CN105548153B - Gold nanoparticle Visual retrieval glucose sensor and its preparation method and application - Google Patents
Gold nanoparticle Visual retrieval glucose sensor and its preparation method and application Download PDFInfo
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000010931 gold Substances 0.000 title claims abstract description 74
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 74
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims abstract description 62
- 239000008103 glucose Substances 0.000 title claims abstract description 62
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 48
- 230000000007 visual effect Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000001514 detection method Methods 0.000 claims abstract description 25
- XIPRTRJDLZVSHO-UHFFFAOYSA-N aminooxy(phenoxy)borinic acid Chemical compound NOB(O)OC1=CC=CC=C1 XIPRTRJDLZVSHO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000009881 electrostatic interaction Effects 0.000 claims abstract description 8
- 239000001509 sodium citrate Substances 0.000 claims abstract description 8
- UTHULKKJYXJZLV-UHFFFAOYSA-N (3-aminophenoxy)boronic acid Chemical compound NC1=CC=CC(OB(O)O)=C1 UTHULKKJYXJZLV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 7
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 7
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims abstract description 6
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000009754 Vitis X bourquina Nutrition 0.000 claims 1
- 235000012333 Vitis X labruscana Nutrition 0.000 claims 1
- 240000006365 Vitis vinifera Species 0.000 claims 1
- 235000014787 Vitis vinifera Nutrition 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 14
- 235000010323 ascorbic acid Nutrition 0.000 description 7
- 229960005070 ascorbic acid Drugs 0.000 description 7
- 239000011668 ascorbic acid Substances 0.000 description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 7
- 235000010338 boric acid Nutrition 0.000 description 7
- 239000004327 boric acid Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 150000002440 hydroxy compounds Chemical group 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002772 monosaccharides Chemical class 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 108010015776 Glucose oxidase Proteins 0.000 description 2
- 239000004366 Glucose oxidase Substances 0.000 description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 229940116332 glucose oxidase Drugs 0.000 description 2
- 235000019420 glucose oxidase Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 210000002700 urine Anatomy 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical class NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 201000003883 Cystic fibrosis Diseases 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- -1 D-sorbite monosaccharide Chemical class 0.000 description 1
- 108020004414 DNA Proteins 0.000 description 1
- 238000002965 ELISA Methods 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229910004042 HAuCl4 Inorganic materials 0.000 description 1
- 235000013878 L-cysteine Nutrition 0.000 description 1
- 239000004201 L-cysteine Substances 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JNFRNXKCODJPMC-UHFFFAOYSA-N aniline;boric acid Chemical compound OB(O)O.NC1=CC=CC=C1 JNFRNXKCODJPMC-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 210000001175 cerebrospinal fluid Anatomy 0.000 description 1
- 229940126678 chinese medicines Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical class Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 208000007278 renal glycosuria Diseases 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 210000004881 tumor cell Anatomy 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Biological Materials (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a kind of gold nanoparticle Visual retrieval glucose sensor and its preparation method and application, which includes：1) gold chloride and trisodium citrate in solvent are subjected to haptoreaction and gold size solution is made；2) pH of gold size solution is adjusted to 6.0-7.5,3- amino phenyl boric acid (APBA) and amino-terminated poly-N-isopropyl acrylamide (PNIPAM-NH is then added2) electrostatic interaction is carried out so that gold nanoparticle Visual retrieval glucose sensor is made.The sensor has good sensitivity, selective and anti-ion interference ability to the detection of glucose, while preparation method is simple to operation, testing result bore hole is readable.
Description
Technical field
The present invention relates to visible sensors, and in particular, to a kind of gold nanoparticle Visual retrieval glucose sensing
Device and its preparation method and application.
Background technology
Gold size solution, that is, solution of gold nanoparticles (AuNPs).Gold nanoparticle has very high extinction coefficient, wherein
The extinction coefficient of 13nm gold nanoparticles is up to 2.7 × 108Mol/ (Lcm), 1000 times higher than general dye molecule or more,
According to Beer-Lambert laws it is found that the attainable detection limit of gold nanoparticle institute is far below dye molecule.On the other hand, by
Different color changes is had under different conditions in gold nanoparticle system, therefore occupies important ground in Visual retrieval
Position.Visual retrieval mechanism based on gold nanoparticle is：Red is presented in monodisperse gold nanometer particle in the solution, when addition quilt
When detectable substance, gold nanoparticle is assembled, and to make interparticle plasmon coupling change, absorption peak occurs red
It moves, the color of solution becomes purple or blue from red.
