CN103666462A - Fluorescent material, and preparation method and application thereof - Google Patents
Fluorescent material, and preparation method and application thereof Download PDFInfo
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- CN103666462A CN103666462A CN201210332291.5A CN201210332291A CN103666462A CN 103666462 A CN103666462 A CN 103666462A CN 201210332291 A CN201210332291 A CN 201210332291A CN 103666462 A CN103666462 A CN 103666462A
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Abstract
The invention provides a fluorescent material which contains a mesoporous material and a modified silicon nanocrystal. The modified silicon nanocrystal is prepared by performing silicon hydrogenation reaction on a silicon nanocrystal and silane compounds of which the general formula is R1Si(OR2)3, wherein R1 is an alkenyl group, and R2 is a substituted or unsubstituted alkyl group. The invention also provides a preparation method of the fluorescent material, which comprises the following step: in the presence of an organic solvent, mixing and contacting the modified silicon nanocrystal and the mesoporous material, wherein the modified silicon nanocrystal is prepared by performing silicon hydrogenation reaction on the silicon nanocrystal and silane compounds of which the general formula is R1Si(OR2)3, wherein R1 is an alkenyl group, and R2 is a substituted or unsubstituted alkyl group. The invention also provides application of the fluorescent material as a drug conduction carrier. The fluorescent material has fluorescent characteristic, and has the advantages of high capacity for resisting photofading and better drug slow-release property.
Description
Technical field
The present invention relates to a kind of fluorescent material, the preparation method of this fluorescent material, and this fluorescent material is as the application of medicine conduction carrier.
Background technology
In the last few years, Materials science has obtained development at full speed, and mesoporous material is as an important branch in Materials science, a lot of features that have with itself, such as large aperture and specific surface area, good thermostability and mechanical stability etc., caused the extensive concern of scientists.Along with the development of mesoporous material, the Application Areas of mesoporous material progressively expands, and from initial absorption, separation, catalytic field, has nowadays expanded to many different field, for example sensing technology and medicine conducting system etc.As the specific examples of silicon-based mesoporous material, mesoporous material SBA-15, it not only has the mesopore orbit of high-sequential, thick inorganic hole wall, good thermostability, and synthetic method is simple, has been subject to the extensive attention of materials chemistry circle.Yet for mesoporous material SBA-15, single inorganic skeleton structure is difficult to meet its requirement in actual applications, therefore, for the functionalization of mesoporous material, require to become more and more higher.
In optical field, mesoporous material is considered to a kind of good optical functional main body.This is mainly because mesoporous material has good hardness and light stability, but also has good hydrophilic/hydrophobic phase, makes mesoporous material meticulousr aspect adjusting guest molecule microenvironment.In report in early days, by introducing in mesoporous material, the method for organic light emission group realizes epipolic mesoporous material often.But in these fluorescent materials, the luminophore of introducing is all generally the organic molecule that contains π key conjugated structure, easily there is photobleaching in organic molecule, thereby destroy the fluorescence property of mesoporous material; And, because fluorescence organic molecule generally has toxicity, in building-up process, can cause environmental pollution, and be difficult to be more widely used such as fields such as biology; In addition, the organic molecule that contains π key conjugated structure of introducing has certain chemical reactivity, and resistance to chemical corrosion is poor.
Summary of the invention
The object of the invention is, in order to overcome the existing above-mentioned shortcoming existing by introduce fluorescent material that organic light emission group makes in mesoporous material, provides a kind of new fluorescent material and its preparation method and application.
The invention provides a kind of fluorescent material, wherein, the si-nanocrystals that described fluorescent material contains mesoporous material and modification, the si-nanocrystals of described modification is by being R by si-nanocrystals and general formula
1si (OR
2)
3silane compound carry out hydrosilation reaction and make, wherein, R
1for thiazolinyl, R
2for replacing or unsubstituted alkyl.
