CN109097029A - A kind of application of silicon nano/gold nanoclusters ratio fluorescent probe synthesized and its rifampin ratio fluorescent is detected - Google Patents
A kind of application of silicon nano/gold nanoclusters ratio fluorescent probe synthesized and its rifampin ratio fluorescent is detected Download PDFInfo
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Abstract
The present invention provides a kind of silicon nano/gold nanoclusters ratio fluorescent probe synthetic methods: preparing the silicon nano of amido protecting using hydrothermal reduction method first；Then the gold nanoclusters of carboxy protective are prepared using stirring reduction method；Silicon nano and gold nanoclusters are finally subjected to self assembly, synthesis rate fluorescence probe.Present invention self assembly silicon nano/gold nanoclusters ratio fluorescent probe at room temperature, process is simple, easy to operate, mild condition, time-consuming short.Silicon nano provided by the invention/gold nanoclusters ratio fluorescent probe accurately can detect rifampin using ratio fluorescent method, the silicon nano/gold nanoclusters ratio fluorescent probe is used to detect the trace rifampin in human serum, the result shows that its rate of recovery is 97.0%~103.5%, and relative standard deviation (RSDs) is below 4%.
Description
Technical field
The present invention relates to fluorescent probe technique fields more particularly to a kind of silicon nano/gold nanoclusters ratio fluorescent to visit
The synthesis of needle and its application that rifampin ratio fluorescent is detected.
Background technique
Rifampin (RIF), also known as sharp Hachimycin, rifampicin, rifampycin, Rifampicin, Rifampicin, power are multiple
Flat or Li meter Ding.Chemical name is 3- [[(4- methyl-1-piperazinyl) imino group] methyl] mould rope of-Li Fu.RIF is belonging to one kind
The broad-spectrum antibiotic drug of rifamycin family has stronger antibacterial action to tubercle bacillus.RIF and the RNA polymerase for relying on DNA
β subunit firm connection, inhibit the synthesis of bacteria RNA, prevent the enzyme from connecting with DNA, to block rna transcription process, make
The synthesis of DNA and albumen stops.The antibiotic is to mycobacterium tuberculosis and part non-tuberculous mycobacteria (including leprosy branch bar
Bacterium etc.) there is apparent bactericidal effect inside and outside host cell.RIF has good antibacterial action, packet to aerobic gram positive bacteria
Include the strain of staphylococcus producing enzyme and methicillin resistance strain, streptococcus pneumonia, other streptococcuses, enterococcus spp, listeria,
Bacillus anthracis, Bacillus perfringens, corynebacterium diphtheriae, anaerobic cocci etc..However RIF is as active drug lungy, it is long-term to take
With that also can cause to damage to human body hepatic and renal function, excessive use RIF can cause hyponea and all kinds of skin syndromes.Have primary
Liver patient, alcoholic or may cause death with taking other hepatotoxic medications person.RIF depends on blood in the intracorporal transport of people
Haemocyanin in liquid, so it is very necessary that the method for highly selective, highly sensitive detection RIF is capable of in exploitation in human serum
's.
The method of detection RIF trace mainly has high performance liquid chromatography, electrochemical process, nuclear magnetic resonance spectroscopy and divides at present
Light photometry.But these methods need expensive equipment either to need the plenty of time to carry out preliminary preparation mostly.
Detection technique of fluorescence has many advantages, such as the good, high sensitivity of selectivity, easy to operate, economical and practical at present, has been widely used for trace
Measure the fields such as detection, fluorescent marker.Traditional fluorescence probe is mainly made of organic dye molecule, has fluorescent brightness low, light
The disadvantages of stability and poor fast light bleaching power, limits the further development and application of detection technique of fluorescence.Occur in recent years
Namo fluorescence probe include Fluorescent silicon nanoparticle (SiNPs) and gold nanoclusters (AuNCs) etc., fluorescent quantum with higher
Yield, good photostability and anti-light bleaching power, good biocompatibility, synthesis and modify it is simple the advantages that, become substitution
The novel fluorescence probe of conventional fluorescent probe.Namo fluorescence probe in the detection process, is typically based on single fluorescence intensity at present
Variation, interference of this method vulnerable to detecting instrument and test environment.Novel nano ratio with ratio fluorescent characteristic
Fluorescence probe detects object using the fluorescence intensity ratio based on two kinds of different emissions, utilizes ratio fluorescent
Self calibration effect can effectively exclude the external interference factor.It therefore can be more accurately to people using ratio fluorescent probe
RIF carries out trace detection in serum.