For gold nanoparticle other than with above-mentioned optical characteristics, it is also Jenner's grain of rice that surface, which is easy to be chemically modified,
Extensive use of the son in analysis detects provides convenient condition, for example, gold nanoparticle surface can by modify small molecule,
Protein, polypeptide, DNA etc. realize to the specific detections of different target substances, including small molecule, heavy metal ion, protein,
Nucleic acid, tumour cell and pathogen etc..Visible detection method based on gold nanoparticle does not depend on any large-scale instrument, solution
Color change can be used as read output signal, and signal detects speed, and material requested cost is more cheap, be particularly suitable for fast
Speed detection, Site Detection need condition for peace to fall behind the region for not having large-scale instrument relatively.
Glucose is a kind of most wide and mostly important monosaccharide of distributed in nature, contains five hydroxyls, an aldehyde in structure
Base, the property with polynary alcohols and aldehydes.Glucose is the energy of generally existing in organism most basic substance and bioprocess
Aliment, but many studies have shown that, renal glucosuria, cystic fibrosis, diabetes etc. are all related with glucose conveying obstacle.
Therefore the quick and precisely detection of glucose is very important.There are many be based on gold nanoparticle Visual retrieval glucose at present
Method.Such as document " Radhakumary C, Sreenivasan K.Naked eye detection of glucose in
urine using glucose oxidase immobilized gold nanoparticles[J].Analytical
chemistry,2011,83(7):2829-2833. " reports：Using carbodiimides, glucose oxidase is modified in gold
The surface of nano-particle is added glucose, gold nanoparticle is made to assemble, when the content of glucose is more than 100mg/L, gold nano
The color of particle solution becomes blue.Also such as " Jiang Y, Zhao H, Lin Y, et al.Colorimetric
detection of glucose in rat brain using gold nanoparticles[J].Angewandte
Chemie,2010,122(28):4910-4914. " reports：It, can be with using the optical property and cascade reaction of gold nanoparticle
The method for building glucose in a kind of fast and convenient Visual retrieval cerebrospinal fluid.It can be occurred using boric acid and adjacent hydroxy compounds
The sensor that boric acid and its derivative are used to detect glucose as recognition component is had certain grind by covalently bound characteristic
Study carefully basis.Such as " Bi X, Liu Z.Facile preparation of glycoprotein-imprinted 96-well again
microplates for enzyme-linked immunosorbent assay by boronate affinity-based
oriented surface imprinting[J].Analytical chemistry,2013,86(1):959-966. " is reported
's：Using 4- aminobenzene boric acid modified graphenes, increase the detection signal to monosaccharide substance, significant effect.Also such as " Ma, Y
and Yang,X,One saccharide sensor based on the complex of the boronic acid and
themonosaccharide using electrochemical impedance spectroscopy[J].Journal of
Electroanalytical Chemistry,2005,580:348-352. " report：In acid condition, will have higher
3- amino phenyl boric acid (APBA) electropolymerization of electron transmission efficiency obtains poly- amino phenyl boric acid (PABA) film to gold electrode surfaces.
PABA films can the different monosaccharide of covalent bond, the different degrees of change of the different initiation film dielectric property of sugared type and concentration.
Four kinds of glucose, fructose, mannitol, D-sorbite monosaccharide are can recognize that in conjunction with AC impedance (EIS), and with good linear
Relationship, high sensitivity, the range of linearity are wider.Last such as " Li Y P, Jiang L, Zhang T, et al.Colorimetric
detection of glucose using a boronic acid derivative receptor attached to
unmodified AuNPs[J].Chinese Chemical Letters,2014,25(1):77-79. " report：By Jenner
The visualization sensing of rice corpuscles is combined with the affinity interaction of boric acid, is realized and is detected to the highly selective of glucose, rapid sensitive
Also there is relevant report, boronic acid derivatives are modified to naked gold nanoparticle surface merely, a kind of colorimetric sensing are prepared, respectively in acid
Property and alkaline condition under quantitative detection is carried out to glucose.
