CN102507952A - Method for detecting protein and metal ions - Google Patents
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- CN102507952A CN102507952A CN2011103066350A CN201110306635A CN102507952A CN 102507952 A CN102507952 A CN 102507952A CN 2011103066350 A CN2011103066350 A CN 2011103066350A CN 201110306635 A CN201110306635 A CN 201110306635A CN 102507952 A CN102507952 A CN 102507952A
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Abstract
The invention relates to the field of biotechnology, and discloses a method for detecting protein and metal ions. The method comprises the following steps: providing a probe molecule with a reporter fluorophore and capable of specifically binding with a target; mixing the probe molecule with a nanoparticle solution rich in pi electrons; and adding the sample to be detected; and detecting fluorescence, wherein the nanoparticle rich in pi electrons is selected from conjugated polymer of phenylenediamine monomer, 3,4-ethylenedioxythiophene or styrene, Ag(I)-4,4'-bipyridyl, Cu(II)-4,4'-bipyridyl, 3,3',5,5'-tetramethylbenzidine chloroplatinate, p-phenylenediamine chloroplatinate or 4,4'-bipyridyl tetrachloroaurate coordination polymers, porphyrin cluster, mesoporous carbon and nano C60. The detection method provided by the invention has the advantages of low cost, simple operation, short detection time, high sensitivity and wide application range.
Description
Technical field
The present invention relates to biological technical field, relate to a kind of method that detects protein and metallic ion specifically.
Background technology
Protein is biomacromolecule important in the human body, and it not only is very important and requisite for earning a bare living, and simultaneously, it all has substantial connection for duplicating of the transcribing of the translation of life genetic code, information, DNA etc.The content of protein in body fluid can be used as the important indicator of human nutrition health, medical diagnosis on disease; Content like urine protein is one of foundation of diagnosis ephritis and diabetes; Protein content is at 20～80mg in the normal person 24h urine, and having surpassed this limit is undesired value, is the sign of morbidity.Like haemocyanin is a kind of important living matter in the human body, and its content in body fluid can be used as the important indicator of human nutrition health, medical diagnosis on disease etc.And for example Alzheimer sick (AD) is one group of agnogenic central nervous system abiotrophic degeneration's disease; Be still a kind of disease that can not cure at present; Tau albumen in the quantitative determination cerebrospinal fluid possibly become a useful indicators of AD early diagnosis; Biology is measured, and like cerebrospinal fluid Tau protein determination, possibly help the clinician to reach the purpose of early diagnosis and prevention AD.Therefore, can realize the early diagnosis of disease, thereby treat, prolong patient's life ahead of time the trace detection of specified protein.
Metallic ion is being played the part of important role at environment, biological and medical field, and its concentration, kind and valence state all have material impact to vital movement and environment.Such as metallic ions such as potassium, iron, zinc is the indispensable element that life entity is kept normal physiological activity.And some heavy metal ion, owing in environment, not decomposing and can being prone to cause slow poisoning through food chain gradually in the enrichment of biologic chain upper strata.Certificate " Beijing Youth Daily ": since 1974, Long Ling village, Hua County, Shaanxi is dead 58 people altogether, 29 people that die from cancer, and 22 people that die from pulmonary heart disease, cerebrovascular disease, only 1 Genus Homo is in natural death.Mainly receive pollution plumbous and arsenic through looking into this ground soil, the flour that local villager eats then receives the severe contamination of lead, arsenic, zinc, 4 kinds of elements of chromium, and cadmium, plumbous content are respectively 5.3 times and 2.55 times of standard value, the vegetables of genus severe contamination in the fresh kidney beans.Therefore, the detection to metallic ion has great importance at aspects such as environmental monitoring and medicals diagnosis on disease.At present, mainly use the luminous and absorption spectrum of atom for metal ion detection, though this method has highly sensitive, accuracy advantages of higher needs to use large-scale instrument, it is higher to detect cost, is unfavorable for extensive popularization.Therefore, need exploitation a kind of simple, fast, high selectivity, highly sensitive metal ion inspection.
