CN104371705B - A kind of difunctionalization nano material, Preparation Method And The Use - Google Patents

A kind of difunctionalization nano material, Preparation Method And The Use Download PDF

Info

Publication number
CN104371705B
CN104371705B CN201310356017.6A CN201310356017A CN104371705B CN 104371705 B CN104371705 B CN 104371705B CN 201310356017 A CN201310356017 A CN 201310356017A CN 104371705 B CN104371705 B CN 104371705B
Authority
CN
China
Prior art keywords
noble metal
difunctionalization
luminol
amino
metal nanometer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201310356017.6A
Other languages
Chinese (zh)
Other versions
CN104371705A (en
Inventor
崔华
刘孟晓
张宏丽
舒江南
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Science and Technology of China USTC
Original Assignee
University of Science and Technology of China USTC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Science and Technology of China USTC filed Critical University of Science and Technology of China USTC
Priority to CN201310356017.6A priority Critical patent/CN104371705B/en
Publication of CN104371705A publication Critical patent/CN104371705A/en
Application granted granted Critical
Publication of CN104371705B publication Critical patent/CN104371705B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The present invention relates to a kind of difunctionalization nano material, Preparation Method And The Use.Being specifically related to a kind of difunctionalization noble metal nanometer material, it comprises noble metal nano particles；It is derived from the luminous fragment of the luminol class chemical illuminating reagent of logical formula (I)；Luminescence enhancement fragment with the coordination of metal ion chelate being derived from containing sulfydryl or amino；The luminous fragment of the described luminol class chemical illuminating reagent being derived from logical formula (I) is connected to the surface of described noble metal nano particles with the luminescence enhancement fragment being derived from the coordination of metal ion chelate containing sulfydryl or amino: in formula, A represents C6 C14 aryl；R1And R2Can represent that hydrogen, end group are this NR by the substituted or unsubstituted straight or branched of amino (C1 C30) alkyl, precondition independently1R2There is at least one NH2End group.The difunctionalization noble metal nanometer material of the present invention has the characteristics of luminescence of brilliance, and compared with prior art, luminescent properties is greatly improved, and achieves beyond thought technique effect.

