CN103666463A - Fluorescent material, and preparation method and application thereof - Google Patents
Fluorescent material, and preparation method and application thereof Download PDFInfo
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- CN103666463A CN103666463A CN201210332383.3A CN201210332383A CN103666463A CN 103666463 A CN103666463 A CN 103666463A CN 201210332383 A CN201210332383 A CN 201210332383A CN 103666463 A CN103666463 A CN 103666463A
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Abstract
The invention provides a fluorescent material which contains an ordered 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. 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 ordered 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. 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
Mesoporous material is all regarded as very useful material in many scientists' eye, they can develop into organic/inorganic composite material, these matrix materials have unique catalysis, sensing, optics, magnetics or electric property, meanwhile, the mesoporous material of functionalization also plays very important effect in material supply section educational circles.Since mesoporous material MCM41 comes out, people constantly in all sorts of ways and synthesize the mesoporous material of organic composite.In the last few years, by bridging silsesquioxane (R ' O)
3siRSi (OR ')
3the material of self assembly, has become organic mesoporous material of new class, is commonly referred to order mesoporous organosilicon (PMO) material.
Compare with inorganic mesoporous material, the presoma of PMO material is to be closed and formed by Si-C bond by organic unit and methyl-monosilane or ethylsilane, wherein the range of choice of organic unit is very wide, such as thinking the functional groups such as two dialkylenes, alkylene, crown ether base, porphyryl.The structure of described organic unit and size etc. can suitably be selected according to the requirement of material requested.The PMO material of surface modification, when organic unit is scattered on inorganic materials hole wall, the new unit of introducing makes PMO material have the function of more diversification, and then improves the bulk property of material.
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.
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 (ncSi-PMO), wherein, the si-nanocrystals (ncSi) that described fluorescent material contains order mesoporous organosilicon material (PMO) 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, the method comprises: under the existence of organic solvent, the si-nanocrystals of modification is mixed and contacted with order mesoporous organosilicon material, 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.
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 by the si-nanocrystals of described modification is introduced in order mesoporous organosilicon 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 described 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 order mesoporous organosilicon material (PMO) and the photo of described fluorescent material provided by the invention (ncSi-PMO) under ultra violet lamp;
Fig. 2 is the infrared spectrogram (FTIR) of order mesoporous organosilicon material (PMO) and described fluorescent material provided by the invention (ncSi-PMO);
Fig. 3 is the X-ray diffractogram (XRD) of order mesoporous organosilicon material (PMO) and described fluorescent material provided by the invention (ncSi-PMO);
Fig. 4 is the nitrogen adsorption data of order mesoporous organosilicon material (PMO);
Fig. 5 is the nitrogen adsorption data of described fluorescent material provided by the invention (ncSi-PMO);
Fig. 6 is order mesoporous organosilicon material (PMO) and described fluorescent material provided by the invention (ncSi-PMO) release graphics to ibuprofen pharmaceutical separately;
Fig. 7 is the electron scanning micrograph of described fluorescent material provided by the invention (ncSi-PMO).
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 order mesoporous organosilicon 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 order mesoporous organosilicon 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 order mesoporous organosilicon material (PMO) can be used for this area is conventional passes through bridging silsesquioxane (R ' O)
3siRSi (OR ')
3the material of self assembly.In the present invention, 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; Term " mesoporous " refers to that average pore diameter is the hole between 2-50 nanometer, is also that mesoporous material refers to the material of average pore diameter between 2-50 nanometer.
Described order mesoporous organosilicon material can be commercially available, and also can prepare.The preparation of described order mesoporous organosilicon material can be implemented according to the method for this area routine, for example, the preparation method of described order mesoporous organosilicon material can comprise: polyoxyethylene-poly-oxypropylene polyoxyethylene (P123) is dissolved in the aqueous solution of Repone K, then add successively hydrochloric acid soln and 1, the two silica-based ethane of trimethoxy (BTME) of 2-, at 10-60 ℃, be uniformly mixed 1-30 minute afterwards and place 5-50 hour, then in autoclave, at 80-120 ℃, react 5-50 hour, reaction finishes rear collection solid product, and from solid product, isolate order mesoporous organosilicon material.
In the method for the orderly mesoporous organosilicon material of above-mentioned preparation, the weight ratio of the consumption of P123 and the consumption of BTME can be 100:80-200, is preferably 100:100-180, more preferably 100:130-150.
In the method for the orderly mesoporous organosilicon material of above-mentioned preparation, the concentration of the potassium chloride solution using can be 0.5-2mol/L.And with respect to the P123 of 100 weight parts, the consumption of potassium chloride solution can be 100-600 weight part, is preferably 200-400 weight part.