Covalently bound characteristic can occur in above-mentioned detection method or using boric acid and adjacent hydroxy compounds, by boron
Acid and its derivative are used to detect the sensor of glucose as recognition component.It is sensitive in order to further increase detection
The combination of gold nanoparticle and boric acid and adjacent hydroxy compounds is detected glucose by degree.However since gold nanoparticle is to receive
Meter level material, the problem of being inevitably faced with reunion, the especially excessively high salt of ion concentration present in detection environment
When solution, agglomeration is apparent, severe jamming testing result.
Invention content
The object of the present invention is to provide a kind of gold nanoparticle Visual retrieval glucose sensor and preparation method thereof and
Using the sensor has good sensitivity, selective and anti-ion interference ability, while the side of preparation to the detection of glucose
Method is simple to operation, testing result bore hole is readable.
To achieve the goals above, the present invention provides a kind of systems of gold nanoparticle Visual retrieval glucose sensor
Preparation Method, which is characterized in that including
1) gold chloride and trisodium citrate in solvent are subjected to haptoreaction and gold size solution is made；
2) pH of gold size solution is adjusted to 6.0-7.5,3- amino phenyl boric acid (APBA) and amino-terminated is then added
Poly-N-isopropyl acrylamide (PNIPAM-NH2) electrostatic interaction is carried out so that gold nanoparticle Visual retrieval glucose biography is made
Sensor.
The present invention also provides a kind of gold nanoparticle Visual retrieval glucose sensor, which passes through above-mentioned
Method is prepared.
Invention further provides a kind of above-mentioned gold nanoparticle Visual retrieval glucose sensors to examine in glucose
Application in survey.
Through the above technical solutions, the present invention directly synthesizes particle diameter distribution 13nm's or so using reduction of sodium citrate method
Gold size solution, gold nanoparticle surface prepared by this method is dispersed with excessive citrate ion, negatively charged, and effect is
On the one hand the Van der Waals force between gold nanoparticle is offset by electrostatic repulsion, to ensure that gold nanoparticle dispersion is equal
It is even, be not easy to reunite；On the other hand, being can be with amino-terminated poly-N-isopropyl acrylamide (PNIPAM-NH2) and 3- aminobenzenes
Electrostatic interaction occurs for the amino group in boric acid (APBA), and successfully gold nanoparticle table is arrived in modification to two kinds of compounds to make
Face.Wherein, the recognition component for functioning as sensor of 3- amino phenyl boric acid goes selective binding to contain using its boric acid base group
There is the glucose of adjacent hydroxyl group, realizes highly sensitive, the highly selective detection to glucose.Amino-terminated poly-N-isopropyl third
Acrylamide is a kind of chain-like macromolecule compound, and at 25 DEG C, a kind of extended position is presented in it so that solution keeps hydrophily,
Can stablize gold nanoparticle in the higher salting liquid of ion concentration not reunite, improve the sensor resist from
Sub- interference performance provides possibility for detection of the sensor in complex environment.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Fig. 1 is the ultraviolet spectrogram for detecting sensors A 1 in example 1 and detecting different glucose；
Fig. 2 is to detect in example 2 sensors A 1 to the optics of the selective enumeration method of Glu, Lcy, Gly, His, AA, DA and UA
Figure；
Fig. 3 be detection example 2 in sensors A 1 to K+、Na+、Cl-And Ca2+Anti- ion interference detection optical picture；
Fig. 4 is to detect the optical picture that sensor B1 detects the anti-ion interference of K+, Na+, Cl- and Ca2+ in example 2；
Fig. 5 is the optical picture for detecting sensors A 1 in example 1 and detecting different glucose.