Description

A kind of difunctionalization nano material, Preparation Method And The Use
Technical field
The present invention relates to a kind of difunctionalization noble metal nanometer material containing chemiluminescence fragment and luminescence enhancement fragment.The invention still further relates to preparation and the application of this difunctionalization noble metal nanometer material.
Background technology
Noble metal nanometer material has the optical property of uniqueness, catalysis activity and biocompatibility etc., and these characteristics make noble metal nanometer material be widely used in chemiluminescence analytical field.Existing noble metal nanometer material carries out surface modification makes its surface have light emitting molecule, and the noble metal nanometer material i.e. preparing lighting function causes the extensive concern of people.
Such as, known in the art directly utilize luminol reduction gold chloride, one-step synthesis has obtained gold nano-material (Cui, the H. of luminol functionalization;Wang,W.;Duan,C.F.;Dong,Y.P.;Guo, J.Z.Chem.Eur.J.2007,13,6975), the gold nano-material of this luminol functionalization is assembled into the surface of gold electrode, a H can be built2O2Chemiluminescence sensor.Prior art is it is also mentioned that utilize N-(4-aminobutyl)-N-ethyl different luminol reduction gold chloride to obtain gold copper-base alloy (Tian, the D. of N-(4-aminobutyl)-N-ethyl different luminol functionalization by seeded growth method;Zhang,H.;Chai,Y.;Cui, H.Chem.Commun.2011,47,4959), this nano material is compared with luminol functionalization gold nano-material, and luminescent properties is more preferable, and therefore this nano material is used successfully to the high-sensitive chemiluminescence immunoassay sensor of development and nucleic acid sensor.
The application in immunoassay of the nanometer gold of the open directly bonded with luminol of CN101900723A, it relates to the nanometer gold immunoassay probe of directly bonded with luminol, this analysis probe is made up of the antibody of the nano gold mark of directly bonded with luminol, wherein, the nanometer gold of directly bonded with luminol is obtained by luminol one step reduction gold chloride；It further relates to the chemiluminescence immune analysis method of nanometer gold immunoassay probe based on this directly bonded with luminol.According to the document, this chemiluminescence immune analysis method has highly sensitive, range of linearity width, favorable reproducibility, the advantage such as simple to operate, with low cost.
Open N-(4-aminobutyl)-N-ethyl different luminol lighting function nanometer gold of WO2011/107003 and its preparation method and application, described functional gold nanoparticles comprises golden nanometer particle and N-(4-aminobutyl) the different luminol of-N-ethyl being connected on this golden nanometer particle surface.This functional gold nanoparticles is used for being formed such as analysis probe with the molecular detection selected from lower group after being connected: (a) has the binding molecule of binding specificity to target analytes；Or (b) and the competitive molecule of target analytes competition binding capture probe.According to the document, its analysis probe has high analyte sensitivity.
Although prior art has been provided for analysis probe based on N-(4-aminobutyl)-N-ethyl different luminol lighting function nanometer gold, it has higher sensitivity for analysis, but its sensitivity also has the leeway of raising.
Transition metal or the ion of rare earth elemental metals or containing transition metal or material (e.g., Co (II)-EDTA chelate, the Fe (CN) of rare earth elemental metals6 3-, containing iron porphyrin etc.) and chemical luminous system had the strongest catalytic action, it is possible to it is greatly enhanced the chemiluminescence intensity of luminol class chemical luminous system.Such as having document to report, Co (II)-EDTA chelate can strengthen luminol-H2O2Chemiluminescence.However it has been found that add in existing lighting function nano material by this catalytic specie, its luminous intensity still fails to improve to meeting the degree required.
Summary of the invention
It is an object of the present invention to existing such as N-(4-aminobutyl)-N-ethyl different luminol lighting function nanometer gold is improved, to improve its luminous intensity further, thus improve the sensitivity for analysis of the analysis probe formed by this nanometer gold material further.
Another object of the present invention is to provide the preparation method and its usage of the nano material of a kind of above-mentioned improvement.
Therefore, one aspect of the present invention provides a kind of difunctionalization noble metal nanometer material, it comprises noble metal nano particles, the luminous fragment being derived from the luminol class chemical illuminating reagent of logical formula (I) and is derived from the luminescence enhancement fragment of coordination of metal ion chelate containing sulfydryl or amino, described in be derived from the luminous fragment of luminol class chemical illuminating reagent of logical formula (I) and be derived from the luminescence enhancement fragment of the coordination of metal ion chelate containing sulfydryl or amino and be connected to the surface of described noble metal nano particles:
In formula, A represents C6-C14 aryl；
R1And R2Can represent that hydrogen, end group are this NR by amino substituted or unsubstituted straight or branched (C1-C30) alkyl, precondition independently1R2There is at least one NH2End group.
A second aspect of the present invention provides a kind of method preparing the present invention difunctionalization noble metal nanometer material, and described method comprises the steps:
1) provide containing sulfydryl or the coordination of metal ion chelate of amino；
2) the luminol class chemical illuminating reagent of logical formula (I) and aqueous noble metal precursor compound is made to react, in this course of reaction or after the reaction was complete, add described containing sulfydryl or the coordination of metal ion chelate of amino in reaction system, obtain difunctionalization noble metal nanometer material.
The present invention is that another further aspect relates to a kind of method preparing the present invention difunctionalization noble metal nanometer material, and described method comprises the steps:
1) provide containing sulfydryl or the coordination of metal ion chelate of amino, luminol class chemical illuminating reagent and aqueous noble metal precursor compound；
2) make above-claimed cpd hybrid reaction, obtain difunctionalization noble metal nanometer material.
A third aspect of the present invention provides the difunctionalization noble metal nanometer material of the present invention as the purposes of analysis probe, and this analysis probe can be used for detection and the analysis of following various fields sample: biological sample, Foods or drinks sample, drug sample, environmental sample, chemical example.
Compared with prior art, present invention have the advantage that:
1. the difunctionalization noble metal nanometer material that the present invention is novel achieves and is coated luminol class chemical illuminating reagent on noble metal nano particles simultaneously and has the coordination of metal ion chelate of luminescence enhancement effect, compared with existing lighting function nano material, the luminous intensity of the present invention difunctionalization noble metal nanometer material is greatly improved, such as at least three orders of magnitude of luminous intensity height of N-(4-aminobutyl)-N-ethyl different luminol lighting function gold nano-material disclosed in luminous strength ratio CN101900723A and WO2011/107003；
2. the preparation method of the present invention difunctionalization noble metal nanometer material has simple, quick, without advantages such as specific conditions；
It is used for preparing analysis probe by difunctionalization noble metal nanometer material first, especially make it as immunoassay probe and foranalysis of nucleic acids probe, develop new analysis method (such as immunity and method for nucleic acid analysis) further, highly sensitive, highly sensitive, the favorable reproducibility of the method, highly reliable；
Therefore, the difunctionalization noble metal nanometer material of the present invention has huge application potential and good application prospect in fields such as clinical analysis, food safety, environment measuring and pharmaceutical analysiss.
The invention will be further described below in conjunction with the accompanying drawings.
Accompanying drawing explanation
Fig. 1 is the ES-MS spectrogram of sulfhydrylation diethylene-triamine pentaacetic acid.
Fig. 2 is (a) diethylene-triamine pentaacetic acid (DTPA) and the FT-IR spectrogram of (b) sulfhydrylation diethylene-triamine pentaacetic acid.
Fig. 3 is sulfhydrylation diethylene-triamine pentaacetic acid1HNMR spectrogram (300MHz, D2O, 298K).
Fig. 4 shows the synthetic method schematic diagram of a preference of the present invention.
The electromicroscopic photograph of Fig. 5 several functions gold nano-material.
Fig. 6 is thermogravimetric analysis and the differential thermal analysis curve of one preference of the present invention.
Fig. 7 is the ultraviolet visible absorption spectra figure of a preference of the present invention.
Fig. 8 is the x-ray photoelectron power spectrum of a preference of the present invention.
Fig. 9 is the comparison of the chemiluminescence effect of the difunctional gold nano-material containing different metal ion chelate complex.
Figure 10 is the figure of the preference comparing the present invention and the chemiluminescence intensity of other chemiluminescence functionalization gold nano-material.
Detailed description of the invention
Below the detailed description of the invention of difunctionalization noble metal nanometer material of the present invention and preparation method thereof, analysis probe based on this difunctionalization noble metal nanometer material and analysis method based on this analysis probe is described in detail.
A. difunctionalization noble metal nanometer material
The invention provides a kind of difunctionalization noble metal nanometer material, it comprises noble metal nano particles, is attached on this noble metal nano particles be derived from the luminous fragment of luminol class chemical illuminating reagent and is also attached on this noble metal nano particles be derived from the luminescence enhancement fragment of the coordination of metal ion chelate containing sulfydryl or amino.
1. noble metal nano particles
Noble metal nano particles of the present invention is without particular limitation, can be any noble metal nano particles known in the art.Those of ordinary skill in the art is readily able to select applicable metal nanoparticle according to actual needs.In an example of the present invention, described metal nanoparticle is selected from: golden nanometer particle, Nano silver grain, nano platinum particle or their alloy nano particle, and combinations thereof.In another example of the present invention, above-mentioned metal nanoparticle is selected from: the alloy that golden nanometer particle, Nano silver grain and/or nano platinum particle are each formed with base metal, condition be in alloy the amount of noble metal account for 50 weight % or more than, such as account for 50-98 weight %, preferably account for 60-95 weight %, preferably account for 70-93 weight %, more preferably account for 80-90 weight %, preferably 85-88 weight %.
In one preferred embodiment, described noble metal nano particles is golden nanometer particle.
In one embodiment, the pattern of described noble metal nano particles is that single dispersing is spherical, and its particle diameter is 1-100 nanometer, preferable 5-80 nanometer, more preferable 10-50 nanometer.
Noble metal nano particles of the present invention is commercially available, it is also possible to obtained by in-situ reducing.In an example of the present invention, make noble metal precursor compound (such as gold chloride, chloroplatinic acid, silver nitrate or its mixture) and reducing agent the luminol class chemical illuminating reagent of reproducibility (the such as present invention have) react, be formed in situ the noble metal nano particles that particle diameter is 1-100 nanometer.
2. luminol class chemical illuminating reagent
It is applicable to the luminol class chemical illuminating reagent of the present invention and there is general formula I:
In formula, A represents C6-C14 aryl, preferable C6-C10 aryl, more preferably has the aryl of 6 carbon atoms.Term " A represents C6-C14 aryl " refers to the aryl with the carbon atom including two adjacent ring carbon atoms in the present invention, and such as it can be phenyl, naphthyl and anthryl.
R1And R2Can represent that hydrogen, end group are this NR by amino substituted or unsubstituted straight or branched C1-C30, preferable C1-C20, more preferable C1-C10, best C1-C8, preferred C1-C6 alkyl, precondition independently1R2There is at least one NH2End group.
In the present invention, term " NR1R2There is at least one NH2End group " refer to NR1R2Itself it is NH2, or R1、R2In at least one with NH2The alkyl of end group.
In an example of the present invention, R1And R2Methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group, amyl group, isopentyl, hexyl, amino methyl, amino-ethyl, 1-aminopropyl, 2-Methyl-amino ethyl, 1-aminobutyl, 2-Methyl-amino propyl group etc. can each be selected from.
In an example of the present invention, described luminol class chemical illuminating reagent is selected from:
Wherein, R1And R2As defined above.
In a preferable example of the present invention, the luminol class chemical illuminating reagent of above-mentioned logical formula (II) is selected from:
Wherein,R1And R2As defined above.
A luminol class chemical illuminating reagent at least amino (NH of the present invention2) end group, utilize this group can be by such chemical illuminating reagent by being covalently bonded to the surface of noble metal nano particles of the present invention.On the other hand, owing to such luminescence reagent belongs to hydrazide kind compound, its hydrazides group has reproducibility, can be as the precursor compound of reducing agent in-situ reducing noble metal nano particles.
In the present invention, term " connected by covalent bond " lone pair electrons and the metal referred in amino or sulfydryl unoccupied orbital interact formed be bonded.
