CN113502153A - Non-aromatic luminous micromolecule/SiO2Hybrid fluorescent nano material and preparation method and application thereof - Google Patents
Non-aromatic luminous micromolecule/SiO2Hybrid fluorescent nano material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a non-aromatic luminous micromolecule/SiO2A preparation method and application of a hybridized fluorescent nano material are disclosed, specifically, a novel non-traditional organic luminescent molecule, namely N-stearoyl-L-hydroxyproline, is synthesized by two-step reaction of L-hydroxyproline and stearic acid. The luminescent molecule can emit weak blue light in a solid state, and an AIE phenomenon can be observed in a solution. The fluorescent nano material is used as a soft template to be assembled and integrated with a siloxane precursor on a nano scale through hydrogen bond action, and a sol-gel method is adopted to prepare the fluorescent nano material. The non-aromatic luminous micromolecule/SiO2Hybrid fluorescenceThe shape of the nano material is in a twisted worm shape, and the nano material is regular and rich in mesopores. The material has a remarkable emission spectrum at 410-440 nm, has excellent fluorescence stability, and can be applied to the fields of potential fingerprint detection, biological imaging and the like.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to non-aromatic luminescent micromolecules/SiO2A hybridized fluorescent nano material, a preparation method and application thereof.
Background
In recent years, aggregation-induced emission (AIE) materials continue to attract the attention of basic research and related industries due to the characteristics of simple preparation, abundant types, stable optical properties, low toxicity and the like. The AIE organic light emitting material has a wide variety of types, and generally contains a chromophore such as an aromatic group or a conjugated heterocyclic ring in a molecular structure, and a generally recognized light emitting mechanism is one of the chromophores which generates a light emitting phenomenon due to the restriction of intramolecular movement. At present, researchers develop a plurality of AIE luminescent systems successively, and the AIE luminescent systems have respective characteristics in both luminescent mechanism, physicochemical property and application, and provide abundant design ideas and technical supports for the research of luminescent materials. However, common luminescent materials such as organic molecular dyes containing phenyl, semiconductor quantum dots, noble metals and rare earth materials generally have the problems of high cost, complex synthesis, toxicity, possible harm to the environment and the like, and further practical application of the luminescent materials is limited.
Unlike the conventional luminescent molecules, there is a special class of luminescent materials whose chemical structure does not contain large conjugated aromatic rings or large pi-conjugated units, but still has AIE properties. The non-traditional luminous molecule only contains small non-conjugated functional groups (such as amino groups, amide groups, carbamido groups, ester groups, acid anhydride groups, carbonyl groups and other groups) in the structure, which is similar to the structure composition of biological molecules, so the non-traditional luminous molecule has the advantages of good hydrophilicity, excellent biocompatibility, low biotoxicity, environmental friendliness and the like, the preparation raw materials are cheap and easy to obtain, and the preparation method and the modification means are simple and mild, and is particularly suitable for the application in the fields of biological related tracing, imaging, detection and the like. Therefore, the development and the intensive research of the non-traditional luminescent materials certainly inject new vitality into the field of enriching and perfecting the luminescent materials.