Summary of the invention
In view of this, the present invention seeks to defective, the detection protein that provide a kind of simple to operate, highly sensitive, selectivity is strong and the method for metallic ion to conventional detection.
For realizing the object of the invention, the present invention adopts following technical scheme:
A kind of method that detects protein and metallic ion,
The probe molecule that can combine with the target specificity of band report fluorophor is provided;
Said probe molecule is mixed with the nano material solution that is rich in pi-electron, add testing sample then, detect fluorescence;
Wherein, said target is protein and metallic ion, and it is phenylenediamine, 3 that the said nano material that is rich in pi-electron is selected from monomer; 4-ethene dioxythiophene or cinnamic conjugated polymer, silver (I)-4,4 '-dipyridine, copper (II)-4; 4 '-dipyridine, chloroplatinic acid-3,3 ', 5; 5 '-tetramethyl biphenyl diamines, chloroplatinic acid-p-phenylenediamine (PPD) or tetrachloro alloy acid-4,4 '-dipyridine coordination polymer, porphyrin bunch collective, mesoporous carbon and nanometer C
60
The development of the technology of evolving along with DNA is external, the screening of dna probe molecular sequences and synthetic cost are more and more lower, and therefore the detection platform based on dna molecular has broad application prospects.The specific recognition effect of dna molecular and protein is a hot research in recent years; Be widely used in the identification and the detection of specific protein; Human DNA such as Landegren like the biomedical center of Uppsala, SWE have realized the high sensitivity and the high selectivity of PDGF albumen are detected as probe, and its minimal detectable concentration is 40 * 10
-21Mol [Fredriksson, S.Gullberg, M.; Jarvius, J.; Olsson, C.; Pietras, K.; Gustafsdottir, S.M.; Ostman, A.; Landegren, U., Nat.Biotechnol, 2002,20,473-477].The dna sequence dna of special screening can form stable complex with metallic ion, shows the specificity of effect, like a kind of Hg
2+The colorimetric detection method of ion utilizes Hg
2+The effect of T base among ion and the dna sequence dna AGR0100 detects and is limited to 50nM [Li, T.; Dong, S.J.; Wang, E.K., Anal Chem, 2009,81,2144-2149].Dna molecular through external evolution screening; Can with the effect of organic molecule generation specific recognition; Thereby the conversion of inducing DNA molecular conformation, the selection effect as the people such as Liu of NUS utilize fluorescently-labeled DNA and ATP has realized the selectivity of ATP is detected; Its detection is limited to 20 μ M [Wang, Y.; Liu, B., Analyst, 2008,133,1593-1598].
The present invention detects the method for protein and metallic ion and utilizes π-π to interact; The probe molecule that will combine with the target specificity is adsorbed on the nano-material surface that is rich in pi-electron, the fluorescence of cancellation probe molecule, and probe molecule mixes with testing sample then; Probe molecule combines with target; Probe molecule is broken away from from nano-material surface, and the fluorescent quenching effect disappears, and realizes the detection to testing sample through detecting fluorescence signal.And, also can confirm the content of target in the testing sample according to the fluorescence intensity variation.The method of detection protein according to the invention and metallic ion is with low cost, and the said preparation method of nano material that is rich in pi-electron is simple, and the prices of raw and semifnished materials are cheap, and can mass preparation; Simple to operate, the nano material, probe molecule and the testing sample that only need to be rich in pi-electron in the testing process mix, and use simple fluoroscopic examination instrument to detect fluorescence, need not use expensive large-sized analytic instrument; Detect excellent performance, detection time is short, highly sensitive, be a kind of easy, quick, cost is low, the detection protein of applied range and the method for metallic ion.