In one embodiment, the luminol class chemical illuminating reagent of representative logical formula (II) is selected from lower group, but is not limited to this:
In another embodiment, the luminol class chemical illuminating reagent of described logical formula (III) is N-(4-aminobutyl)-N-ethylnaphthalene hydrazides；
In one embodiment, luminol class chemical illuminating reagent of the present invention forms covalent bond by amino with noble metal nano particles interaction, thus it is connected to the surface of described noble metal nano particles, such as, described covalent bond includes Au-N key, Pt-N key or Ag-N key.
3. containing sulfydryl or the chelate of metal ion of amino
The present invention coordination of metal ion chelate containing sulfydryl or amino comprises metal ion and containing sulfydryl or the chelating agen of amino.It is true that chelate of metal ion of the present invention is without particular limitation, as long as it has luminescence enhancement effect and makes it covalently bound with surfaces of metal nanoparticles containing sulfydryl or amino.
In an example of the present invention, described metal ion is selected from group VIII, IB race, Group IIB, group vib transition metal ions, rare earth element ion, IVA race metal or a combination thereof.In an example of the present invention, described transition metal ions is selected from: Co2+、Cu2+、Ni2+、Hg2+、Cr3+、Pd2+、Pt2+、Fe2+、Fe3+、Ru2+；Described rare earth element ion is selected from Eu3+, La3+、Gd3+、Sm3+、Er3+、Dy3+、Ce4+、Ce3+；Described IVA race metal is Pb2+。
Described chelating agen has selected from mercapto, amino or first active group of a combination thereof (preferably sulfydryl) and the second active group, wherein said first active group is for being connected with described noble metal nano particles, and described second active group is used for and described metal ion generation complexation.
As it has been described above, the present invention contains two metalloids, one type metal is the metal for forming nanoparticle, and another kind of is the metal that can play enhancing luminous function included in coordination of metal ion chelate.For clarity sake, in this article, the present invention is used for being formed the metal of nanoparticle to use term " noble metal " to represent, such as it can be Au, Ag and Pt；The present invention is used for being formed the metal of chelate of metal ion to use term " coordinating metal " to represent, it includes transition metal ions and rare earth element ion etc..
In one embodiment, the first active group and second active group of described chelating agen can be identical or different from each other.In another embodiment, the second active group of described chelating agen includes the active group with complexing power containing O, N, S, such as carboxyl, hydroxyl, secondary amino group, tertiary amino or a combination thereof.
In one embodiment of the invention, sulfydryl contained by the first active group or amino are positioned at the terminal sites of chelating agen.
The non-limitative example of described chelating agen has, such as: sulfhydrylation chelating agen, such as sulfhydrylation ethylenediaminetetraacetic acid, sulfhydrylation diethylene-triamine pentaacetic acid, sulfhydrylation 1,4,7,10-tetraazacyclododecanands-1, the sub-second triamine tetraacethyl of 4,7,10-tetrabasic carboxylic acids, sulfhydrylation two；Amination chelating agen, such as amination ethylenediaminetetraacetic acid, amination diethylene-triamine pentaacetic acid, amination Isosorbide-5-Nitrae, 7,10-tetraazacyclododecanands-Isosorbide-5-Nitrae, the sub-second triamine tetraacethyl of 7,10-tetrabasic carboxylic acids, amination two, or the combination of two or more in above-mentioned chelating agen.
In another embodiment, the described coordination of metal ion chelate containing sulfydryl or amino is interacted with noble metal nano particles by sulfydryl or amino, forms covalent bond and is connected to the surface of described noble metal nano particles.
In another embodiment, described covalent bond includes Au-N key, Au-S key, Pt-N key, Pt-S key, Ag-N key or Ag-S key；Preferably Au-S key, Pt-S key or Ag-S key.
In this article, except as otherwise noted, chemiluminescent " luminescence enhancement fragment " is used interchangeably with " luminous catalytic fragment ", all referring in chemiluminescence reaction, joins the fragment that chemiluminescence intensity can be made in chemiluminescence reaction system to be greatly enhanced.
The luminous fragment being derived from luminol class chemical illuminating reagent in the present invention difunctionalization noble metal nanometer material is without particular limitation with the relative quantity of the luminescence enhancement fragment of the coordination of metal ion chelate being derived from containing sulfydryl or amino, as long as this luminescence enhancement fragment be enough to improve the luminous intensity of luminous fragment.In an embodiment of the invention, described luminescence enhancement fragment is 1000:1 to 1:1000, preferably 500:1-1:500 with the mol ratio of luminous fragment, more preferably 100:1-1:100, preferably 50:1-1:50, preferably 30:1-1:30, preferably 10:1-1:10.
The present invention difunctionalization noble metal nanometer material is by reacting generation chemiluminescence with oxidant.The oxidant being suitable for is without particular limitation, can be any oxidant known in the art.In an example of the present invention, described oxidant includes but not limited to H2O2、O2、ClO-、I2、IO4 -、MnO4.In an example of the present invention, the condition of described chemiluminescence reaction is: by 10-1000 microlitre 0.1M H2O2Solution is injected in the purified difunctionalization noble metal nanometer material aqueous solution of 10-1000 microlitre, produces chemiluminescence.
In a preferred embodiment, described difunctionalization noble metal nanometer material is difunctionalization gold nano-material, its chemiluminescence fragment is derived from N-(4-aminobutyl) the different luminol of-N-ethyl, its luminescence enhancement fragment is derived from the coordination of metal ion chelate containing sulfydryl, N-(4-aminobutyl) the different luminol of-N-ethyl is bonded the surface being connected to golden nanometer particle by Au-N, and the described coordination of metal ion chelate containing sulfydryl is connected to the surface of golden nanometer particle by Au-S.
Compared with the existing lighting function nano material only comprising chemiluminescence fragment, the difunctionalization noble metal nanometer material of the present invention is except the pan coating at noble metal nano particles in addition to one or more luminous fragments, also it is coated one or more coordination of metal ion chelate fragment, this coordination of metal ion chelate fragment has enhancing or catalytic action to the chemiluminescence of luminol class chemical luminous system, so that the difunctionalization noble metal nanometer material of the present invention is greatly improved in terms of luminescent properties, there is the characteristics of luminescence of brilliance.In the case of luminescence reagent kind and consumption, gold chloride consumption and luminescence experiments condition equivalent, the difunctionalization noble metal nanometer material of the present invention is than the highest three orders of magnitude of luminous efficiency of existing luminescence reagent list functionalization noble metal nanometer material.
As used herein, term " lighting function ", " luminescence reagent functionalization " or " chemiluminescence functionalization " etc. are used interchangeably, and each mean and make nano material have chemiluminescent properties owing to comprising luminescence reagent.
B. the preparation method of difunctionalization noble metal nanometer material
The present invention also provides for the method simply and quickly preparing the noble metal nanometer material of the present invention difunctionalization, and it comprises the following steps:
1. provide containing sulfydryl or the coordination of metal ion chelate of amino
As hereinbefore defined, it comprises coordination of metal ion and chelating agen to the described coordination of metal ion chelate containing sulfydryl or amino, and wherein said chelating agen can prepare by the chelating agen without sulfydryl or amino known in the art carries out sulfhydrylation or amination.The sulfhydrylation of this chelating agen or amination are known, see, for example: Christophe Alric, Jacqueline Taleb, G é raldine Le Duc, C é line Mandon, Claire Billotey, Alice Le Meur-Herland, Thierry Brochard, Francis Vocanson, Marc Janier, Pascal Perriat, St é phane Roux, and Olivier Tillement.J.Am.Chem.Soc.2008,130,5,908 5915.
Additionally, coordination of metal ion of the present invention and chelating agen generation complexation can be made by conventional method known in the art, obtain the required coordination of metal ion chelate containing sulfydryl or amino.
In a specific embodiment of the present invention, as a example by sulfhydrylation diethylene-triamine pentaacetic acid, the described coordination of metal ion chelate containing sulfydryl or amino is prepared by the following: described sulfhydrylation diethylene-triamine pentaacetic acid is configured to the aqueous solution of 1-20mM, then mix with the volume ratio of 5:1 to 1:5 with the described coordination of metal ion aqueous solution of 1-20mM, obtain the aqueous solution of coordination of metal ion chelate containing sulfydryl or amino.
2. luminol class chemical illuminating reagent and aqueous noble metal precursor compound react
The reaction of luminol class chemical illuminating reagent and aqueous noble metal precursor compound that the present invention leads to formula (I) is carried out under conditions of more fortunately stirring.The condition of reaction is without particular limitation, can be normal temperature and pressure.In this article, term " noble metal precursor compound " is intended to indicate that any aqueous compounds that can form noble metal nano particles, and its non-limitative example has gold chloride, chloroplatinic acid, silver nitrate or its mixture.
As described above, owing to meeting the luminol class chemical illuminating reagent of the logical formula (I) of structure above, there is hydrazides group, thus it has reproducibility, make such luminescence reagent can form noble metal nano particles as reducing agent reduction noble metal precursor compound in the method for the invention.
In one embodiment, the luminol class chemical illuminating reagent of the logical formula (I) added in the reaction and the mol ratio of aqueous noble metal precursor compound are 0.4-5, preferably 0.5-3.
It addition, in this course of reaction (before such as having reacted half) or after the reaction was complete, add described containing sulfydryl or the coordination of metal ion chelate of amino in reaction system, obtain difunctionalization noble metal nanometer material.
The luminol class chemical illuminating reagent of logical formula (I) is without particular limitation with the addition of the coordination ion chelate containing sulfydryl or amino, as long as the luminous intensity of final products can be strengthened.In an example of the present invention, described luminol class chemical illuminating reagent is 1000:1 to 1:1000 with the addition mol ratio of the coordination ion chelate containing sulfydryl or amino, it is preferably 500:1-1:500, more preferably 100:1-1:100, preferably 50:1-1:50, preferably 30:1-1:30, preferably 10:1-1:10.
Lead to the luminol class chemical illuminating reagent of formula (I) due to the present invention and there is at least one amino end group; and the present invention comprises sulfydryl or amino containing the coordination of metal ion chelate of sulfydryl or amino; therefore they all can protect reagent as nanoparticle in the forming process of noble metal nano particles; prevent nano-particle from reuniting, the described difunctionalization noble metal nanometer material of final acquisition.
In the present invention, difunctionalization noble metal nanometer material can use any one of following preparation method to prepare:
I () is first with luminol class chemical illuminating reagent of the present invention reduction noble metal precursor compound and be coated the nano metal that obtains of reduction, obtain the noble metal nanometer material of primary luminescence reagent functionalization, then add containing sulfydryl or the coordination of metal ion chelate of amino to reaction system situ, it is made to utilize the interaction of sulfydryl or amino and noble metal nano particles to be connected on the primary lighting function noble metal nanometer material of gained, it is thus achieved that final difunctionalization noble metal nanometer material；Or
(ii) luminol class chemical illuminating reagent of the present invention, noble metal precursor compound, coordination of metal ion chelate containing sulfydryl or amino are simultaneously introduced in reaction system and carry out redox reaction; in course of reaction; luminol class chemical illuminating reagent act as reducing agent and protection reagent (being coated reagent), the luminescence enhancer containing sulfydryl or amino as common protection reagent (being coated reagent altogether) participate in noble metal nano particles formation.
In above two preparation method, the consumption of each reaction raw materials and reaction condition can be substantially the same, and differ only in the time that the coordination of metal ion chelate containing sulfydryl or amino adds.The character of two kinds of difunctionalization that method is obtained noble metal nanometer materials is identical.
The inventors found that, for the existing noble metal nano particles ((4-the aminobutyl)-N-ethyl different luminol lighting function nanometer gold of N-disclosed in such as WO2011/107003) being coated luminol luminous agent, it is added thereto to the luminous intensity being favorably improved solution without being coated the coordination of metal ion chelate (being equivalent to single function noble metal nano particles+luminescence enhancer) of ability (i.e. without sulfydryl or amino) with luminescence enhancement function.But, when there was added the coordination of metal ion chelate of the ability of being coated (containing sulfydryl or amino), compared with the coordination of metal ion chelate added without being coated ability, find that the chemiluminescence intensity of solution has to significantly improve further, it was demonstrated that the covalent bond between described coordination ion chelate and noble metal nano particles containing sulfydryl or amino also has catalytic action to the chemiluminescence of the difunctionalization nano material of the present invention.