The present invention also provides a kind of preparation method of fluorescent material, and the method comprises: under the existence of organic solvent, the si-nanocrystals of modification and mesoporous material are mixed and contacted, the si-nanocrystals of described modification is by being R by si-nanocrystals and general formula
1si (OR
2)
3silane compound carry out hydrosilation reaction and make, wherein, R
1for thiazolinyl, R
2for replacing or unsubstituted alkyl.
The present invention also provides the application of above-mentioned fluorescent material as medicine conduction carrier.
In described fluorescent material of the present invention, the si-nanocrystals of described modification not only has adjustable band gap and high photoluminescence efficiency, and has extraordinary bio-compatibility; And compare with organic light emission group, the light stability of the si-nanocrystals of described modification is better, absorbs and the wavelength launched can regulate simultaneously.Therefore, in the present invention, pass through the si-nanocrystals of described modification to introduce in mesoporous material, make described fluorescent material provided by the invention not only there is the ability of stronger anti-photobleaching, but also there is good bio-compatibility, thereby can be widely used in field of biology.
And fluorescent material of the present invention is especially suitable for use as medicine conduction carrier.When adopting described fluorescent material as medicine conduction carrier, described medicine conduction carrier has fluorescent characteristic, has the ability of stronger anti-photobleaching, can carry out good fluorescent tracing, but also have good medicament slow release performance.
Other features and advantages of the present invention partly in detail are described the embodiment subsequently.
Accompanying drawing explanation
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is mesoporous material SBA-15 and the photo of described fluorescent material provided by the invention (ncSi-SBA-15) under ultra violet lamp;
Fig. 2 is the infrared spectrogram (FTIR) of mesoporous material SBA-15 and described fluorescent material provided by the invention (ncSi-SBA-15);
Fig. 3 is the X-ray diffractogram (XRD) of mesoporous material SBA-15 and described fluorescent material provided by the invention (ncSi-SBA-15);
Fig. 4 is the nitrogen adsorption data of mesoporous material SBA-15;
Fig. 5 is the nitrogen adsorption data of described fluorescent material provided by the invention (ncSi-SBA-15);
Fig. 6 is mesoporous material SBA-15 and described fluorescent material provided by the invention (ncSi-SBA-15) release graphics to ibuprofen pharmaceutical separately;
Fig. 7 is the electron scanning micrograph of described fluorescent material provided by the invention (ncSi-SBA-15).
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of fluorescent material, wherein, the si-nanocrystals that described fluorescent material contains mesoporous material and modification, the si-nanocrystals of described modification is by being R by si-nanocrystals and general formula
1si (OR
2)
3silane compound carry out hydrosilation reaction and make, wherein, R
1for thiazolinyl, R
2for replacing or unsubstituted alkyl.
In described fluorescent material, the weight ratio of the content of the content of described mesoporous material and the si-nanocrystals of described modification can be 1:0.1-10, is preferably 1:0.5-5, more preferably 1:0.8-2.5.
Described mesoporous material refers to that mean pore size is the cellular solid of 2-50 nanometer.Described mesoporous material can be the mesoporous material of various routines.In the preferred case, described mesoporous material is silicon-based mesoporous material.Described silicon-based mesoporous material can be pure silicon mesoporous material, can be also organosilicon mesoporous material.Described pure silicon mesoporous material for example can, for SBA series mesoporous material and/or M41S series mesoporous material, be preferably at least one mesoporous material in SBA-15, SBA-16, MCM-41 and MCM-48.Described organosilicon mesoporous material can be for example order mesoporous organosilicon material (PMO), also by bridging silsesquioxane (R ' O)
3siRSi (OR ')
3the silicon-based mesoporous material of self assembly.Term " in order " refers to that bill of material reveals regular duct and arranges, and in the present invention, referring in particular to pore structure is the ordered arrangement of six side's phase arrangement architectures.
Above-mentioned mesoporous material, particularly above-mentioned pure silicon mesoporous material, all can be commercially available.