Summary of the invention
It is an object of that present invention to provide a kind of silicon nano/gold nanoclusters (SiNPs/AuNCs) ratio fluorescent probes
Synthesis and its application that RIF ratio fluorescent is detected.Ratio fluorescent probe consists of two parts in the present invention, and respectively amino is protected
The silicon nano (SiNPs) of shield and the gold nanoclusters (AuNCs) of carboxy protective.Ratio fluorescent probe directly passes through in the present invention
SiNPs and AuNCs with different emission carry out self assembly realization, and process is simple, easy to operate, and mild condition, time-consuming are short；
The SiNPs/AuNCs ratio fluorescent probe being prepared can be applied to the trace detection of RIF by ratio fluorescent method.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of synthetic methods of SiNPs/AuNCs ratio fluorescent probe, include the following steps.
(1) SiNPs of amido protecting is prepared using hydro-thermal method
(a) water-soluble silicon source, reducing agent and water are mixed, obtains just mixed object；
(b) object will be just mixed in the step (a) and 10~20 min are stirred at room temperature, obtain precursors；
(c) precursors in the step (b) are put into the reaction kettle for the Teflon liner that volume is 20 mL, in
1~3 h of hydro-thermal reaction at 220~240 DEG C, obtains the SiNPs of amido protecting.
(2) AuNCs of carboxy protective is prepared using stirring reduction method
(a) by gold chloride (HAuCl4·3H2O), mercaptoundecylic acid (MUA) and water mixing obtain just mixed object；
(b) it uses pH adjusting agent to adjust in the step (a) the just pH value of mixed object and obtains precursors for 10~12；
(c) precursors in the step (b) are stirred at room temperature, react 4~7 h, obtains carboxy protective
AuNCs。
(3) by the step (1) and (2) SiNPs and AuNCs carry out self assembly, synthesis SiNPs/AuNCs ratio it is glimmering
Light probe
(a) SiNPs and AuNCs are mixed in buffer solution, obtains just mixed object；
(b) object will be just mixed in the step (a) at room temperature and mixes and be incubated for 0.5~2 h, it is glimmering to obtain SiNPs/AuNCs ratio
Light probe.
Preferably, water-soluble silicon source employed in the step (1) includes 3- aminopropyl triethoxysilane (APTES)
Or 3- aminopropyl trimethoxysilane (APTMS).
Preferably, reducing agent employed in the step (1) includes ascorbic acid (AA) or sodium citrate.
Preferably, the molar ratio of reducing agent and water-soluble silicon source is 1:(50~150 in the step (1)), wherein restoring
The substance withdrawl syndrome of agent is 100 mM.
Preferably, it includes that sodium hydroxide is molten that pH regulator used by just mixed object pH value is adjusted in the step (2)
Liquid or potassium hydroxide solution.
Preferably, the concentration of the pH regulator is 1.0~1.2 M.
Preferably, HAuCl in the step (2)4·3H2The molar ratio of O and MUA is 1:(4~8), it is final just to mix in object
HAuCl4·3H2The concentration of the amount of the substance of O is 500 μM.
Preferably, buffer solution includes HEPES, Tris-HCl and PBS buffer solution, pH value model in the step (3)
Enclose is 7.0~8.0.
Preferably, the mass ratio of SiNPs and AuNCs is 200:1 in the step (3), wherein preferred SiNPs mass is dense
Degree is 4 mg/mL；AuNCs mass concentration is 20 μ g/mL.
The present invention provides a kind of SiNPs/AuNCs ratio fluorescents that preparation method described in above-mentioned technical proposal is prepared
Probe, including SiNPs and AuNCs, process is simple, easy to operate, and mild condition, time-consuming are short.It is preferably based on the step (3) conjunction
At SiNPs/AuNCs ratio fluorescent probe, use excitation wavelength for 300~310 nm, launch wavelength 440~445 nm a left side
Right and 610~615 nm or so have ratio fluorescent feature (as shown in Figure 3).
A kind of application the present invention provides SiNPs/AuNCs ratio fluorescent probe to RIF progress ratio fluorescent detection.
AuNCs is protected and is modified by MUA, and the carboxyl function group chelating RIF contained in MUA leads to SiNPs/AuNCs ratio fluorescent probe
In most strong launch wavelength 610~615 nm or so fluorescence (I 615) quenching；And most strong launch wavelength is on the left side 440~445 nm
Right fluorescence (I 440) intensity remains unchanged (as shown in Figure 4).Illustrate that SiNPs/AuNCs ratio fluorescent probe can use ratio
Fluorescent method, that is, fluorescence intensity ratio (I 615/I 440) variation may be implemented to the detection of the ratio fluorescent of RIF.Common yin, yang
Ion and 20 kinds of natural amino acids do not influence SiNPs/AuNCs ratio fluorescent probe in detecting RIF, illustrate that the ratio is glimmering
Light probe can realize specific recognition and detection to RIF.It is used for the composite Nano ratio fluorescent probe to detect human serum
Middle trace RIF, the results showed that its rate of recovery is 97.0%~103.5%, and relative standard deviation (RSDs) is below 4%.
Detailed description of the invention
Fig. 1 is the column diagram that AA and APTES solution molar ratio influence SiNPs fluorescence intensity in embodiment 1；
Fig. 2 is HAuCl in embodiment 24·3H2The column diagram that O and MUA molar ratio influence AuNCs fluorescence intensity；
Fig. 3 is SiNPs/AuNCs ratio fluorescent probe emission fluorogram prepared in embodiment 3；
Fig. 4 be SiNPs/AuNCs ratio fluorescent fluorescence probe intensity rate prepared in embodiment 3 (I 615/I 440) with RIF
The fluorescence spectra of concentration variation；
Fig. 5 is the SiNPs/AuNCs ratio fluorescent fluorescence probe intensity rate after 20 μM of RIF of addition described in embodiment 4
(I 615/I 440), the curve graph changed with incubation time；
Fig. 6 be SiNPs/AuNCs ratio fluorescent fluorescence probe intensity rate prepared in embodiment 5 (I 615/I 440) with RIF
The graph of relation of concentration variation；
Fig. 7 be SiNPs/AuNCs ratio fluorescent probe prepared in embodiment 6 to RIF fluorescence response in anions and canons
Selectivity analyze column diagram；
Fig. 8 is for SiNPs/AuNCs ratio fluorescent probe prepared in embodiment 7 to RIF fluorescence response in 20 kinds of native aminos
Selectivity in acid analyzes column diagram.
Specific embodiment
A kind of application the present invention provides SiNPs/AuNCs ratio fluorescent probe to RIF progress ratio fluorescent detection, packet
Include following steps:
(1) SiNPs of amido protecting is prepared using hydrothermal reduction method；
(2) AuNCs of carboxy protective is prepared using stirring reduction method；
(3) the SiNPs and AuNCs in the step (1) and (2) is subjected to self assembly, synthesis SiNPs/AuNCs ratio fluorescent is visited
Needle.
Water-soluble silicon source, reducing agent and water are mixed in the step (1) of the present invention, obtain just mixed object.In the present invention
The molar ratio of the reducing agent and water-soluble silicon source is preferably 1:(50~150)；More preferably 1:(75~150)；Most preferably
1:(75~100), wherein the substance withdrawl syndrome of reducing agent is 100 mM.In the present invention, the water-soluble silicon source includes
3- aminopropyl triethoxysilane (APTES) or 3- aminopropyl trimethoxysilane (APTMS).In the present invention, it is described also
Former agent includes ascorbic acid (AA) or sodium citrate.In the present invention, the water is preferably ultrapure water.
The present invention does not have special restriction for the mixed method of the water-soluble silicon source, reducing agent and water, using ability
The technical solution of the mixing of material known to field technique personnel.In the present invention, the present invention preferably first by water-soluble silicon source and
Water mixing, gained mixture is mixed with reducing agent again, to guarantee that material is sufficiently mixed.
After obtaining just mixed object, 10~20 min are stirred at room temperature in the just mixed object, obtain precursors；It will be described
Precursors are put into the reaction kettle that volume is 20 mL Teflon liners, the hydro-thermal reaction 1~3 at 220~240 DEG C
H obtains the SiNPs of amido protecting.In the present invention, hydrothermal temperature is preferably 220~240 DEG C, more preferably 225~240
DEG C, most preferably 235~240 DEG C.Reaction time is preferably 1~3 h, more preferably 2~3 h, most preferably 2.5~3 h.
By HAuCl in step (2) of the present invention4·3H2O, MUA and water mixing obtain just mixed object.In the present invention, institute
State HAuCl4·3H2The molar ratio of O and MUA is preferably 1:(4~8)；More it is selected as 1:(4~7)；Most preferably 1:(5~6),
HAuCl in final just mixed object4·3H2The concentration of the amount of the substance of O is 500 μM.In the present invention, the water is preferably ultrapure
Water.
The present invention is for the HAuCl4·3H2O, the mixed method of MUA and water does not have special restriction, using this field
The technical solution of the mixing of material known to technical staff.In the present invention, the present invention is preferably first by HAuCl4·3H2O and water
Mixing, gained mixture are mixed with MUA again, 10~15 min are stirred, to guarantee that material is sufficiently mixed.
After obtaining just mixed object, the pH value that the present invention adjusts the just mixed object is 10~12, obtains precursors.At this
In invention, the pH regulator includes sodium hydroxide solution or potassium hydroxide solution.In the present invention, the pH regulator
Concentration is preferably 1.0~1.2 M；More preferably 1.0~1.1 M；Most preferably 1.0~1.05 M.
The precursors are stirred at room temperature, are reacted 4~7 h, are obtained the AuNCs of carboxy protective.The present invention
In, the reaction time is preferably 4~7 h, more preferably 5~7 h, most preferably 5~6 h.
The present invention does not have special restriction for carrying out equipment used by the hydro-thermal reaction and stirring reduction reaction,
Using the equipment well known to those skilled in the art for carrying out hydro-thermal and stirring reduction reaction.Specifically, of the invention
Hydro-thermal reaction is carried out using the reaction kettle of Teflon liner, it is anti-as stirring reduction using DF-101S heat collecting type thermostatic mixer
Answer equipment.
After completing the reaction, the present invention preferably post-processes obtained reaction mass, obtain solid phase SiNPs and
AuNCs.In the present invention, the post-processing preferably includes following steps: successively by gained hydro-thermal and stirring reduction reaction material
It is dialysed and is dried, respectively obtain solid phase SiNPs and AuNCs.Present invention preferably employs the bag filters of 3500 Da molecular weight
Carry out the dialysis；The time of the dialysis is preferably 20~28 h, more preferably 22~26 h, most preferably 22~24
h.In the present invention, the drying is preferably dried in vacuo；The vacuum drying temperature is preferably 35~45 DEG C, more preferably
It is 40 DEG C；The vacuum drying time is preferably 10~24 h, more preferably 15~20 h；It is described vacuum drying true
Reciprocal of duty cycle is preferably -0.1 MPa.
Solid phase SiNPs, AuNCs and buffer solution are mixed in step (3) of the present invention, obtain just mixed object.This
In invention, the mass ratio of the SiNPs/AuNCs is most preferably 200:1, wherein SiNPs mass concentration is 4 mg/mL;
AuNCs mass concentration is 20 μ g/mL.The present invention is not special for the mixed method of described SiNPs, AuNCs and buffer solution
Restriction, using material well known to those skilled in the art mix technical solution.In the present invention, the present invention is preferably first
The solid phase SiNPs and buffer solution are mixed；It is mixed again with AuNCs.
The just mixed object is mixed and is incubated for 0.5~2 h at room temperature, the SiNPs/AuNCs ratio for obtaining self assembly is glimmering
Light probe.In the present invention, the buffer solution includes HEPES, Tris-HCl and PBS buffer solution, and pH value range is preferably
7.0~8.0；More preferably 7.0~7.5.It mixes and standing time is preferably 0.5~1 h；More preferably 0.5~0.6 h.
The present invention provides the SiNPs/AuNCs ratio fluorescent spies that preparation method described in above-mentioned technical proposal is prepared
Needle, including two kinds of fluorescent materials of SiNPs and AuNCs.There are two types of not by self-assembling technique formation tool for two kinds of fluorescent nano materials
With the ratio fluorescent probe of launch wavelength.
The present invention provides the SiNPs/AuNCs ratio fluorescent probes described in above-mentioned technical proposal to detect in ratio fluorescent
Application in RIF.In an embodiment of the present invention, described in being specifically added in HEPES buffer solution (pH 7.4)
(wherein SiNPs concentration is 4 mg/mL to SiNPs/AuNCs ratio fluorescent probe；AuNCs concentration is 20 μ g/mL), then distinguish
The RIF of various concentration is added, after being incubated for 18 min, obtaining RIF concentration is respectively 0,0.1,0.5,1,2,3,5,10,20 μM
Testing liquid, carry out at room temperature fluorometric investigation (excitation wavelength be 300 nm).With glimmering at 615 nm and 440 nm
Intensity ratio (I 615/I 440) it is ordinate, the substance withdrawl syndrome (C) of RIF is that abscissa establishes the SiNPs/AuNCs ratio
The linearity curve (as shown in Figure 6) that rate fluorescence probe detects RIF.The line curve is speciallyI 615/I 440=-0.034036C+
3.9377.At 440 nm and 615 nm fluorescence intensity ratio (I 615/I 440) for RIF substance withdrawl syndrome (C) it is linear
Response is in 0.1~5 μM of (R2=0.99952) between, detection is limited to 0.04 μM.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious
So, the described embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the implementation in the present invention
Example, every other embodiment obtained by those of ordinary skill in the art without making creative efforts belong to
The scope of protection of the invention.
Example 1
The APTES of the amount of different material is mixed with 12 mL water, obtains APTES solution.The amount of substance for being separately added into 30 μ L is dense
Degree is the AA of 100 mM, and making the molar ratio of AA and APTES is respectively 1:50,1:75,1:100 and 1:150, stirs 10 min；
It is put into the reaction kettle of Teflon liner of 20 mL, in 240 DEG C of 3 h of hydro-thermal reaction, obtains SiNPs fluorescence probe.
Fig. 1 is the column diagram that AA and APTES liquor capacity compare the influence of SiNPs fluorescence intensity.As shown in Figure 1, when AA with
When the molar ratio of APTES is 1:100, the fluorescence intensity highest of SiNPs fluorescence probe.
Example 2
The HAuCl for being 10 mM by different volumes concentration4·3H2O is mixed with the water of 10 mL, obtains HAuCl4·3H2O solution, point
The amount of substance concentration that different amounts of MUA and 100 μ L is not added is the NaOH of 1 M, makes HAuCl4·3H2Mole score of O and MUA
Not Wei 1:4,1:5,1:6,1:7,1:8, stir 5 h, obtain AuNCs fluorescence probe.
Fig. 2 is HAuCl4·3H2O and MUA liquor capacity compare the column diagram of AuNCs fluorescence intensity influence, as shown in Figure 1,
Work as HAuCl4·3H2When the molar ratio of O and MUA solution is 1:6, AuNCs fluorescence intensity highest.
Example 3
The solid phase SiNPs is added in HEPES buffer solution (pH~7.4), makes 4 mg/mL of its mass concentration, then plus
Enter solid phase AuNCs, make 20 μ g/mL of its mass concentration, mix and be incubated for 0.5 h, obtains the spy of SiNPs/AuNCs ratio fluorescent
Needle.
Fig. 3 is the SiNPs/AuNCs ratio fluorescent probe emission fluorescence spectra.From the figure 3, it may be seen that being 300 in wavelength
Under the excitation spectrum of nm, the emission spectrum peak position of SiNPs/AuNCs ratio fluorescent probe is respectively in~440 nm and~615 nm.
Example 4
(wherein SiNPs concentration is 4 mg/mL to SiNPs/AuNCs ratio fluorescent probe;AuNCs concentration is 20 μ g/mL)
20 μM of RIF are added in HEPES buffer solution (pH~7.4).Different incubation times are obtained to visit SiNPs/AuNCs ratio fluorescent
The influence of the fluorescence intensity of needle.
Fig. 5 be the SiNPs/AuNCs ratio fluorescent fluorescence probe intensity rate (I 615/I 440) it is being added 20 μM
After RIF, with the curve graph of incubation time variation.As shown in Figure 5, as time increases, the SiNPs/AuNCs ratio is glimmering
Light probe fluorescence intensity ratio (I 615/I 440) be gradually reduced and finally reach stable after being incubated for 18 min.
Example 5
The SiNPs/AuNCs ratio fluorescent probe is added in HEPES buffer solution (pH 7.4), and (wherein SiNPs concentration is 4
Mg/mL, AuNCs concentration are 20 μ g/mL), it is then respectively adding the RIF of various concentration, after being incubated for 18 min, it is dense to obtain RIF
Degree is respectively 0,0.1,0.5,1,2,3,5,10,20 μM of testing liquid, carries out fluorometric investigation (excitation wave at room temperature
A length of 300 nm).With fluorescence intensity ratio at 615 nm and 440 nm (I 615/I 440) it is ordinate, the amount of the substance of RIF
Concentration (C) is that abscissa establishes the linearity curve (as shown in Figure 7) that the SiNPs/AuNCs ratio fluorescent probe detects RIF.
The line curve is speciallyI 615/I 440=-0.034036C+3.9377.Fluorescence intensity ratio at 440 nm and 615 nm
(I 615/I 440) for RIF substance withdrawl syndrome (C) linear response in 0.1~5 μM of (R2=0.99952) between, detection
It is limited to 0.04 μM.
Example 6
By 20 μM of different common ion (Na+、K+、Ca2+、Mg2+、Zn2+、Cl-、NO3 -、SO4 2-、CO3 2-、PO4 3-) be separately added into
The SiNPs/AuNCs ratio fluorescent probe solution arrived (wherein SiNPs concentration is 4 mg/mL, and AuNCs concentration is 20 μ g/mL)
In, 18 min are incubated for, influence of the different ions to RIF selectivity is obtained.
Fig. 7 be SiNPs/AuNCs ratio fluorescent probe prepared in embodiment 6 to RIF fluorescence response yin, yang from
Selectivity in son analyzes column diagram.As shown in Figure 7, there is no significant shadows for selectivity of the various common anions and canons to RIF
It rings.
Example 7
By common 20 kinds of natural amino acids (glycine Gly, alanine Ala, valine Val, leucine Leu, isoleucine
Ile, phenylalanine Phe, proline Pro, tryptophan Trp, serine Ser, tyrosine Tyr, cysteine Cys, methionine
Met, asparagine Asn, glutamine Gln, threonine Thr, aspartic acid Asp, glutamic acid Glu, lysine Lys, arginine
Arg and histidine) be added separately in SiNPs/AuNCs ratio fluorescent probe solution (wherein SiNPs concentration be 4 mg/
ML, AuNCs concentration are 20 μ g/mL), wherein amino acid concentration is 20 μM, is incubated for 18 min, obtains different aminoacids to RIF
The influence of selectivity.
Fig. 8 is that SiNPs/AuNCs ratio fluorescent probe prepared in embodiment 7 is natural at 20 kinds to RIF fluorescence response
Selectivity in amino acid analyzes column diagram.As shown in Figure 8,20 kinds of natural amino acids have no significant effect RIF fluorescence response.
Example 8
The RIF(1.00 of various concentration, 2.00,4.00 μM) is added separately to SiNPs/AuNCs ratio fluorescent probe (wherein
SiNPs concentration is 4 mg/mL, and AuNCs concentration is 20 μ g/mL) human serum carry out detection in kind, in available sample one
RIF concentration is 0.97 μM, and the rate of recovery is 97 %, and relative standard deviation is 3.4 %.RIF concentration in test sample two is 2.07 μ
M, the rate of recovery are 103.5 %, and relative standard deviation is 2.6 %.RIF concentration is 4.11 μM in test sample three, and the rate of recovery is
102.8 %, relative standard deviation are 2.1 %.And the relative standard deviation (RSDs) of three is below 4 %.Thus illustrate SiNPs/
AuNCs ratio fluorescent probe can be applied in material object detection (as shown in table 1).