The above-mentioned reaction of the present invention can be carried out under conditions of adding thermally or ultrasonically.
In an embodiment of the invention, described reaction system also can comprise other organic solvent, such as ethanol, ether, acetone etc..
When the amount of luminol class chemical illuminating reagent of the present invention be enough to make the reduction of noble metal precursor compound form noble metal nano particles, without adding extra reducing agent in the method for the present invention.But the inventive method can also add extra reducing agent to guarantee the formation of noble metal nano particles, and the not limiting example of described reducing agent has, such as sodium borohydride, citrate, ascorbic acid, hydrazine hydrate, aminoacid, polyvinylpyrrolidone etc..The purpose adding additional reducing agent is assisted Reduction noble metal precursor compound, and to form noble metal nano particles, but this is optional.
In an embodiment of the invention, described method also includes the step being purified the difunctionalization noble metal nanometer material of gained, and described purification is to include such as being centrifuged, dialysing or combinations thereof, is preferably purified by centrifugal.In another preference, described purification is by the nano material that will obtain under 12500*g centrifugal 10-50 minute, preferably 10-20 minute.
C. the analysis probe of difunctionalization noble metal nanometer material based on the present invention
The difunctionalization noble metal nanometer material of the present invention is because having the luminescent properties of brilliance, thus can be used as the luminous signal source in various analysis probe, thus is further used for detection field.
As used in the present invention, term " analysis probe " or " analysis probe of the present invention " refer to that a class of difunctionalization noble metal nanometer material and the molecular detection comprising the present invention has the complex identifying function, wherein difunctionalization noble metal nanometer material can produce chemiluminescence signal under suitable luminescent condition, described molecular detection can with target analytes produce specific binding, described difunctionalization noble metal nanometer material be joined directly together with described molecular detection or by combination to or linking group be indirectly connected to.Such analysis probe can be used for various analysis detection field.
In this article, term " in conjunction with to " refers to by High affinities to each other, specific binding biomolecule to occur, or relies on Coulomb force that the ion pair of combination occurs by the ion of two opposite charges.Described combination is to including that member and second are combined member by the first combination.In this article, " the first combination is to member " and " second combines member " represents that the combination of complementation, to one of member, is acted on by High affinities or Coulomb force and combined between the two member, and it is right that formation combines." first " used herein and " second " there is no dividing of primary and secondary, are only used for the purpose of difference.
In yet another embodiment of the present invention, described combination is to being selected from: biotin-Streptavidin, biotin-avidin, biotin-neutrality Avidin, agglutinin and saccharide, staphylococcal protein A and IgG, antigen and antibody, cation and anion or hormone vitamin and lipid and receptor etc..
Described linking group is selected from: sulfydryl or amino.
As used herein, term " molecular detection " is the molecule being connected with the difunctionalization noble metal nanometer material producing luminous signal in analysis probe, and detection analysis can produce specific binding with target analytes.Molecular detection can be selected by those of ordinary skill in the art according to analysis method used and the kind of target analytes, and can select it with the connected mode of difunctionalization noble metal nanometer material by concrete structure based on selected molecular detection.
In an embodiment of the invention, described target analytes is selected from: protein or polypeptide (antigen, antibody, polypeptide), nucleic acid (DNA, RNA, aptamers), microorganism (such as virus, antibacterial, fungus), fatty acid, vitamin, medicine, metal ion, Organic substance, aminoacid, biotoxin, chemical toxicant or cell.
In yet another embodiment of the present invention, described specific binding it is selected from: the hybridization between specific binding or nucleic acid molecules between specific binding, aptamers and the antigen between antibody and antigen；Described nucleic acid molecules includes DNA and RNA molecule.In this article, term " antigen " is intended to indicate that can stimulate body to produce (specificity) immunne response, and can be combined in vivo and in vitro with immunne response product antibodies and primed lymphocyte, and the material of immunological effect (specific reaction) occurs.In this article, term " antibody " is intended to include with corresponding antigens specific binding immunoglobulin to occur, and modifies this immunoglobulin like protein further and make it comprise the above-mentioned combination material to member, the most biotinylated antibody.Term " aptamers " refers to, with corresponding antigens, specific binding RNA or DNA fragmentation occur.
The exemplary analysis probe of the present invention can be divided into the type such as immunoassay probe, foranalysis of nucleic acids probe according to the difference of molecular detection, and its using method can be for example, see WO2011/107003, and this article inserts a this paper part as the present invention by reference.
In yet another embodiment of the present invention, it is characterised in that described analysis probe is chemiluminescence analysis probe.
The analysis probe of the present invention can be widely used for various field and the detection of various sample and analysis, includes, but is not limited to biological sample, Foods or drinks sample, drug sample, environmental sample, the detection of chemical example and analysis.Biological sample can include such as blood, blood plasma, serum, urine, feces, sputum, secretions (such as perspiration, tear etc.), culture etc.；Described environmental sample can be air sample, water sample, pedotheque；Described chemical example can include intermedium, end-product etc..
Purposes, using method and the effect of the Bifunctionalized nano material of the present invention is the Chinese patent application of 135012 referring also to the attorney submitted on the same day by applicant, and this article inserts a this paper part as the present invention by reference.
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention rather than limit the scope of the present invention.
Embodiment
Method of testing:
(1) transmission electron microscope；
Method of testing: transmission electron microscope (TEM, JEOL Ltd, JEOL-2010, Japan).Prepared sample is centrifuged, after 12500*g15min, removes supernatant.After gained precipitation is dispersed in ethanol solution, carry out transmission electron microscope analysis.
(2) thermogravimetric analysis and differential thermal analysis；
Method of testing: prepared sample is centrifuged by (TGA/DTG, Q5000V3.15), removes supernatant after 12500*g15min.Gained precipitation is dried under vacuum, carries out thermogravimetric analysis and differential thermal analysis.
(3) uv-vis spectra；
Method of testing: prepared sample is centrifuged by (Agilent8453 ultraviolet-visual spectrometer), removes supernatant after 12500*g 15min.Gained precipitation is dispersed in pH=12NaOH solution, carries out ultraviolet-visible absorption spectroscopy mensuration.
(4) x-ray photoelectron power spectrum；
Method of testing: prepared sample is centrifuged by (ESCALABMK II electron spectrograph, VG Scientific, UK), removes supernatant after 12500*g15min.Gained precipitation is dried under vacuum, carries out X-ray photoelectron spectroscopic analysis.
(5) chemiluminescent properties:
Use Centro LB960 type microwell plate luminometer (Berthold, Germany) that the chemiluminescent properties of difunctionalization gold nano-material is studied.In the aperture of microwell plate, inject 90 μ L difunctionalization gold nano-material solution (being dissolved in pH=12NaOH solution), then add 50 μ L0.1M H by the injection port of microwell plate luminometer2O2Solution.By microwell plate luminometer, chemiluminescence intensity is detected, record chemiluminescent kinetic curve simultaneously.
Synthesis example 1 : prepare sulfhydrylation diethylene-triamine pentaacetic acid (chelating agen 1 )
1g diethylene-triamine pentaacetic acid dicarboxylic anhydride is dissolved in 20mL DMF, is heated to 70 DEG C and obtains solution A.0.55g2-aminoothyl mercaptan is dissolved in 15mL DMF, and adds the triethylamine of 0.87mL, be heated to 70 DEG C and obtain solution B.Solution B being added in solution A, 70 DEG C of heated and stirred are overnight.In course of reaction, solution is gradually become faint yellow by colourless, illustrates that diethylene-triamine pentaacetic acid dicarboxylic anhydride and 2-aminoothyl mercaptan there occurs amidation process, generates the chelating agen with sulfydryl.After solution is cooled to room temperature, then carry out ice bath, filter out white precipitate.Gained filtrate concentrated by rotary evaporation, obtains white precipitate after adding chloroform.After gained white precipitate filters and with chloroform, finally it is vacuum dried and i.e. obtains sulfhydrylation diethylene-triamine pentaacetic acid white powder (chelating agen 1).
Chelating agen 1 is carried out ES-MS, FT-IR and1H NMR tests, and result is as Figure 1-3.
Fig. 1 is the ES-MS spectrogram of chelating agen 1.Molecular ion peak [sulfhydrylation diethylene-triamine pentaacetic acid+H] is can be clearly seen that from figure+(m/z=512).
Fig. 2 is the FT-IR spectrogram of (a) diethylene-triamine pentaacetic acid (DTPA) and (b) chelating agen 1.In figure (a), 3432cm-1Corresponding to the vibration absorption peak of OH, 2932cm in COOH-1Corresponding to the vibration absorption peak of-CH-, 1672cm-1Corresponding in COOH=vibration absorption peak of CO.In figure (b), 3429cm-1Corresponding to the vibration absorption peak of OH in COOH, compared with figure (a), the reduction of peak area is that chelating agen 1 tails off compared to the COOH content of diethylene-triamine pentaacetic acid owing to diethylene-triamine pentaacetic acid dicarboxylic anhydride and 2-aminoothyl mercaptan define amido link；3016cm-1Corresponding to the vibration absorption peak of-CH-, 2530cm-1Corresponding to the vibration absorption peak of SH, 1735cm-1Corresponding in COOH=vibration absorption peak of CO.It addition, 1696cm-1Corresponding to RCONR ' R " in=vibration absorption peak of CO, 1634cm-1Corresponding in RCONHR '=vibration absorption peak of CO.Pass through comparative analysis, it is clear that chelating agen 1 is many 2530cm than diethylene-triamine pentaacetic acid-1The SH vibration absorption peak at place.
Fig. 3 is chelating agen 11H NMR spectra (300MHz, D2O, 298K).By this1H NMR(300MHz, D2O, 298K) spectrogram, can certainly have the successful synthesis of the chelating agen 1 of composition requirement.It is right to be presented herein below1The pointing out and explaining of H NMR peak: δ 3.64(s, 4H ,-N-CH2-CO-N-), 3.61(s, 4H ,-N-CH2-COOH), 3.39(s, 2H ,-N-CH2-COOH), 3.23 3.14(m, 12H ,-N-CH2-CH2-SH,-N-CH2-CH2-N), 2.50(t, 4H, N-CH2-CH2-SH).
Result above fully confirms, has successfully synthesized chelating agen 1.
Further chelating agen 1 is carried out thermogravimetric analysis and differential thermal analysis, shown in result such as Fig. 6 (b).Chelating agen 1 is carried out uv-vis spectra test, and result is as shown in the curve a in Fig. 7.
Synthesis example 2 : prepare sulfhydrylation 1,4,7,10- Tetraazacyclododecanand -1,4,7,10- Tetrabasic carboxylic acid (chelating agen 2 )
By the Isosorbide-5-Nitrae of 1g, 7,10-tetraazacyclododecanand-Isosorbide-5-Nitrae, 7,10-tetrabasic carboxylic acid is dissolved in 20mL thionyl chloride solution, is added dropwise over 3mL dimethylformamide and is heated to reflux 24h, obtains 1 after rotated for gained solution evaporimeter is concentrated and is vacuum dried, 4,7,10-tetraazacyclododecanands-Isosorbide-5-Nitrae, 7,10-tetra-acyl chlorides solids.Products therefrom is dissolved in acetonitrile solution, then add 0.5mL2-aminoothyl mercaptan solution, under nitrogen atmosphere 50 DEG C be stirred at reflux 48h after i.e. obtain sulfhydrylation 1,4,7,10-tetraazacyclododecanands-1,4,7,10-tetrabasic carboxylic acids, the rotated evaporimeter of products therefrom concentrates and is vacuum dried, and i.e. obtains sulfhydrylation Isosorbide-5-Nitrae, 7,10-tetraazacyclododecanands-Isosorbide-5-Nitrae, 7,10-tetrabasic carboxylic acids (chelating agen 2).
The characterization result of infrared spectrum is, 1730cm-1Corresponding in COOH=vibration absorption peak of CO, 2509cm-1Vibration absorption peak corresponding to SH.It addition, 1650cm-1Place is corresponding to amido link (the stretching vibration absworption peak of (-C (O) NH-).
Synthesis example 3 : preparation amination diethylene-triamine pentaacetic acid (chelating agen 3 )
1g diethylene-triamine pentaacetic acid dicarboxylic anhydride is dissolved in 20mL DMF, is heated to 70 DEG C to dissolving.After 2.5mL ethylenediamine is added above-mentioned solution, 70 DEG C of heated and stirred are overnight.After solution is cooled to room temperature, then carry out ice bath, filter out white precipitate.Gained filtrate concentrated by rotary evaporation, obtains white precipitate after adding chloroform.After gained white precipitate filters and with chloroform, finally it is vacuum dried and i.e. obtains amination diethylene-triamine pentaacetic acid white powder (chelating agen 3).
The characterization result of infrared spectrum is, compared with before ammoxidation, and 3429cm-1Place reduces corresponding to the peak area of the vibration absorption peak of OH in COOH, and this is that chelating agen 3 tails off compared to the COOH content of diethylene-triamine pentaacetic acid owing to diethylene-triamine pentaacetic acid dicarboxylic anhydride and ethylenediamine define amido link；1715cm-1Corresponding in COOH=absorption of vibrations of CO, 3360cm-1And 3440cm-1Stretching vibration absworption peak corresponding to N-H.
