CN104927866A - Preparation method and application of hollow porous silica sphere-coated quantum dot fluorescent sensor - Google Patents
Preparation method and application of hollow porous silica sphere-coated quantum dot fluorescent sensor Download PDFInfo
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Abstract
The invention belongs to Materials Science and Engineerings and contemporary optics field of sensing technologies, are related to a kind of preparation method and applications of hollow porous silicon ball coated quantum dots fluorescent optical sensor. Steps are as follows: preparing CdTe quantum colloidal solution using Aqueous phase; Using
Method prepares monodisperse SiO2 microballoon by raw material of ethyl orthosilicate; Alkaline etching is added under non-ionic macromolecule compound protection in microballoon, and hollow porous SiO2 microballoon is made; It is modified with amino silicane coupling agent; The hollow porous SiO2 microballoon after modification is added into quantum dispensing liquid solution, is protected from light, hollow porous silicon ball coated quantum dots material is made, the as described hollow porous silicon ball coated quantum dots fluorescent optical sensor. Hollow porous silicon ball coated quantum dots material of the invention has good quantum dot fluorescence performance, stability and biocompatibility, and PARA FORMALDEHYDE PRILLS(91,95) has selective response, the analysis detection of trace formaldehyde suitable for the complex samples such as biology, food, environment.
Description
Technical field
The invention belongs to Materials Science and Engineering and contemporary optics field of sensing technologies, relate to preparation method and application thereof that hollow porous silicon bag covers quantum dot fluorescence matrix material.This fluorescent optical sensor PARA FORMALDEHYDE PRILLS(91,95) has good response, is applicable to the analyzing and testing of trace formaldehyde in the complex samples such as biology, food, environment.
Background technology
Nearly ten years, fluorescent optical sensor has highly sensitive, highly selective, the advantage such as simple to operation, more and more extensive in field application such as food, biology, environment, chemical industry; Various fluorescent optical sensors based on fluorescence quenching design are one of them important research directions, and sensing novel material receives much concern as the cross knot chalaza of Materials science and analytical chemistry.
Quantum dot (QDs) is primarily of II-VI group or the elementary composition semi-conductor of iii-v, it has the special character such as wide excitation spectrum, narrow emmission spectrum, high fluorescence quantum yield and life-span length, be a kind of than luminescent dye molecule more preferably bioprobe, be used widely in genomics, proteomics, molecular biology, biological chemistry etc.For improving the biocompatibility of quantum dot and stability, mode carries out modification to it usually to adopt the surface modification methods such as silanization or suitably embedded by quantum dot etc.
Porous material has regularly arranged, that size is adjustable pore passage structure, and it has the features such as exclusive machinery, absorption, infiltration, photoelectricity and biological activity.Wherein mesoporous silicon oxide has the advantages such as superior optical transparence, good biocompatibility, high perviousness, in targeted drug, biomagnification and be separated, there is good application prospect in the field such as magnetic thermotherapy, immobilized enzyme, bulky molecular catalysis, fractionation by adsorption.For improving the charge capacity of mesoporous silicon oxide, the people such as Zhang, by the porous silica adopting the synthesis of self-template method to have internal cavities, for nano particle provides large attachment space, promote its carrying capacity and expand its range of application; The people such as Li utilize hollow porous silicon-dioxide as a kind of multifunctional nano susceptor, successfully catch nanometer small-particle.
Formaldehyde is a kind of important industrial raw material, is also conventional sanitas and sterilizing agent, is defined as carcinogenic, teratogen and potential strong mutagen by the World Health Organization.Formaldehyde harm in recent years in room air, fishery products, food and ambient water has caused the extensive concern of people.Porousness, adsorptivity, the modifiability of the fluorescence property that incorporating quantum point is good and porous silica mesoporous material, carry out the development of porous hollow silicon dioxide-coated quantum dots fluorescent optical sensor and the detection being applied to trace formaldehyde in environment, food has important theory significance and practical value.
Summary of the invention
The present invention is directed to the demand of the fields such as environment food to fluorescent optical sensor needed for trace formaldehyde rapid detection, in conjunction with at present domestic and international based on quantum dot and mesoporous material research development trend, provide a kind of hollow porous silicon bag newly to cover the preparation method of quantum dot fluorescence sensor.
