CN108250133A - It is a kind of to be used to detect double probe materials of fluorescence-Raman of zinc ion and preparation method thereof - Google Patents
It is a kind of to be used to detect double probe materials of fluorescence-Raman of zinc ion and preparation method thereof Download PDFInfo
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- CN108250133A CN108250133A CN201810226836.1A CN201810226836A CN108250133A CN 108250133 A CN108250133 A CN 108250133A CN 201810226836 A CN201810226836 A CN 201810226836A CN 108250133 A CN108250133 A CN 108250133A
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- pyridine
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- gold nano
- raman
- zinc ion
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 36
- 239000000523 sample Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 title claims abstract description 15
- 239000010931 gold Substances 0.000 claims abstract description 34
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052737 gold Inorganic materials 0.000 claims abstract description 32
- KNRABANRKFDREP-UHFFFAOYSA-N SCC(=O)N.N1=CC=CC=C1 Chemical class SCC(=O)N.N1=CC=CC=C1 KNRABANRKFDREP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 10
- 150000003222 pyridines Chemical class 0.000 claims abstract description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005119 centrifugation Methods 0.000 claims abstract description 4
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001338 self-assembly Methods 0.000 claims abstract description 4
- NJWIMFZLESWFIM-UHFFFAOYSA-N 2-(chloromethyl)pyridine Chemical compound ClCC1=CC=CC=N1 NJWIMFZLESWFIM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000000903 blocking effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 11
- 239000000084 colloidal system Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 3
- 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 claims description 3
- 238000011534 incubation Methods 0.000 claims description 2
- 230000004224 protection Effects 0.000 claims description 2
- AOCSUUGBCMTKJH-UHFFFAOYSA-N tert-butyl n-(2-aminoethyl)carbamate Chemical class CC(C)(C)OC(=O)NCCN AOCSUUGBCMTKJH-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 2
- 230000009435 amidation Effects 0.000 claims 1
- 238000007112 amidation reaction Methods 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004458 analytical method Methods 0.000 abstract description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011938 amidation process Methods 0.000 abstract description 2
- 230000004044 response Effects 0.000 abstract description 2
- -1 tertbutyloxycarbonyl ethylenediamines Chemical class 0.000 abstract 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical class CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000003384 imaging method Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 8
- 101000674278 Homo sapiens Serine-tRNA ligase, cytoplasmic Proteins 0.000 description 7
- 101000674040 Homo sapiens Serine-tRNA ligase, mitochondrial Proteins 0.000 description 7
- 102100040516 Serine-tRNA ligase, cytoplasmic Human genes 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000004069 differentiation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012921 fluorescence analysis Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JPMRGPPMXHGKRO-UHFFFAOYSA-N 2-(chloromethyl)pyridine hydrochloride Chemical class Cl.ClCC1=CC=CC=N1 JPMRGPPMXHGKRO-UHFFFAOYSA-N 0.000 description 1
- 206010013883 Dwarfism Diseases 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 238000003705 background correction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000019522 cellular metabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229940038879 chelated zinc Drugs 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VXSZRLNZRUBXJG-UHFFFAOYSA-N n',n'-diaminoethane-1,2-diamine Chemical compound NCCN(N)N VXSZRLNZRUBXJG-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 230000009870 specific binding Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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- General Health & Medical Sciences (AREA)
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- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention belongs to technical field of analysis and detection, specially a kind of fluorescence Raman pair probe materials for detecting zinc ion and preparation method thereof.(1) N tertbutyloxycarbonyl ethylenediamines with chloromethylpyridine are reacted first, generates boc-protected two pyridine compounds of N；Then Boc blocking groups are removed with hydrofluoric acid, N, N lutidines ethylenediamines is prepared；(2) by N, N lutidines ethylenediamine occurs amidation process with thioacetic acid, two pyridine mercaptoacetylamides is prepared；(3) by self-assembly method, two pyridine mercaptoacetyls are amine-modified to gold nano grain surface, and room temperature is incubated, centrifugation obtains the double probe materials of fluorescence Raman for detecting zinc ion.The method processed of the present invention for simple and practicable, obtain the double probe materials of fluorescence Raman can specific recognition zinc ion, and high sensitivity, fast response time.There is potential application prospect in fields such as bio-imaging, environment.
Description
Technical field
The invention belongs to technical field of analysis and detection, specifically, are related to a kind of fluorescence-Raman for being used to detect zinc ion
Double probe materials and preparation method thereof.