The si-nanocrystals of described modification (ncSi) can be commercially available modified silicon nanocrystal product, as long as this modified silicon nanocrystal product is by by si-nanocrystals and described silane compound, (general formula is R
1si (OR
2)
3) carry out hydrosilation reaction and make.The condition of described hydrosilation reaction can comprise: temperature of reaction is between 150-200 ℃, and the weight ratio of the consumption of described si-nanocrystals and the consumption of described silane compound can, for below 0.1:6, be preferably 0.01-0.1:6.Described hydrosilation reaction can carry out under normal pressure.The reaction times of hydrosilation can be 8-16 hour, is preferably reaction overnight.
In one embodiment, the preparation method of ncSi can comprise: under the existence of organic solvent, si-nanocrystals is mixed with described silane compound, being cooled to-50 ℃ to-100 ℃ carries out freezing degassed, then be warming up to 150-200 ℃, and at this temperature, react 8-16 hour (as reaction overnight), then carry out underpressure distillation to remove unreacted described silane compound and described organic solvent, thereby obtain ncSi.Described organic solvent is for dissolving the solvent of described si-nanocrystals, such as thinking n-decane, ethanol, chloroform etc.
Described si-nanocrystals can be commercially available, also can be according to conventional method preparation, its preparation method for example can comprise: by trichlorosilane and excessive deionized water contact reacts 1-2 hour at 0-78 ℃, then filter and collecting precipitation thing, this throw out is carried out to calcination (as calcination 0.5-3 hour at 800-1500 ℃), the mixture obtaining after calcination is ground, then with deionized water, ethanol mixes and contacts (preferably contacting 2-3 hour) with hydrofluoric acid, use afterwards organic solvent (as n-decane, ethanol, chloroform etc.) extraction, can obtain the solution of the organic solvent of si-nanocrystals.
The particle size of described si-nanocrystals can be preferably 1-8 nanometer for below 10 nanometers, most preferably is 2-3 nanometer.The size Expressing of the particle that the particle size of described si-nanocrystals obtains after can being contacted by the mixture after grinding and deionized water, ethanol and hydrofluoric acid mixing.In the present invention, described particle size refers to the maximum linear distance between two differences on particle, and when described particle is while being spherical, particle size refers to the diameter of this particle.
For general formula, be R
1si (OR
2)
3silane compound, R
1for thiazolinyl, be preferably C2-C10 thiazolinyl, C2-C6 thiazolinyl more preferably, more preferably vinyl, propenyl, butenyl or pentenyl, most preferably be vinyl; R
2for replacing or unsubstituted alkyl, be preferably and replace or unsubstituted C1-C10 alkyl, more preferably replace or unsubstituted C1-C6 alkyl, more preferably replace or unsubstituted methyl, replacement or unsubstituted ethyl, replacement or unsubstituted propyl group, replacement or unsubstituted butyl or replacement or unsubstituted amyl group, most preferably be ethyl.For the substituted radical on described alkyl, such as being halogen (as Cl, Br), amino, nitro etc.Under preferable case, described silane compound is one or more in vinyltriethoxysilane, vinyltrimethoxy silane, propenyl triethoxyl silane and propenyl Trimethoxy silane.
For described fluorescent material of the present invention, its related property parameter is preferably in suitable scope.Concrete, the mean pore size of described fluorescent material is preferably 3-30 nanometer, more preferably 5-6 nanometer; Pore volume is preferably more than 0.2cm
3g
-1and be less than or equal to 1cm
3g
-1, 0.3-0.9cm more preferably
3g
-1; Specific surface area is preferably more than 200m
2g
-1and be less than or equal to 1000m
2g
-1, 300-900m more preferably
2g
-1.Wherein, mean pore size, pore volume and specific surface area adopt respectively nitrogen adsorption method to measure.When the related property parameter of described fluorescent material is in above-mentioned preferable range, described fluorescent material can show sustained release performance more stably when as medicine conduction carrier.