The present invention is achieved through the following technical solutions:
Hollow porous silicon bag covers a preparation method for quantum dot fluorescence sensor, prepares according to the following steps:
(1) Aqueous phase is adopted to prepare CdTe quantum colloid;
(2) adopt
method is that single dispersing SiO prepared by raw material with tetraethoxy
2microballoon; Microballoon adds alkaline etching under non-ionic macromolecule compound protection, obtained hollow porous SiO
2microballoon;
(3) by hollow porous SiO obtained for step (2)
2microballoon amino silicane coupling agent is modified;
(4) in the obtained quantum dot colloidal solution of step (1), the hollow porous SiO after modification prepared in step (3) is added
2microballoon, lucifuge is reacted, and obtained hollow porous silicon bag covers quanta point material, is described hollow porous silicon bag and covers quantum dot fluorescence sensor.
Further, in described step (1), the CdTe quantum prepared with Aqueous phase, its particle size range is 1-4nm.
Further, in described step (3), described amino silicane coupling agent is aminopropyl triethoxysilane, and the mol ratio of described hollow porous silicon ball and aminopropyl triethoxysilane is 1:3.
Further, described step (4) is specially: add quantum dot and the hollow porous silicon ball of amination respectively in aqueous ethanolic solution, lucifuge reaction 24h, wherein the volume fraction of aqueous ethanolic solution is 60-70%, adds amination hollow porous silicon ball 2mg in every milliliter of quantum dot solution.
Content of the present invention also comprises the hollow porous silicon bag prepared according to the method described above and covers quantum dot fluorescence sensor.
Further, when the concentration that described hollow porous silicon bag covers quantum dot fluorescence sensor is 1mg/mL, PARA FORMALDEHYDE PRILLS(91,95) has selectivity quenching effect in the basic conditions.
Further, described hollow porous silicon bag covers quanta point material sensor and have satisfactory stability under the condition such as ul-trasonic irradiation and room temperature leave standstill, and in 30 days, its fluorescence property is substantially constant.
Content of the present invention also comprises described hollow porous silicon bag and covers quantum dot fluorescence sensor, the application of the analyzing and testing of trace formaldehyde in complex sample.
Further, described complex sample is environmental water sample or fishery products etc.
Further, described hollow porous silicon bag covers quantum dot fluorescence sensor and is limited to 0.07mg/L to detecting of formaldehyde in fishery products.
The present invention adopts self-assembling technique to prepare the fluorescence nano capsule with strong luminescent properties and open system, directly enter in the amination mesoporous silicon dioxide micro-sphere of macropore by coated for quantum dot, obtain the fluorescent optical sensor of simple, stable and good fluorescent characteristic.Hollow porous silicon bag of the present invention covers quantum dot fluorescence sensor, PARA FORMALDEHYDE PRILLS(91,95) can have and optionally respond, and meets the analysis requirement that in environment or food, trace formaldehyde is residual.
Accompanying drawing explanation
fig. 1the signal of the preparation process of porous hollow silicon dioxide-coated quantum dots fluorescent optical sensor
figure.
fig. 2for hollow porous silica spheres scanning electron microscope
figure (a), amido modified porous hollow silicon-dioxide transmission electron microscope (B) and porous hollow silicon dioxide-coated quantum dots transmission electron microscope (C).
fig. 3the fluorescence Spectra of porous hollow silicon dioxide-coated quantum dots (c) of quantum dot (a) and porous hollow silicon dioxide-coated quantum dots (b) and unmodified
figure.
fig. 4for the UV spectrum of silicon dioxide-coated quantum dots fluorescent optical sensor
figureand fluorescence spectrum
figure (and the UV spectrum of response of its PARA FORMALDEHYDE PRILLS(91,95) a)
figureand fluorescence spectrum
figure (b).
fig. 5the stability of porous hollow silicon dioxide-coated quantum dots.
fig. 6the selectivity of porous hollow silicon dioxide-coated quantum dots
fig. 7porous hollow silicon dioxide-coated quantum dots is to the fluorescence response of different concns formaldehyde standardized solution.