CloseBecome example 4 : preparation ( Sulfhydrylation diethylene-triamine pentaacetic acid ) Close cobalt (II) (chelate 1 )
Chelating agen 1 is configured to the aqueous solution of 6mM, then with the CoCl of 6mM2Aqueous solution is mixed to get 3Mm (sulfhydrylation diethylene-triamine pentaacetic acid) with the volume ratio of 1:1 and closes cobalt (II) (chelate 1) aqueous solution.Chelate 1 is carried out uv-vis spectra test, and result is as shown in the curve c in Fig. 7.
Synthesis example 5 : preparation ( Sulfhydrylation 1,4,7,10- Tetraazacyclododecanand -1,4,7,10- Tetrabasic carboxylic acid ) Close cobalt (II) (chelate 2 )
Chelating agen 2 is configured to the aqueous solution of 6mM, then with the CoCl of 6mM2Aqueous solution is mixed to get 3Mm (sulfhydrylation Cyclen-1,4,7,10-tetrabasic carboxylic acid) with the volume ratio of 1:1 and closes cobalt (II) (chelate 2) aqueous solution.
Embodiment 1 : prepare difunctionalization noble metal nanometer material 1( Material 1)
In the present embodiment, the coordination of metal ion chelate containing sulfydryl is sulfhydrylation diethylene-triamine pentaacetic acid (chelating agen 1) and Co2+The chelate (chelate 1) formed, luminol class chemical illuminating reagent is N-(4-aminobutyl) the different luminol of-N-ethyl, and noble metal nano particles is golden nanometer particle.Preparation method is following and as shown in Figure 4:
A () at room temperature, by chlorauric acid solution and the mixing of 45mL pure water of 7mL6mM, it is rapidly added 5mL4mM N-(4-aminobutyl) the different luminol solution of-N-ethyl under conditions of being stirred vigorously, after 2h is stirred at room temperature, adds the chlorauric acid solution of 6mL6mM.The colloidal sol of claret primary N-(4-aminobutyl)-N-ethyl different luminol functionalization gold nano-material is i.e. obtained after 2h is stirred at room temperature.
B chelating agen 1 is configured to the aqueous solution of 6mM by (), then with the CoCl of 6mM2Aqueous solution is mixed to get 3Mm (sulfhydrylation diethylene-triamine pentaacetic acid) with the volume ratio of 1:1 and closes cobalt (II) (chelate 1) aqueous solution.4mL3mM chelate 1 solution is joined in 20mL primary golden nanometer particle colloidal sol, after vigorous stirring overnight, obtain purple solution.Gained solution is centrifugal 15min under 12500rpm rotating speed.Remove after supernatant, precipitate with 24mL water or NaOH solution ultrasonic disperse and i.e. obtain N-(4-aminobutyl) the different luminol of-N-ethyl and the coordination of metal ion chelate difunctionalization noble metal nanometer material 1(material 1 containing sulfydryl) colloidal sol.This colloidal sol can stable under the conditions of 4 DEG C preserve.
Material 1 carries out transmission electron microscope, thermogravimetric analysis and differential thermal analysis, uv-vis spectra, the test of x-ray photoelectron power spectrum, and result is respectively as shown in curve e and Fig. 8 in Fig. 5 (b), Fig. 6 (c), Fig. 7.Measure the luminous intensity of material 1 according to above-mentioned method of testing (5), result is shown in the curve a in the left figure of Fig. 9 and table 2.
Example 2 below-19 is respectively adopted in table 1 below listed raw material, prepares difunctionalization noble metal nanometer material 2-20(and is hereafter denoted as " material 2-20 ").
Embodiment 2 : prepare difunctionalization noble metal nanometer material 2( Material 2)
According to preparing the same procedure of material 1 in embodiment 1.1, difference is, uses CuCl2·2H2O replaces CoCl2, obtain material 2.Test with transmission electron microscope, shown in result such as Fig. 5 (c).Electromicroscopic photograph according to Fig. 5 (c) is it can be seen that it is a kind of nano-particle with good dispersion.Measure the luminous intensity of material 2 according to above-mentioned method of testing (5), result is shown in the curve b in the left figure of Fig. 9.
Embodiment 3 : prepare difunctionalization noble metal nanometer material 3( Material 3)
According to preparing the same procedure of material 1 in embodiment 1.1, difference is, uses Pb (NO3)2Replace CoCl2, obtain material 3.Test with transmission electron microscope, shown in result such as Fig. 5 (d).Electromicroscopic photograph according to Fig. 5 (d) is it can be seen that it is a kind of nano-particle with good dispersion.Measure the luminous intensity of material 3 according to above-mentioned method of testing (5), result is shown in the curve c in the left figure of Fig. 9.
Embodiment 4 : prepare difunctionalization noble metal nanometer material 4( Material 4)
According to preparing the same procedure of material 1 in embodiment 1.1, difference is, uses NiCl2Replace CoCl2, obtain material 4.Test with transmission electron microscope, shown in result such as Fig. 5 (e).Electromicroscopic photograph according to Fig. 5 (e) is it can be seen that it is a kind of nano-particle with good dispersion.Measure the luminous intensity of material 4 according to above-mentioned method of testing (5), result is shown in the curve d in the left figure of Fig. 9.
Embodiment 5 : prepare difunctionalization noble metal nanometer material 5( Material 5)
According to preparing the same procedure of material 1 in embodiment 1.1, difference is, uses HgCl2Replace CoCl2, obtain material 5.Test with transmission electron microscope, shown in result such as Fig. 5 (f).Electromicroscopic photograph according to Fig. 5 (f) is it can be seen that it is a kind of nano-particle with good dispersion.Measure the luminous intensity of material 5 according to above-mentioned method of testing (5), result is shown in the curve e in the left figure of Fig. 9.
Embodiment 6 : prepare difunctionalization noble metal nanometer material 6( Material 6)
According to preparing the same procedure of material 1 in embodiment 1.1, difference is, uses CrCl3Replace CoCl2, obtain material 6.Test with transmission electron microscope, shown in result such as Fig. 5 (g).Electromicroscopic photograph according to Fig. 5 (g) is it can be seen that it is a kind of nano-particle with good dispersion.Measure the luminous intensity of material 6 according to above-mentioned method of testing (5), result is shown in the curve f in the left figure of Fig. 9.
Embodiment 7 : prepare difunctionalization noble metal nanometer material 7( Material 7)
According to preparing the same procedure of material 1 in embodiment 1.1, difference is, uses EuCl3Replace CoCl2, obtain material 7.Test with transmission electron microscope, shown in result such as Fig. 5 (h).Electromicroscopic photograph according to Fig. 5 (h) is it can be seen that it is a kind of nano-particle with good dispersion.Measure the luminous intensity of material 7 according to above-mentioned method of testing (5), result is shown in the curve h in the right figure of Fig. 9.
Embodiment 8 : prepare difunctionalization noble metal nanometer material 8( Material 8)
According to preparing the same procedure of material 1 in embodiment 1.1, difference is, uses La (NO3)3Replace CoCl2, obtain material 8.Test with transmission electron microscope, shown in result such as Fig. 5 (i).Electromicroscopic photograph according to Fig. 5 (i) is it can be seen that it is a kind of nano-particle with good dispersion.Measure the luminous intensity of material 8 according to above-mentioned method of testing (5), result is shown in the curve j in the right figure of Fig. 9.
Embodiment 9 : prepare difunctionalization noble metal nanometer material 9( Material 9)
According to preparing the same procedure of material 1 in embodiment 1.1, difference is, uses GdCl3Replace CoCl2, obtain material 9.Test with transmission electron microscope, shown in result such as Fig. 5 (j).Electromicroscopic photograph according to Fig. 5 (j) is it can be seen that it is a kind of nano-particle with good dispersion.Measure the luminous intensity of material 9 according to above-mentioned method of testing (5), result is shown in the curve i in the right figure of Fig. 9.
Embodiment 10 : prepare difunctionalization noble metal nanometer material 10( Material 10)
According to preparing the same procedure of material 1 in embodiment 1.1, difference is, uses SmCl3Replace CoCl2, obtain material 10.Test with transmission electron microscope, shown in result such as Fig. 5 (k).Electromicroscopic photograph according to Fig. 5 (k) is it can be seen that it is a kind of nano-particle with good dispersion.Measure the luminous intensity of material 10 according to above-mentioned method of testing (5), result is shown in the curve k in the right figure of Fig. 9.
Embodiment 11 : prepare difunctionalization noble metal nanometer material 11( Material 11)
According to preparing the same procedure of material 1 in embodiment 1.1, difference is, uses ErCl3Replace CoCl2, obtain material 11.Test with transmission electron microscope, shown in result such as Fig. 5 (1).Electromicroscopic photograph according to Fig. 5 (1) is it can be seen that it is a kind of nano-particle with good dispersion.Measure the luminous intensity of material 11 according to above-mentioned method of testing (5), result is shown in the curve l in the right figure of Fig. 9.
Embodiment 12 : prepare difunctionalization noble metal nanometer material 12( Material 12)
According to preparing the same procedure of material 1 in embodiment 1.1, difference is, uses DyCl3Replace CoCl2, obtain material 12.Test with transmission electron microscope, shown in result such as Fig. 5 (m).Electromicroscopic photograph according to Fig. 5 (m) is it can be seen that it is a kind of nano-particle with good dispersion.Measure the luminous intensity of material 12 according to above-mentioned method of testing (5), result is shown in the curve m in the right figure of Fig. 9.
Embodiment 13 : prepare difunctionalization noble metal nanometer material 13( Material 13)
According to preparing the same procedure of material 1 in embodiment 1.1, difference is, uses Ce (SO4)2·4H2O replaces CoCl2, obtain material 13.Test with transmission electron microscope, shown in result such as Fig. 5 (n).Electromicroscopic photograph according to Fig. 5 (n) is it can be seen that it is a kind of nano-particle with good dispersion.Measure the luminous intensity of material 13 according to above-mentioned method of testing (5), result is shown in the curve n in the right figure of Fig. 9.
Embodiment 14 : prepare difunctionalization noble metal nanometer material 14( Material 14)
According to preparing the same procedure of material 1 in embodiment 1.1, difference is, uses Ce2(SO4)3·8H2O replaces CoCl2, obtain material 14.Test with transmission electron microscope, shown in result such as Fig. 5 (o).Electromicroscopic photograph according to Fig. 5 (o) is it can be seen that it is a kind of nano-particle with good dispersion.Measure the luminous intensity of material 14 according to above-mentioned method of testing (5), result is shown in the curve o in the right figure of Fig. 9.
Embodiment 15 : prepare difunctionalization noble metal nanometer material 15( Material 15)
According to preparing the same procedure of material 1 in embodiment 1.1, difference is, uses Pd (NO3)2Replace CoCl2, obtain material 15.Test with transmission electron microscope, shown in result such as Fig. 5 (p).Electromicroscopic photograph according to Fig. 5 (p) is it can be seen that it is a kind of nano-particle with good dispersion.Measure the luminous intensity of material 8 according to above-mentioned method of testing (5), result is shown in the curve g in the left figure of Fig. 9.
Embodiment 16 : prepare difunctionalization noble metal nanometer material 16( Material 16)
According to preparing the same procedure of material 1 in embodiment 1.1, difference is, uses chelating agen 2 to replace chelating agen 1, obtains material 16.
Embodiment 17 : prepare difunctionalization noble metal nanometer material 17( Material 17)
A (), under heated reflux condition, by chlorauric acid solution and the mixing of 95mL ultra-pure water of 5mL6mM, is heated to boiling.1.6mL10mM luminol solution it is rapidly added, to colour stable after backflow 2h under conditions of being stirred vigorously.The colloidal sol of claret primary luminol functionalization gold nano-material is i.e. obtained after continuing stirring 30min after closing heating.
B chelating agen 1 is configured to the aqueous solution of 6mM by (), then with the CoCl of 6mM2Aqueous solution is mixed to get 3Mm (sulfhydrylation diethylene-triamine pentaacetic acid) with the volume ratio of 1:1 and closes cobalt (II) (chelate 1) aqueous solution.4mL3mM chelate 1 solution is joined in 200mL primary golden nanometer particle colloidal sol, after vigorous stirring overnight, obtain required solution.Gained solution is centrifugal 15min under 12500rpm rotating speed.After removing supernatant, with 24mL water or NaOH solution ultrasonic disperse precipitation i.e. obtains luminol and containing the coordination of metal ion chelate difunctionalization noble metal nanometer material 17(material 17 of sulfydryl) colloidal sol.This colloidal sol can stable under the conditions of 4 DEG C preserve.
Embodiment 18 : prepare difunctionalization noble metal nanometer material 18( Material 18)
(a) at ambient temperature under, by the chlorauric acid solution of 2mL6mM and the mixing of 10mL pure water, be rapidly added the different luminol solution of 1mL10mM under conditions of being stirred vigorously, after 2h is stirred at room temperature, add the chlorauric acid solution of 1mL6mM.The colloidal sol of the primary different luminol functionalization gold nano-material of claret is i.e. obtained after 2h is stirred at room temperature.
B chelating agen 1 is configured to the aqueous solution of 6mM by (), then with the CoCl of 6mM2Aqueous solution is mixed to get 3Mm (sulfhydrylation diethylene-triamine pentaacetic acid) with the volume ratio of 1:1 and closes cobalt (II) (chelate 1) aqueous solution.4mL3mM chelate 1 solution is joined in 200mL primary golden nanometer particle colloidal sol, after vigorous stirring overnight, obtain required solution.Gained solution is centrifugal 15min under 12500rpm rotating speed.Remove after supernatant, precipitate with 24mL water or NaOH solution ultrasonic disperse and i.e. obtain different luminol and the coordination of metal ion chelate difunctionalization noble metal nanometer material 18(material 18 containing sulfydryl) colloidal sol.This colloidal sol can stable under the conditions of 4 DEG C preserve.
Embodiment 19 : prepare difunctionalization noble metal nanometer material 19( Material 19)