Background technology
Zinc is second largest abundant transition metal in human body, it is trace element necessary to human body, not only in many lifes
During reason, such as gene expression, cell metabolism, DNA identification play a key effect, and can promote growth in humans development,
Strengthen immunity and the effect for adjusting various enzymes and receptor.The shortage of zinc ion will lead to that nanism, intellectual development be bad, tire
The symptoms such as youngster's hypoevolutism, therefore find a kind of method for detecting zinc ion concentration in real time in original position and be of great significance.
The detection method of zinc ion mainly has fluorescence analysis, atomic absorption spectrophotometry and electrochemical analysis at present
Method.So far, fluorescence analysis combines it and is imaged advantage, has developed a large amount of Zn2+Fluorescent optical sensor still, needs
Zn2+It connecting organic fluorogen and forms ligand, cause its pretreatment process very cumbersome, analysis time is long and cost of drugs is high,
It is difficult to distinguish Zn simultaneously2+And Cd2+The similar ion of two kinds of structures.Therefore, urgent need will be developed a kind of highly selective, highly sensitive
It spends and Zn can be distinguished2+And Cd2+The detection technique of two kinds of ions.
In recent years, a kind of surface-enhanced Raman (SERS) spectral technique based on noble metal substrate causes the wide of researcher
General interest.SERS technologies due to it is highly sensitive, without the destructive, advantages such as detection line is low, be widely used in detecting biomolecule,
The fields such as food additives, metal ion.
Invention content
For overcome the deficiencies in the prior art, the purpose of the present invention is to provide it is a kind of can be used for it is quick, accurately detect zinc
Double probe materials of fluorescence-Raman of ion and preparation method thereof.The double probe material detection zinc ions of fluorescence-Raman of the present invention,
High sensitivity, selectivity are good.
The present invention is using two pyridine compounds as fluorescent molecular indicator, energy and Zn2+Specific binding, fluorescence intensity with
Zn2+Concentration increase and it is linearly increasing；Two pyridine compounds effectively modification simultaneously forms MDPA- to metallic plasma surface
AuNPs gives expression to higher SERS activity, and Surface enhanced Raman spectroscopy is in 1024cm-1Place there is new peak and Raman signal with
Zn2+Concentration increase and it is linearly increasing.
Technical scheme of the present invention is specifically described as follows.
The present invention provides a kind of preparation method for the double probe materials of fluorescence-Raman for being used to detect zinc ion, specific steps
It is as follows：(1) N- tertbutyloxycarbonyl ethylenediamines are reacted with chloromethylpyridine first, two pyridine compounds of generation N-Boc protections；
Then Boc blocking groups are removed with hydrofluoric acid, N, N- lutidines ethylenediamines is prepared
(2) by N, N- lutidines ethylenediaminesAmide occurs under EDC/NHS effects with thioacetic acid
Change reaction, two pyridine mercaptoacetylamides are prepared
(3) by self-assembly method, by two pyridine mercaptoacetylamidesModify gold nano grain table
Face, room temperature is incubated, centrifugation obtains the double probe materials of fluorescence-Raman for detecting zinc ion.
In the present invention, in step (3), the average grain diameter of gold nano grain is between 2~100nm.
In the present invention, in step (3), the average grain diameter of gold nano grain is between 30~70nm.
In the present invention, in step (3), gold nano grain is by HAuCl4.4H2O aqueous solutions and sodium citrate aqueous solution reflux are anti-
It should obtain.
In the present invention, in step (3), room temperature incubation time is 30~90min, and centrifugal rotational speed is 7000~9000rpm, from
The heart time is 3~10min.
In the present invention, in step (3), 0.05~0.2mmol/L of two pyridine mercaptoacetamide solutions；Gold nano colloid is dense
It spends for 0.2~0.8nmol/L.
In the present invention, in step (3), the molecular concentration of two pyridine mercaptoacetamide solutions is 0.08~0.12mmol/L；
Gold nano colloid concentration is 0.4~0.6nmol/L.
In the present invention, in step (3), two pyridine mercaptoacetamide solutions and gold nano colloidal volume ratio are 1:20~1:
100。
In the present invention, in step (3), two pyridine mercaptoacetamide solutions and gold nano colloidal volume ratio are 1:40~1:
60。
The present invention also provides the double probe materials of fluorescence-Raman for being used to detect zinc ion made from a kind of above-mentioned preparation method
Material.
