CN104310407B - 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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- CN104310407B CN104310407B CN201410469196.9A CN201410469196A CN104310407B CN 104310407 B CN104310407 B CN 104310407B CN 201410469196 A CN201410469196 A CN 201410469196A CN 104310407 B CN104310407 B CN 104310407B
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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 bioanalysiss detection technique field, it is related to a kind of preparation of fluorescence silicon nano particles
Method is and in particular to a kind of method of bionically preparing water-soluble fluorescence silicon nano particles.
Background technology
Functionalized silicon nano material has unique performance such as good optical/electrical/mechanical performance, surface modificability,
Thus people have extremely strong interest to the silicon nano material of functionalization（Referring to：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 well
Biocompatibility and hypotoxicity and be expected in biology and medically be applied（Referring to：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 mistake
In several years going, the preparation of fluorescence silicon nano particles achieves important progress, has successfully prepared at present and has used hydrophilic
Molecular modification（As acrylic acid and allylamine）, polymer wrapped, micelle parcel water soluble fluorescence nano silicon particles, and by with
On in the application of bio-imaging（Referring to：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.）.
However, it is worth noting that, the silicon source preparing nano silicon particles so far is mostly expensive and poisonous or easy
Combustion（Such as bulk silicon, silicon chip and organosilicon small molecule）；And also need in preparation process add extra reagent（Such as hydrogen fluorine
Acid, 1,3-propanedicarboxylic acid or the sour sodium of Fructus Citri Limoniae three etc.）.Additionally, the nano silicon particles fluorescence spectrum half-peak breadth of current report is all larger, typically
All between 70～150nm, it is unfavorable for the application in the imaging of biological multicolor fluorescence（Referring to：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, development green, the preparation method of the fluorescence silicon nano particles of environmental protection are needed exist for；Meanwhile, how to prepare
The fluorescence silicon nano particles of narrow fluorescence spectrum half-peak breadth, are still a difficult problem urgently to be resolved hurrily.
Content of the invention
In view of this, it is an object of the invention to provide a kind of environmental protection, safe operation, fast and convenient bionical preparation
The method of water soluble fluorescence nano silicon particles.
For achieving the above object, with diatom aqueous solution for reacting precursor, under microwave radiation, reacting by heating is first for the present invention
Prepare and there is extremely narrow half-peak breadth, compared with high fluorescent, the fluorescence silicon nano particles of superior water dispersibility.
Specifically, the present invention provides following technical scheme：
The method of the bionically preparing water-soluble fluorescence silicon nano particles of the present invention, comprises the steps：
（1）The diatom cleaned or kieselguhr are placed in ultra-pure water, are stirred at room temperature uniformly, obtain precursor solution；
Preferably, described diatom be quarrel algae, double pointed quarrel algae, piece algae, rhombus algae, narrow heteropole algae, the crisp bar such as common
Algae, shank algae, Chaetoceros muelleri, Phaeodactylum, prunus mume (sieb.) sieb.et zucc. Buddhist nun little ring algae, variation melosira, Chinese toon shape stitch algae partially, algae is stitched in spring life partially,
At least one in fine cloth stricture of vagina algae.
Kieselguhr is the ordinary silicon diatomaceous earth of commercial type.
Step（1）In, diatom and kieselguhr are both needed to be cleaned with ultra-pure water, clean and require：Diatom removes the culture medium of residual；
Kieselguhr removes ionic impurity；Again the diatom cleaned or kieselguhr are placed in ultra-pure water.
Preferably, step（1）In, stir 5～20min under room temperature.
（2）To step（1）The precursor solution of gained carries out reacting by heating, obtains water miscible fluorescence silicon nano particles.
Preferably, described reacting by heating mode is heating in water bath, oil bath heating, electric jacket heat or microwave radiation adds
Heat.
Further, step（2）Using microwave radiation heating, by step（1）The precursor solution of gained power 15～
1000W, at 100～200 DEG C of temperature, microwave radiation heats 1～200min.
Further, step（2）Using the heating of heating in water bath, oil bath heating or electric jacket, by step（1）The precursor of gained
Solution reacting by heating 3～48h at 100～300 DEG C.