Fingerprint detection is an important component in criminal science and technology and plays a key role in case detection. However, the latent fingerprints existing in the crime scene are difficult to distinguish and fix by human eyes through a visible light method, and special optical detection technology must be used for effective visualization and extraction. Among many methods for developing fingerprints, the powder optical inspection method is widely used because of its ease of operation. The method combines the advantages of a powder method and a light detection method, can simply, quickly and efficiently identify the detail characteristics of the fingerprint, and is applied to information acquisition of an actual field. Among them, the fluorescent nanomaterial using silica as a matrix has become one of the hot spots in research. Since the silicon substrate has the advantages of controllable size, good optical transparency, easy modification, easy synthesis, low toxicity and the like, the silicon substrate is widely used for preparing fingerprint developing materials. Fernandes et al introduced carbon sites into SiO2In the method, carbon-doped SiO with adjustable color is synthesized2Nanoparticles, exploratory for fingerprint detection and product labeling (see: Fernandes, D.chem.Commun.2016,52, 8294-8296.); kim et al, silane-modified organic dye molecules with SiO2Preparing fluorescent nanoparticles by covalent bonding, and performing post-modification on the surface of the nanoparticles by using polyvinylpyrrolidone to realize potential fingerprint detection on hydrophilic and hydrophobic substrates (see: Kim, Y.J. Langmuir,2016,32(32), 8077-8083.); zhang et al conjugated fluorescent oligomers to SiO by reverse micelle method2Ultra-bright fluorescent nanoparticles are synthesized in a matrix and used for efficient detection of potential fingerprints (see Zhang, S.J.ACS appl.Mater.interfaces 2017,9, 44134-44145.); zhang et al by
The method synthesizes non-conjugated organic silicon fluorescent nanoparticles, and the effectiveness of the non-conjugated organic silicon fluorescent nanoparticles on potential fingerprint detection is proved on various substrates (see: Zhang, H.J.Lumin.,2019,215,116582). However, mostly incorporating silicon substratesThe fluorescent nano material is still based on the traditional fluorescent system, has high cost, complex synthesis and time-consuming treatment, and is not beneficial to large-scale preparation and application. Therefore, designing and developing non-toxic, low-cost and easily-prepared fluorescent nano-materials based on a novel non-traditional luminescent system becomes a leading-edge problem to be solved urgently and shows a wide application prospect.
Disclosure of Invention
The invention aims to provide a novel non-aromatic luminous micromolecule/SiO which has the advantages of cheap and easily obtained raw materials, simple and convenient synthesis operation, mild reaction conditions, strong fluorescence stability, no toxicity and environmental friendliness2A preparation method and application of a hybridized fluorescent nano material. Specifically, L-hydroxyproline and stearic acid are subjected to two-step reaction to synthesize a novel non-traditional organic luminescent molecule, namely N-stearoyl-L-hydroxyproline. The luminescent molecule can emit weak blue light in a solid state, and an AIE phenomenon can be observed in a solution. The fluorescent nano material is used as a soft template to be assembled and integrated with a siloxane precursor on a nano scale through hydrogen bond action, and a sol-gel method is adopted to prepare the fluorescent nano material. The non-aromatic luminous micromolecule/SiO2The hybridized fluorescent nano material is in a twisted worm shape, is regular and is rich in mesopores. The material has a remarkable emission spectrum at 410-440 nm, has excellent fluorescence stability, and can be applied to the fields of potential fingerprint detection, biological imaging and the like.
The technical scheme of the invention is as follows:
non-aromatic luminous micromolecule/SiO2A hybridized fluorescent nanomaterial comprising a non-aromatic luminescent small molecule and a matrix material; the non-aromatic luminous micromolecules are biological amino acid organic matters (N-stearoyl-L-hydroxyproline and the like), the matrix material is mesoporous worm-shaped silicon dioxide, and the non-aromatic luminous micromolecules exist in the matrix material in an aggregate form.
A non-aromatic luminescent small molecule is N-stearoyl-L-hydroxyproline and the like, and has the following structural formula:
the method specifically comprises the following steps:
(1) stearic acid (40mmol), di-tert-butyl dicarbonate, N-hydroxysuccinimide and chloroform are weighed and put in a flask, stirred at room temperature until the stearic acid, the di-tert-butyl dicarbonate, the N-hydroxysuccinimide and the chloroform are completely dissolved, 4- (dimethylamino) pyridine and triethylamine are added, and the mixture is continuously stirred and reacted for 12 hours, so that the intermediate compound stearic acid-N-hydroxysuccinimide ester is obtained. Wherein the molar ratio of stearic acid, di-tert-butyl dicarbonate, N-hydroxysuccinimide, 4- (dimethylamino) pyridine and triethylamine is 1: 1.4: 1: 0.2: 1;
(2) dissolving the synthesized stearic acid-N-hydroxysuccinimide ester (7.0mmol) in tetrahydrofuran, adding the tetrahydrofuran into a sodium bicarbonate aqueous solution containing L-hydroxyproline, stirring until the solid is completely dissolved, heating to 40 ℃, and reacting for 12 hours to obtain the target compound N-stearoyl-L-hydroxyproline. The molar ratio of stearic acid-N-hydroxysuccinimide ester to L-hydroxyproline to sodium bicarbonate is 1: 1.1: 1;
(3) at room temperature, N-stearoyl-L-hydroxyproline (0.1mmol) is dissolved in an ethanol/butanol mixture, added to an aqueous solution of potassium hydroxide and stirred slowly for 30 minutes. Then, in the process of self-assembling N-stearoyl-L-hydroxyproline to form an aggregate, adding tetraethoxysilane (1.5mmol) and 3-aminopropyltriethoxysilane according to a certain molar ratio, heating to 70 ℃, and under the initiation of ammonium persulfate, hydrolyzing a siloxane prepolymer and carrying out polycondensation on the surface of a molecular aggregate to obtain a silicon substrate coated N-stearoyl-L-hydroxyproline aggregate nanostructure, namely a non-aromatic luminous micromolecule/SiO2Hybrid fluorescent nanomaterials.