A 5mL chloroplatinic acid (4mM) is joined in 45mL water by (), be heated to reflux.Under the conditions of magnetic agitation, add 2mL luminol (10mM), continue stirring stable to solution colour.Continue stirring 30min after stopping heating and can prepare the colloidal sol of brown primary luminol functionalization platinum nano material.
B chelating agen 1 is configured to the aqueous solution of 6mM by (), then with the CoCl of 6mM2Aqueous solution is mixed to get 3Mm (sulfhydrylation diethylene-triamine pentaacetic acid) with the volume ratio of 1:1 and closes cobalt (II) (chelate 1) aqueous solution.4mL3mM chelate 1 solution is joined in 20mL primary nano platinum particle colloidal sol, after vigorous stirring overnight, obtain required solution.Gained solution is centrifugal 15min under 12500rpm rotating speed.Remove after supernatant, precipitate with 24mL water or NaOH solution ultrasonic disperse and i.e. obtain luminol and the coordination of metal ion chelate difunctionalization noble metal nanometer material 19(material 19 containing sulfydryl) colloidal sol.This colloidal sol can stable under the conditions of 4 DEG C preserve.
Embodiment 20 : prepare difunctionalization noble metal nanometer material 20( Material 20)
A 10mL1.0mM silver nitrate aqueous solution, 9mL dehydrated alcohol and 5mL ultra-pure water (resistivity is 18.2M Ω * cm) are mixed under 25 DEG C of stirrings by (), 0.5mL0.01mol/L luminol is added under stirring condition, after continuing stirring 2 hours, i.e. obtain stable primary Luminol-luminescent functionalized nano-silver as well as preparation method and application for same colloidal sol.
B chelating agen 1 is configured to the aqueous solution of 6mM by (), then with the CoCl of 6mM2Aqueous solution is mixed to get 3Mm (sulfhydrylation diethylene-triamine pentaacetic acid) with the volume ratio of 1:1 and closes cobalt (II) (chelate 1) aqueous solution.4mL3mM chelate 1 solution is joined in 20mL primary Nano silver grain colloidal sol, after vigorous stirring overnight, obtain required solution.Gained solution is centrifugal 15min under 12500rpm rotating speed.Remove after supernatant, precipitate with 24mL water or NaOH solution ultrasonic disperse and i.e. obtain luminol and the coordination of metal ion chelate difunctionalization noble metal nanometer material 20(material 20 containing sulfydryl) colloidal sol.This colloidal sol can stable under the conditions of 4 DEG C preserve.
The raw material of difunctionalization noble metal nanometer material 2-20 prepared by table 1
Comparative example 1 : the single function of preparation N-(4- Aminobutyl )-N- Ethyl different luminol lighting function gold nano-material ( Relatively material 1)
By chlorauric acid solution and the mixing of 45mL ultra-pure water of 7mL6mM, it is rapidly added 5mL4mM N-(4-aminobutyl) the different luminol solution of-N-ethyl under conditions of being stirred vigorously, after 2h is stirred at room temperature, adds the chlorauric acid solution of 6mL6mM.After 2h is stirred at room temperature, obtain N-(4-aminobutyl)-N-ethyl different luminol lighting function gold nano-material (comparing material 1).Test with transmission electron microscope, shown in result such as Fig. 5 (a).Measure the luminous intensity comparing material 1 according to above-mentioned method of testing (5), result is shown in curve F and table 2 in Figure 10 (c).
Comparative example 2 : the single function luminol lighting function gold nano-material of preparation ( Relatively material 2)
Under heated reflux condition, by chlorauric acid solution and the mixing of 95mL ultra-pure water of 5mL6mM, it is heated to boiling.1.6mL10mM luminol solution it is rapidly added, to colour stable after backflow 2h under conditions of being stirred vigorously.The colloidal sol of claret luminol functionalization gold nano-material is i.e. obtained after continuing stirring 30min after closing heating.Measure the luminous intensity comparing material 2 according to above-mentioned method of testing (5), result is shown in curve H and table 2 in Figure 10 (c).
Comparative example 3 : material is compared in preparation 1 With ( Diethylene-triamine pentaacetic acid ) Close cobalt (II) Mixture (compare material 3 )
In N-(4-the aminobutyl)-N-ethyl different luminol lighting function gold nano-material aqueous solution of comparative example 1, add 1.5mM (diethylene-triamine pentaacetic acid) close cobalt (II), obtain the aqueous solution of this chelate and the mixture (comparing material 3) of lighting function gold nano-material.Owing to this chelate lacks the first active group can being connected with lighting function gold nano-material, thus not can connect to the surface of lighting function golden nanometer particle, and be only capable of having an independent existence in solution, strengthen the luminescence of lighting function gold nano-material aqueous solution as luminescence enhancer.Measure the luminous intensity comparing material 3 according to above-mentioned method of testing (5), result is shown in curve D and table 2 in Figure 10 (c).
Comparative example 4 : material is compared in preparation 1 With Co 2+ Mixture (compare material 4 )
3mM Co is added in N-(4-the aminobutyl)-N-ethyl different luminol lighting function gold nano-material aqueous solution of comparative example 12+, obtain Co2+Aqueous solution with the mixture (comparing material 4) of lighting function gold nano-material.Measure the luminous intensity comparing material 4 according to above-mentioned method of testing (5), result is shown in curve E and table 2 in Figure 10 (c).
Comparative example 5 : preparation N-(4- Aminobutyl )-N- The different luminol of ethyl and chelating agen 1 Difunctionalization gold nano-material (compare material 5 )
In N-(4-the aminobutyl)-N-ethyl different luminol lighting function gold nano-material aqueous solution of comparative example 1, add 3mM chelating agen 1, obtain the gold nano-material (comparing material 5) of N-(4-aminobutyl) the different luminol of-N-ethyl and chelating agen 1 difunctionalization.Measure the luminous intensity comparing material 5 according to above-mentioned method of testing (5), result is shown in curve B and table 2 in Figure 10 (b).
Comparative example 6 : preparation N-(4- Aminobutyl )-N- The different luminol of ethyl and thioctic acid functionalization gold nano-material ( Relatively material 6)
The thioctic acid of ABEI with 2mL4mM of 1mL4mM is mixed, it is subsequently adding the gold chloride of 3.5mL6mM, 24h is stirred at room temperature, can be prepared by tufted N-(4-aminobutyl) the different luminol of-N-ethyl and thioctic acid functionalization gold nano-material (comparing material 6).Measure the luminous intensity comparing material 6 according to above-mentioned method of testing (5), result is shown in curve C and table 2 in Figure 10 (b).
Fig. 5 is material 1-15 and the transmission electron microscope photo comparing material 1.Wherein: (a) correspondence compares material 1；The material 1-15 of the most corresponding present invention of (b)-(p).It can be seen that material 1-15 does not the most assemble, having more preferable dispersibility compared with comparing material 1 on the contrary, this is owing to chelate 1 is with negative charge, adds golden nanometer particle electrostatic repulsion forces each other.
Fig. 6 is N-(4-aminobutyl) the different luminol of-N-ethyl (as shown in Fig. 6 (a)), chelating agen 1 (as shown in Fig. 6 (b)) and the thermogravimetric analysis of material 1 (as shown in Fig. 6 (c)) and differential thermal analysis curve.As shown in Fig. 6 (c), due to chelating agen 1 and Co2+Complexation and being connected with golden nanometer particle with Au-S covalent bond, heat decomposition temperature is increased to 330 DEG C by 260 DEG C.
The uv-visible absorption spectra result of below Fig. 7 material.Wherein, the aqueous solution of a correspondence 60mM chelating agen 1；B correspondence 60mM Co2+Aqueous solution；The aqueous solution of c correspondence 30mM chelate 1；D correspondence 0.5mM N-(4-aminobutyl)-N-ethyl different luminol aqueous solution；The aqueous solution of e correspondence material of the present invention 1.Curve b is it can be seen that Co2+There is individual absworption peak at about 510nm, and chelating agen 1 does not absorb (curve a).The chelate 1 absworption peak at 503nm shows being successfully formed of chelate 1, and blue shift is (the curve c) caused by the strong electronegativity of cheating atoms N and O.(curve e) has N-(4-aminobutyl) the different luminol of-N-ethyl characteristic absorption peak (curve d) and the chelate 1 absworption peak (curve c) at 529nm at 292nm to material 1 simultaneously.Therefore show that the golden nanometer particle in this material 1 is coated with N-(4-aminobutyl) the different luminol of-N-ethyl and chelate 1 simultaneously.
Fig. 8 is the x-ray photoelectron power spectrum result of material 1.Wherein, figure (a) is score；Figure (b) corresponding A u4f；The corresponding N1s of figure (c)；The corresponding C1s of figure (d)；The corresponding Co2p of figure (e)；The corresponding S2p of figure (f).From full spectrum (a) it can be seen that Au, N, C, O, S and Co are present in the surface of material 1.The wherein power spectrum of Au, N and C and document (Tian, D.;Zhang,H.;Chai,Y.;Cui, H.Chem.Commun.2011,47,4959) identical, show that N-(4-aminobutyl) the different luminol of-N-ethyl and its oxidation product are concurrently present in the surface of golden nanometer particle.Co2+Being chelated by two kinds of atoms of N and O, so Co2p1/2 and Co2p3/2 all has two components to split, CoN is positioned at 801.2 and 785.8eV, and CoO is positioned at 796.7 and 781.0eV, Co2p1/2 and 2p3/2 splits point distance for 15eV, and these are all consistent with standard power spectrum.S2p is positioned at 162.4eV, shows that chelate 1 is covalently bonded to the surface of golden nanometer particle with Au-S.
More than characterizing data to show, successfully synthesizing connection has N-(4-aminobutyl) the different luminol of-N-ethyl and the difunctionalization gold nano-material of chelate 1, i.e. material 1.
Using identical characterization method, characterize material 2-20, result all can prove that successfully prepares various difunctionalization noble metal nanometer material.
Chemiluminescent properties
Fig. 9 is the chemiluminescence curve of the difunctionalization gold nano-material (material 1-15) containing different coordination of metal ion chelates.Wherein, a correspondence Co2+, b correspondence Cu2+, c correspondence Pb2+, d correspondence Ni2+, e correspondence Hg2+, f correspondence Cr3+；G correspondence Pd2+；H correspondence Eu3+；I correspondence Gd3+；J correspondence La3+；K correspondence Sm3+；L correspondence Er3+；M correspondence Dy3+；N correspondence Ce4+；O correspondence Ce3+.It can be seen that these materials are respectively provided with the chemiluminescent properties of brilliance, this characteristic should give the credit to the catalytic effect that each coordination of metal ion is good to N-(4-aminobutyl)-N-ethyl different luminol luminescence system.Due to Co2+Catalytic effect preferably (curve a), therefore in subsequent experimental, selects Co2+As example, carry out various test.It is known that rare earth element also has other optical properties (such as up-conversion fluorescence and Gd3+Have the character increasing NMR relaxation rate), therefore the golden nanometer particle of our difunctionalization is that multi-modal technology provides a kind of possibility.
Significantly improve to verify that the difunctionalization noble metal nanometer material of the present invention has than existing lighting function nano material on luminescent properties, carry out following control experiment.Comparing such as the chemiluminescence of material aqueous solutions various in table 2 below, result is as shown in Figure 10.Described chemiluminescent assay is carried out under identical luminescent condition.
Table 2
Analyze object Maximum emission intensity (A.U.)
(A) material 1 of the present invention 1,200,000
(B) material 5 is compared 56,200
(C) material 6 is compared 15,000
(D) material 3 is compared 7,300
(E) material 4 is compared 2,400
(D compares material 1 900
(G) (D) is centrifuged the solution after redispersion 1,700
(H) material 2 is compared 520
It can be seen that compared with comparing material 1 (curve F) and 2 (curve H), the chemiluminescence intensity of material 1 (curve A) of the present invention is the highest by 103.Owing to comparing material 6 (curve C), itself there is tufted pattern, in the case of other condition is identical, this special appearance can make its chemiluminescence performance be better than spherical nano material (as compared material 1), and this point can be seen that higher than the luminous intensity comparing material 1 from the luminous intensity comparing material 6.But though the material of the present invention 1 is also spherical, its luminous intensity remains above and compares the luminous intensity of material 6 and reach 80 times.Relatively material 4 (curve B) is the difunctionalization gold nano-material of N-(4-aminobutyl) the different luminol of-N-ethyl and chelating agen 1, wherein chelating agen 1 is connected with golden nanometer particle itself by Au-S key, this also has the strongest catalytic capability to chemiluminescence, therefore, compared with comparing material 1, the chemiluminescence intensity comparing material 4 is higher.In (G), being centrifuged off without being coated ability owing to (diethylene-triamine pentaacetic acid) closes cobalt (II), the chemiluminescence intensity of rear solution is suitable with N-(4-aminobutyl)-N-ethyl different luminol functionalization golden nanometer particle the most by centrifugation.If from curve D and E it can be seen that directly material 1 adds 1.5mM (diethylene-triamine pentaacetic acid) close cobalt (II) or 3mM Co to comparing respectively2+As catalyst, chemiluminescence intensity is increased to 7 from 900 respectively, 300 and 2,400, but its luminous intensity is also with the luminous intensity of the material 1 far below the present invention, this explanation, when coordination of metal ion chelate is coated on lighting function noble metal nano particles surface, has more preferable catalytic effect than coordination of metal ion to chemiluminescence when existing only in aqueous solution.Therefore, the difunctionalization noble metal nanometer material of the present invention has the characteristics of luminescence of brilliance, and compared with prior art, luminescent properties is greatly improved, and achieves beyond thought technique effect.

