CN103666463B - Fluorescent material, and preparation method and application thereof - Google Patents
Fluorescent material, and preparation method and application thereof Download PDFInfo
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- CN103666463B CN103666463B CN201210332383.3A CN201210332383A CN103666463B CN 103666463 B CN103666463 B CN 103666463B CN 201210332383 A CN201210332383 A CN 201210332383A CN 103666463 B CN103666463 B CN 103666463B
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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 conducting carrier.
Background technology
Mesoporous material is all regarded as very useful material in the eye of many scientists, they can develop into organic/inorganic composite material, these matrix materials then 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 are constantly with the mesoporous material of various method synthesis 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.
Compared with inorganic mesoporous material, the presoma of PMO material is bonded by Si-C key by organo units and methyl-monosilane or ethylsilane, wherein the range of choice of organo units is very wide, such as, can be the functional groups such as two dialkylene, alkylene, crown ether base, porphyryls.The structure of described organo units and size etc. suitably can be selected according to the requirement of material requested.The PMO material of surface modification, while organo units is scattered on inorganic materials hole wall, the new unit introduced 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 well optical functional main body.This mainly has good hardness and light stability due to mesoporous material, but also has good hydrophilic/hydrophobic phase, makes mesoporous material meticulousr in adjustment guest molecule microenvironment.In report in early days, epipolic mesoporous material realizes often by the method introducing organic luminophores in mesoporous material.But in these fluorescent materials, the luminophore introduced is all generally the organic molecule containing π key conjugated structure, and organic molecule easily photobleaching occurs, thus destroy the fluorescence property of mesoporous material.And, because fluorescent organic molecule generally has toxicity, can environmental pollution be caused in building-up process, and be difficult to be more widely used in fields such as such as biology.
Summary of the invention
The object of the invention is, in order to overcome the existing above-mentioned shortcoming that obtained fluorescent material exists by introducing organic luminophores in mesoporous material, to provide a kind of new fluorescent material and its preparation method and application.
The invention provides a kind of fluorescent material (ncSi-PMO), wherein, described fluorescent material contains the si-nanocrystals (ncSi) of order mesoporous organosilicon material (PMO) 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 obtain, wherein, R
1for thiazolinyl, R
2for substituted or unsubstituted alkyl.
Present invention also offers a kind of preparation method of fluorescent material, the method comprises: in presence of organic solvent, mixed with order mesoporous organosilicon material by the si-nanocrystals of modification and contact, 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 obtain, wherein, R
1for thiazolinyl, R
2for substituted or unsubstituted alkyl.
Present invention also offers the application of above-mentioned fluorescent material as medicine conducting 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 compared with organic luminophores, the light stability of the si-nanocrystals of described modification is better, and the wavelength of simultaneously stability and transmitting can regulate.Therefore, by the si-nanocrystals of described modification is introduced in order mesoporous organosilicon material in the present invention, described fluorescent material provided by the invention is made not only to have the ability of stronger anti-photobleaching, but also there is good bio-compatibility, thus can be widely used in field of biology.
And described fluorescent material of the present invention is especially suitable for use as medicine conducting carrier.When adopting described fluorescent material as medicine conducting carrier, described medicine conducting carrier has fluorescent characteristic, has the ability of stronger anti-photobleaching, can carry out good fluorescent tracing, but also has good medicament slow release performance.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is 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 (ncSi-PMO) provided by the invention under ultra violet lamp;
Fig. 2 is the infrared spectrogram (FTIR) of order mesoporous organosilicon material (PMO) and described fluorescent material (ncSi-PMO) provided by the invention;
Fig. 3 is the X-ray diffractogram (XRD) of order mesoporous organosilicon material (PMO) and described fluorescent material (ncSi-PMO) provided by the invention;
Fig. 4 is the adsorption of nitrogen gas data of order mesoporous organosilicon material (PMO);
Fig. 5 is the adsorption of nitrogen gas data of described fluorescent material (ncSi-PMO) provided by the invention;
Fig. 6 is the release graphics of order mesoporous organosilicon material (PMO) with described fluorescent material (ncSi-PMO) provided by the invention separately to ibuprofen pharmaceutical;
Fig. 7 is the electron scanning micrograph of described fluorescent material (ncSi-PMO) provided by the invention.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of fluorescent material, wherein, described fluorescent material contains the si-nanocrystals of 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 obtain, wherein, R
1for thiazolinyl, R
2for substituted 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, is more preferably 1:0.8-2.5.