The method of the bionically preparing water-soluble fluorescence silicon nano particles of the present invention, is carried out completely in aqueous phase, safe operation,
Fast and convenient, small toxicity, raw material is diatom or the kieselguhr of pure natural, is easy to get safely and can recycle.Gained water-soluble
Property fluorescence silicon nano particles have extremely narrow fluorescence spectrum half-peak breadth, good monodispersity, and quantum yield is higher, has good
Water solublity, can be widely used in biological detection and analysis as fluorescent marker, be expected to the commercial production for related optical
On（Such as laser, Organic Light Emitting Diode）.
Brief description
For the technical scheme being illustrated more clearly that in the embodiment of the present invention, will make to required in embodiment description below
Accompanying drawing be briefly described it should be apparent that, below describe in accompanying drawing for the present invention be only the present invention one
A little embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to these
Accompanying drawing obtains other accompanying drawings.
Fig. 1 is the transmission electron microscope of the fluorescence silicon nano particles that preferred embodiment 1 prepares（TEM）Figure and high score
Resolution transmission electron microscope（HRTEM）Figure, wherein a) schemes for TEM, b) schemes for HRTEM；
Fig. 2 is the UV-fluorescence spectrogram of the fluorescence silicon nano particles that preferred embodiment 1 prepares, and excites
Wavelength is 400nm, and maximum emission wavelength is 620nm, and wherein UV represents ultraviolet light, and PL represents fluorescence.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, detailed retouching is carried out to the technical scheme in the embodiment of the present invention
State.
Raw material used by the present invention freely can be buied by market, is analysis pure；
There is the microwave reactor model of the water soluble fluorescence nano silicon particles of extremely narrow half-peak breadth for preparation：NOVA-2S,
It is purchased from the Preekem company in Shanghai.
Diatom（Bacillariophyceae）A class Eukaryotic Algae, most is unicellular organism, cell wall contain pectin and
Silicon dioxide, outer layer is siliceous, and internal layer is pectic substance.Kieselguhr（Diatomite）It is a kind of biogenic silicastone,
It is mainly made up of the remains of ancient times diatom, and its chemical composition is based on SiO2.
Respectively the various diatoms cleaned or kieselguhr are placed in ultra-pure water, 5～20min is stirred at room temperature, obtain each
Plant precursor solution, standby.
Embodiment 1
By absorbance A value=0.3（λ=420nm）Double pointed quarrel algae and ultra-pure water mixed solution 8ml add microwave anti-
In the functionalized glass container answered, control condition is as follows：
The condition of microwave radiation is：Microwave power 200W；150 DEG C of reaction temperature；Response time 10min.
Obtain half-peak breadth extremely narrow（About 30nm）, and the good fluorescence silicon nano particles of biocompatibility, its fluorescent quantum
Efficiency（PLQY）It is about 20%.
Embodiment 2
By absorbance A value=0.8（λ=420nm）Double pointed quarrel algae and ultra-pure water mixed solution 10ml add microwave
In the functionalized glass container of reaction, control condition is as follows：
The condition of microwave radiation is：Microwave power 130W；140 DEG C of reaction temperature；Response time 8min.
Embodiment 3
By absorbance A value=0.5（λ=420nm）Quarrel algae and the mixed solution 5ml of ultra-pure water add microwave reaction
In functionalized glass container, control condition is as follows：
The condition of microwave radiation is：Microwave power 100W；130 DEG C of reaction temperature；Response time 12min.
Embodiment 4
By absorbance A value=1.5（λ=420nm）Rhombus algae and the mixed solution 7ml of ultra-pure water add microwave reaction
In functionalized glass container, control condition is as follows：
The condition of microwave radiation is：Microwave power 500W；170 DEG C of reaction temperature；Response time 5min.
Embodiment 5
By absorbance A value=3（λ=420nm）Hubei little ring algae and ultra-pure water mixed solution 10ml add microwave anti-
In the functionalized glass container answered, control condition is as follows：
The condition of microwave radiation is：Microwave power 1000W；190 DEG C of reaction temperature；Response time：1min.
Embodiment 6
By absorbance A value=1.2（λ=420 nm）Quarrel algae and ultra-pure water mixed solution 6ml add microwave reaction
Functionalized glass container in, control condition is as follows：
The condition of microwave radiation is：Microwave power 50W；100 DEG C of reaction temperature；Response time 18min.