The present invention also provides a kind of preparation method of fluorescent material, and the method comprises: under the existence of organic solvent, the si-nanocrystals of modification and mesoporous material are mixed and contacted, the si-nanocrystals of described modification is by being R by si-nanocrystals and general formula
1si (OR
2)
3silane compound carry out hydrosilation reaction and make, wherein, R
1for thiazolinyl, R
2for replacing or unsubstituted alkyl.
In the preparation method of above-mentioned fluorescent material, the weight ratio of the consumption of the consumption of described mesoporous material and the si-nanocrystals of described modification can be 1:0.1-10, is preferably 1:0.5-5, more preferably 1:0.5-2.
In the preparation method of above-mentioned fluorescent material, the contact process of mixing of the si-nanocrystals of described modification and described mesoporous material is mainly to make the trialkenyl alkoxysilane polymer hydrolysis on the si-nanocrystals of described modification generate silicon hydroxyl, and with mesoporous material on silicon hydroxyl generation condensation reaction.Said process can be under acidic conditions, under alkaline condition and all can occur under neutrallty condition.In the preferred case, the si-nanocrystals of described modification carries out under acidic conditions with the contact process of mixing of described mesoporous material, under the condition that is more preferably 1-5 in pH value, carries out, and further preferably in pH value, under the condition for 1-2, carries out.The temperature of described mixing contact is preferably 0-100 ℃, more preferably 20-40 ℃.The time of described mixing contact is preferably 1-100 hour, more preferably 5-50 hour.
In the preparation method of above-mentioned fluorescent material, si-nanocrystals of modification and preparation method thereof, si-nanocrystals and preparation method thereof and mesoporous material are all with above-described identical.
In the preparation method of described fluorescent material, the mixing contact process and can carry out under the existence of solvent of the si-nanocrystals of modification and mesoporous material.Described solvent requires to dissolve each other with water and is volatile, and for example, described solvent can, for methyl alcohol, ethanol, propyl alcohol, Virahol, acetone etc., be preferably ethanol.
In the preparation method of described fluorescent material, after the si-nanocrystals of modification and mesoporous material mix and contact, described method can also comprise carries out centrifugation by mixing the product contacting, and isolated solid product is washed, and be dried.Described dry can, under vacuum condition or under protection of inert gas, carrying out at the temperature of 40-200 ℃ (being preferably 70-100 ℃).
The present invention also provides the application of described fluorescent material as medicine conduction carrier.Concrete application process can comprise: on fluorescent material, load adsorbent, then, under 0-100 ℃ (being preferably 36-38 ℃), the fluorescent material that is mounted with adsorbent is scattered in the solution of pH value for 1-9.Described adsorbent is such as thinking cardiovascular agent, antibiotic medicine, antitumor drug, medicine for respiratory system, hematological system drugs etc.
The invention will be further described by the following examples.
Preparation example
The preparation of the si-nanocrystals of modification
At-75 ℃, the deionized water of 25ml is mixed with the trichlorosilane of 10ml, react and within 1.5 hours, obtain white precipitate afterwards, isolate white precipitate, and this white precipitate is carried out to vacuum-drying, be transferred to afterwards in tube furnace, at 1100 ℃, calcination is 1 hour, obtains brown mixture.It is below 1 millimeter that this mixture is ground to particle diameter, then the described mixture through grinding of 0.6g is placed in plastic beaker, add wherein 9ml deionized water, 18ml ethanol and 30ml hydrofluoric acid (aqueous solution of 48 % by weight), react after 3 hours, obtain the si-nanocrystals that particle size is approximately 3 nanometers, then with n-decane, this si-nanocrystals is extracted, obtain the solution of the n-decane of si-nanocrystals.