Described order mesoporous organosilicon material (PMO) can be this area routine use by 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 the duct arrangement of rule, refers in particular to the ordered arrangement that pore structure is six side's phase arrangement architectures in the present invention; Term " mesoporous " refers to that average pore diameter is the hole between 2-50 nanometer, and also namely 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, such as, the preparation method of described order mesoporous organosilicon material can comprise: be dissolved in the aqueous solution of Repone K by polyoxyethylene-poly-oxypropylene polyoxyethylene (P123), then hydrochloric acid soln and 1 is added successively, the two silica-based ethane of trimethoxy (BTME) of 2-, at 10-60 DEG C, be uniformly mixed 1-30 minute afterwards and place 5-50 hour, then in autoclave, at 80-120 DEG C, 5-50 hour is reacted, reaction terminates rear collection solid product, and from solid product, isolate order mesoporous organosilicon material.
In the method for the order 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, is more preferably 100:130-150.
In the method for the order mesoporous organosilicon material of above-mentioned preparation, the concentration of the potassium chloride solution used can be 0.5-2mol/L.And relative to the P123 of 100 weight parts, the consumption of potassium chloride solution can be 100-600 weight part, be preferably 200-400 weight part.
In the method for the order mesoporous organosilicon material of above-mentioned preparation, the concentration of the hydrochloric acid soln used can be 0.1-0.5mol/L.And relative to the P123 of 100 weight parts, the consumption of hydrochloric acid soln can be 1000-10000 weight part, be preferably 2000-6000 weight part.
In the method for the order mesoporous organosilicon material of above-mentioned preparation, the pressure in described autoclave can be the pressure itself of the reaction system of relevant temperature.The concrete grammar that reaction terminates rear collection PMO material can comprise: from reaction product, collect solid product by filtering, at room temperature that this solid product is dry, use deionized water wash again, then with ethanol, surname extraction is carried out to the solid product after washing, thus obtain PMO material.
The si-nanocrystals (ncSi) of described modification 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 obtain.The condition of described hydrosilation reaction can comprise: temperature of reaction is between 150-200 DEG C, and the weight ratio of the consumption of described si-nanocrystals and the consumption of described silane compound can be below 0.1:6, is preferably 0.01-0.1:6.Described hydrosilation reaction can carry out at ambient 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: in presence of organic solvent, si-nanocrystals is mixed with described silane compound, being cooled to-50 DEG C to-100 DEG C carries out freezing degassed, then 150-200 DEG C is warming up to, and react 8-16 hour (as reaction overnight) at such a temperature, then carry out underpressure distillation to remove unreacted described silane compound and described organic solvent, thus obtain ncSi.Described organic solvent is the solvent that can dissolve described si-nanocrystals, such as, can be n-decane, ethanol, chloroform etc.
Described si-nanocrystals can be commercially available, also can prepare according to the method for routine, its preparation method such as can comprise: the contact reacts 1-2 hour at 0-78 DEG C by trichlorosilane and excessive deionized water, then filter and collecting precipitation thing, this throw out is carried out calcination (as at 800-1500 DEG C calcination 0.5-3 hour), the mixture obtained after calcination is ground, then with deionized water, ethanol contacts with hydrofluoric acid mixing (preferably contact 2-3 hour), use organic solvent (as n-decane afterwards, ethanol, chloroform etc.) extraction, the solution of the organic solvent of si-nanocrystals can be obtained.
The particle size of described si-nanocrystals can be below 10 nanometers, is preferably 1-8 nanometer, most preferably is 2-3 nanometer.The particle size of described si-nanocrystals can by the mixture after grinding and deionized water, ethanol and hydrofluoric acid mix contact after the size Expressing of particle that obtains.In the present invention, described particle size refers to the maximum linear distance between two differences on particle, and when described particle is spherical, then particle size refers to the diameter of this particle.