The sol-gel process in the preparation method is similar to the whole process of preparing mesoporous silica gel by a conventional soft template method, and is different in that the N-stearoyl-L-hydroxyproline aggregate in the post-treatment process is not removed as a template.
(4) The fluorescent nano material subjected to vacuum freeze drying is uniformly dispersed on the surface of a substrate on which fingerprints are deposited as developing powder, residues on the surfaces of the fingerprints contain lipid or bloodstains, and the fingerprints which are subjected to fluorescent display are recorded by a digital camera under the irradiation of a handheld ultraviolet lamp (365nm), so that the detection of potential fingerprints and bloodstain fingerprints is realized. The substrate material for fingerprint deposition includes glass, Plastic (PVC), transparent adhesive tape and other common materials.
The fluorescent nano material provided by the technical scheme of the invention is prepared from raw materials in the preparation process, and is characterized in that L-hydroxyproline can be replaced by L-proline and the like.
The raw materials used in the preparation process of the fluorescent nano material provided by the technical scheme of the invention are characterized in that stearic acid can be replaced by lauric acid, myristic acid, palmitic acid and the like.
The raw materials used in the preparation process of the fluorescent nano material in the technical scheme of the invention are characterized in that the alkaline condition of amidation reaction can use sodium bicarbonate, sodium carbonate, sodium hydroxide and the like.
The raw materials used in the preparation process of the fluorescent nano material are characterized in that siloxane precursors in a sol-gel reaction, namely ethyl orthosilicate and 3-aminopropyltriethoxysilane, can be adjusted according to the molar ratio of 1:0, 1:1, 2:1, 3:2, 3:1 and the like.
Compared with the prior art, the invention has the following advantages:
1. the non-aromatic luminescent micromolecules/SiO prepared by the invention2The hybridized fluorescent nano material has a structure which does not contain conjugated aromatic rings or large pi-conjugated units, can still perform photoluminescence to generate stronger blue fluorescence, and belongs to a novel non-traditional luminescent material.
2. The novel non-aromatic luminous micromolecule N-stearoyl-L-hydroxyproline synthesized by the invention creatively adopts biological amino acid (namely L-hydroxyproline) which has wide sources, low cost, biocompatibility and no toxicity as an important structural unit of the luminous molecule. The tertiary amide generated by the reaction of the tertiary amide with stearic acid is used as a main sub-luminescent group, and a non-aromatic luminescent aggregate with AIE characteristics is formed under the combined action of hydrogen bonds and an aggregation effect.
3. The fluorescent nano material prepared by the invention is prepared by SiO2The synergistic effect of the matrix provides a limited microspace for the organic luminescent molecular aggregate, and simultaneously plays an effective protection role, reduces the influence of environmental factors such as temperature, pH, solvent, photobleaching and the like, and enhances the tolerance and fluorescence stability of the fluorescent nano material.
4. The fluorescent nano material prepared by the invention has a regular shape, is in a twisted worm shape and has a rich mesoporous structure.
5. The fluorescent nano material prepared by the invention has the advantages of simple synthetic process, low cost, mild reaction conditions and good reproducibility, and can be prepared on a large scale.
6. The fluorescent nano material prepared by the invention can be dispersed in most organic solvents and can show stable blue fluorescence in solvents or under solid conditions. The material has good biocompatibility, nontoxicity and fluorescence stability, and has application potential in the aspects of potential fingerprint detection, fluorescent probes, biological imaging and the like.
