CN104310407A - Method for biomimetic preparation of water-soluble fluorescent silicon nano-particles - Google Patents
Method for biomimetic preparation of water-soluble fluorescent silicon nano-particles Download PDFInfo
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Abstract
The invention discloses a method for biomimetic preparation of water-soluble fluorescent silicon nano-particles. The method comprises that diatom or a diatomite aqueous solution as a reaction precursor undergoes a heating reaction to produce the fluorescent silicon nano-particles having very narrow half-peak width, high fluorescence intensity and good water dispersibility. According to the method, the reaction occurs completely in a water phase, operation is safe, fast and simple, toxicity is small, and pure natural diatom or diatomite is used as a raw material, is safe and easily available and can be recycled. The water-soluble fluorescent silicon nano-particles have very narrow half-peak width, good monodispersity, a high quantum yield and good water solubility, can be used as a fluorescence indicator widely for biological detection and analysis, and can be used in the optics-related industrial production.
Description
Technical field
The invention belongs to nano material and bioanalysis detection technique field, relate to a kind of preparation method of fluorescence silicon nano particles, be specifically related to a kind of method of bionically preparing water-soluble fluorescence silicon nano particles.
Background technology
The performance that functionalized silicon nano material has good optical/electrical/mechanical property, surface modificability etc. unique, thus the silicon nano material of people to functionalization has extremely strong interest (see Pavesi, L.; Negro, L. D.; Mazzoleni, C.; Franzo, G.; Priolo, F. Nature 2000,408,440-444. Ding, Z. F.; Quinn, B. M.; Haram, S. K.; Pell, L. E.; Korgel, B. A.; Bard, A. J. Science 2002,296,1293-1297. Ma, D. D. D.; Lee, C. S.; Au, F. C. K.; Tong, S. Y.; Lee, S. T. Science 2003,299,1874-1877. Patolsky, F.; Timko, B. P.; Yu, G. H.; Fang, Y.; Greytak, A. B.; Zheng, G. F.; Lieber, C. M. Science 2006,313,1100-1104.).Typical fluorescence silicon nano particles point is very representational zero dimension silicon nano material, because it has good biocompatibility and a hypotoxicity and is expected at biology and is medically applied (see Michalet, X.; Pinaud, F. F.; Bentolila, L. A.; Tsay, J. M.; Doose, S.; Li, J. J.; Sundaresan, G.; Wu, A. M.; Gambhir, S. S.; Weiss, S. Science 2005,307,538-544. Song, S. P.; Qin, Y.; He, Y.; Huang, Q.; Fan, C. H.; Chen, H. Y. Chem. Soc. Rev. 2010,39,4234-4243. He, Y.; Fan, C. H.; Lee, S. T. Nano Today 2010,5,282-295.).In the past few years; the preparation of fluorescence silicon nano particles achieves important progress; successfully prepare the water soluble fluorescence nano silicon particles modifying (as vinylformic acid and allylamine), polymer wrapped, micella parcel with hydrophilic molecule at present; and to be used in the application of bio-imaging (see: Li, Z. F.; Ruckenstein, E. Nano Lett. 2004,4,1463-1467. Warner, J. H.; Hoshino, A.; Yamamoto, K.; Tilley, R. D. Angew. Chem., Int. Ed. 2005,44,4550-4554. Erogbogbo, F.; Yong, K. T.; Roy, I.; Xu, G. X.; Prasad, P. N.; Swihart, M. T. ACS Nano 2008,2,873-878. 14. He, Y.; Su, Y. Y.; Yang, X. B.; Kang, Z. H.; Xu, T. T.; Zhang, R. Q.; Fan, C. H.; Lee, S. T. J. Am. Chem. Soc. 2009,131,4434-4438. Zhong, Y. L.; Peng, F.; Bao, F.; Wang, S. Y.; Ji, X. Y.; Yang, L.; Su, Y. Y.; Lee, S. T.; He, Y. J. Am. Chem. Soc. 2013,135,8350-8356.).