Specific implementation mode
The present invention provides a kind of preparation method of gold nanoparticle Visual retrieval glucose sensor, feature exists
In, including
1) gold chloride and trisodium citrate in solvent are subjected to haptoreaction and gold size solution is made；
2) pH of gold size solution is adjusted to 6.0-7.5,3- amino phenyl boric acid (APBA) and amino-terminated is then added
Poly-N-isopropyl acrylamide (PNIPAM-NH2) electrostatic interaction is carried out so that gold nanoparticle Visual retrieval glucose biography is made
Sensor.
In the step 1) of the present invention, the specific type of solvent can select in a wide range, but be examined from cost
Consider, it is preferable that solvent is deionized water.
In the step 1) of the present invention, the dosage of each substance can select in a wide range, but in order to improve Jenner
The yield of rice corpuscles, it is preferable that relative to the water of 100 parts by weight, the dosage of gold chloride is 0.015-0.02 parts by weight, citric acid
The dosage of trisodium is 0.25-0.3 parts by weight.
In the step 1) of the present invention, catalytic condition can select in a wide range, but in order to improve gold
The yield of nano-particle, it is preferable that haptoreaction at least meets the following conditions：98-105 DEG C of reaction temperature, reaction time 20-
40min。
In the step 2) of the present invention, the dosage of each material can select in a wide range, but in order to improve
PNIPAM-NH2, APBA and gold nanoparticle combination quantity, it is preferable that in step 2), the gold size relative to 1mL is molten
The dosage of liquid, APBA is 1.5 × 10-4-2.5×10-4Mmol, PNIPAM-NH2Dosage be 3.5 × 10-5-4.5×10- 5mmol。
In the step 2) of the present invention, the specific steps and condition of electrostatic interaction can select in a wide range, but
It is to improve PNIPAM-NH2, APBA and gold nanoparticle combination quantity, it is preferable that electrostatic interaction is by first will be golden
Sol solution, APBA and PNIPAM-NH2Mixing, is then allowed to stand；It wherein stands and at least meets the following conditions：Dwell temperature is 15-30
DEG C, time of repose 10-20min.
In the step 2) of the present invention, the method for the adjusting of pH can be the adjusting side of any type routine in this field
Method, but in order to improve the efficiency of adjusting, it is preferable that in step 2), pH's is adjusted to：First gold size solution is diluted to former dense
The 40%-60% of degree, then adjusts pH by sodium hydroxide solution.
The present invention also provides a kind of gold nanoparticle Visual retrieval glucose sensor, which passes through above-mentioned
Method is prepared.
Invention further provides a kind of above-mentioned gold nanoparticle Visual retrieval glucose sensors to examine in glucose
Application in survey.
The present invention will be described in detail by way of examples below.In following embodiment, three hydration gold chlorides are for I
Fourth companies market product, trisodium citrate are the commercially available product of Chinese medicines group, and 3- amino phenyl boric acids are the commercially available product of Shanghai uncle's card chemistry,
Amino-terminated poly-N-isopropyl acrylamide is the commercially available product that the number-average molecular weight of Sigma-Aldrich is 2500.
Embodiment 1
1) according to " Frens G.Controlled nucleation for the regulation of the
particle size in monodisperse gold suspensions[J].Nature,1973,241(105):20-
22. " the methods recorded carry out the preparation of gold size solution：First by glass apparatus chloroazotic acid (HCl：HNO3=3：1, volume ratio) cleaning
Removal of impurities, then eluted totally with deionized water, naturally dry is for use；Then by 5mL HAuCl4(0.01mol/L) is added to 100mL
In deionized water, magnetic agitation is uniform；Then acquired solution is heated to reflux (100 DEG C), then the trisodium citrate of 5mL is molten
Liquid (1 weight %) is added rapidly in above-mentioned solution.Observing the color of solution, to become purple final from colourless in a few minutes
Become claret, continue to heat 30min, that is, obtain the firm gold size solution of uniform citric acid, remove heating device, at 25 DEG C
Cooling, closing is stored in for use in 4 DEG C of refrigerator.
2) at 25 DEG C, the gold size solution addition deionized water for taking 0.5mL is diluted to 1mL, adds NaOH solution
(0.05mol/L) adjusts pH to 7.0；It is subsequently added into the PNIPAM-NH of 10 μ L2The APBA solution of solution (10mmol/L) and 20 μ L
It is uniformly mixed in (1mmol/L) to above-mentioned gold size solution, stands 15min so that gold nanoparticle Visual retrieval glucose is made
Sensors A 1.
