08-23 | 2022-11-18 | 西北工业大学 | Gold nanoflower and preparation method and application thereof |
| CN115870494A (en) * | 2022-10-20 | 2023-03-31 | 武汉理工大学 | Pentenoic acid-isopropyl acrylamide copolymer modified ultra-small gold nano material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101832937A (en) * | 2010-04-23 | 2010-09-15 | 中国科学院上海应用物理研究所 | Method for detecting glucose based on nanometer materials |
| CN102070756A (en) * | 2010-12-10 | 2011-05-25 | 北京化工大学 | Sugar-responsive medicament delivery material and preparation method thereof |
| CN102565162A (en) * | 2012-01-30 | 2012-07-11 | 石谨 | Biological nanometer material sensor electrode and manufacturing method and using method thereof |
-
2012
- 2012-11-13 CN CN201210452723.6A patent/CN102962471B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101832937A (en) * | 2010-04-23 | 2010-09-15 | 中国科学院上海应用物理研究所 | Method for detecting glucose based on nanometer materials |
| CN102070756A (en) * | 2010-12-10 | 2011-05-25 | 北京化工大学 | Sugar-responsive medicament delivery material and preparation method thereof |
| CN102565162A (en) * | 2012-01-30 | 2012-07-11 | 石谨 | Biological nanometer material sensor electrode and manufacturing method and using method thereof |
Non-Patent Citations (4)
| Title |
|---|
| MINGXI ZHANG ET AL: "Dual-Responsive Gold Nanoparticles for Colorimetric Recognition and Testing of Carbohydrates with a Dispersion-Dominated Chromogenic Process", 《ADVANCED MATERIALS》, vol. 25, no. 5, 6 February 2013 (2013-02-06), pages 749 - 754 * |
| TAOLEI SUN ET AL: "Biomimetic Smart Interface Materials for Biological Applications", 《ADVANDED HEALTHCARE MATERIALS》, vol. 23, no. 12, 23 March 2011 (2011-03-23), pages 57 - 77 * |
| TODD HOARE ET AL: "Engineering glucose swelling responses in poly (N-isopropylacrylamide)-based microgels", 《MACROMOLECULES》, vol. 40, no. 3, 1 March 2007 (2007-03-01), pages 670 - 678 * |
| 赵英曲等: "对巯基苯硼酸/纳米金修饰玻碳电极用于葡萄糖的识别", 《分析测试学报》, vol. 28, no. 3, 31 March 2009 (2009-03-31), pages 301 - 305 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448333A (en) * | 2014-12-11 | 2015-03-25 | 湖南科技大学 | Preparation method and product of dual-sensitive polymer hybrid nanoparticle |
| CN104625045A (en) * | 2015-01-26 | 2015-05-20 | 华东师范大学 | Ultra-small gold nanometer particle and synthetic method thereof |
| CN104826119B (en) * | 2015-04-16 | 2018-04-24 | 厦门大学 | The preparation of the mesoporous silicon oxide@polymer drug carriers of pH and glucose doubling sensitivity |
| CN104826119A (en) * | 2015-04-16 | 2015-08-12 | 厦门大学 | Preparation method of pH and glucose dual-sensitive mesoporous silica@polymer drug carrier |
| CN105136784A (en) * | 2015-07-27 | 2015-12-09 | 济南大学 | Preparation method and application of saccharide sensor based on colorimetric analysis |
| CN105136784B (en) * | 2015-07-27 | 2016-06-22 | 济南大学 | The preparation method of a kind of saccharide sensor device based on colorimetric analysis and application |
| CN106770867A (en) * | 2016-11-18 | 2017-05-31 | 武汉理工大学 | A kind of method for being enriched with detection phosphorylated protein |
| CN108489869A (en) * | 2018-04-10 | 2018-09-04 | 吉林工程技术师范学院 | A kind of kit and its application changing detection glucose in urine exception based on contact angle |
| CN108489869B (en) * | 2018-04-10 | 2021-07-27 | 吉林工程技术师范学院 | Kit for detecting urine glucose abnormality based on contact angle change and application thereof |
| CN109622985A (en) * | 2018-12-11 | 2019-04-16 | 有研亿金新材料有限公司 | A kind of preparation method of high decentrality submicron grade bronze |
| CN111658668A (en) * | 2019-03-07 | 2020-09-15 | 国家纳米科学中心 | Functional antibacterial combined medicine and application |
| CN115351288A (en) * | 2022-08-23 | 2022-11-18 | 西北工业大学 | Gold nanoflower and preparation method and application thereof |
| CN115351288B (en) * | 2022-08-23 | 2023-06-23 | 西北工业大学 | Gold nanoflowers and preparation method and application thereof |
| CN115870494A (en) * | 2022-10-20 | 2023-03-31 | 武汉理工大学 | Pentenoic acid-isopropyl acrylamide copolymer modified ultra-small gold nano material and preparation method thereof |