Specific embodiment
Be described below in conjunction with embodiments of the invention, should be appreciated that preferred embodiment described herein is only for instruction and explanation of the present invention, is not intended to limit the present invention.
The hollow porous silicon bag of embodiment 1 covers the preparation of quanta point material sensor
The present embodiment is the preparation that hollow porous silicon bag covers quantum dot fluorescence sensor, its step
as Fig. 1shown in, concrete steps are as follows:
(1) preparation of the hollow porous silicon-dioxide of amination: adopt
the silicon-dioxide of the standby about 120nm of legal system; Getting SiO 2 powder 0.3g joins in 10mL deionized water, adds 0.25g Polyvinylpyrolidone (PVP) (PVP) and 0.6g NaBH after ultrasonic 10min
4, the lower 50 DEG C of heating in water bath 6h of vigorous stirring.Centrifugal (8000rpm) obtains white solid, and with deionized water repetitive scrubbing three times, 50 DEG C of vacuum-drying 24h, grind hollow porous silica microballoon is stand-by.Hollow porous silicon dioxide microsphere is joined in 200mL dehydrated alcohol, 100 μ L 3-aminopropyl triethoxysilanes and 100 μ L deionized waters are added after ultrasonic 30min, 45 DEG C of return stirring 6h, use ethanol and deionized water wash 2-3 time, vacuum-drying 24h at 45 DEG C respectively.
(2) preparation of CdTe quantum (QDs): add 1mL deionized water, 0.042g NaBH in 2mL vial respectively
4with 0.064g Te powder.Slowly stir 40min under sealing, until bottle at the bottom of black powder disappear after again leave standstill 20min, obtain NaHTe presoma clear liquid; Accurately take 0.0228g CdCl
22.5H
2o joins in 250mL there-necked flask, adds the thiohydracrylic acid (MPA) of 100mL deionized water and 25.5 μ L, and after stirring 20min, adjust ph is 11.0, logical nitrogen 20min, then inject 100 μ L NaHTe presoma clear liquids fast, 96 DEG C of water-bath backflow 6h, obtain CdTe quantum.
(3) preparation of porous hollow silicon dioxide-coated quantum dots
Take the porous hollow silicon-dioxide of 10mg, add 4mL dehydrated alcohol and 6mL water, after ultrasonic 20min, add 1.0mL CdTe quantum, continue ultrasonic 10min, then lucifuge stirring reaction 24h under room temperature, low-speed centrifugal removes the quantum dot do not adsorbed, and obtains porous hollow silicon dioxide-coated quantum dots.During use, porous hollow silicon dioxide-coated quantum dots is scattered in 5mL water.
Obtained porous hollow silicon dioxide-coated quantum dots
as Fig. 2shown in, wherein 2 (A) are hollow porous silica spheres scanning electron microscope
figure, 2 (B) for amido modified porous hollow silicon-dioxide transmission electron microscope and 2 (C) be porous hollow silicon dioxide-coated quantum dots transmission electron microscope.
embodiment 2:the fluorescence property of porous hollow silicon dioxide-coated quantum dots fluorescent optical sensor and selectivity
(1) fluorescence property
fig. 3give the fluorescence spectrum of not coated CdTe quantum (a), the quantum dot (b) of amido modified coated with silica and the quantum dot (c) of not amido modified coated with silica
figure,
in figurecan find out, adopt amido modified porous silica tiny balloon coated after, the fluorescence intensity of quantum dot remains on about 60%, and not amido modified silicon-dioxide cannot stably coated quantum dots.
fig. 4give the UV spectrum of silicon dioxide-coated quantum dots fluorescent optical sensor
figureand fluorescence spectrum
figure (and the UV spectrum of response of its PARA FORMALDEHYDE PRILLS(91,95) a)
figureand fluorescence spectrum
figure (b).
in figureobviously can find out that formaldehyde can the quantum dot fluorescence of quencher coated with silica; Can find out in photo that the color that formaldehyde adds rear solution there occurs obvious change, can be used for direct visual sensing detection.