But it is worth noting, the silicon source of preparing nano silicon particles is up to now mostly expensive and poisonous or inflammable (such as bulk silicon, silicon chip and organosilicon small molecules); And also need in preparation process to add extra reagent (such as hydrofluoric acid, pentanedioic acid or the sour sodium of lemon three etc.).In addition, the nano silicon particles fluorescence spectrum peak width at half height reported at present is all comparatively large, generally all between 70 ~ 150nm, is unfavorable for that application in biological multicolor fluorescence imaging is (see Li, Z. F.; Ruckenstein, E. Nano Lett. 2004,4,1463-1467. Warner, J. H.; Hoshino, A.; Yamamoto, K.; Tilley, R. D. Angew. Chem., Int. Ed. 2005,44,4550-4554. Erogbogbo, F.; Yong, K. T.; Roy, I.; Xu, G. X.; Prasad, P. N.; Swihart, M. T. ACS Nano 2008,2,873-878. 14. He, Y.; Su, Y. Y.; Yang, X. B.; Kang, Z. H.; Xu, T. T.; Zhang, R. Q.; Fan, C. H.; Lee, S. T. J. Am. Chem. Soc. 2009,131,4434-4438.).
Therefore, the preparation method of the fluorescence silicon nano particles of green, environmental protection is still needed to develop at present; Meanwhile, how preparing the fluorescence silicon nano particles of narrow fluorescence spectrum peak width at half height, is still a difficult problem urgently to be resolved hurrily.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of method of environmental protection, operational safety, fast and convenient bionically preparing water-soluble fluorescence silicon nano particles.
For achieving the above object, the present invention is with the diatom aqueous solution for reaction precursor, and under microwave radiation, reacting by heating prepares first and has extremely narrow peak width at half height, fluorescence silicon nano particles compared with high fluorescent, superior water dispersibility.
Concrete, the invention provides following technical scheme:
The method of bionically preparing water-soluble fluorescence silicon nano particles of the present invention, comprises the steps:
(1) clean diatom or diatomite are placed in ultrapure water, at room temperature stir, obtain precursor solution;
Preferably, described diatom is quarrel algae, two sharp quarrel algae, the sheet algae such as common, rhombus algae, narrow heteropole algae, crisp bar algae, shank algae, Chaetoceros muelleri, Phaeodactylum tricornutum, the little ring algae of plum Buddhist nun, variation melosira, Chinese toon shape stitch algae, the raw at least one of partially stitching in algae, fine cloth line algae of spring partially.
Diatomite is the common diatomite of commercial type.
In step (1), diatom and diatomite all need to clean with ultrapure water, clean and require: diatom removes residual substratum; Diatomite removes ionic impurity; Again clean diatom or diatomite are placed in ultrapure water.
Preferably, in step (1), stirred at ambient temperature 5 ~ 20min.
(2) reacting by heating is carried out to the precursor solution of step (1) gained, obtain water miscible fluorescence silicon nano particles.
Preferably, described reacting by heating mode is heating in water bath, oil bath heating, electric mantle heating or carry out microwave radiation heating.
Further, step (2) adopts carry out microwave radiation heating, by the precursor solution of step (1) gained at power 15 ~ 1000W, and carry out microwave radiation heating 1 ~ 200min at temperature 100 ~ 200 DEG C.
Further, step (2) adopts heating in water bath, oil bath heating or electric mantle heating, by the precursor solution of step (1) gained reacting by heating 3 ~ 48h at 100 ~ 300 DEG C.
The method of bionically preparing water-soluble fluorescence silicon nano particles of the present invention, carries out completely in aqueous phase, and operational safety, fast and convenient, toxicity is little, and raw material is diatom or the diatomite of pure natural, and safety is easy to get and can recycle.The water soluble fluorescence nano silicon particles of gained has extremely narrow fluorescence spectrum peak width at half height, good monodispersity, quantum yield is higher, have good water-soluble, biological detection and analysis can be widely used in as fluorescent marker, also be expected to the industrial production (such as laser, Organic Light Emitting Diode) for related optical.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, apparently, accompanying drawing for the present invention in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is transmission electron microscope (TEM) figure and high resolution TEM (HRTEM) figure of the fluorescence silicon nano particles that preferred embodiment 1 prepares, wherein a) be TEM figure, b) be HRTEM figure;
Fig. 2 is the UV-fluorescence spectrogram of the fluorescence silicon nano particles that preferred embodiment 1 prepares, and excitation wavelength is 400nm, and maximum emission wavelength is 620nm, and wherein UV represents UV-light, and PL represents fluorescence.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is described in detail.
The present invention's raw material used freely can be buied by market, is analytical pure;
The microwave reactor model of water soluble fluorescence nano silicon particles for the preparation of having extremely narrow peak width at half height: NOVA-2S, is purchased from the Preekem company in Shanghai.