Description of drawings
Fig. 1 shows the principle schematic of detection method according to the invention, and wherein, the nano material of pi-electron is rich in spherical only representative, does not show material originally as sphere, and target comprises protein and metallic ion; On behalf of its conformation, dna probe is folding change, but is not limited only to fold;
Fig. 2 shows that the poly m-phenylene diamine nanometer rods detects the figure as a result of fibrin ferment albumen.A is dna probe (20nMT
A) fluorescence emission spectrum; B is dna probe (20nM T
A)+target protein (100nM T
B) fluorescence emission spectrum; C is dna probe (20nM T
A)+target protein (100nM T
BThe fluorescence emission spectrum of)+PMPD nanometer rods; D is dna probe (20nM T
AThe fluorescence emission spectrum of)+PMPD nanometer rods; E is the fluorescence emission spectrum of PMPD nanometer rods self;
Fig. 3 shows the specificity selection result figure of poly m-phenylene diamine nanometer rods to fibrin ferment; Other two kinds of immunoglobulin (Ig)s (IgG) that disturb albumen to be respectively bovine serum albumin(BSA) (BSA) and people, concentration is 100nM.
Fig. 4 shows the result of fibrin ferment in the mesoporous carbon detection of particulates human serum sample;
Fig. 5 shows nanometer C
60(nano-C
60) to metallic ion Hg
2+Testing result figure, dna probe (P
H, the 100nM) fluorescence emission spectrum under different condition: (a) P
H, (b) P
H+ Hg
2+(8 μ M), (c) P
H+ nano-C60, (d) P
H+ nano-C
60+ Hg
2+(8 μ M);
Fig. 6 shows nano-C
60To metallic ion Hg
2+Selectivity figure as a result.Wherein, Hg
2+Concentration is that the concentration of other interfering ion among the 8 μ M figure A is 5 μ M, and the concentration of other interfering ion is 50 μ M among the figure B;
Fig. 7 shows nano-C
60Detect metallic ion Hg in the lake water
2+Figure as a result.A is the fluorescence emission spectrum of lake water, and b is lake water+30nM Hg
2+Fluorescence emission spectrum.
Embodiment
The embodiment of the invention discloses a kind of method that detects protein and metallic ion.Those skilled in the art can use for reference this paper content, suitably improve technological parameter and realize.Special needs to be pointed out is that all similarly replace and change apparent to those skilled in the art, they all are regarded as and are included in the present invention.Method of the present invention is described through preferred embodiment, and the related personnel obviously can change or suitably change and combination method as herein described in not breaking away from content of the present invention, spirit and scope, realizes and use technology of the present invention.
For realizing the object of the invention, the present invention adopts following technical scheme:
The probe molecule that can combine with the target specificity of band report fluorophor is provided;
Said probe molecule is mixed with the nano material solution that is rich in pi-electron, add testing sample then, detect fluorescence;
Wherein, said target is protein and metallic ion, and it is phenylenediamine, 3 that the said nano material that is rich in pi-electron is selected from monomer; 4-ethene dioxythiophene or cinnamic conjugated polymer, silver (I)-4,4 '-dipyridine, copper (II)-4; 4 '-dipyridine, chloroplatinic acid-3,3 ', 5; 5 '-tetramethyl biphenyl diamines, chloroplatinic acid-p-phenylenediamine (PPD) or tetrachloro alloy acid-4,4 '-dipyridine coordination polymer, porphyrin bunch collective, mesoporous carbon and nanometer C
60
The probe molecule that the method for detection protein according to the invention and metallic ion will combine with the target specificity mixes with the nano material that is rich in pi-electron; Because π-π interacts; Probe molecule is adsorbed on material surface, and the report fluorophor can be with the cancellation of fluorophor emitted fluorescence with the energy transfer takes place between the nano material that is rich in pi-electron on the probe molecule afterwards.After adding testing sample, the target in the testing sample combines with probe molecule, and probe molecule is broken away from from nano-material surface, and the fluorescent quenching effect disappears, and probe molecule recovers fluorescence, realizes the detection to testing sample through detecting fluorescence signal.And, also can confirm the content of target in the testing sample according to the fluorescence intensity variation.