The solution of the n-decane of described si-nanocrystals is moved in round-bottomed flask, add wherein the vinyltriethoxysilane of 9ml; Then freezing at-75 ℃, then reduce pressure and bleed, pass into afterwards nitrogen and make system return to room temperature, and such cyclical operation three times; Then, be warming up to 175 ℃, and at this temperature, slowly stir and carry out reaction overnight.After reaction finishes, centrifugation goes out precipitation, and supernatant liquor is carried out to underpressure distillation, thereby obtains the nanocrystalline silicon of modification.
Embodiment 1
The present embodiment is used for illustrating described fluorescent material of the present invention and preparation method thereof.
The si-nanocrystals of modification prepared by the above-mentioned preparation example of 1.025g is dissolved in 8.074g ethanol, stirring is fully dissolved the si-nanocrystals of described modification, get the solution that 0.36g obtains, with adding 50mg mesoporous material SBA-15 (purchased from high-tech limited liability company of Jilin University) in backward this solution, under agitation dispersed, then in dispersion system, add 0.1molL
-1the ethanolic soln of HCl, pH value is adjusted to 1.5, and at 25 ℃ stirring reaction 24 hours.After reaction finishes, centrifugation, collects solid product, washs afterwards with ethanol, finally carries out vacuum-drying, obtains fluorescent material A1.
Comparative example 1
According to the method for embodiment 1, prepare fluorescent material, difference is with the AEC (purchased from sigma-Aldrich company) of identical weight, to replace the si-nanocrystals of described modification, thereby obtain fluorescent material D1.
The present embodiment is used for illustrating described fluorescent material of the present invention and preparation method thereof.
According to the method for embodiment 1, prepare fluorescent material, difference is to use 0.1molL
-1naOH solution the pH value of reaction system is adjusted to 9, thereby make fluorescent material A2.
Embodiment 3
The present embodiment is used for illustrating described fluorescent material of the present invention and preparation method thereof.
The si-nanocrystals of modification prepared by the above-mentioned preparation example of 0.513g is dissolved in 8.074g ethanol, stirring is fully dissolved the si-nanocrystals of described modification, get the solution that 0.36g obtains, in this solution, add 50mg Mesoporous silica MCM 41 (purchased from Tianjin Chemist Technology Development Co., Ltd), under agitation dispersed, then in dispersion system, add 0.1molL
-1the ethanolic soln of HCl, pH value is adjusted to 1, and at 20 ℃ stirring reaction 24 hours.After reaction finishes, centrifugation, collects solid product, washs afterwards with ethanol, finally carries out vacuum-drying, obtains fluorescent material A3.
The present embodiment is used for illustrating described fluorescent material of the present invention and preparation method thereof.
The si-nanocrystals of modification prepared by the above-mentioned preparation example of 1.367g is dissolved in 8.074g ethanol, stirring is fully dissolved the si-nanocrystals of described modification, get the solution that 0.36g obtains, in this solution, add 50mg mesoporous material SBA-15 (purchased from high-tech limited liability company of Jilin University), under agitation dispersed, then in dispersion system, add 0.1molL
-1the ethanolic soln of HCl, pH value is adjusted to 2, and at 40 ℃ stirring reaction 24 hours.After reaction finishes, centrifugation, collects solid product, washs afterwards with ethanol, finally carries out vacuum-drying, obtains fluorescent material A4.
Test case 1
Detect respectively mean pore size, pore volume and the specific surface area of above-mentioned fluorescent material A1-A4, wherein, the full-automatic specific surface area of TriStar 3000 and the lacunarity analysis instrument that adopt U.S. Micromeritics instrument company to produce detect, obtain nitrogen adsorption-desorption curve, by the absorption branch in adsorption isothermal line and according to Barrett-Joyner-Halenda(BJH) formula calculates mean pore size and pore volume, specific surface area is according to Brunauer-Emmett-Teller(BET) linear formula calculates, and result is as shown in table 1 below.