Diatom (Bacillariophyceae) is a class Eukaryotic Algae, and majority is unicellular organism, and cell walls is containing pectin and silicon-dioxide, and skin is siliceous, and internal layer is pectin substance.Diatomite (Diatomite) is a kind of biogenic silicastone, and it formed primarily of the remains of diatom in ancient times, and its chemical composition is based on SiO2.
Respectively the various diatom cleaned or diatomite are placed in ultrapure water, at room temperature stir 5 ~ 20min, obtain various precursor solution, for subsequent use.
Embodiment 1
The two sharp quarrel algae of (λ=420nm) of absorbance A value=0.3 and the mixing solutions 8ml of ultrapure water are added in the functionalized glass container of microwave reaction, control condition is as follows:
The condition of microwave radiation is: microwave power 200W; Temperature of reaction 150 DEG C; Reaction times 10min.
Obtain peak width at half height extremely narrow (about 30nm), and the good fluorescence silicon nano particles of biocompatibility, its fluorescence quantum efficiency (PLQY) is about 20%.
Embodiment 2
The two sharp quarrel algae of (λ=420nm) of absorbance A value=0.8 and the mixing solutions 10ml of ultrapure water are added in the functionalized glass container of microwave reaction, control condition is as follows:
The condition of microwave radiation is: microwave power 130W; Temperature of reaction 140 DEG C; Reaction times 8min.
Embodiment 3
The quarrel algae of (λ=420nm) of absorbance A value=0.5 and the mixing solutions 5ml of ultrapure water are added in the functionalized glass container of microwave reaction, control condition is as follows:
The condition of microwave radiation is: microwave power 100W; Temperature of reaction 130 DEG C; Reaction times 12min.
Embodiment 4
The rhombus algae of (λ=420nm) of absorbance A value=1.5 and the mixing solutions 7ml of ultrapure water are added in the functionalized glass container of microwave reaction, control condition is as follows:
The condition of microwave radiation is: microwave power 500W; Temperature of reaction 170 DEG C; Reaction times 5min.
Embodiment 5
Added in the functionalized glass container of microwave reaction by the mixing solutions 10ml of little for the Hubei of (λ=420nm) of absorbance A value=3 ring algae and ultrapure water, control condition is as follows:
The condition of microwave radiation is: microwave power 1000W; Temperature of reaction 190 DEG C; Reaction times: 1min.
Embodiment 6
The quarrel algae of (λ=420 nm) of absorbance A value=1.2 and the mixing solutions 6ml of ultrapure water are added in the functionalized glass container of microwave reaction, control condition is as follows:
The condition of microwave radiation is: microwave power 50W; Temperature of reaction 100 DEG C; Reaction times 18min.
Embodiment 7
Added in the functionalized glass container of microwave reaction by the mixing solutions 8ml of two to (λ=420nm) of absorbance A value=1.0 sharp quarrel algae and ultrapure water, control condition is as follows:
The condition of microwave radiation is: microwave power 200W; Temperature of reaction 160 DEG C; Reaction times 60min.
Embodiment 8
(λ=420nm) rhombus algae of absorbance A value=0.6 and the mixing solutions 6ml of ultrapure water are added in the functionalized glass container of microwave reaction, control condition is as follows:
The condition of microwave radiation is: microwave power 100W; Temperature of reaction 130 DEG C; Reaction times 120min.
Embodiment 9
Add in glass round bottom flask by the two sharp quarrel algae of (λ=420nm) of absorbance A value=2.7 and the mixing solutions 20ml of ultrapure water, by heating in water bath, control condition is as follows:
Reaction conditions is: temperature of reaction 100 DEG C; Reaction times 24h.
Embodiment 10
Add in glass round bottom flask by the Phaeodactylum tricornutum of (λ=420nm) of absorbance A value=6 and the mixing solutions 25ml of ultrapure water, heated by oil bath, control condition is as follows:
Reaction conditions is: temperature of reaction 180 DEG C; Reaction times 15h.
Embodiment 11
Add in glass round bottom flask by the Nitzschia palea of (λ=420nm) of absorbance A value=8 and the mixing solutions 15ml of ultrapure water, heated by electric mantle, control condition is as follows:
Reaction conditions is: temperature of reaction 200 DEG C; Reaction times 10h.