Probe molecule according to the invention has the report fluorophor, can also can hold with tense marker report fluorophor at 3 ' end and 5 ' at probe molecule 3 ' end or 5 ' end mark report fluorophor, to improve fluorescence intensity, improves the sensitivity that detects.The report fluorophor of probe mark includes but not limited to following fluorescent material: FAM, TET, JOE, VIC, HEX, ROX, TAMRA, CY3, CY3.5, CY5, CY5.5, Oregon Green, CAL Red, Red640 and Texas Red.
It is phenylenediamine, 3 that the nano material that is rich in pi-electron according to the invention is selected from monomer, 4-ethene dioxythiophene or cinnamic conjugated polymer.Wherein, the preparation method of said conjugated polymer mixes the solution of monomer and oxygenant according to mol ratio 1: 0.1～20, place 1min～24h, makes.Said monomer is a phenylenediamine, 3,4-ethene dioxythiophene or styrene, and said oxygenant is preferably ammonium persulfate or ferric trichloride.
Coordination polymer according to the invention is silver (I)-4,4 '-dipyridine, copper (II)-4,4 '-dipyridine, chloroplatinic acid-3; 3 ', 5,5 '-tetramethyl biphenyl diamines, chloroplatinic acid-p-phenylenediamine (PPD) or tetrachloro alloy acid-4; 4 '-dipyridine coordination polymer, by containing 4 of pi-electron, 4 '-dipyridine and tetramethyl biphenyl two amine molecules are as monomer; Transition metal ion silver, copper, platinum or gold are polymerized as initiating agent.The preparation method of said coordination polymer places 1min～24h for the solution with transition metal ion and the organic molecule that contains pi-electron mixes according to mol ratio 1: 0.1～20, makes.
Organic molecule bunch collective is in the mixed system of water or water and organic solvent, and organic molecule is under hydrophobic lipotropism drives, each other near the simple molecules aggregate that forms.Porphyrin according to the invention bunch collective is formed near a bunch collection in the mixed solution of water and organic solvent by the porphyrin molecule that contains pi-electron each other.Wherein, the preparation method of said porphyrin bunch collective is that the porphyrin molecular melting that contains pi-electron obtains the solution that concentration is 1mmol/L～0.5mol/L in organic solvent, is with water to mix at 0.001～1: 1 according to volume ratio then, places 1min～24h, makes.Wherein, said organic solvent is preferably methyl alcohol, ethanol, propyl alcohol, monoethylene glycol, dimethyl sulfoxide (DMSO), tetrahydrofuran or N-Methyl pyrrolidone.
Mesoporous carbon according to the invention and nanometer C
60All belong to material with carbon element; Wherein, The preparation method of said mesoporous carbon is for introducing the carbon source precursor thing in the duct of mesopore silicon oxide through infusion process, under acid catalysis, makes the precursor thermal decomposition and is deposited in the duct of template mesoporous material, and the calcining carbonization makes carbon-silicon compound; Remove the silicon template then, make mesoporous carbon.Wherein, said carbon source precursor thing is preferably glucose, sucrose acetylene, mesophase pitch, furancarbinol, phenol/formaldehyde resins.Nanometer C according to the invention
60The preparation method be with C
60Powder dissolution mixes with acetonitrile in acetone then, collects the khaki deposition, is dispersed in the water then to make.
In order further to understand the present invention, the present invention is elaborated below in conjunction with embodiment.