Compared with prior art, the beneficial effects of the present invention are：
1st, the present invention is modified using two pyridine mercaptoacetylamide MDPA as fluorescence and the double Properties Molecular indicator of Raman
On gold nano grain, the functionalized nano material of noble metal is prepared, it is simple for process, conveniently promote the use of；
2nd, the present invention is detected zinc ion using fluorescence and the double probe patterns of Raman, and fast response time, detection are sensitive
Degree is high, and detection range existsBetween, minimum concentration is detected up to 3pM by Raman spectrum, detection limit is low；
3rd, probe of the invention can faster sequestration zinc ion, inducing function gold nano grain is from reuniting, and then effectively
Enhance Raman enhancement factor, realization Raman enhances, the sensing effect of multifunction, improves zinc ion detection sensitivity；
4th, the present invention utilizes double probes to Zn2+With Cd2+Raman characteristic peak analysis, find two kinds of molecules due to difference outside
The sequestering power of electronic shell shows the signal of different SERS, and Cd is presented2+1014cm-1, Zn2+1024cm-1Raman shift is inclined
Difference, therefore effectively qualitative both structure comparable ionics can be distinguished, realize Zn2+And Cd2+Differentiation；
5th, in the present invention, fluorescence detector selection 320nm excitation wavelengths, Raman spectrometer selection 785nm excitation wavelengths,
Fluorescence intensity increases as zinc ion concentration increases at 420nm, and Raman shift is in 1024cm-1There is new peak, while Raman in place
Intensity increases as zinc ion concentration increases.Therefore, the present invention can be with quantitative detecting analysis zinc ion；
6th, it is detected using double probes of the present invention, it can be by Zn2+And K+, Ca2+, Al3+, Fe2+, Ni2+, Co2+, Cu2+,
Cd2+It mutually distinguishes, high specificity.
Description of the drawings
Fig. 1 is the nmr spectrum of two pyridine compounds MDPA prepared in embodiment 1.
Fig. 2 be in embodiment 1 functional gold with the increased ultraviolet spectrogram of zinc ion concentration.
Fig. 3 is the transmission electron microscope picture (left side) of functional gold in embodiment 1, Zn2+Transmission electricity under existence condition
Mirror figure (right side).
Fig. 4 is fluorescence spectra of the probe in embodiment 1 to different ions.
Fig. 5 is probe in embodiment 1 with the increased Raman spectrogram of zinc ion concentration.
Fig. 6 is probe in embodiment 1 to Zn2+With Cd2+The Raman spectrogram of qualitative difference.
Specific embodiment
It describes in detail with reference to the accompanying drawings and examples to technical scheme of the present invention.
Embodiment 1
(1) gold nanoparticle is prepared
Weigh 10mgHAuCl4It is dissolved in 100ml distilled waters, is heated to boiling, be vigorously stirred down and be rapidly injected 1ml 1%
Sodium citrate, keep continuous backflow 30min, be cooled to room temperature.Claret solution is prepared, in 4 DEG C of preservations, it is dense to obtain colloid
Spend 0.5nmol/L, the AuNPs of diameter 50nm.
(2) bis- pyridine compounds of MDPA are prepared.
First, 2.24gN- tertbutyloxycarbonyls ethylenediamine and 4.6g chloromethyl pyridine hydrochlorides are dissolved in 50mL 5mol/L
NaOH aqueous solutions, be stirred overnight；It adds in 50mL distilled water and is extracted with dichloromethane, then anhydrous Na2SO4It is dry, pass through revolving
Purification；Crude product is used into methylene chloride/methanol (95 by silicagel column:5) it is further purified as eluant, eluent, obtains product N-
Tert-butoxycarbonyl-N, N- diamino ethylenediamine is pale tan oil.
Secondly, 1.9g above compounds are dissolved in 15mL dichloromethane, by the trifluoroacetic acid of 45mL under the conditions of ice-water bath
Used time 1.5h, which is added dropwise to, to be reacted and continues to stir 1.5h.After revolving purification, residue is dissolved in the NaOH aqueous solutions of 15mL2M,
It is extracted with dichloromethane, finally by compound N, N- diamino ethylenediamine anhydrous Nas2SO4It dries and purifies.
Finally, second compound with thioacetic acid is reacted by EDC/NHS cross-linking methods, 1g compounds is taken to be suspended in EDC/
NHS 1:1 and 3h being stirred, amidation process easily occurs for this reaction, obtains two pyridine mercaptoacetylamide MDPA of oily compound,
Its hydrogen nuclear magnetic resonance spectrogram is shown in Fig. 1.