Embodiment 7
By absorbance A value=1.0（λ=420nm）The mixed solution 8ml of double pointed quarrel algae and ultra-pure water adds microwave reaction
Functionalized glass container in, control condition is as follows：
The condition of microwave radiation is：Microwave power 200W；160 DEG C of reaction temperature；Response time 60min.
Embodiment 8
By absorbance A value=0.6（λ=420nm）The mixed solution 6ml of rhombus algae and ultra-pure water adds the special of microwave reaction
In door glass container, control condition is as follows：
The condition of microwave radiation is：Microwave power 100W；130 DEG C of reaction temperature；Response time 120min.
Embodiment 9
By absorbance A value=2.7（λ=420nm）Double pointed quarrel algae and ultra-pure water mixed solution 20ml add glass
In round-bottomed flask, by heating in water bath, control condition is as follows：
Reaction condition is：100 DEG C of reaction temperature；Response time 24h.
Embodiment 10
By absorbance A value=6（λ=420nm）Phaeodactylum and ultra-pure water mixed solution 25ml add glass circle
In the flask of bottom, by oil bath heating, control condition is as follows：
Reaction condition is：180 DEG C of reaction temperature；Response time 15h.
Embodiment 11
By absorbance A value=8（λ=420nm）Nitzschia palea and ultra-pure water mixed solution 15ml add glass circle
In the flask of bottom, heated by electric jacket, control condition is as follows：
Reaction condition is：200 DEG C of reaction temperature；Response time 10h.
Embodiment 12
The mixed solution 12ml of the kieselguhr of about 1.0g and ultra-pure water is added in the functionalized glass container of microwave reaction, control
Condition processed is as follows：
The condition of microwave radiation is：Microwave power 400W；160 DEG C of reaction temperature；Response time 3h.
Embodiment 1 is highly preferred embodiment of the present invention, the water soluble fluorescence nano silicon particles being prepared according to embodiment 1
TEM figure（Fig. 1）Can find, the water soluble fluorescence nano silicon particles preparing are shaped as spherical and have good single dispersing
Property；Can be seen that from HRTEM figure, the fluorescence silicon nano particles preparing have good lattice fringe, illustrate that it possesses well
Crystallinity.It is glimmering that the UV-fluorescence spectrogram of the fluorescence silicon nano particles being prepared by the embodiment 1 of Fig. 2 can be seen that this
Light nano silicon particles have clear and legible absworption peak and well-balanced emission peak.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of the spirit or essential attributes of the present invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires rather than described above limits, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.
Moreover, it will be appreciated that although this specification is been described by according to embodiment, not each embodiment only wraps
Containing an independent technical scheme, only for clarity, those skilled in the art should for this narrating mode of description
Using description as an entirety, the technical scheme in each embodiment can also form those skilled in the art through appropriately combined
Understandable other embodiment.
Claims (4)
1. a kind of method of bionically preparing water-soluble fluorescence silicon nano particles is it is characterised in that comprise the steps：
(1) diatom cleaned or kieselguhr are placed in ultra-pure water, are stirred at room temperature uniformly, obtain precursor solution；
(2) reacting by heating is carried out to the precursor solution of step (1) gained, micro- at power 15～1000W, 100～200 DEG C of temperature
Wave radiation heats 1～200min, obtains water miscible fluorescence silicon nano particles.
2. method according to claim 1 it is characterised in that：Described diatom is quarrel algae, double pointed quarrel algae, common etc.
Piece algae, rhombus algae, narrow heteropole algae, crisp bar algae, shank algae, Chaetoceros muelleri, Phaeodactylum, prunus mume (sieb.) sieb.et zucc. Buddhist nun little ring algae, variation straight chain
Algae, Chinese toon shape stitch that algae, spring are raw to stitch algae, at least one in fine cloth stricture of vagina algae partially partially.
3. method according to claim 1 it is characterised in that：In step (1), under room temperature, stir 5～20min.
4. method according to claim 1 it is characterised in that：Step (2) adopts heating in water bath, oil bath heating or electric jacket
Heating, by the precursor solution of step (1) gained at 100～300 DEG C reacting by heating 3～48h.
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