Wherein, the present invention is the target protein (T of detection in an embodiment with human thrombin albumen
B), with what fluorophore (FAM) was modified human thrombin albumen there be the fluorescence probe (T of the single stranded DNA sequence of specific recognition capability as fluoroscopic examination albumen
A).In an embodiment with Hg
2+And Ag
+Respectively as the metal target ion that detects, with fluorophore (FAM) modify be rich in the T base to Hg
2+The single stranded DNA sequence that specific binding capacity is arranged is as fluoroscopic examination Hg
2+Dna probe (P
H), with fluorophore (FAM) modify be rich in the C base to Ag
+The single stranded DNA sequence that specific binding capacity is arranged is as fluoroscopic examination Ag
+Dna probe (P
Ag).Each probe sequence sees table 1 for details.
Table 1 probe sequence of being correlated with
Embodiment 1: the preparation of the nanometer rods of poly m-phenylene diamine (PMPD) and detection albumen
Material preparation and processing: under the room temperature, be that the ammonium persulfate aqueous solution of 0.5M mixes with 0.84mL water with 0.06mL concentration, adding 0.1mL concentration then is the WS and the vibration of 0.1M m-phenylene diamine, and the nanosphere of visible a large amount of poly m-phenylene diamines deposition occurs afterwards.Gained deposition is also centrifugal with the flushing of secondary water, and repeatable operation and then is dispersed in the water several times, makes poly m-phenylene diamine (PMPD) nanometer rods, and 4 ℃ store for future use.
Detect albumen: human thrombin albumen is had the fluorescence probe (T of the single stranded DNA sequence of specific recognition capability as detection albumen with what fluorophore (FAM) was modified
A), be the target protein (T of detection with human thrombin albumen
B).Detection method: at first the PMPD nanometer rods is joined fluorescence probe (50nM T
A) solution in, the dna probe of strand is adsorbed onto the surface of PMPD nanometer rods, causes fluorescent quenching.Through one period reaction time (60min), fluorescent quenching reaches balance (98%).Add human thrombin albumen (100nM T
B), then owing to the existence of albumen, the cancellation of fluorescence is suppressed, and has only 50% cancellation generation (60min reaches balance).Testing result is seen Fig. 2.The result shows, can reach 100pM based on the detection method detectability of PMPD nanometer rods.When adding other albumen (100nM bovine serum albumin BSA or people's immunoglobulin (Ig) 100nM IgG) to fluorescence probe (50nM T
A) solution in after, add the PMPD nanometer rods again, the result sees Fig. 3.Be not suppressed by the cancellation of Fig. 3 visible fluorescence, and BSA and the IgG fluorescence intensity contrast T when existing
BThe ratio of the fluorescence intensity when existing is 10.6% and 8.6%, and therefore the detection method based on the PMPD nanometer rods has very high specific detection ability to human thrombin albumen.
Embodiment 2:nano-C
60Preparation and detect albumen and metallic ion
Material preparation and processing: with the C of 2.5mg
60Be dissolved in the 2mL acetone, be added dropwise to the 12mL acetonitrile then while stirring, next a large amount of khaki depositions occur.To precipitate with acetonitrile flushing and centrifugal, repeatable operation several times, ultrasonic again 30min makes the Nano-C that obtains
60Be dispersed in the 8mL water subsequent use.
The detection of albumen: human thrombin albumen is had the fluorescence probe (T of the single stranded DNA sequence of specific recognition capability as fluoroscopic examination albumen with what fluorophore (FAM) was modified
A), be the target protein (T of detection with human thrombin albumen
B).At first with nano-C
60Join fluorescence probe (50nMT
A) solution in, the dna probe of strand can be adsorbed onto nano-C
60The surface, cause fluorescent quenching.Through one period reaction time (60min), fluorescent quenching reaches balance (86%).Add human thrombin albumen (100nM T
B), add nano-C again
60, then owing to the existence of albumen, the cancellation of fluorescence is suppressed, and has only 60% cancellation generation (60min reaches balance).Based on nano-C
60The detection method detectability can reach 1nM.When adding other albumen (100nM bovine serum albumin BSA or people's immunoglobulin (Ig) 100nM IgG) to fluorescence probe (50nM T
A) solution in after, add nano-C again
60, fluorescent quenching is not suppressed, and BSA and the IgG fluorescence intensity contrast T when existing
BThe ratio of the fluorescence intensity when existing is 27.3% and 29.3%, therefore based on nano-C
60Detection method human thrombin albumen is had very high specific detection ability.