| CN115870494B (en) * | 2022-10-20 | 2024-05-28 | 武汉理工大学 | Pentenoic acid-isopropyl acrylamide copolymer modified ultra-small gold nano material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102962471B (en) | 2014-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102962471B (en) | Glucose responsive gold nanoparticle and preparation method and application thereof | |
| Das et al. | Stimuli-responsive discriminative detection of Cu2+ and Hg2+ with concurrent sensing of S2-from aqueous medium and bio-fluids by CN fused azophenine functionalized “smart” hydrogel assay@ A potential biomarker sensor for Wilson’s disease | |
| US8058075B2 (en) | Molecular fluorescence sensor for highly sensitive and selective detection of mercury | |
| Zheng et al. | An enzyme-free fluorescent sensing platform for the detection of uric acid in human urine | |
| CN110372829B (en) | Preparation and application of polymer gel fluorescent probe based on azo reduction response | |
| CN110240683A (en) | A kind of covalent organic frame material and preparation method thereof and the application in fluorescent optical sensor | |
| CN112209871B (en) | Zinc ion fluorescent probe based on tetraphenylethylene and preparation method and application thereof | |
| Liu et al. | Enhancing detection sensitivity of responsive microgel-based Cu (II) chemosensors via thermo-induced volume phase transitions | |
| Rasheed et al. | Rhodol assisted alternating copolymer based chromogenic vesicles for the aqueous detection and quantification of hydrazine via switch-on strategy | |
| Aziz et al. | Design of a highly sensitive and selective bulk optode based on fluorescence enhancement of N, N′-bis-(1-hydroxyphenylimine) 2, 2′-pyridil Schiff base: Monitoring of zinc (II) ion in real samples and DFT calculation | |
| CN107245334A (en) | A kind of water soluble polymer fluoresceins fluorescence probe for detecting mercury ion and preparation method thereof | |
| Huo et al. | Multistimuli-responsive pyrene-based lanthanide (III)-MOF construction and applied as dual-function fluorescent chemosensors for trace water and vitamins molecules | |
| CN102702242A (en) | Preparation and application of novel phenazine imidazo phenylboronic acid fluorescence sugar probe | |
| CN108587613A (en) | A kind of preparation method of butyl thiosemicarbazide modified carbon quantum dot fluorescence probe and its application in Selective recognition copper ion | |
| Yan et al. | A novel hydrolytically stable fluorescent Cd (II) coordination polymer showing solvent-dependent multi-responsive fluorescence sensing to pH and some metal ions | |
| Zheng et al. | High porosity fluorescent aerogel with new molecular probes for formaldehyde gas sensors | |
| CN107033331A (en) | A kind of fluorescence conjugated macromolecule of side-chain amino group protonation, preparation method and applications | |
| Li et al. | Rational design of a functionalized metal–organic framework for ratiometric fluorimetric sensing of Hg 2+ in environmental water | |
| CN105085340B (en) | Diphenylethene group dual cyano benzene two-photon fluorescence probe for detecting and displaying intracellular Hg ion | |
| CN104946237B (en) | Palladium ion fluorescent probe compound and application thereof | |
| CN109913206A (en) | A kind of RNA fluorescence probe and its preparation method and application | |
| CN103254371B (en) | Synthetic method of amphiphilic block polymer with near-infrared fluorescence characteristic | |
| CN109369569A (en) | The fluorescence probe and its preparation method and application of one kind detection pyroracemic aldehyde | |
| KR101494542B1 (en) | Gloucose sensor | |
| Fu et al. | Sensitive detection of quorum signaling molecules (N-acyl homoserine lactones) in activated sludge based on surface molecularly imprinted polymers on CQDs@ MIL-101 |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141001 Termination date: 20151113 |
|
| EXPY | Termination of patent right or utility model |