(3) synthesis of MDPA-AuNPs
Functional gold MDPA-Au is mainly prepared by self assembly, by the 0.5nmol/L AuNPs of 5ml and
0.1ml 0.1mM MDPA are incubated 1h at ambient temperature, then mixture is centrifuged 5 minutes to remove excess with 8000rpm
Lower sediment after centrifugation, is redispersed in the amine-modified gold of two pyridine mercaptoacetyls that 5ml distilled waters prepare 0.45nM by MDPA
Nano-colloid is preserved at a temperature of 4 DEG C.It prepares with the compound of Au-S Covalent bonding togethers, works as Zn2+Under existence condition, this two
Pyridine can effective chelated zinc ions, pass through the double probes of fluorescence/Raman and carry out qualitative and quantitative detection zinc ions.The left figure of Fig. 3 is real
Apply the transmission electron microscope picture of double probes of Au-S Covalent bonding togethers in example 1.
(4) proportion optimizing of MDPA-AuNPs
Due to trace in environmental and biological samples and the Zn of ultra trace2+, the matched proportion density of MDPA-AuNPs is needed to select
Most preferably.The molecular concentration of the two pyridine mercaptoacetamide solutions prepared according to experiment condition is 0.05~0.2mmol/L, gold nano
Colloid concentration is 0.2~0.8nM, is usually counted by purification step with calculating the proportioning of molecule, single AuNPs and two pyridine sulfydryl second
The proportioning of amide about 1:5000, obtain prepared by optimal conditions the molecular concentrations of two pyridine mercaptoacetamide solutions for 0.08~
0.12mmol/L, gold nano colloid concentration are 0.4~0.6nM, two pyridine mercaptoacetamide solutions and gold nano colloidal volume ratio
It is 1:20~1:100.With the increase of MDPA dosages, fluorescence intensity and 1024cm at 425nm-1The SERS intensity at place is 1:
4000 to 1:It keeps stablizing in the range of 6000, two pyridine mercaptoacetamide solutions and gold nano colloidal volume ratio are 1 at this time:40
~1:60.In addition, MDPA-AuNPs and Zn2+Between chelatropic reaction can be rapidly completed.
Embodiment 2
(1)Zn2+To the chelating of MDPA-AuNPs probes
Fig. 2 be in embodiment 1 functional gold with zinc ion concentration (0~10 μm of ol/L) increased ultraviolet light
Spectrogram.
The ultraviolet plasma absorption peak of the gold nano grain of preparation is 520nm, and Fig. 2 can be seen that adding with zinc ion
Enter, chelation occurs with two pyridine compounds, generate gold nano grain from reunion, while reach with zinc ion concentration
0.1 μm of ol/L occurs new plasma absorption peak in 680nm.Simultaneously according to fig. 3 transmission electron microscope as a result, add in 0.1
After μm ol/L zinc ions, the gold nano grain after modification is reunited.The reunion can enhance Raman enhancement factor simultaneously, right
It is of great significance in Raman microprobe.
(2)Zn2+Fluoroscopic examination
As shown in figure 4, by 4ml nano-probes in quartz colorimetric utensil, 0.1 μm of ol/L different metal ions is sequentially added,
It is investigated with excitation wavelength 320nm；Zn2+With Cd2+Two kinds of ions all to Fluorescence Increasing, other without ion without enhancing effect, from
It and can qualitative detection analysis zinc ion.
(3)Zn2+Raman detection
It is measured using the Portable Raman spectrometer of 785nm excitation wavelengths.By the zinc ion of 10 μ l various concentrations
(10-6μmol/L,10-5μmol/L,10-4μmol/L,10-3μmol/L,10-2μmol/L,2×10-2μmol/L,10-1μmol/L)
MDPA-Au nano-probes are added to, is uniformly mixed, then takes a drop on silicon, are measured from each six points of sample collection
SERS signal, while using background correction, linear multi fitting correction baseline, from fig. 5, it can be seen that Raman shift exists
1024cm-1As zinc ion concentration increase successively increases, fluorescence intensity gradually increases, and finally reaches saturation.
It is of great significance for quantitative analysis and trace detection.
(4)Zn2+With Cd2+Qualitative differentiation
By the Zn of 1mmol/L2+、Cd2+、Zn2+With Cd2+The test analysis of mixed solution progress Raman, SERS spectrograms 6,
Raman shift 1024cm-1And 1014cm-1Two at represent Zn2+With Cd2+, while be all corresponding two kinds of features occur after mixing
Peak, so as to effectively distinguish the similar ion of two kinds of structures.Therefore by fluorescence and Raman two-probe me- thod can quickly, it is specific
Detect zinc ion.