Drawings
FIG. 1 is a reaction equation of non-aromatic luminescent small molecules (N-stearoyl-L-hydroxyproline, etc.) synthesized in example 1 of the present invention.
FIG. 2 shows the synthesis of N-stearoyl-L-hydroxyproline according to example 1 of the present invention1H NMR chart.
FIG. 3 is a photograph of an actual fluorescent nanomaterial prepared in example 1 under a fluorescent lamp and an ultraviolet lamp (note that in the actual fluorescent lamp, black (dark) represents no light emission, and white (light) represents light emission).
FIG. 4 is a fluorescence emission spectrum of the fluorescent nanomaterial prepared in example 1 of the present invention at different excitation wavelengths.
FIG. 5 is an SEM image of the fluorescent nanomaterial prepared in example 1 of the present invention.
FIG. 6 is a TEM image of the fluorescent nanomaterial prepared in example 1 of the present invention.
FIG. 7 is a nitrogen isothermal adsorption-desorption curve and a pore size distribution diagram (inset) of the fluorescent nanomaterial prepared in example 1 of the present invention.
FIG. 8 is a photograph of the fluorescent nanomaterial prepared in example 1 applied to latent fingerprint detection and fingerprint feature detail enlargement.
Detailed Description
The invention will be further elucidated with reference to a specific embodiment and a drawing. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Synthesis of target compound (I), N-stearoyl-L-hydroxyproline (N ═ 16)
First, 40mmol of stearic acid was weighed out and dissolved in 120mL of chloroform, and 56mmol of di-tert-butyl dicarbonate and 40mmol of N-hydroxysuccinimide were added under magnetic stirring. After the solid was completely dissolved, 40mmol of triethylamine and 8mmol of 4- (dimethylamino) pyridine were added, and the reaction was stirred at room temperature for 12 hours. After completion of the reaction, the reaction mixture was washed with 2M aqueous hydrochloric acid (20 mL. times.3), and the organic phase was dried over anhydrous magnesium sulfate. After filtration, the solvent was removed by rotary evaporation, and the crude product was recrystallized from ethanol to give stearic-N-hydroxysuccinimide ester as an intermediate compound.
Then, 7.7mmol of L-hydroxyproline was dissolved in an aqueous solution of sodium bicarbonate (0.154M, 50mL) in a 250mL reaction flask. After the solid was completely dissolved, 7.0mmol of N-hydroxysuccinimide stearate was dissolved in 50mL of tetrahydrofuran and added to the above solution, and the reaction was stirred at 40 ℃ for 12 hours. After the reaction was completed, the reaction solution was adjusted to pH 2 with dilute hydrochloric acid, and the solvent was removed by rotary evaporation. And recrystallizing the crude product in acetone to obtain the target compound (I), namely the N-stearoyl-L-hydroxyproline.
(2) Preparation of fluorescent nano material
0.1mmol of N-stearoyl-L-hydroxyproline was dissolved in a mixed solution of butanol/ethanol (v/v, 1: 1) and then added to an aqueous solution of potassium hydroxide (0.01M, 100mL) with slow stirring. After 30 minutes, 0.6mmol of ammonium persulfate is added into the mixed solution, and the mixture is stirred according to a molar ratio of 1:1 (or 3: 2) while adding 1.5mmol of ethyl orthosilicate and 3-aminopropyltriethoxysilane. After the mixture was stirred at room temperature, it was heated to 70 ℃ in a water bath and allowed to react for 48 hours. And after the reaction is finished, centrifuging the reaction solution, repeatedly washing the precipitate with absolute ethyl alcohol and deionized water, and freeze-drying to obtain light yellow powder, namely the fluorescent nano material.
Example 2
(1) Synthesis of target Compound (II), N-lauroyl-L-hydroxyproline (N ═ 10)
First, 40mmol of lauric acid was weighed out and dissolved in 120mL of chloroform, and 56mmol of di-tert-butyl dicarbonate and 40mmol of N-hydroxysuccinimide were added under magnetic stirring. After the solid was completely dissolved, 40mmol of triethylamine and 8mmol of 4- (dimethylamino) pyridine were added, and the reaction was stirred at room temperature for 12 hours. After completion of the reaction, the reaction mixture was washed with 2M aqueous hydrochloric acid (20 mL. times.3), and the organic phase was dried over anhydrous magnesium sulfate. After filtration, the solvent was removed by rotary evaporation, and the crude product was recrystallized from ethanol to obtain lauric acid-N-hydroxysuccinimide ester as an intermediate compound.