Metallic ion (Hg
2+, Ag
+) detection: with fluorophore (FAM) modify be rich in the T base to Hg
2+Fluorescence probe (the P of the single stranded DNA sequence of specific binding capacity as fluoroscopic examination arranged
H), with Hg
2+Be the metal target ion that detects.At first with nano-C
60Join fluorescence probe (50nM P
H) solution in, the dna probe of strand can be adsorbed onto nano-C
60The surface, cause 88% fluorescent quenching.And at Hg
2+Under the condition that exists, because T-Hg
2+The formation of the caused foldable structure of-T, the cancellation of fluorescence is suppressed, and the fluorescence intensity of this moment is no Hg
2+When existing 6 times.Through above process, based on nano-C
60Detection Hg
2+The method of ion, detectability can be low to moderate 500pM.The result sees Fig. 5 and Fig. 6.When adding other metallic ion, this detection method also has very high selectivity, and this method can detect in actual sample lake water, and the result sees Fig. 7.In addition, this method can be applicable to Ag
+Detect, detectability reaches 1nM.
Embodiment 3: the preparation of mesoporous silicon and detection albumen and metallic ion
Material preparation and processing: the mesoporous silicon (MS) of 1g is added in the 5g water, then add 1.25 glucose and 0.14g 98%H
2SO
4, behind the stirring 5h, let the gained potpourri react 6h respectively under the room temperature at 100 ℃ and 160 ℃.Afterwards, reaction mixture is added in the 5g water, then adds 0.75g sugar and 0.09g 98%H
2SO
4After stirring 12h, with reaction mixture dry 6h under 160 ℃.At last, at 800 ℃ of N
2Protective condition is calcining 4h down, accomplishes carbonization process.The carbon-silicon compound of gained is removed the silicon template with 1M NaOH (water/alcohol mixeding liquid) flushing 12h, dry under the room temperature afterwards, obtain the particulate of mesoporous carbon (MC).
The detection of albumen: human thrombin albumen is had the fluorescence probe (T of the single stranded DNA sequence of specific recognition capability as fluoroscopic examination albumen with what fluorophore (FAM) was modified
A), be the target protein (T of detection with human thrombin albumen
B).At first MC is joined fluorescence probe (50nM T
A) solution in, the dna probe of strand can be adsorbed onto the surface of MC, causes fluorescent quenching.Through one period reaction time (60min), fluorescent quenching reaches balance (97%).Add human thrombin albumen (100nM T
B), add MC again, then owing to the existence of albumen, the cancellation of fluorescence is suppressed, and has only 38% cancellation generation (60min reaches balance), and the result sees Fig. 4.The result shows, can be low to moderate 250pM based on the detection method detectability of MC.When adding other albumen (100nM bovine serum albumin BSA or people's immunoglobulin (Ig) 100nM IgG) to fluorescence probe (50nM T
A) solution in after, add MC again, fluorescent quenching is not suppressed, and BSA and the IgG fluorescence intensity contrast T when existing
BThe ratio of the fluorescence intensity when existing is 6.2% and 7.4%, and therefore this detection method based on MC has very high specific detection ability to human thrombin albumen.