Claims (10)
1. a kind of preparation method for the double probe materials of fluorescence-Raman for being used to detect zinc ion, which is characterized in that specific steps are such as
Under：
(1) N- tertbutyloxycarbonyl ethylenediamines are reacted with chloromethylpyridine first, two pyridine compounds of generation N-Boc protections；
Then Boc blocking groups are removed with hydrofluoric acid, N, N- lutidines ethylenediamines is prepared
(2) by N, N- lutidines ethylenediaminesGeneration amidation is anti-under EDC/NHS effects with thioacetic acid
Should, two pyridine mercaptoacetylamides are prepared
(3) by self-assembly method, by two pyridine mercaptoacetylamidesGold nano grain surface is modified,
Room temperature is incubated lower Au-S and easily spontaneously forms, and gold nano colloid is assembled with two pyridine mercaptoacetylamides by covalent bond, is centrifuged
To for detecting the double probe materials of fluorescence-Raman of zinc ion.
2. preparation method according to claim 1, which is characterized in that in step (3), the average grain diameter of gold nano grain exists
Between 2~100nm.
3. preparation method according to claim 1 or 2, which is characterized in that in step (3), the average grain of gold nano grain
Diameter is between 30~70nm.
4. preparation method according to claim 1, which is characterized in that in step (3), gold nano grain is by HAuCl4.4H2O
Aqueous solution and sodium citrate aqueous solution back flow reaction obtain.
5. preparation method according to claim 1, which is characterized in that in step (3), room temperature incubation time for 30~
90min, centrifugal rotational speed are 7000~9000rpm, and centrifugation time is 3~10min.
6. preparation method according to claim 1, which is characterized in that in step (3), two pyridine mercaptoacetamide solutions
A concentration of 0.05~0.2mmol/L of molecule；Gold nano colloid concentration is 0.2~0.8nmol/L.
7. the preparation method according to claim 1 or 6, which is characterized in that in step (3), two pyridine mercaptoacetylamides are molten
A concentration of 0.08~0.12mmol/L of liquid；Gold nano colloid concentration is 0.4~0.6nmol/L.
8. preparation method according to claim 1, which is characterized in that in step (3), two pyridine mercaptoacetamide solutions and
Gold nano colloidal volume ratio is 1:20~1:100.
9. the preparation method according to claim 1 or 8, which is characterized in that in step (3), two pyridine mercaptoacetylamides are molten
Liquid and gold nano colloidal volume ratio are 1:40~1:60.
10. a kind of double probe materials of the fluorescence-Raman for being used to detect zinc ion that preparation method according to claim 1 obtains.
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| CN109825283A (en) * | 2019-01-30 | 2019-05-31 | 云南民族大学 | One kind is based on GNPs-L-Cys-Rh6G2 fluorescence probe and its preparation method and application |
| CN110531071A (en) * | 2019-09-03 | 2019-12-03 | 上海交通大学 | A kind of preparation and application of highly sensitive Sidestream chromatography immunity test strip |
| CN111551534A (en) * | 2020-05-18 | 2020-08-18 | 上海交通大学 | Kit based on surface enhanced Raman probe, application thereof and imaging method |
| CN114106004A (en) * | 2021-11-30 | 2022-03-01 | 福建师范大学 | Chelate zinc ion fluorescent probe and preparation method and biological application thereof |
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| CN109825283A (en) * | 2019-01-30 | 2019-05-31 | 云南民族大学 | One kind is based on GNPs-L-Cys-Rh6G2 fluorescence probe and its preparation method and application |
| CN110531071A (en) * | 2019-09-03 | 2019-12-03 | 上海交通大学 | A kind of preparation and application of highly sensitive Sidestream chromatography immunity test strip |
| CN110531071B (en) * | 2019-09-03 | 2022-03-15 | 上海交通大学 | Preparation and application of high-sensitivity lateral flow chromatography immunoassay test paper |
| CN111551534A (en) * | 2020-05-18 | 2020-08-18 | 上海交通大学 | Kit based on surface enhanced Raman probe, application thereof and imaging method |
| CN114106004A (en) * | 2021-11-30 | 2022-03-01 | 福建师范大学 | Chelate zinc ion fluorescent probe and preparation method and biological application thereof |
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