Claims (19)

1. a difunctionalization noble metal nanometer material, it comprises:
Noble metal nano particles；
It is derived from the luminous fragment of the luminol class chemical illuminating reagent of logical formula (I)；With
It is derived from the luminescence enhancement fragment of coordination of metal ion chelate containing sulfydryl or amino；
The luminous fragment of the described luminol class chemical illuminating reagent being derived from logical formula (I) and being derived from containing sulfydryl or ammonia The luminescence enhancement fragment of the coordination of metal ion chelate of base is connected to the surface of described noble metal nano particles:
In formula,
A represents C6-C14 aryl；
R1And R2Represent hydrogen, the end group C1-C30 by the substituted or unsubstituted straight or branched of amino independently Alkyl, precondition is NR1R2There is at least one NH2End group.
Difunctionalization noble metal nanometer material the most as claimed in claim 1, it is characterised in that your gold described Belong to nanoparticle and be selected from golden nanometer particle, Nano silver grain, nano platinum particle, their alloy nano particle, And combinations thereof.
Difunctionalization noble metal nanometer material the most as claimed in claim 1 or 2, it is characterised in that described Noble metal nano particles is golden nanometer particle or Nano silver grain.
Difunctionalization noble metal nanometer material the most as claimed in claim 1 or 2, it is characterised in that described Noble metal nano particles is golden nanometer particle.
Difunctionalization noble metal nanometer material the most as claimed in claim 1 or 2, it is characterised in that described The luminol class chemical illuminating reagent of logical formula (I) is selected from logical formula (II) and the luminol class chemical illuminating reagent of (III):
Wherein, R1And R2As defined in claim 1.
Difunctionalization noble metal nanometer material the most as claimed in claim 1 or 2, it is characterised in that described The luminol class chemical illuminating reagent of logical formula (II) is selected from:
Wherein, R1And R2As defined in claim 1.
Difunctionalization noble metal nanometer material the most as claimed in claim 5, it is characterised in that described formula (II) luminol class chemical illuminating reagent is selected from: luminol, different luminol, N-(4-aminobutyl)-N-ethyl Different luminol and N-(4-Aminohexyl) the different luminol of-N-ethyl；
The luminol class chemical illuminating reagent of described logical formula (III) is selected from: N-(4-aminobutyl)-N-ethyl naphthoyl Hydrazine.
Difunctionalization noble metal nanometer material the most as claimed in claim 5, it is characterised in that described formula (II) luminol class chemical illuminating reagent is N-(4-aminobutyl) the different luminol of-N-ethyl.
Difunctionalization noble metal nanometer material the most as claimed in claim 6, it is characterised in that described formula (II) luminol class chemical illuminating reagent is selected from: luminol, different luminol, N-(4-aminobutyl)-N-ethyl Different luminol and N-(4-Aminohexyl) the different luminol of-N-ethyl.
Difunctionalization noble metal nanometer material the most as claimed in claim 6, it is characterised in that described logical The luminol class chemical illuminating reagent of formula (II) is N-(4-aminobutyl) the different luminol of-N-ethyl.
11. difunctionalization noble metal nanometer materials as claimed in claim 1 or 2, it is characterised in that
In the described coordination of metal ion chelate containing sulfydryl or amino, metal ion is selected from group VIII, IB Race, Group IIB, group vib transition metal ions, rare earth element ion, IVA race metal or a combination thereof；
The chelating agen of described chelate has first active group and second of selected from mercapto, amino or a combination thereof Active group, wherein said first active group is for being connected with described noble metal nano particles, described Second active group is used for and described metal ion generation complexation.
12. difunctionalization noble metal nanometer materials as claimed in claim 11, it is characterised in that described mistake Cross metal ion to be selected from: Co2+、Cu2+、Ni2+、Hg2+、Cr3+、Pd2+、Pt2+、Fe2+、Fe3+、Ru2+；
Described IVA race metal is Pb2+；
Described rare earth element ion is selected from Eu3+, La3+、Gd3+、Sm3+、Er3+、Dy3+、Ce4+、Ce3+；
First active group selected from mercapto of described chelating agen；
Described second active group includes the active group with complexing power containing O, N, S.
13. difunctionalization noble metal nanometer materials as claimed in claim 12, it is characterised in that described contain The active group with complexing power of O, N, S is carboxyl, hydroxyl, secondary amino group, tertiary amino or a combination thereof.
14. difunctionalization noble metal nanometer materials as claimed in claim 1 or 2, it is characterised in that institute The chelating agen stating chelate of metal ion is selected from: sulfhydrylation chelating agen, amination chelating agen or combinations thereof.
15. difunctionalization noble metal nanometer materials as claimed in claim 1 or 2, it is characterised in that institute State sulfhydrylation chelating agen to be selected from: sulfhydrylation ethylenediaminetetraacetic acid, sulfhydrylation diethylene-triamine pentaacetic acid, mercapto The sub-second triamine tetraacethyl of base Cyclen-1,4,7,10-tetrabasic carboxylic acid, sulfhydrylation two；
Described amination chelating agen is selected from: amination ethylenediaminetetraacetic acid, amination diethylenetriamines five second Acid, the sub-second triamine tetrem of amination Cyclen-1,4,7,10-tetrabasic carboxylic acid, amination two Acid.
The difunctionalization noble metal nanometer material that 16. 1 kinds are prepared as according to any one of claim 1-15 Method, it comprises the following steps:
1) provide containing sulfydryl or the coordination of metal ion chelate of amino；
2) the luminol class chemical illuminating reagent of logical formula (I) and aqueous noble metal precursor compound is made to react, In course of reaction or after the reaction was complete, add in reaction system described containing sulfydryl or amino Coordination of metal ion chelate, obtains difunctionalization noble metal nanometer material；
Or, said method comprising the steps of:
1) provide containing sulfydryl or the coordination of metal ion chelate of amino, luminol class chemical illuminating reagent and water Property noble metal precursor compound；
2) make above-claimed cpd hybrid reaction, obtain difunctionalization noble metal nanometer material.
17. methods as claimed in claim 16, it is characterised in that described aqueous noble metal precursor compound Including gold chloride, chloroplatinic acid, silver nitrate or its mixture.
18. methods as claimed in claim 16, it is characterised in that described aqueous noble metal precursor compound For gold chloride.
The 19. difunctionalization noble metal nanometer materials as according to any one of claim 1-15 are prepared being used for Application in analysis probe, this analysis probe is for the detection of following various fields sample and analysis: biological sample Product, Foods or drinks sample, drug sample, environmental sample, chemical example.
CN201310356017.6A 2013-08-15 2013-08-15 A kind of difunctionalization nano material, Preparation Method And The Use Active CN104371705B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310356017.6A CN104371705B (en) 2013-08-15 2013-08-15 A kind of difunctionalization nano material, Preparation Method And The Use