Be R for general formula
1si (OR
2)
3silane compound, R
1for thiazolinyl, be preferably C2-C10 thiazolinyl, be more preferably C2-C6 thiazolinyl, more preferably vinyl, propenyl, butenyl or pentenyl, most preferably be vinyl; R
2for substituted or unsubstituted alkyl, be preferably substituted or unsubstituted C1-C10 alkyl, be more preferably substituted or unsubstituted C1-C6 alkyl, more preferably substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl group, substituted or unsubstituted butyl or substituted or unsubstituted amyl group, most preferably be ethyl.For the substituted radical on described alkyl, such as, can be 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, is more preferably 5-6 nanometer; Pore volume is preferably greater than 0.2cm
3g
-1and be less than or equal to 1cm
3g
-1, be more preferably 0.3-0.9cm
3g
-1; Specific surface area is preferably greater than 200m
2g
-1and be less than or equal to 1000m
2g
-1, be more preferably 300-900m
2g
-1.Wherein, mean pore size, pore volume and specific surface area adopt nitrogen adsorption methods to measure respectively.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 being used as medicine conducting carrier.
Present invention also offers a kind of preparation method of fluorescent material, the method comprises: in presence of organic solvent, mixed with order mesoporous organosilicon material by the si-nanocrystals of modification and contact, 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 obtain, wherein, R
1for thiazolinyl, R
2for substituted 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, is more preferably 1:0.5-2.
In the preparation method of above-mentioned fluorescent material, the contact process that mixes of the si-nanocrystals of described modification and described order mesoporous organosilicon material mainly makes the trialkenyl alkoxysilane polymer on the si-nanocrystals of described modification be hydrolyzed to generate silicone hydroxyl, and with the silicone hydroxyl generation condensation reaction on order mesoporous organosilicon material.Said process can in acid condition, under alkaline condition and all can occur under neutrallty condition.In the preferred case, the si-nanocrystals of described modification carries out in acid condition with the contact process that mixes of described order mesoporous organosilicon material, more preferably in pH value is to carry out under the condition of 1-5, and preferred is further carry out under the condition of 1-2 in pH value.The temperature of described mixing contact is preferably 0-90 DEG C, is more preferably 20-40 DEG C.The time of described mixing contact is preferably 1-100 hour, is 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 respective preparation methods all identical with above-described.
In the preparation method of described fluorescent material, the mixing contact process and can carry out in the presence of the solvent of the si-nanocrystals of modification and order mesoporous organosilicon material.Described solvent requirement and water dissolve each other and volatile, and such as, described solvent can be methyl alcohol, ethanol, propyl alcohol, Virahol, acetone etc., are preferably ethanol.
In the preparation method of described fluorescent material, after si-nanocrystals and the order mesoporous organosilicon material of modification mix and contact, described method can also comprise carries out centrifugation by the product of mixing contact, is washed by isolated solid product, and carries out drying.Described drying under vacuum or under protection of inert gas, can be carried out at the temperature of 40-200 DEG C (being preferably 70-100 DEG C).
Present invention also offers the application of described fluorescent material as medicine conducting carrier.Concrete application process can comprise: on fluorescent material, load adsorbent, and then under 0-100 DEG C (being preferably 36-38 DEG C), the fluorescent material being mounted with adsorbent being scattered in pH value is in the solution of 1-9.Described adsorbent can be such as 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 DEG C, 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 40g concentration be wherein 0.167molL
-1hydrochloric acid soln, afterwards by the BTME(of 1.40g purchased from sigma-Aldrich company) join in mixing solutions, and to stir.Stop after 10 minutes stirring, reaction system leaves standstill 1 day at 40 DEG C.Subsequently, mixture is transferred in autoclave, reacts 24 hours at 100 DEG C.After reaction terminates, solid collected by filtration product, and at room temperature dry.Finally, utilize ethanol to carry out surname extraction to solid product, obtain PMO material.