In the method for the orderly mesoporous organosilicon material of above-mentioned preparation, the concentration of the hydrochloric acid soln using can be 0.1-0.5mol/L.And with respect to the P123 of 100 weight parts, the consumption of hydrochloric acid soln can be 1000-10000 weight part, is preferably 2000-6000 weight part.
In the method for the orderly mesoporous organosilicon material of above-mentioned preparation, the pressure in described autoclave can be self pressure of the reaction system of relevant temperature.The concrete grammar that reaction finishes rear collection PMO material can comprise: by filtering, collect solid product from reaction product, at room temperature that this solid product is dry, use again deionized water wash, then with ethanol, the solid product after washing is carried out to Soxhlet extraction, thereby obtain PMO material.
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, the method comprises: under the existence of organic solvent, the si-nanocrystals of modification is mixed and contacted with order mesoporous organosilicon material, 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.
In the preparation method of above-mentioned fluorescent material, the weight ratio of the consumption of the consumption of described order mesoporous organosilicon 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 order mesoporous organosilicon material is mainly to make the trialkenyl alkoxysilane polymer hydrolysis on the si-nanocrystals of described modification generate silicon hydroxyl, and with order mesoporous organosilicon 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 order mesoporous organosilicon 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 0-90 ℃, 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, the si-nanocrystals of modification and order mesoporous organosilicon material and their preparation methods are separately 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 order mesoporous organosilicon 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 contacts with order mesoporous organosilicon material mixing, described method can also comprise carries out centrifugation by the product that mixes contact, 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 1
The preparation of PMO material
At 40 ℃, by the P123(of 1g purchased from sigma-Aldrich company) to be dissolved in 2.98g concentration be 1.0molL
-1the KCl aqueous solution in, then to add wherein 40g concentration be 0.167molL
-1hydrochloric acid soln, afterwards by the BTME(of 1.40g purchased from sigma-Aldrich company) join in mixing solutions, and stir.After 10 minutes, stop stirring reaction system at 40 ℃ standing 1 day.Subsequently, mixture is transferred in autoclave, at 100 ℃, reacts 24 hours.After reaction finishes, solid collected by filtration product, and at room temperature dry.Finally, utilize ethanol to carry out Soxhlet extraction to solid product, obtain PMO material.
Preparation example 2
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 the modification of above-mentioned preparation example 2 preparations 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, to the PMO material that adds above-mentioned preparation example 1 preparation of 50mg in 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.
Embodiment 2
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 the modification of above-mentioned preparation example 2 preparations 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, to the PMO material that adds above-mentioned preparation example 1 preparation of 50mg in this solution, 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.
Embodiment 4
The present embodiment is used for illustrating described fluorescent material of the present invention and preparation method thereof.
The si-nanocrystals of the modification of above-mentioned preparation example 2 preparations 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, to the PMO material that adds above-mentioned preparation example 1 preparation of 50mg in this solution, 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, nitrogen adsorption-desorption curve is to adopt the full-automatic specific surface area of TriStar3000 and the lacunarity analysis instrument that U.S. Micromeritics instrument company produces to measure acquisition, 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 | 5.60 | 0.68 | 609.20 |
| A2 | 4.76 | 0.50 | 512.89 |
| A3 | 5.07 | 0.61 | 591.72 |
| A4 | 4.98 | 0.53 | 568.14 |
Test case 2
Under the ultra violet lamp that is 365nm at wavelength, observe the fluorescent material (ncSi-PMO) of PMO material 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-PMO demonstrates obvious fluorescent red-orange.Visible, fluorescent material according to the present invention has fluorescent characteristic.
Test case 3
Respectively the fluorescent material (ncSi-PMO) of PMO material 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, PMO and ncSi-PMO are at 3440cm
-1and 1090cm
-1there is very strong absorption peak at place, and in the FTIR of ncSi-PMO spectrogram, at 2960cm
-1and 2899cm
-1the vibration peak intensity at place has obviously strengthened with respect to PMO.Explanation thus, in described fluorescent material of the present invention, the si-nanocrystals of modification (ncSi) has successfully been modified PMO material.
Test case 4
Respectively the fluorescent material (ncSi-PMO) of PMO material 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, PMO material has obvious diffraction peak when 2 θ are 0.88 °, and ncSi-PMO has obvious diffraction peak when 2 θ are 0.91 ° simultaneously.Illustrate that thus described fluorescent material of the present invention is still ordered structure after ncSi modifies.
Detect respectively the nitrogen adsorpting data of the fluorescent material (ncSi-PMO) of PMO material and embodiment 1 preparation.Detected result separately respectively as shown in Figure 4 and Figure 5.