Embodiment 2
It carries out that sensors A 2 is made according to the method for embodiment 1, except that：PH is adjusted to 6.0 in step 2).
Embodiment 3
It carries out that sensors A 3 is made according to the method for embodiment 1, except that：PH is adjusted to 7.5 in step 2).
Embodiment 4
It carries out that sensors A 4 is made according to the method for embodiment 1, except that：PNIPAM-NH in step 2)2Solution
The dosage of (10mmol/L) is 12.5 μ L.
Embodiment 5
It carries out that sensors A 5 is made according to the method for embodiment 1, except that：PNIPAM-NH in step 2)2Solution
The dosage of (10mmol/L) is 7.5 μ L.
Embodiment 6
It carries out that sensors A 6 is made according to the method for embodiment 1, except that：APBA solution (1mmol/ in step 2)
L dosage) is 22.5 μ L.
Embodiment 7
It carries out that sensors A 7 is made according to the method for embodiment 1, except that：APBA solution (1mmol/ in step 2)
L dosage) is 17.5 μ L.
Comparative example 1
It carries out that sensor B1 is made according to the method for embodiment 1, except that：PNIPAM-NH is not used in step 2)2
Solution.
Detect example 1
Under conditions of pH=7.0, T=25 DEG C, the glucose solution of various concentration is added into sensors A 1
(0.25mM-3mM), then by UV-vis, optical photograph (see Fig. 5, wherein a-g indicates that the glucose of 0.25mM is molten successively
Liquid, the glucose solution of 0.75mM, the glucose solution of 1mM, the glucose solution of 1.5mM, the glucose solution of 2mM, 2.5mM
Glucose solution and the glucose solution of 3mM optical effect figure is added into sensors A 1) characterize, gold size reunion degree with
Relationship between glucide concentration.
According to the characteristic peak of gold nanoparticle the ratio between absorbance at 520nm and 610nm (A respectively520/A610) can be right
Glucose carries out quantitative detection, establishes A520/A610Linear relationship between the concentration of glucose is the foundation of qualitative detection.Such as
Shown in Fig. 1, wherein interior list of illustrations shows the calibration curve of sensor detection glucose, and the detection range of glucose is 0.25-
3mM, linear equation：Y(A520/A610)=7.52-2.08cglu(mmol/L).It follows that gold nanoparticle provided by the invention
Visual retrieval glucose sensor efficiently can quantitatively detect glucose solution.
Similarly, also glucose solution efficiently can quantitatively be detected by A2-A7 known to above-mentioned method.And
B1 (as shown in Figure 3) can not carry out glucose quantitative inspection since ion interference, gold size solution can not be resisted to be easy to happen reunion
It surveys.
Detect example 2
1) Glu of 3mM (glucose) is added to the sensors A 1 (see a in Fig. 2) being displayed in red, observes sensors A 1
Color become au bleu (see the b in Fig. 2)；By Lcy (L-cysteine) solution of 3mM, 3mM Gly (glycine) solution,
His (histidine) solution of 3mM, AA (ascorbic acid) solution of 3mM, 30 μM of DA (dopamine) solution and 30 μM of UA (urine
Acid) solution adds to respectively in sensors A 1, and concrete outcome is shown in that Fig. 2, the c in wherein Fig. 2 refer to that Lcy is added into sensors A 1
Design sketch, d refers to that Gly is added to the design sketch in sensors A 1, and e refers to that His is added to the effect in sensors A 1
Figure, f refer to that AA is added to the design sketch in sensors A 1, and g refers to that DA is added to the design sketch in sensors A 1, what h referred to
It is that UA is added to the design sketch in sensors A 1；By result it is found that relative to sensors A 1, the color of solution is several in c-e, g-h
Do not change, and after adding AA, solution colour has slight intensification, this may be due to one side AA concentration compared with
Greatly, on the other hand may be because AA is also adjacent hydroxy compounds.It follows that sensors A 1 has excellent choosing for Glu
Selecting property.Similarly, A2-A7 also has excellent selectivity.