Preparation example 2
The preparation of the si-nanocrystals of modification
At-75 DEG C, the deionized water of 25ml is mixed with the trichlorosilane of 10ml, react and obtain white precipitate afterwards in 1.5 hours, isolate white precipitate, and vacuum-drying is carried out to this white precipitate, be transferred in tube furnace afterwards, at 1100 DEG C, calcination 1 hour, obtains brown mixture.This mixture being ground to particle diameter is less than 1 millimeter, then the described mixture through grinding of 0.6g is placed in plastic beaker, add 9ml deionized water, 18ml ethanol and 30ml hydrofluoric acid (aqueous solution of 48 % by weight) wherein, react after 3 hours, obtain the si-nanocrystals that particle size is about 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, adds the vinyltriethoxysilane of 9ml wherein; Then freezing at-75 DEG C, then carry out decompression and bleed, pass into nitrogen afterwards and make system return to room temperature, and cyclical operation three times like this; Then, be warming up to 175 DEG C, and slowly stir and carry out reaction overnight at such a temperature.After reaction terminates, centrifugation goes out precipitation, and carries out underpressure distillation to supernatant liquor, thus obtains the nanocrystalline silicon of modification.
Embodiment 1
The present embodiment is for illustration of described fluorescent material of the present invention and preparation method thereof.
The si-nanocrystals of the modification above-mentioned for 1.025g preparation example 2 prepared is dissolved in 8.074g ethanol, stirring makes the si-nanocrystals of described modification fully dissolve, get the solution that 0.36g obtains, PMO material prepared by the above-mentioned preparation example 1 of 50mg is added 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 DEG C stirring reaction 24 hours.After reaction terminates, centrifugation, collects solid product, washs afterwards, finally carry out vacuum-drying, obtain fluorescent material A1 with ethanol.
Comparative example 1
Method according to embodiment 1 prepares fluorescent material, and difference is, replaces the si-nanocrystals of described modification, thus obtain fluorescent material D1 with the AEC (purchased from sigma-Aldrich company) of identical weight.
Embodiment 2
The present embodiment is for illustration of described fluorescent material of the present invention and preparation method thereof.
Method according to embodiment 1 prepares fluorescent material, and difference is, uses 0.1molL
-1naOH solution the pH value of reaction system is adjusted to 9, thus obtained fluorescent material A2.
Embodiment 3
The present embodiment is for illustration of described fluorescent material of the present invention and preparation method thereof.
The si-nanocrystals of the modification above-mentioned for 0.513g preparation example 2 prepared is dissolved in 8.074g ethanol, stirring makes the si-nanocrystals of described modification fully dissolve, get the solution that 0.36g obtains, PMO material prepared by the above-mentioned preparation example 1 of 50mg is added 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 DEG C stirring reaction 24 hours.After reaction terminates, centrifugation, collects solid product, washs afterwards, finally carry out vacuum-drying, obtain fluorescent material A3 with ethanol.
Embodiment 4
The present embodiment is for illustration of described fluorescent material of the present invention and preparation method thereof.
The si-nanocrystals of the modification above-mentioned for 1.367g preparation example 2 prepared is dissolved in 8.074g ethanol, stirring makes the si-nanocrystals of described modification fully dissolve, get the solution that 0.36g obtains, PMO material prepared by the above-mentioned preparation example 1 of 50mg is added 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 DEG C stirring reaction 24 hours.After reaction terminates, centrifugation, collects solid product, washs afterwards, finally carry out vacuum-drying, obtain fluorescent material A4 with ethanol.
Test case 1
Detect the mean pore size of above-mentioned fluorescent material A1-A4, pore volume and specific surface area respectively, wherein, nitrogen adsorption-desorption curve is the full-automatic specific surface area of TriStar3000 and lacunarity analysis instrument measurement acquisition that adopt Micromeritics instrument company of the U.S. to produce, by the desorption branch in adsorption isothermal line and according to Barrett-Joyner-Halenda(BJH) formulae discovery goes out 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
It is the fluorescent material (ncSi-PMO) observing PMO material and embodiment 1 preparation under the ultra violet lamp of 365nm at wavelength.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
Carry out Infrared spectroscopy to fluorescent material (ncSi-PMO) prepared by PMO material and embodiment 1 respectively, their respective FTIR spectrum figure as shown in Figure 2.
As can be seen from Figure 2, PMO and ncSi-PMO is at 3440cm
-1and 1090cm
-1there is very strong absorption peak at place, and in the FTIR spectrum figure of ncSi-PMO, at 2960cm
-1and 2899cm
-1the vibration peak intensity at place clearly enhances relative to PMO.Illustrate thus, in described fluorescent material of the present invention, the si-nanocrystals (ncSi) of modification has successfully modified PMO material.