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310356017.6A CN104371705B (en) 2013-08-15 2013-08-15 A kind of difunctionalization nano material, Preparation Method And The Use

Publications (2)

Publication Number Publication Date
CN104371705A CN104371705A (en) 2015-02-25
CN104371705B true CN104371705B (en) 2016-12-28

Family

ID=52550908

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310356017.6A Active CN104371705B (en) 2013-08-15 2013-08-15 A kind of difunctionalization nano material, Preparation Method And The Use

Country Status (1)

Country Link
CN (1) CN104371705B (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106833618B (en) * 2016-12-19 2019-04-05 中国科学技术大学 Difunctionalization aquogel polymer composite material, preparation method and use
CN107228848B (en) * 2017-06-16 2020-09-08 上海市第十人民医院 Wide fluorescence spectrum and MRI (magnetic resonance imaging) dual-image functional microsphere tracing mesenchymal stem cells and application
CN109100400B (en) * 2018-07-17 2019-11-08 西南大学 Sensor and its preparation method and application for detecting concanavalin A
CN110836924B (en) * 2018-08-15 2021-03-23 北京大学 Difunctional laser cleavable probe and preparation method and mass spectrum application thereof
CN109517596B (en) * 2018-10-11 2020-08-28 中国科学技术大学 Color-adjustable long-time luminous hydrogel composition and preparation method thereof
CN110208529B (en) * 2019-06-28 2020-08-07 中国科学技术大学 Multilayer flow control optical detection device and detection method using same
CN111909286A (en) * 2020-08-14 2020-11-10 大连工业大学 Biomass-based chemiluminescent polymer and preparation method thereof
CN112496336A (en) * 2020-11-13 2021-03-16 武汉纺织大学 Preparation method of gold nanocluster with multiple optical signal channels
CN113416534B (en) * 2021-06-25 2023-03-10 中国科学技术大学 Composite material and kit for antigen detection
CN115894301A (en) * 2022-10-25 2023-04-04 武汉大学中南医院 Dimerized gadolinium-based T1 magnetic resonance contrast agent, and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101900723A (en) * 2009-05-27 2010-12-01 中国科学技术大学 Application of nano-gold directly bonded with luminol in immunoassay
CN102191034A (en) * 2010-03-03 2011-09-21 中国科学技术大学 N-(4-aminobutyl)-N-ethylisoluminol luminescence functionalized nanogold, and preparation method and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7537934B2 (en) * 2005-12-30 2009-05-26 Intel Corporation Chemiluminescence sensor array

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101900723A (en) * 2009-05-27 2010-12-01 中国科学技术大学 Application of nano-gold directly bonded with luminol in immunoassay
CN102191034A (en) * 2010-03-03 2011-09-21 中国科学技术大学 N-(4-aminobutyl)-N-ethylisoluminol luminescence functionalized nanogold, and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Distance measurements in Au nanoparticles functionalized with nitroxide radicals and Gd3+–DTPA chelate complexes;Maxim Yulikov等;《Phys.Chem.Chem.Phys.》;20120524;第14卷;第10732–10746页 *

Also Published As

Publication number Publication date
CN104371705A (en) 2015-02-25

Similar Documents

Publication Publication Date Title
CN104371705B (en) A kind of difunctionalization nano material, Preparation Method And The Use
CN104374764B (en) Analysis probe, preparation method and uses thereof
Zhu et al. Nitrogen-doped carbon nanoparticle modulated turn-on fluorescent probes for histidine detection and its imaging in living cells
Cai et al. MUC-1 aptamer-conjugated dye-doped silica nanoparticles for MCF-7 cells detection
Qu et al. Fluorescent gold nanoclusters: synthesis and recent biological application
Montalti et al. Dye-doped silica nanoparticles as luminescent organized systems for nanomedicine
CN102362182B (en) N-(4-aminobutyl)-N-ethylisoluminol functionalized gold nanoparticles, preparation method and application thereof
Liu et al. Gold nanoparticles bifunctionalized by chemiluminescence reagent and catalyst metal complexes: synthesis and unique chemiluminescence property
Wei et al. Ratiometric method based on silicon nanodots and Eu3+ system for highly-sensitive detection of tetracyclines
Azzazy et al. Gold nanoparticles in the clinical laboratory: principles of preparation and applications
Li et al. Fluorescence probe based on an amino-functionalized fluorescent magnetic nanocomposite for detection of folic acid in serum
Liu et al. Recent progress on gold-nanocluster-based fluorescent probe for environmental analysis and biological sensing
Yang et al. Gold–silver nanocomposite-functionalized graphene based electrochemiluminescence immunosensor using graphene quantum dots coated porous PtPd nanochains as labels
Yan et al. Magnetic capture of sulfur quantum dots encapsulated in MOF-5-NH2 via a target-driven self-cycling catalyzed hairpin assembly for the sensitive detection of patulin
Haghighi et al. Antibody conjugated onto surface modified magnetic nanoparticles for separation of HER2+ breast cancer cells
Arunjegan et al. A Turn-ON fluorometric biosensor based on ssDNA immobilized with a metal phenolic nanomaterial for the sequential detection of Pb (ii) and epirubicin cancer drug
CN112375561B (en) Up-conversion fluorescent nanoprobe and application thereof
Zhang et al. A magnetic-based SERS approach for highly sensitive and reproducible detection of cancer-related serum microRNAs
CN102636649A (en) Kit for detecting carcinoembryonic antigen based on antibody functionalized magnetic nanometer material and up-conversion fluorescence nanometer material
Zhang et al. A molecularly imprinted fluorescence sensor for sensitive detection of tetracycline using nitrogen-doped carbon dots-embedded zinc-based metal-organic frameworks as signal-amplifying tags
Reddy et al. A simple approach to the design and functionalization of Fe3O4–Au nanoparticles for biomedical applications
Rashid et al. Surface modification and bioconjugation of anti-CD4 monoclonal antibody to magnetic nanoparticles as a highly efficient affinity adsorbent for positive selection of peripheral blood T CD4+ lymphocytes
Ma et al. A sensitive and selective chemosensor for GSSG detection based on the recovered fluorescence of NDPA-Fe3O4@ SiO2-Cu (II) nanomaterial
Lyu et al. Enhanced Chemiluminescence under the Nanoconfinement of Covalent–Organic Frameworks and Its Application in Sensitive Detection of Cancer Biomarkers
Zhang et al. Microwave-assisted one-step rapid synthesis of folic acid modified gold nanoparticles for cancer cell targeting and detection

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant