CN107084963A - A kind of silicon quantum dot detection Pd of utilization amino functional2+Method - Google Patents
A kind of silicon quantum dot detection Pd of utilization amino functional2+Method Download PDFInfo
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- CN107084963A CN107084963A CN201710400063.XA CN201710400063A CN107084963A CN 107084963 A CN107084963 A CN 107084963A CN 201710400063 A CN201710400063 A CN 201710400063A CN 107084963 A CN107084963 A CN 107084963A
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
Pd is detected the invention discloses a kind of silicon quantum dot of utilization amino functional2+Method, step includes：(1) preparation of silicon quantum dot；(2) particle diameter is less than the preparation of 5.0nm amino functional silicon quantum dot；(3) amino functional silicon quantum dot is to Pd2+Detection.The silicon quantum dot fluorescent stability and good biocompatibility of the amino functional, good water solubility, preparation method are simple, and the time is short, and cost is low.
Description
Technical field
The present invention relates to analysis field of sensing technologies, and in particular to a kind of silicon quantum dot detection of utilization amino functional
Pd2+Method.
Technical background
Metal Palladium is widely used in the fields such as jewelry, medical treatment, fuel cell and Industrial Catalysis as rare transition metal,
But the palladium ion in environment enters organism and organism generation greatly can be injured, due to the complexation property of palladium ion, energy
Important macromolecular complex in enough and organism, such as DNA, RNA, protein etc. are so as to suppress the normal function of cell.Secondly,
It has recently been demonstrated that palladium ion is the second largest metal sensitizer for being only second to nickel metal ion, particularly palladium bichloride, to human eye
There is very strong excitant with skin.Therefore, in the urgent need to it is a kind of have to palladium ion highly sensitive, selectivity, it is quick, easily detect
Means.
Silicon quantum dot, as a kind of zero dimension silicon wafer, when particle radii are less than or draw during close to exciton Bohr radiuses (5nm)
The quantum confined effect of hair makes silicon quantum dot possess many unique photoelectric properties.Silicon quantum dot mainly has size to rely on hair
Light, chemism (reproducibility) height, good biocompatibility, anti-light Bleachability, nontoxic, environmentally friendly, economical, easy prepare, easily modify
Advantage, makes it be opened in medical imaging, the research of tumour, the measure of metal ion content, the detection of microorganism and targeted drug
In terms of sending out treatment, the research to disease, clinical diagnosis and treatment all has very big potential using value.
Also there is the document report of detection palladium ion in recent years：
The A of Chinese patent CN 101735277, disclose " fluorescent probe compounds and its production and use ",
That the property based on loop coil " open-close " in rhodamine molecule devises fluorescent chemicals probe, using within the probe plus
Enter fluorescence intensity increase after palladium ion, when especially detecting 0-10ppb palladium ion concentrations, the phenomenon that fluorescence intensity is significantly increased reaches
To testing goal, minimum detectable 5nm palladium ion.
The A of Chinese patent CN 102995052, disclose " one kind detection Pd2+Poly- benzanthrone fluorescent sensor molecule
Preparation method ", the poly- benzanthrone fluorescent sensor molecule prepared using palladium ion to it has good fluorescent quenching effect, can
Realize to the efficient, sensitive of palladium ion, selective enumeration method.
The A of Chinese patent CN 104962278 disclose " a kind of palladium ion fluorescence probe and its preparation method and application ", with
Formic acid allyl fat is prepared for palladium ion fluorescence probe for response group, adds absorption spectrum and fluorescence emission spectrum after palladium ion equal
Generation red shift, can quantitatively be detected by ratio manner to the palladium ion of low concentration.
Patent document described above is all prepared for fluorescence probe, recycles fluorescence probe to be quenched with colorimetric, Fluorescence Increasing, fluorescence
Effect of going out realizes palladium ion detection, has the advantages that certain, but the preparation process of fluorescence probe is complicated, and generated time is long,
And the stability of fluorescence probe is not considered.
The content of the invention
Pd is detected it is an object of the invention to provide a kind of silicon quantum dot of amino functional2+Method, the amino work(
The silicon quantum dot fluorescent stability and good biocompatibility of energyization, good water solubility, preparation method are simple, and the time is short, and cost is low.
A kind of silicon quantum dot detection Pd for amino functional that the present invention is provided2+Method, comprise the following steps：
(1) preparation of silicon quantum dot：In nitrogen environment, 1-2g TOAB are dissolved in 60-130mL dry toluenes, added
0.8mmol SiCl490-100 μ L, add the LiAlH that 200-250 μ L concentration is 1mol/L4THF solution；The mixing of formation
Thing is reacted after 3h at ambient temperature, is slowly added to the excessive reducing agent of absolute methanol quenching；
(2) preparation of amino functional silicon quantum dot：In the silicon quantum dot of above-mentioned preparation add 1-5mL allylamines and
30-50 μ L concentration is 0.05mol/L H2PtCl6Aqueous isopropanol, reaction obtain the amine-modified silicon quantum dot of allyl, from nitrogen
Taken out in compression ring border, solvent is removed with Rotary Evaporators revolving, remaining white precipitate is TOAB and SiQDs；Then by white
40-60mL secondary waters are added in precipitation, TOAB is repeatedly removed with 0.22 μm of filter membrane device filtering, obtains SiQDs storing solution.
(3) amino functional silicon quantum dot is to Pd2+Detection：Sequentially added in colorimetric cylinder 20mmol/L PBS solutions,
The 1mmol/L palladium bichloride storing solutions of SiQDs storing solutions, different volumes, and secondary water constant volume is used, 50- is stood after shaking up at room temperature
60min.The fluorescence intensity of the amine-modified silicon quantum dot solution of the allyl containing different volumes palladium bichloride is surveyed, amino functional is set up
Silicon quantum dot fluorescence intensity with Pd2+The relation curve of change in concentration, and then can realize and treat test sample Pd2+Detection.
Compared with prior art, beneficial effects of the present invention：
The silicon quantum dot particle diameter of amino functional prepared by the present invention is less than 5.0nm, fluorescent stability and biocompatibility
Good, good water solubility can be realized and treat test sample Pd2+Detection, and preparation method is simple, and the time is short, and cost is low.
Brief description of the drawings
The transmission electron microscope picture of Fig. 1 different-grain diameter amino functional silicon quantum dots.
Fig. 2 different-grain diameter amino functional silicon quantum dots Fluorimetric Quenching Method detects Pd2+Fluorescence spectra.
Fig. 3 particle diameters are less than the fluorescence intensity of 5nm amino functional silicon quantum dot with Pd2+The graph of a relation of change in concentration
Embodiment
The particle diameter of embodiment 1 is less than the preparation of 5nm amino functional silicon quantum dot and to Pd2+Detection
(1) preparation of silicon quantum dot：In nitrogen environment, 1.5g TOAB are dissolved in 100mL dry toluenes, 92 μ L are added
SiCl4(0.8mmol), adds double superfluous reducing agent 1mol/L LiAlH4THF solution.The mixture room temperature of formation is anti-
Answer after 3h, be slowly added to 20mL absolute methanols to be quenched excessive reducing agent.
(2) preparation of amino functional silicon quantum dot：In the hydrogen end silicon quantum dot of above-mentioned preparation add 2mL allylamines and
40 μ L as catalyst H2PtCl6The aqueous isopropanol of (0.05mol/L), reaction obtains the amine-modified silicon quantum dot of allyl.It is complete
Into after surface modification, sample is taken out from nitrogen environment, handled with Rotary Evaporators, revolving removes remaining white after solvent
It is precipitated as TOAB and SiQDs.50mL secondary waters, the hydrophilic dissolvings of SiQDs, with 0.22 μm of filter membrane device mistake will be added in white precipitate
3 removing TOAB of filter, obtain SiQDs storing solution, and TEM is characterized such as A, the particle diameter of gained amino functional silicon quantum dot in Fig. 1
For 2.4 ± 0.1nm (being less than 5nm).