Test case 4
Carry out X-ray diffraction analysis to fluorescent material (ncSi-PMO) prepared by PMO material and embodiment 1 respectively, their respective XRD figure 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 described fluorescent material of the present invention is still ordered structure after ncSi modifies thus.
Test case 5
Detect the N2 adsorption data of the fluorescent material (ncSi-PMO) of PMO material and embodiment 1 preparation respectively.Respective detected result respectively as shown in Figure 4 and Figure 5.
By can obtain the aperture parameters of PMO and ncSi-PMO to the research of nitrogen adsorption-desorption thermoisopleth, according to the definition of International Union of Pure and Applied Chemistry IUPAC, it is the 4th class thermoisopleth that this H1 type returns stagnant ring thermoisopleth, is specific to mesoporous material.In figures 4 and 5, bi-material demonstrates the 4th class thermoisopleth.Illustrate that described fluorescent material of the present invention still keeps six side's phase arrangement architectures of high-sequential thus, reaction process central hole structure is not destroyed.
Test case 6
Obtain the electron scanning micrograph of fluorescent material (ncSi-PMO) prepared by embodiment 1, as shown in Figure 7.As can be seen from Figure 7, ncSi-PMO presents ordered arrangement.
Embodiment 5-8 and comparative example 2
Compound concentration is 10mgmL
-1ibuprofen BP/EP hexane solution, respectively above-mentioned for 25mg fluorescent material is joined in the above-mentioned Ibuprofen BP/EP hexane solution of 2.5mL, at room temperature stirs 24h, obtain carrier loaded Z1-Z4 and DZ1.Then, measure the uv-absorbing intensity of solution with ultraviolet spectrophotometer, calculate the loading capacity of Ibuprofen BP/EP in each fluorescent material respectively by the change before and after Ibuprofen BP/EP solution absorbance, result is as shown in table 2 below.
Table 2
| Carrier loaded | Fluorescent material | Loading capacity (mgg -1） | |
| Embodiment 5 | 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
The PMO dispersion of materials above-mentioned carrier loaded Z1, the DZ1 of 25mg and preparation example 1 prepared respectively is in the PBS buffered soln of 7.4 in the pH value of 30.0mL, shakes in 37 ± 1 ° of C water-baths.Respectively when 10min, 1h, 2h, 4h, 8h, 12h, 24h, 48h, 96h, from system, take out 3.0mL mixing solutions, in system, add the fresh PBS buffered soln of 3.0mL simultaneously.The 3.0mL mixed solution of taking-up is carried out centrifugation, collecting by filtration supernatant liquid, measures its uv-absorbing with ultraviolet spectrophotometer, calculates 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
As can be seen from the data of table 3, fluorescent material according to the present invention has good sustained release performance.Concrete, carrier loaded DZ1 prominent is released very little, and the burst size namely 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; PMO material prominent is released very high, and the burst size namely within 10 minutes is very high, and up to 57.2 % by weight, although burst size has the trend increased gradually within the follow-up time, the amplitude that burst size increases gradually is very little, thus shows poor sustained release performance; Carrier loaded Z1 prominent is released relatively moderate, and be about 29.16 % by weight, and the trend comparison that burst size increases gradually within the follow-up time is stablized, the amplitude of increase is obvious, thus shows good medicament slow release performance.
Test case 8
Adopt fluorescence spectrophotometer instrument (purchased from Varian company, model C ARY Eclipse), detect the anti-light of fluorescent material A1 and D1 according to solid fluorescence method and cause performance of fading.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 and anti-lightly preferably causes performance of fading.
Claims (25)
1. a fluorescent material, is characterized in that, described fluorescent material contains the si-nanocrystals of 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 obtain, wherein, R
1for thiazolinyl, R
2for substituted or unsubstituted alkyl; The preparation method of described order mesoporous organosilicon material comprises: be dissolved in by polyoxyethylene-poly-oxypropylene polyoxyethylene in the aqueous solution of Repone K, then hydrochloric acid soln and 1 is added successively, the two silica-based ethane of trimethoxy of 2-, at 10-60 DEG C, be uniformly mixed 1-30 minute and place 5-50 hour, then in autoclave, at 80-120 DEG C, 5-50 hour is reacted, reaction terminates rear collection solid product, and separation obtains described order mesoporous organosilicon material from solid product.