(2) stability
fig. 5give the stability result of the quantum dot fluorescence sensor of coated with silica, wherein a is the quantum dot stoste of coated with silica; B is the ultrasonic redispersion solution of quantum dot after centrifugal of coated with silica; 1-30 is the fluorescence intensity of ultrasonic redispersion solution after the quantum dot of coated with silica places corresponding number of days.
in figureobviously can find out that the quantum dot of the coated with silica of preparation has satisfactory stability.
(3) selectivity
fig. 6give the fluorescence response of the materials such as the quantum dot fluorescence sensor PARA FORMALDEHYDE PRILLS(91,95) of coated with silica, ethanol, acetone, methylene dichloride, trichloromethane and toluene, result shows that fluorescent optical sensor PARA FORMALDEHYDE PRILLS(91,95) has and optionally responds; Other organic solvents such as ethanol a small amount of inside solution system do not affect its fluorescence property.
embodiment 3:porous hollow silicon dioxide-coated quantum dots fluorescent optical sensor detects the formaldehyde in fishery products
(1) foundation of analytical procedure
Prepare the formaldehyde standardized solution that a series of concentration gradient is 0.2 to 15.5mg/L, respond drawing standard curve by fluorescence spectrum and calculate linearity range, relation conefficient and method detection limit.Result shows, the linear relationship of formaldehyde within the scope of 0.2-15.5mg/L good (
fig. 7), linear equation is Δ F=351.4C-7.770, and relation conefficient 0.9997, detects and be limited to 0.07mg/L.
(2) actual sample is analyzed
Institute's construction method is applied to the analyzing and testing of formaldehyde in squid.Accurately take the dry squid of 2g, with 100mL water for after solvent supersonic extraction 30min, at 15000rpm high speed centrifugation 5min, getting supernatant liquor is due to extracting solution, for subsequent use.
Pipette 20 μ L respectively, 50 μ L and 100 μ L squid extracting solutions join in 0.5mL silicon dioxide-coated quantum dots solution, fully shake up rear standing 8min, measure its fluorescence intensity.Simultaneously with the squid extracting solution adding 31ppm formaldehyde respectively and do not add formaldehyde for reference.According to formula:
(formula 1)
Result shows, the concentration containing formaldehyde in squid is the rate of recovery 95.25%-106.5% of 4.6ppm, formaldehyde, and RSD is less than 2.0%.
The above, the present invention adopts self-assembling technique to prepare the fluorescence nano capsule with strong luminescent properties and open system, directly enter in the amination mesoporous silicon dioxide micro-sphere of macropore by coated for quantum dot, obtain the fluorescent optical sensor of simple, stable and good fluorescent characteristic.Hollow porous silicon bag of the present invention covers quantum dot fluorescence sensor, PARA FORMALDEHYDE PRILLS(91,95) can have and optionally respond, and meets the analysis requirement that in environment or food, trace formaldehyde is residual.
It is to be understood that, below be only preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention, any those skilled in the art, do not departing within the scope of technical solution of the present invention, make a little change when the technology contents of above-mentioned announcement can be utilized or be modified to the Equivalent embodiments of equivalent variations, in every case be do not depart from technical solution of the present invention content, according to any simple modification that technical spirit of the present invention is done above embodiment, equivalent variations and modification, all still, belong in the scope of technical solution of the present invention.
Claims (10)
1. the preparation method that a hollow porous silicon bag covers quantum dot fluorescence sensor is characterized in that, prepares according to the following steps:
(1) Aqueous phase is adopted to prepare CdTe quantum colloidal solution;
(2) adopt
method is that single dispersing SiO prepared by raw material with tetraethoxy
2microballoon; Microballoon adds alkaline etching under non-ionic macromolecule compound protection, obtained hollow porous SiO
2microballoon;
(3) by hollow porous SiO obtained for step (2)
2microballoon amino silicane coupling agent is modified;
(4) in the obtained quantum dot colloidal solution of step (1), the hollow porous SiO after modification prepared in step (3) is added
2microballoon, lucifuge is reacted, and obtained hollow porous silicon bag covers quanta point material, is described hollow porous silicon bag and covers quantum dot fluorescence sensor.
2. hollow porous silicon bag as claimed in claim 1 covers the preparation method of quantum dot fluorescence sensor, it is characterized in that: in described step (1), the CdTe quantum prepared with Aqueous phase, and its particle size range is 1-4nm.