Then, 7.7mmol of L-hydroxyproline was dissolved in an aqueous solution of sodium bicarbonate (0.154M, 50mL) in a 250mL reaction flask. After the solid was completely dissolved, 7.0mmol of lauric acid-N-hydroxysuccinimide ester was dissolved in 50mL of tetrahydrofuran and added to the above solution, and the reaction was stirred at 40 ℃ for 12 hours. After the reaction was completed, the reaction solution was adjusted to pH 2 with dilute hydrochloric acid, and the solvent was removed by rotary evaporation. Recrystallizing the crude product in acetone to obtain the target compound (II), namely N-lauroyl-L-hydroxyproline.
(2) Preparation of fluorescent nano material
0.1mmol of N-lauroyl-L-hydroxyproline was dissolved in a mixed solution of butanol/ethanol (v/v, 1: 1) and then added to an aqueous solution of potassium hydroxide (0.01M, 100mL) under slow stirring. After 30 minutes, 1.5mmol of ethyl orthosilicate, 1mmol of 3-aminopropyltriethoxysilane and 0.6mmol of ammonium persulfate were added to the above mixture. After the mixture was stirred at room temperature, it was heated to 70 ℃ in a water bath and allowed to react for 48 hours. And after the reaction is finished, centrifuging the reaction solution, repeatedly washing the precipitate with absolute ethyl alcohol and deionized water, and freeze-drying to obtain light white powder, namely the fluorescent nano material.
Example 3
The fluorescent nanomaterial prepared in example 1 was applied to latent fingerprint detection.
Firstly, lightly wiping clean thumbs on parts with vigorous grease secretion such as cheeks, forehead and the like to ensure that grease is uniformly distributed on the surfaces of the thumbs, pressing different types of fingerprints on the surfaces of glass (cover glass) and depositing the fingerprints for 30 minutes; then, taking a proper amount of fluorescent nano material powder to be uniformly dispersed on the surface of the base material, and blowing to remove the redundant powder. Under the irradiation of an ultraviolet lamp (365nm), the latent fingerprint detection can be successfully realized by recording and developing the fingerprint through a digital camera, as shown in fig. 8. By digitally amplifying the fingerprint image, the detail characteristics of the potential fingerprint can be acquired, and information acquisition and individual identification are further realized.
Example 4
The fluorescent nanomaterial prepared in example 1 was applied to latent fingerprint detection.
Firstly, smearing a proper amount of blood (rabbit blood) on a clean thumb, pressing different types of fingerprints on the surface of glass (cover glass) after the surface of the thumb is soaked with blood stains, and depositing the fingerprints for 50 minutes; then, taking a proper amount of fluorescent nano material powder to be uniformly dispersed on the surface of the base material, and blowing to remove the redundant powder. Under the irradiation of an ultraviolet lamp (365nm), fingerprints are recorded and developed through a digital camera, and the detection of fingerprints dipped with bloodstains can be realized.
The fluorescent nanomaterial prepared in the above embodiment 1 of the present invention was subjected to the following performance tests:
(1) in example 1 of the present invention, a typical synthesis method of the target compound (i), N-stearoyl-L-hydroxyproline (N ═ 16), is shown in the reaction equation shown in fig. 1. The molecular structure was analyzed by hydrogen nuclear magnetic resonance spectroscopy, as shown in FIG. 2. Nuclear magnetic data1H NMR(500M Hz，CDCl3)：δ4.61(t,1H),4.54,4.49(d,1H),3.68(dd,1H),3.54(d,1H),2.32(pt,2H),2.26(pt,2H),1.73,1.60(pt,2H),1.24(s,28H),0.87(t,3H), indicating that the resulting compound is the desired product.
(2) The photo of the fluorescent nanomaterial obtained in embodiment 1 of the invention is shown in fig. 3, and under the irradiation of an ultraviolet lamp (365nm), the material shows strong blue fluorescence in both solid state and ethanol solution. The fluorescence property of the prepared silicon optical nano material is measured by a fluorescence spectrophotometer, as shown in figure 4, the excitation wavelength is 335-365 nm, and the emission wavelength has obvious fluorescence intensity in the range of 410-440 nm.