2) since glucose is Energy supply material important in organism, it during atual detection may be by
The interference for carrying out common ion in organism, in order to verify the anti-ion interference ability of the sensor, this experiment is selected in human body often
The ion K seen+, Na+, Cl-, Ca2+, the results are shown in Figure 3, represents four sensors As prepared 1 successively to a, b, c, d respectively
In add the K of 5mM+Solution, the Na of 100mM+Solution, the Cl of 100mM-Solution, the Ca of 2mM2+Solution, solution still keep red,
There is no agglomeration generation, this is because effectively ion can be hindered for gold size containing PNIPAM macromolecular chains in the sensor
Influence.Similarly, the testing result of A2-A7 and A1 is consistent.
3) e, f, g, h of Fig. 4 represents the K that 5mM is added in the sensor B1 that Xiang Si prepare+Solution, the Na of 100mM+
Solution, the Cl of 100mM-Solution, the Ca of 2mM2+Solution observes apparent agglomeration.This further demonstrates this from the negative
The sensor that invention provides not only has good selectivity, and also has good anti-ion interference ability.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (7)
1. a kind of preparation method of gold nanoparticle Visual retrieval glucose sensor, which is characterized in that including
1) gold chloride and trisodium citrate in solvent are subjected to haptoreaction and gold size solution is made；
2) pH of the gold size solution is adjusted to 6.0-7.5,3- amino phenyl boric acid (APBA) and amino-terminated is then added
Poly-N-isopropyl acrylamide (PNIPAM-NH2) electrostatic interaction is carried out so that the gold nanoparticle Visual retrieval grape is made
Sugared sensor；
Wherein, in step 2), relative to the gold size solution of 1mL, the dosage of the APBA is 1.5 × 10-4-2.5×10- 4Mmol, the PNIPAM-NH2Dosage be 3.5 × 10-5-4.5×10-5mmol；The electrostatic interaction is by first will be described
Gold size solution, APBA and PNIPAM-NH2Mixing, is then allowed to stand；The wherein described standing at least meets the following conditions：Dwell temperature
It is 15-30 DEG C, time of repose 10-20min.
2. preparation method according to claim 1, wherein the solvent is water.
3. preparation method according to claim 2, wherein relative to the water of 100 parts by weight, the dosage of the gold chloride is
The dosage of 0.015-0.02 parts by weight, the trisodium citrate is 0.25-0.3 parts by weight.
4. preparation method according to claim 3, wherein the haptoreaction at least meets the following conditions：Reaction temperature
It is 98-105 DEG C, reaction time 20-40min.
5. according to the preparation method described in any one of claim 1-4, wherein in step 2), pH's is adjusted to：First will
The gold size solution is diluted to the 40%-60% of original content, then adjusts pH by sodium hydroxide solution.
6. a kind of gold nanoparticle Visual retrieval glucose sensor, which is characterized in that the sensor passes through claim
Method described in any one of 1-5 is prepared.
7. gold nanoparticle Visual retrieval glucose sensor the answering in glucose detection described in a kind of claim 6
With.
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| CN110393725B (en) * | 2018-04-20 | 2022-09-02 | 国家纳米科学中心 | Phenylboronic acid with gram selectivity and gold nanoparticle modified by derivative of phenylboronic acid, and preparation method and application of phenylboronic acid and gold nanoparticle |
| CN108956734A (en) * | 2018-04-25 | 2018-12-07 | 安徽师范大学 | Sensor and its preparation method and application based on boric acid affinity interaction |
| CN109765279B (en) * | 2019-01-14 | 2020-12-01 | 安徽师范大学 | Sandwich type electrochemical sensor constructed based on boric acid affinity and preparation method and application thereof |
| CN110672544A (en) * | 2019-10-12 | 2020-01-10 | 天津科技大学 | Glucose visualization sensor based on cyclic peptide recognition element and preparation method and application thereof |
| CN111375355B (en) * | 2019-12-17 | 2022-02-01 | 中科康磁医疗科技（苏州）有限公司 | Boric acid hydrogel synthesis method for continuous monitoring of saliva glucose |
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