Embodiment 12
Added in the functionalized glass container of microwave reaction by the mixing solutions 12ml of the diatomite of about 1.0g and ultrapure water, control condition is as follows:
The condition of microwave radiation is: microwave power 400W; Temperature of reaction 160 DEG C; Reaction times 3h.
Embodiment 1 is most preferred embodiment of the present invention, and TEM figure (Fig. 1) of the water soluble fluorescence nano silicon particles prepared according to embodiment 1 can find, the water soluble fluorescence nano silicon particles shape prepared is spherical and has good monodispersity; Can find out from HRTEM figure, the fluorescence silicon nano particles prepared have good lattice fringe, illustrate that it possesses good crystallinity.The UV-fluorescence spectrogram of the fluorescence silicon nano particles prepared as can be seen from the embodiment 1 of Fig. 2, these fluorescence silicon nano particles have clear and legible absorption peak and well-balanced emission peak.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and when not deviating from spirit of the present invention or essential characteristic, the present invention can be realized in other specific forms.Therefore, no matter from which point, all should embodiment be regarded as exemplary, and be nonrestrictive, scope of the present invention is limited by claims instead of above-mentioned explanation, and all changes be therefore intended in the implication of the equivalency by dropping on claim and scope are included in the present invention.
In addition, be to be understood that, although this specification sheets is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of specification sheets is only for clarity sake, those skilled in the art should by specification sheets integrally, and the technical scheme in each embodiment also through appropriately combined, can form other embodiments that it will be appreciated by those skilled in the art that.
Claims (6)
1. a method for bionically preparing water-soluble fluorescence silicon nano particles, is characterized in that, comprises the steps:
(1) clean diatom or diatomite are placed in ultrapure water, at room temperature stir, obtain precursor solution;
(2) reacting by heating is carried out to the precursor solution of step (1) gained, obtain water miscible fluorescence silicon nano particles.
2. method according to claim 1, is characterized in that: described diatom is quarrel algae, two sharp quarrel algae, the sheet algae such as common, rhombus algae, narrow heteropole algae, crisp bar algae, shank algae, Chaetoceros muelleri, Phaeodactylum tricornutum, the little ring algae of plum Buddhist nun, variation melosira, Chinese toon shape stitch algae, the raw at least one of partially stitching in algae, fine cloth line algae of spring partially.
3. method according to claim 1, is characterized in that: in step (1), stirred at ambient temperature 5 ~ 20min.
4. method according to claim 1, is characterized in that: described reacting by heating mode is heating in water bath, oil bath heating, electric mantle heating or carry out microwave radiation heating.
5. method according to claim 4, is characterized in that: step (2) adopts carry out microwave radiation heating, by the precursor solution of step (1) gained at power 15 ~ 1000W, and carry out microwave radiation heating 1 ~ 200min at temperature 100 ~ 200 DEG C.
6. method according to claim 4, is characterized in that: step (2) adopts heating in water bath, oil bath heating or electric mantle heating, by the precursor solution of step (1) gained reacting by heating 3 ~ 48h at 100 ~ 300 DEG C.
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Cited By (2)
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| CN106479487A (en) * | 2016-09-27 | 2017-03-08 | 苏州大学 | A kind of preparation method of fluorescence silicon nano particles |
| CN114621747A (en) * | 2022-03-15 | 2022-06-14 | 青岛大学 | Europium-natural polysaccharide doped active diatom efficient luminescent material and preparation method thereof |
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| US6365192B1 (en) * | 1999-04-15 | 2002-04-02 | Nippon Zoki Pharmaceutical Co., Ltd. | Bioactivating substance |
| US20100237768A1 (en) * | 2009-03-17 | 2010-09-23 | Sony Corporation | Luminescent material, luminescent material complex and method of manufacturing the same, fluorescent labeling reagent and method of manufacturing the same, and light emitting element |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106479487A (en) * | 2016-09-27 | 2017-03-08 | 苏州大学 | A kind of preparation method of fluorescence silicon nano particles |
| CN114621747A (en) * | 2022-03-15 | 2022-06-14 | 青岛大学 | Europium-natural polysaccharide doped active diatom efficient luminescent material and preparation method thereof |
| CN114621747B (en) * | 2022-03-15 | 2023-05-16 | 青岛大学 | Europium-natural glycan doped living diatom efficient luminescent material and preparation method thereof |
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