(3) amidized silicon quantum dot is to Pd2+Detection：1mL PBS (20mmol/ are sequentially added in 10mL colorimetric cylinders
L) the amine-modified silicon quantum dot storing solution of solution, 100 μ L allyls, different volumes (0 μ L, 500 μ L, 1000 μ L, 1500 μ L, 2000 μ
L, 2500 μ L) palladium bichloride storing solution (1mmol/L), and use secondary water constant volume, stand 60min after shaking up at room temperature.Survey contains
The fluorescence intensity of the amino functional silicon quantum dot solution of different volumes palladium bichloride, as a result such as A in Fig. 2.Set up amino functional
The fluorescence intensity of silicon quantum dot is with Pd2+The relation curve of change in concentration, as a result such as Fig. 3, linear correlation curve y=-31.37143x
+ 1005.47619, coefficient R2=0.98625.Measure when test sample, except add 1mL unknown concentrations treat test sample in addition to, remaining
Step ibid, is measured after after the fluorescence intensity of test sample, test sample concentration is treated in substitution linear correlation curve calculating.
The particle diameter of embodiment 2 is less than the preparation of 5nm amino functional silicon quantum dot and to Pd2+Detection
(1) preparation of silicon quantum dot：Be the same as Example 1
(2) preparation of amino functional silicon quantum dot：Be the same as Example 1
(3) amidized silicon quantum dot is to Pd2+Detection：Except the amine-modified silicon quantum dot deposit of the allyl for detection
Liquid is to placed three months outer, remaining be the same as Examples 1.The results contrast change of testing result and embodiment 1 is little, illustrates allyl
Amine-modified silicon quantum dot has good fluorescent stability.
Comparative example particle diameter is more than the preparation of 5nm amino functional silicon quantum dot and to Pd2+Detection
(1) preparation of silicon quantum dot：In nitrogen environment, 0.5g TOAB are dissolved in 100mL dry toluenes, 92 μ L are added
SiCl4(0.8mmol), adds 0.8mL reducing agent 1mol/L LiAlH4THF solution.The mixture room temperature reaction 3h of formation
Afterwards, 20mL absolute methanols are slowly added to be quenched excessive reducing agent.
(2) preparation of amino functional silicon quantum dot：In the hydrogen end silicon quantum dot of above-mentioned preparation add 2mL allylamines and
40 μ L as catalyst H2PtCl6The aqueous isopropanol of (0.05mol/L), reaction obtains the amine-modified silicon quantum dot of allyl.It is complete
Into after surface modification, sample is taken out from nitrogen environment, handled with Rotary Evaporators, revolving removes remaining white after solvent
It is precipitated as TOAB and SiQDs.50mL secondary waters, the hydrophilic dissolvings of SiQDs, with 0.22 μm of filter membrane device mistake will be added in white precipitate
3 removing TOAB of filter, obtain SiQDs storing solution, and TEM is characterized such as B, the particle diameter of gained amino functional silicon quantum dot in Fig. 1
For 7.8 ± 0.3nm (being more than 5nm).
(3) amidized silicon quantum dot is to Pd2+Detection：1mL PBS (20mmol/ are sequentially added in 10mL colorimetric cylinders
L) the amine-modified silicon quantum dot storing solution of solution, 100 μ L allyls, different volumes (0 μ L, 500 μ L, 1000 μ L, 1500 μ L, 2000 μ
L, 2500 μ L) palladium bichloride storing solution (1mmol/L), and use secondary water constant volume, stand 60min after shaking up at room temperature.Survey contains
The fluorescence intensity of the amino functional silicon quantum dot solution of different volumes palladium bichloride, as a result such as B in Fig. 2.