Table 1
| Mesoporous material | Mean pore size (nm) | Pore volume (cm 3·g -1） | Specific surface area (m 2·g -1） |
| A1 | 5.62 | 0.36 | 297.26 |
| A2 | 5.01 | 0.31 | 274.59 |
| A3 | 3.24 | 0.73 | 769.84 |
| A4 | 5.07 | 0.31 | 258.49 |
Under the ultra violet lamp that is 365nm at wavelength, observe the fluorescent material (ncSi-SBA-15) of mesoporous material SBA-15 and embodiment 1 preparation.Photo under their each comfortable ultra violet lamps as shown in Figure 1.
As can be seen from Figure 1, ncSi-SBA-15 demonstrates obvious fluorescent red-orange.Visible, fluorescent material according to the present invention has fluorescent characteristic.
Test case 3
Respectively the fluorescent material (ncSi-SBA-15) of mesoporous material SBA-15 and embodiment 1 preparation is carried out to Infrared spectroscopy, their FTIR spectrograms separately as shown in Figure 2.
As can be seen from Figure 2, SBA-15 and ncSi-SBA-15 are at 3420cm
-1and 1080cm
-1there is very strong absorption peak at place, and in the FTIR of ncSi-SBA-15 spectrogram, at 2960cm
-1and 2850cm
-1the vibration peak intensity at place has obviously strengthened with respect to SBA-15, simultaneously at 1460cm
-1and 1380cm
-1also there is the flexural vibration peak of carbon-hydrogen singly-bound in place.Explanation thus, in described fluorescent material of the present invention, the si-nanocrystals of modification (ncSi) has successfully been modified SBA-15.
Respectively the fluorescent material (ncSi-SBA-15) of mesoporous material SBA-15 and embodiment 1 preparation is carried out to X-ray diffraction analysis, their XRD figure separately as shown in Figure 3.
As can be seen from Figure 3, mesoporous material SBA-15 has obvious diffraction peak when 2 θ are 0.93 °, and ncSi-SBA-15 has obvious diffraction peak when 2 θ are 1.02 ° simultaneously.Illustrate that thus described fluorescent material of the present invention is still ordered structure after ncSi modifies.
Test case 5
Detect respectively the nitrogen adsorpting data of the fluorescent material (ncSi-SBA-15) of mesoporous material SBA-15 and embodiment 1 preparation.Detected result separately respectively as shown in Figure 4 and Figure 5.
By obtaining the aperture parameters of SBA-15 and ncSi-SBA-15 to the research of nitrogen adsorption-desorption thermoisopleth, according to the definition of the IUPAC of International Union of Pure and Applied Chemistry, it is the 4th class thermoisopleth that this H1 type returns stagnant ring thermoisopleth, is that mesoporous material is peculiar.In Fig. 4 and Fig. 5, bi-material demonstrates the 4th class thermoisopleth.Illustrate that thus described fluorescent material of the present invention still keeps six side's phase arrangement architectures of high-sequential, reaction process central hole structure is not destroyed.
Obtain the electron scanning micrograph of the fluorescent material (ncSi-SBA-15) of embodiment 1 preparation, as shown in Figure 7.As can be seen from Figure 7, ncSi-SBA-15 presents six orderly side's phase arrangement architectures.
Embodiment 5-8 and comparative example 2
Compound concentration is 10mgmL
-1ibuprofen BP/EP hexane solution, respectively the above-mentioned fluorescent material of 25mg is joined in the above-mentioned Ibuprofen BP/EP hexane solution of 2.5mL, at room temperature stir 24h, obtain carrier loaded Z1-Z4 and DZ1.Then, measure the uv-absorbing intensity of solution with ultraviolet spectrophotometer, by the change before and after Ibuprofen BP/EP solution absorbance, calculate respectively the loading capacity of Ibuprofen BP/EP in each fluorescent material, result is as shown in table 2 below.