By obtaining the aperture parameters of PMO and ncSi-PMO 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.
Test case 6
Obtain the electron scanning micrograph of the fluorescent material (ncSi-PMO) of embodiment 1 preparation, as shown in Figure 7.As can be seen from Figure 7, ncSi-PMO presents orderly arrangement mode.
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） | |
| |
Z1 | A1 | 306.11 |
| Comparative example 2 | DZ1 | D1 | 289.37 |
| Embodiment 6 | Z2 | A2 | 246.75 |
| Embodiment 7 | Z3 | A3 | 291.54 |
| Embodiment 8 | Z4 | A4 | 265.91 |
Test case 7
In the PBS buffered soln that is 7.4 by the PMO dispersion of materials of above-mentioned carrier loaded Z1, the DZ1 of 25mg and preparation example 1 preparation in the pH of 30.0mL value respectively, 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 PMO material.
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 very little, only has 13.64 % by weight, and the trend that burst size does not increase gradually within the follow-up time, does not show sustained release performance completely; It is very high that PMO material prominent released, and the burst size within 10 minutes is very high, and up to 57.2 % by weight, although burst size has the trend increasing gradually within the follow-up time, the amplitude that burst size increases is gradually very little, thereby shows poor sustained release performance; It is relatively moderate that carrier loaded Z1 prominent released, and is about 29.16 % by weight, and the trend comparison that burst size increases gradually within the follow-up time is stable, and the amplitude of increase is obvious, thereby shows good medicament slow release performance.
Test case 8
Adopt fluorescence spectrophotometer instrument (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 (13)
1. a fluorescent material, is characterized in that, the si-nanocrystals that described fluorescent material contains order mesoporous organosilicon 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 order mesoporous organosilicon 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, wherein, R
1for C2-C10 thiazolinyl, be preferably vinyl; R
2for replacing or unsubstituted C1-C10 alkyl, be preferably ethyl.
4. according to the fluorescent material described in any one in claim 1-3, 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.
5. according to the fluorescent material described in any one in claim 1-4, wherein, the particle size of described si-nanocrystals is below 10 nanometers, is preferably 1-8 nanometer.
6. fluorescent material according to claim 1, wherein, the mean pore size of described fluorescent material is 3-30 nanometer, 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.
7. 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 order mesoporous organosilicon 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.
8. method according to claim 7, wherein, the weight ratio of the consumption of the consumption of described order mesoporous organosilicon material and the si-nanocrystals of described modification is 1:0.1-10, is preferably 1:0.5-5.
9. according to the method described in claim 7 or 8, wherein, the si-nanocrystals of described modification comprises with the contact conditions that mixes of described order mesoporous organosilicon material: pH value is 1-5, is preferably 1-2; Temperature is 0-90 ℃, is preferably 20-40 ℃.
10. according to the method described in claim 7 or 8, wherein, the particle size of described si-nanocrystals is below 10 nanometers, is preferably 1-8 nanometer.
11. methods according to claim 7, wherein, R
1for C2-C10 thiazolinyl, be preferably vinyl; R
2for replacing or unsubstituted C1-C10 alkyl, be preferably ethyl.
12. according to the method described in claim 7 or 11, 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 13. claim 1-6 described in any one is as the application of medicine conduction carrier.
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| CN109476992A (en) * | 2016-06-30 | 2019-03-15 | 艾利迪公司 | The method for producing photoluminescent particles |
| CN115746838A (en) * | 2022-11-18 | 2023-03-07 | 电子科技大学长三角研究院(湖州) | Preparation method and application of novel blue-green fluorescent powder |
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Non-Patent Citations (2)
| Title |
|---|
| MIN GUAN ET AL.: "Assembling Photoluminescent Silicon Nanocrystals into Periodic Mesoporous Organosilica", 《J. AM. CHEM. SOC.》 * |
| ZHUOYING XIE ET AL.: "Periodic Mesoporous Hydridosilica-Synthesis of an "Impossible" Material and Its Thermal Transformation into Brightly Photoluminescent Periodic Mesoporous Nanocrystal Silicon-Silica Composite", 《J. AM. CHEM. SOC.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109476992A (en) * | 2016-06-30 | 2019-03-15 | 艾利迪公司 | The method for producing photoluminescent particles |
| CN115746838A (en) * | 2022-11-18 | 2023-03-07 | 电子科技大学长三角研究院(湖州) | Preparation method and application of novel blue-green fluorescent powder |
| CN115746838B (en) * | 2022-11-18 | 2024-01-30 | 电子科技大学长三角研究院(湖州) | Preparation method and application of novel blue-green fluorescent powder |
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