Find out from above-described embodiment and comparative example：When the particle diameter of amino functional silicon quantum dot is less than 5.0nm, Pd2+Draw
The quenching phenomenon for playing amino functional silicon quantum dot fluorescence is obvious, and it can be used for detection Pd2+Concentration.When amino functional SiClx amount
When the particle diameter of son point is more than 5.0nm, Pd2+Cause that the quenching phenomenon of amino functional silicon quantum dot fluorescence is not obvious, it should not be used
In detection Pd2+Concentration.
Claims (1)
1. a kind of silicon quantum dot detection Pd of utilization amino functional2+Method, the silicon quantum dot of the amino functional passes through
Following method is prepared：
(1) preparation of silicon quantum dot：In nitrogen environment, 1-2g TOAB are dissolved in 60-130mL dry toluenes, added
0.8mmol SiCl490-100 μ L, add the LiAlH that 200-250 μ L concentration is 1mol/L4THF solution；The mixing of formation
Thing is reacted after 3h at ambient temperature, is slowly added to the excessive reducing agent of absolute methanol quenching；
(2) preparation of amino functional silicon quantum dot：1-5mL allylamines and 30-50 μ are added in the silicon quantum dot of above-mentioned preparation
L concentration is 0.05mol/L H2PtCl6Aqueous isopropanol, reaction obtain the amine-modified silicon quantum dot of allyl, from nitrogen environment
It is middle to take out, solvent is removed with Rotary Evaporators revolving, remaining white precipitate is TOAB and SiQDs；Then by white precipitate
40-60mL secondary waters are added, TOAB is repeatedly removed with 0.22 μm of filter membrane device filtering, obtains SiQDs storing solution.
(3) amino functional silicon quantum dot is to Pd2+Detection：20mmol/L PBS solutions, SiQDs are sequentially added in colorimetric cylinder
The 1mmol/L palladium bichloride storing solutions of storing solution, different volumes, and secondary water constant volume is used, 50-60min is stood after shaking up at room temperature.
The fluorescence intensity of the amine-modified silicon quantum dot solution of the allyl containing different volumes palladium bichloride is surveyed, the silicon amount of amino functional is set up
The fluorescence intensity of son point is with Pd2+The relation curve of change in concentration, and then test sample Pd is treated in realization2+Detection.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105567219A (en) * | 2016-01-08 | 2016-05-11 | 深圳大学 | Fluorescent probe for detecting palladium ions, preparation method and applications thereof |
| US20160251227A1 (en) * | 2013-09-13 | 2016-09-01 | Ndsu Research Foundation | Synthesis of si-based nano-materials using liquid silanes |
| CN106323893A (en) * | 2016-07-28 | 2017-01-11 | 山东师范大学 | Palladium-ion multi-channel response probe and synthesis method and application thereof |
| CN106350061A (en) * | 2016-08-29 | 2017-01-25 | 北京化工大学 | Silicon quantum dot as well as preparation method and application thereof |
-
2017
- 2017-05-31 CN CN201710400063.XA patent/CN107084963A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160251227A1 (en) * | 2013-09-13 | 2016-09-01 | Ndsu Research Foundation | Synthesis of si-based nano-materials using liquid silanes |
| CN105567219A (en) * | 2016-01-08 | 2016-05-11 | 深圳大学 | Fluorescent probe for detecting palladium ions, preparation method and applications thereof |
| CN106323893A (en) * | 2016-07-28 | 2017-01-11 | 山东师范大学 | Palladium-ion multi-channel response probe and synthesis method and application thereof |
| CN106350061A (en) * | 2016-08-29 | 2017-01-25 | 北京化工大学 | Silicon quantum dot as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 姚娇丽等: "《硅量子点支撑钯纳米粒子的可控制备》", 《分析科学学报》 * |
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