Table 2
| Carrier loaded | Fluorescent material | Loading capacity (mgg -1） | |
| Embodiment 5 | Z1 | A1 | 299.29 |
| Comparative example 2 | DZ1 | D1 | 281.68 |
| |
Z2 | A2 | 276.86 |
| Embodiment 7 | Z3 | A3 | 241.73 |
| Embodiment 8 | Z4 | A4 | 239.61 |
Test case 7
In the PBS buffered soln that the pH value that respectively above-mentioned carrier loaded Z1, the DZ1 of 25mg and mesoporous material SBA-15 is dispersed in to 30.0mL is 7.4, in 37 ± 1 ° of C water-baths, shake.When 10min, 1h, 2h, 4h, 8h, 12h, 24h, 48h, 96h, from system, take out 3.0mL mixing solutions respectively, in system, add the PBS buffered soln that 3.0mL is fresh simultaneously.The 3.0mL mixed solution of taking-up is carried out to centrifugation, filter and collect supernatant liquid, with ultraviolet spectrophotometer, measure its uv-absorbing, calculate the burst size of Ibuprofen BP/EP, calculation result is as shown in table 3 below, and draws out the chart shown in Fig. 6 by the result of carrier loaded Z1 and mesoporous material SBA-15.
Table 3
Data by table 3 can find out, fluorescent material according to the present invention has good sustained release performance.Concrete, it is very little that carrier loaded DZ1 prominent released, and the burst size within 10 minutes is less, only has 20.31 % by weight, and the trend that burst size does not increase gradually within the follow-up time, does not show sustained release performance; It is very high that mesoporous material SBA-15 prominent released, and the burst size within 10 minutes is very high, and burst size has the amplitude increasing gradually less within the follow-up time; It is relatively moderate that carrier loaded Z1 prominent released, and that within the follow-up time, burst size increases gradually is obvious, thereby show medicament slow release performance relatively preferably.
Test case 8
Adopt fluorescence spectrophotometer (purchased from Varian company, model C ARY Eclipse), according to solid fluorescence method, detect the anti-photobleaching performance of fluorescent material A1 and D1.As a result, fluorescent material A1 still has very strong fluorescent characteristic after standing storage, but the fluorescence property of fluorescent material D1 obviously weakens.
As can be seen here, fluorescent material according to the present invention has good anti-photobleaching performance.
Claims (17)
1. a fluorescent material, is characterized in that, the si-nanocrystals that described fluorescent material contains mesoporous material and modification, and the si-nanocrystals of described modification is by being R by si-nanocrystals and general formula
1si (OR
2)
3silane compound carry out hydrosilation reaction and make, wherein, R
1for thiazolinyl, R
2for replacing or unsubstituted alkyl.
2. fluorescent material according to claim 1, wherein, the weight ratio of the content of the content of described mesoporous material and the si-nanocrystals of described modification is 1:0.1-10, is preferably 1:0.5-5.
3. fluorescent material according to claim 1 and 2, wherein, described mesoporous material is silicon-based mesoporous material.
4. fluorescent material according to claim 3, wherein, described mesoporous material is at least one in SBA-15, SBA-16, MCM-41 and MCM-48.
5. fluorescent material according to claim 1, wherein, R
1for C2-C10 thiazolinyl, be preferably vinyl; R
2for replacing or unsubstituted C1-C10 alkyl, be preferably ethyl.
6. fluorescent material according to claim 1 or 5, wherein, the condition of described hydrosilation reaction comprises: temperature of reaction is 150-200 ℃, and the weight ratio of the consumption of described si-nanocrystals and the consumption of described silane compound is, below 0.1:6, to be preferably 0.01-0.1:6.
7. according to the fluorescent material described in claim 1 or 6, wherein, the particle size of described si-nanocrystals is below 10 nanometers, is preferably 1-8 nanometer.