Table 1 uses SiO2NPs/AuNCs ratio fluorescent probe measures the trace data of RIF in human serum
It should also be noted that, specific embodiments of the present invention are used only to exemplary illustration, this is not limited in any way
The related technical personnel of the protection scope of invention, this field can be improved or be changed according to above-mentioned some explanations, but all
Such modifications and variations all should belong to the protection scope of the claims in the present invention.
Claims (10)
1. preparing the silicon nano of amido protecting using hydrothermal reduction method :(a) water-soluble silicon source, reducing agent and water are mixed,
Obtain just mixed object；(b) object will be just mixed in the step (c) and 10~20 min are stirred at room temperature, obtain precursors； (c)
Precursors in the step (b) are put into the reaction kettle for the Teflon liner that volume is 20 mL, in 220~240
1~3 h of hydro-thermal reaction at DEG C, obtains the silicon nano of amido protecting；The Jenner of carboxy protective is prepared using stirring reduction method
Rice cluster :(a) by gold chloride (HAuCl4·3H2O), mercaptoundecylic acid (MUA) and water mixing obtain just mixed object；(b) pH tune is used
Saving agent and adjusting the pH value of first mixed object in the step (a) is 10~12, obtains precursors；(c) by the step (b)
In precursors be stirred at room temperature, react 4~7 h, obtain the gold nanoclusters of carboxy protective；By the step
(1) and the silicon nano in (2) and gold nanoclusters carry out self assembly, and synthesis silicon nano/gold nanoclusters ratio fluorescent is visited
Needle :(a) silicon nano and gold nanoclusters are mixed in buffer solution, obtain just mixed object；(b) at room temperature by the step
(a) just mixed object mixes and is incubated for 0.5~2 h in, obtains silicon nano/gold nanoclusters ratio fluorescent probe.
2. the preparation method according to claim 1, which is characterized in that reducing agent and water-soluble silicon in the step (1)
The molar ratio in source is 1:(50~150), wherein the substance withdrawl syndrome of reducing agent is 100 mM.
3. according to preparation method described in claim 1 or 2, which is characterized in that water-soluble silicon source includes in the step (1)
3- aminopropyl triethoxysilane (APTES) or 3- aminopropyl trimethoxysilane (APTMS);Reducing agent includes ascorbic acid
(AA) or sodium citrate.
4. the preparation method according to claim 1, which is characterized in that HAuCl in the step (2)4·3H2O and MUA
Molar ratio be 1:(4~8), HAuCl in final just mixed object4·3H2The concentration of the amount of the substance of O is 500 μM.
5. preparation method according to claim 1, which is characterized in that adjust just mixed object pH value institute in the step (2)
The pH regulator of use includes sodium hydroxide solution or potassium hydroxide solution;The concentration of pH regulator is 1.0~1.2 M.
6. the preparation method according to claim 1, which is characterized in that silicon nano and gold nano in the step (3)
The mass ratio of cluster is 200:1, and wherein silicon nano mass concentration is 4 mg/mL；Gold nanoclusters mass concentration is 20 μ g/mL.
7. the preparation method according to claim 1, which is characterized in that in the step (3) buffer solution include HEPES,
Tris-HCl and PBS buffer solution;PH value of buffer solution range is 7.0~8.0.
8. silicon nano/gold nanoclusters ratio fluorescent probe that any one of claim 1~7 preparation method is prepared
Including silicon nano and chelating in the gold nanoclusters on silicon nano surface.
9. the preparation method according to claim 8, which is characterized in that the silicon nano/gold nanoclusters ratio fluorescent
Probe, obtaining most strong excitation wavelength is 300~310 nm, and most strong launch wavelength is in 440~445 nm or so and 610~615
Nm or so has ratio fluorescent feature.
10. silicon nano described in claim 8 or 9/gold nanoclusters ratio fluorescent probe detects benefit in ratio fluorescent
Application during good fortune is flat.
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