(3) The fluorescent nanomaterial prepared in the embodiment 1 of the invention is subjected to morphology characterization through a scanning electron microscope and a transmission electron microscope. As shown in fig. 5 and 6, the fluorescent nano material has a unique twisted worm-like morphology, a regular nano structure, and abundant mesopores.
(4) The fluorescent nanomaterial prepared in example 1 of the present invention was subjected to a nitrogen isothermal adsorption-desorption experiment, and the surface area and pore size distribution were analyzed. As shown in FIG. 7, the specific surface area of the material was 437.34m2G, pore diameter of 7.95 nm. The inherent biocompatibility and the abundant mesoporous structure of the fluorescent nano material are beneficial to the nanoparticles to be adhered to the surface of the fingerprint and interact with the residual components of the fingerprint, and the developing capability of the material on the fingerprint is improved. The nano material based on the non-traditional fluorescent micromolecules is expected to become a novel and effective powder optical detection material in criminal investigation and identification.
While the invention has been described with reference to specific preferred embodiments, it will be understood by those skilled in the art that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the protection scope of the present invention should be subject to the appended claims.
The invention discloses a novel non-aromatic luminous micromolecule/SiO2A hybridized fluorescent nano material, a preparation method and application thereof. The material is made of SiO2As matrix material, biological amino acid organic matter (N-stearin)acyl-L-hydroxyproline, etc.) as luminescent molecules, and a matrix material coats luminescent molecular aggregates. The method comprises the following steps: synthesizing N-stearoyl-L-hydroxyproline through amidation reaction of stearic acid-N-hydroxysuccinimide ester and L-hydroxyproline, and preparing the organic-inorganic hybrid fluorescent nano material through self-assembly and alkoxysilane sol-gel reaction. The fluorescent nano material belongs to a novel non-traditional luminescent material, creatively uses a non-aromatic luminescent system with biocompatibility, nontoxicity and low cost, has stable fluorescence property, has an emission wavelength range of 410-440 nm, and can be used in the fields of fingerprint detection, biological imaging and the like. The fluorescent nano material has the advantages of regular appearance, uniform aperture, simple preparation, mild reaction condition and convenient practical application and popularization.
Claims (9)
1. Non-aromatic luminous micromolecule/SiO2The hybridized fluorescent nano material is characterized by comprising non-aromatic luminescent small molecules and a matrix material; the non-aromatic luminous micromolecules are biological amino acid organic matters (N-stearoyl-L-hydroxyproline and the like), the matrix material is mesoporous worm-shaped silicon dioxide, and the non-aromatic luminous micromolecules exist in the matrix material in an aggregate form.
2. A non-aromatic luminescent small molecule is characterized in that the non-aromatic luminescent molecule is N-stearoyl-L-hydroxyproline and the like, and the structural formula of the non-aromatic luminescent small molecule is as follows:
3. the non-aromatic luminescent small molecule as claimed in claim 2, wherein the synthesis method using N-stearoyl-L-hydroxyproline (N ═ 16) as an example comprises the following steps:
(1) weighing stearic acid (40mmol), di-tert-butyl dicarbonate, N-hydroxysuccinimide and chloroform in a flask, stirring at room temperature until the stearic acid, the di-tert-butyl dicarbonate, the N-hydroxysuccinimide and the chloroform are completely dissolved, adding 4- (dimethylamino) pyridine and triethylamine, and continuously stirring for reacting for 12 hours to obtain an intermediate compound, namely stearic acid-N-hydroxysuccinimide ester, wherein the molar ratio of the stearic acid, the di-tert-butyl dicarbonate, the N-hydroxysuccinimide, the 4- (dimethylamino) pyridine and the triethylamine is 1: 1.4: 1: 0.2: 1;
(2) dissolving the synthesized stearic acid-N-hydroxysuccinimide ester (7.0mmol) in tetrahydrofuran, adding the tetrahydrofuran into a sodium bicarbonate aqueous solution containing L-hydroxyproline, stirring until the solid is completely dissolved, heating to 40 ℃ and reacting for 12 hours to obtain the target compound N-stearoyl-L-hydroxyproline, wherein the molar ratio of stearic acid-N-hydroxysuccinimide ester to L-hydroxyproline to sodium bicarbonate is 1: 1.1: 1.