8. according to the fluorescent material described in any one in claim 1-7, wherein, the mean pore size of described fluorescent material is 3-30 nanometer, and pore volume is for being greater than 0.2cm
3g
-1and be less than or equal to 1cm
3g
-1, specific surface area is for being greater than 200m
2g
-1and be less than or equal to 1000m
2g
-1.
9. a preparation method for fluorescent material, the method comprises: under the existence of organic solvent, the si-nanocrystals of modification is mixed and contacted with mesoporous material, the si-nanocrystals of described modification is by being R by si-nanocrystals and general formula
1si (OR
2)
3silane compound carry out hydrosilation reaction and make, wherein, R
1for thiazolinyl, R
2for replacing or unsubstituted alkyl.
10. method according to claim 9, wherein, the weight ratio of the consumption of the consumption of described mesoporous material and the si-nanocrystals of described modification is 1:0.1-10, is preferably 1:0.5-5.
11. according to the method described in claim 9 or 10, and wherein, the si-nanocrystals of described modification comprises with the contact conditions that mixes of described mesoporous material: pH value is 1-5, is preferably 1-2; Temperature is 0-100 ℃, is preferably 20-40 ℃.
12. according to the method described in claim 9 or 10, and wherein, described mesoporous material is silicon-based mesoporous material.
13. methods according to claim 12, wherein, described mesoporous material is at least one in SBA-15, SBA-16, MCM-41 and MCM-48.
14. methods according to claim 9, wherein, the particle size of described si-nanocrystals is below 10 nanometers, is preferably 1-8 nanometer.
15. methods according to claim 9, wherein, R
1for C2-C10 thiazolinyl, be preferably vinyl; R
2for replacing or unsubstituted C1-C10 alkyl, be preferably ethyl.
16. according to the method described in any one in claim 9,14 and 15, wherein, the condition of described hydrosilation reaction comprises: temperature of reaction is 150-200 ℃, and the weight ratio of the consumption of described si-nanocrystals and the consumption of described silane compound is, below 0.1:6, to be preferably 0.01-0.1:6.
Fluorescent material in 17. claim 1-8 described in any one is as the application of medicine conduction carrier.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105271269A (en) * | 2015-11-20 | 2016-01-27 | 上海应用技术学院 | Fluorescent mesoporous silicon oxide nano particle and preparation method thereof |
| CN106466595A (en) * | 2015-08-19 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of feature mesoporous material and preparation method thereof |
| CN107746581A (en) * | 2017-10-25 | 2018-03-02 | 武汉纺织大学 | A kind of ultraviolet-resistant type luminescence generated by light PDMS composites and preparation method thereof |
| CN108993594A (en) * | 2018-06-25 | 2018-12-14 | 中科广化（重庆）新材料研究院有限公司 | A kind of SBA-15 solid-borne platinum catalyst of Organic ligand modification and the preparation method and application thereof |
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| MIN GUAN ET AL.: "Assembling Photoluminescent Silicon Nanocrystals into Periodic Mesoporous Organosilica", 《J. AM. CHEM. SOC.》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106466595A (en) * | 2015-08-19 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of feature mesoporous material and preparation method thereof |
| CN106466595B (en) * | 2015-08-19 | 2018-12-28 | 中国石油化工股份有限公司 | A kind of functionality mesoporous material and preparation method thereof |
| CN105271269A (en) * | 2015-11-20 | 2016-01-27 | 上海应用技术学院 | Fluorescent mesoporous silicon oxide nano particle and preparation method thereof |
| CN107746581A (en) * | 2017-10-25 | 2018-03-02 | 武汉纺织大学 | A kind of ultraviolet-resistant type luminescence generated by light PDMS composites and preparation method thereof |
| CN108993594A (en) * | 2018-06-25 | 2018-12-14 | 中科广化（重庆）新材料研究院有限公司 | A kind of SBA-15 solid-borne platinum catalyst of Organic ligand modification and the preparation method and application thereof |
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| CN103666462B (en) | 2015-06-17 |
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