3. hollow porous silicon bag as claimed in claim 1 covers the preparation method of quantum dot fluorescence sensor, it is characterized in that: in described step (3), described amino silicane coupling agent is aminopropyl triethoxysilane, and the mol ratio of described hollow porous silicon ball and aminopropyl triethoxysilane is 1:3.
4. hollow porous silicon bag as claimed in claim 1 covers the preparation method of quantum dot fluorescence sensor, it is characterized in that: described step (4) is specially: add quantum dot and the hollow porous silicon ball of amination respectively in aqueous ethanolic solution, lucifuge reaction 24h, wherein the volume fraction of aqueous ethanolic solution is 60-70%, adds amination hollow porous silicon ball 2mg in every milliliter of quantum dot solution.
5. the hollow porous silicon bag prepared according to the method for any one of claim 1-4 covers quantum dot fluorescence sensor.
6. hollow porous silicon bag as claimed in claim 5 covers quantum dot fluorescence sensor, it is characterized in that: when its concentration is 1mg/mL, PARA FORMALDEHYDE PRILLS(91,95) has selectivity quenching effect in the basic conditions.
7. hollow porous silicon bag as claimed in claim 5 covers quantum dot fluorescence sensor, it is characterized in that: described hollow porous silicon bag covers quanta point material sensor and have satisfactory stability under the conditions such as ul-trasonic irradiation and room temperature leave standstill, and in 30 days, its fluorescence property is substantially constant.
8. hollow porous silicon bag according to claim 6 covers quantum dot fluorescence sensor, the application of trace formaldehyde analyzing and testing in complex sample.
9. apply as claimed in claim 8, it is characterized in that: described complex sample is environmental water sample or fishery products etc.
10. apply as claimed in claim 8, it is characterized in that: it is limited to 0.07mg/L to detecting of formaldehyde in fishery products.
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| CN108519362A (en) * | 2018-05-08 | 2018-09-11 | 铜仁学院 | A kind of PARA FORMALDEHYDE PRILLS(91,95) realizes the novel nano composite construction chip quickly detected and preparation method |
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| CN112808282A (en) * | 2021-01-20 | 2021-05-18 | 河南大学 | Cesium-lead-bromine perovskite @ silicon dioxide hollow mesoporous spherical core-shell structure, and preparation method and application thereof |
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| CN106939162A (en) * | 2016-01-04 | 2017-07-11 | 内蒙古大学 | SiO2The synthetic method of@Tb (phen-Si) L nuclear shell structure nano luminescent composites |
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| CN108519362A (en) * | 2018-05-08 | 2018-09-11 | 铜仁学院 | A kind of PARA FORMALDEHYDE PRILLS(91,95) realizes the novel nano composite construction chip quickly detected and preparation method |
| CN109266324A (en) * | 2018-10-16 | 2019-01-25 | 南京纳科伟业纳米技术有限公司 | Dendroid silica@carbon dots composite nanometer particle and preparation method thereof |
| CN109609114A (en) * | 2018-11-12 | 2019-04-12 | 天津市中环量子科技有限公司 | A kind of optimized treatment method of fluorescence quantum |
| CN109609114B (en) * | 2018-11-12 | 2022-03-01 | 天津市中环量子科技有限公司 | Optimization processing method of fluorescent quantum dots |
| CN110054192A (en) * | 2019-05-06 | 2019-07-26 | 燕山大学 | A kind of extra small nano SiO 2 particle of monodisperse and preparation method thereof |
| CN110054192B (en) * | 2019-05-06 | 2020-09-11 | 燕山大学 | Preparation method of monodisperse ultra-small silicon dioxide nanoparticles |
| CN112808282A (en) * | 2021-01-20 | 2021-05-18 | 河南大学 | Cesium-lead-bromine perovskite @ silicon dioxide hollow mesoporous spherical core-shell structure, and preparation method and application thereof |
| CN112931934A (en) * | 2021-03-24 | 2021-06-11 | 湖北中烟工业有限责任公司 | Fragrance-holding and cooling additive and preparation method and application thereof |
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