4. the non-aromatic luminescent small molecule/SiO of claim 12The preparation method of the hybrid fluorescent nano material is characterized by comprising the following steps of:
dissolving N-stearoyl-L-hydroxyproline (0.1mmol) in an ethanol/butanol mixed solution at room temperature, adding the solution into a potassium hydroxide aqueous solution, slowly stirring the solution for 30 minutes, adding ethyl orthosilicate (1.5mmol) and 3-aminopropyltriethoxysilane according to a certain molar ratio in the process of self-assembling the N-stearoyl-L-hydroxyproline to form an aggregate, heating the mixture to 70 ℃, and hydrolyzing a siloxane prepolymer and performing polycondensation on the surface of the molecular aggregate under the initiation of ammonium persulfate to obtain a silicon substrate coated N-stearoyl-L-hydroxyproline aggregate nanostructure, namely a non-aromatic luminescent micromolecule/SiO2Hybrid fluorescent nanomaterials.
5. The method of claim 3, wherein the stearic acid is lauric acid, myristic acid, palmitic acid, or the like.
6. The method of claim 3, wherein the L-hydroxyproline is L-proline, or the like.
7. The non-aromatic luminescent small molecule/SiO of claim 42The preparation method of the hybrid fluorescent nano material is characterized in that siloxane precursors, ethyl orthosilicate and 3-aminopropyltriethoxysilane in a sol-gel reaction are adjusted according to the molar ratio of 1:0, 1:1, 2:1, 3:2 and 3: 1.
8. The non-aromatic luminescent small molecule/SiO of claim 42The hybridized fluorescent nano material is characterized in that the post-treatment of the prepared fluorescent nano material comprises the following steps: centrifugally washing, and vacuum freeze-drying.
9. The non-aromatic luminescent small molecule/SiO of claim 12The application of the hybridized fluorescent nano material is characterized in that the fluorescent nano material can be practically applied to the fields of chemical sensing, photoelectric materials, potential fingerprint visual detection, biological fluorescent probes, biological imaging and the like.
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Citations (5)
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|---|---|---|---|---|
| US4208421A (en) * | 1971-09-16 | 1980-06-17 | Lauzanne Morelle Eliane | Therapeutic compositions for the treatment of connective tissues diseases |
| WO1996018600A1 (en) * | 1994-12-14 | 1996-06-20 | Lifegroup S.P.A. | Amides of mono and bicarboxylic acids with amino acids or glycosamines, selectively active on the cannabinoid peripheral receptor |
| DE10341234A1 (en) * | 2003-09-08 | 2005-03-24 | Symrise Gmbh & Co. Kg | Novel N-acyl-hydroxyamino acid alkylamides with a ceramide-like structure are useful in compositions used for protection of skin or hair |
| CN1986402A (en) * | 2006-12-07 | 2007-06-27 | 上海交通大学 | Mesoporous silica tube in homogeneous diameter and its preparing process |
| CN105315990A (en) * | 2015-12-01 | 2016-02-10 | 北京工业大学 | Method for preparing organic-inorganic hybrid fluorescent mesoporous silica nanometer material |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4208421A (en) * | 1971-09-16 | 1980-06-17 | Lauzanne Morelle Eliane | Therapeutic compositions for the treatment of connective tissues diseases |
| WO1996018600A1 (en) * | 1994-12-14 | 1996-06-20 | Lifegroup S.P.A. | Amides of mono and bicarboxylic acids with amino acids or glycosamines, selectively active on the cannabinoid peripheral receptor |
| DE10341234A1 (en) * | 2003-09-08 | 2005-03-24 | Symrise Gmbh & Co. Kg | Novel N-acyl-hydroxyamino acid alkylamides with a ceramide-like structure are useful in compositions used for protection of skin or hair |
| CN1986402A (en) * | 2006-12-07 | 2007-06-27 | 上海交通大学 | Mesoporous silica tube in homogeneous diameter and its preparing process |
| CN105315990A (en) * | 2015-12-01 | 2016-02-10 | 北京工业大学 | Method for preparing organic-inorganic hybrid fluorescent mesoporous silica nanometer material |
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