The detection of metallic ion: with fluorophore (FAM) modify be rich in the C base to Ag
+Fluorescence probe (the P of the single stranded DNA sequence of specific binding capacity as fluoroscopic examination arranged
Ag), with Ag
+Be the metal target ion that detects.At first MC is joined fluorescence probe (50nM P
Ag) solution in, the dna probe of strand can be adsorbed onto the surface of MC, causes 84% fluorescent quenching.And at Ag
+Under the condition that exists, because C-Ag
+The formation of the caused foldable structure of-C, the cancellation of fluorescence is suppressed, and the fluorescence intensity of this moment is no Ag
+When existing 4 times.The result shows, can be low to moderate 500pM based on the detection method detectability of MC.When adding other metallic ion, this detection method also has very high selectivity, and this method can detect in actual sample lake water.In addition, this method can be used for Hg
2+Detection, detectability can reach 10nM.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (1)
1. a method that detects protein and metallic ion is characterized in that,
The probe molecule that can combine with the target specificity of band report fluorophor is provided;
Said probe molecule is mixed with the nano material solution that is rich in pi-electron, add testing sample then, detect fluorescence;
Wherein, said target is protein and metallic ion, and it is phenylenediamine, 3 that the said nano material that is rich in pi-electron is selected from monomer; 4-ethene dioxythiophene or cinnamic conjugated polymer, silver (I)-4,4 '-dipyridine, copper (II)-4; 4 '-dipyridine, chloroplatinic acid-3,3 ', 5; 5 '-tetramethyl biphenyl diamines, chloroplatinic acid-p-phenylenediamine (PPD) or tetrachloro alloy acid-4,4 '-dipyridine coordination polymer, porphyrin bunch collective, mesoporous carbon and nanometer C
60
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| CN103487416A (en) * | 2013-03-06 | 2014-01-01 | 中北大学 | Fluorescent sensor for detecting zinc ions based on asymmetrical porphyrin fluorescence ratio |
| CN107044961A (en) * | 2017-03-24 | 2017-08-15 | 福建工程学院 | A kind of method of spectrophotometry silver ion |
| CN108732348A (en) * | 2017-04-19 | 2018-11-02 | 复旦大学 | A kind of construction method that ligand gates diagnostic and therapeutic system and its application in terms of tumour real-time response |
| CN113030032A (en) * | 2019-12-24 | 2021-06-25 | Tcl集团股份有限公司 | Detection method of tetracycline |
| CN113267464A (en) * | 2021-06-17 | 2021-08-17 | 江苏大学 | Method and device for detecting multi-component heavy metal in edible oil based on near infrared combined colorimetric sensor array |
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| WO2001051665A2 (en) * | 2000-01-13 | 2001-07-19 | Nanosphere Inc. | Nanoparticles having oligonucleotides attached thereto and uses therefor |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103487416A (en) * | 2013-03-06 | 2014-01-01 | 中北大学 | Fluorescent sensor for detecting zinc ions based on asymmetrical porphyrin fluorescence ratio |
| CN103487416B (en) * | 2013-03-06 | 2016-01-20 | 中北大学 | A kind of based on the fluorescent optical sensor of asymmetrical porphyrin fluorescence than detection zinc ion |
| CN107044961A (en) * | 2017-03-24 | 2017-08-15 | 福建工程学院 | A kind of method of spectrophotometry silver ion |
| CN108732348A (en) * | 2017-04-19 | 2018-11-02 | 复旦大学 | A kind of construction method that ligand gates diagnostic and therapeutic system and its application in terms of tumour real-time response |
| CN113030032A (en) * | 2019-12-24 | 2021-06-25 | Tcl集团股份有限公司 | Detection method of tetracycline |
| CN113030032B (en) * | 2019-12-24 | 2022-06-24 | Tcl科技集团股份有限公司 | Detection method of tetracycline |
| CN113267464A (en) * | 2021-06-17 | 2021-08-17 | 江苏大学 | Method and device for detecting multi-component heavy metal in edible oil based on near infrared combined colorimetric sensor array |
| CN113267464B (en) * | 2021-06-17 | 2024-06-07 | 江苏大学 | Method and device for detecting multi-component heavy metals in edible oil based on near infrared combined colorimetric sensor array |
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|---|---|
| CN102507952B (en) | 2014-06-18 |
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