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.
3. fluorescent material according to claim 2, wherein, the weight ratio of the content of the content of described order mesoporous organosilicon material and the si-nanocrystals of described modification is 1:0.5-5.
4. fluorescent material according to claim 1, wherein, R
1for C2-C10 thiazolinyl; R
2for substituted or unsubstituted C1-C10 alkyl.
5. fluorescent material according to claim 4, wherein, R
1for vinyl.
6. fluorescent material according to claim 4, wherein, R
2for ethyl.
7. according to the fluorescent material in claim 1-6 described in any one, wherein, the condition of described hydrosilation reaction comprises: temperature of reaction is 150-200 DEG C, and the weight ratio of the consumption of described si-nanocrystals and the consumption of described silane compound is below 0.1:6.
8. fluorescent material according to claim 7, wherein, the weight ratio of the consumption of described si-nanocrystals and the consumption of described silane compound is 0.01-0.1:6.
9. according to the fluorescent material in claim 1-8 described in any one, wherein, the particle size of described si-nanocrystals is below 10 nanometers.
10. fluorescent material according to claim 9, wherein, the particle size of described si-nanocrystals is 1-8 nanometer.
11. fluorescent materials according to claim 1, 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.
The preparation method of 12. 1 kinds of fluorescent materials, the method comprises: in presence of organic solvent, is mixed by the si-nanocrystals of modification contact 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 obtain, wherein, R
1for thiazolinyl, R
2for substituted or unsubstituted alkyl; The preparation method of described order mesoporous organosilicon material comprises: be dissolved in by polyoxyethylene-poly-oxypropylene polyoxyethylene in the aqueous solution of Repone K, then hydrochloric acid soln and 1 is added successively, the two silica-based ethane of trimethoxy of 2-, at 10-60 DEG C, be uniformly mixed 1-30 minute and place 5-50 hour, then in autoclave, at 80-120 DEG C, 5-50 hour is reacted, reaction terminates rear collection solid product, and separation obtains described order mesoporous organosilicon material from solid product.
13. methods according to claim 12, 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.
14. methods according to claim 13, wherein, the weight ratio of the consumption of the consumption of described order mesoporous organosilicon material and the si-nanocrystals of described modification is 1:0.5-5.
15. according to the method in claim 12-14 described in any one, and 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; Temperature is 0-90 DEG C.
16. methods according to claim 15, wherein, the pH value that the si-nanocrystals of described modification contacts with the mixing of described order mesoporous organosilicon material is 1-2.
17. methods according to claim 15, wherein, the temperature that the si-nanocrystals of described modification contacts with the mixing of described order mesoporous organosilicon material is 20-40 DEG C.
18. according to the method in claim 12-14 described in any one, and wherein, the particle size of described si-nanocrystals is below 10 nanometers.
19. methods according to claim 18, wherein, the particle size of described si-nanocrystals is 1-8 nanometer.
20. methods according to claim 12, wherein, R
1for C2-C10 thiazolinyl; R
2for substituted or unsubstituted C1-C10 alkyl.
21. methods according to claim 20, wherein, R
1for vinyl.
22. methods according to claim 20, wherein, R
2for ethyl.
23. according to the method in claim 12 and 20-22 described in any one, and wherein, the condition of described hydrosilation reaction comprises: temperature of reaction is 150-200 DEG C, and the weight ratio of the consumption of described si-nanocrystals and the consumption of described silane compound is below 0.1:6.
24. methods according to claim 23, wherein, the weight ratio of the consumption of described si-nanocrystals and the consumption of described silane compound is 0.01-0.1:6.
Fluorescent material in 25. claim 1-11 described in any one is as the application of medicine conducting carrier.
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| Periodic Mesoporous Hydridosilica-Synthesis of an "Impossible" Material and Its Thermal Transformation into Brightly Photoluminescent Periodic Mesoporous Nanocrystal Silicon-Silica Composite;Zhuoying Xie et al.;《J. Am. Chem. Soc.》;20110315;5094-5102 * |
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