CN110358064A - A kind of transmitting fluorescent polymer preparation of non-conjugated systems and test method - Google Patents

A kind of transmitting fluorescent polymer preparation of non-conjugated systems and test method Download PDF

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CN110358064A
CN110358064A CN201910624630.9A CN201910624630A CN110358064A CN 110358064 A CN110358064 A CN 110358064A CN 201910624630 A CN201910624630 A CN 201910624630A CN 110358064 A CN110358064 A CN 110358064A
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concentration
wavelength
fluorescence
polylactic acid
test method
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CN110358064B (en
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江金强
高钰梅
李果
刘昭铁
刘忠文
陈建刚
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Shaanxi Normal University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66Polyesters containing oxygen in the form of ether groups
    • C08G63/664Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78Preparation processes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14Macromolecular compounds
    • C09K2211/1441Heterocyclic
    • C09K2211/145Heterocyclic containing oxygen as the only heteroatom
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N2021/6417Spectrofluorimetric devices
    • G01N2021/6419Excitation at two or more wavelengths

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
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  • Biochemistry (AREA)
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  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
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  • Polyesters Or Polycarbonates (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention discloses a kind of transmitting fluorescent polymer preparation of non-conjugated systems and test methods, weigh DEXTROSE ANHYDROUS, lactide, stannous octoate Sn (Oct)2In flask, toluene dissolution is added, 140 DEG C of points of water flow back 24 hours, instill in anhydrous ether and recrystallize after reaction solution concentration, filter, and obtained solid is dried in vacuo 12 hours, obtains brown solid;The brown solid of preparation is dissolved in DMF solution, polymer solution is configured, and tests fluorescence pattern from low concentration to high concentration.The invention has the benefit that using glucose as polyhydroxy center, a series of different polylactic acid of molecular weight has been synthesized using different feed ratios, test the change in fluorescence under various concentration, with the movement of excitation wavelength, launch wavelength shows regular variation, new test method is provided for the detection of ideal green high molecular material polylactic acid, has especially expanded macromolecular self-assembly medicine-carried system significantly using polylactic acid as the test mode of the Micelle-like Nano-structure of Two of block.

Description

A kind of transmitting fluorescent polymer preparation of non-conjugated systems and test method
Technical field
The present invention relates to fluorescent polymer preparation technical fields, in particular to a kind of non-conjugated systems to emit fluorescent polymer Preparation and test method.
Background technique
Luminous organic material applies such as photoelectric device due to unique photophysical property and widely, and chemistry or biology are visited Needle and bio-imaging field and be concerned.In addition to traditional conjugated organic compounds, there are also some without classical chromophore ratio Such as the non-traditional luminescent material of aromatic rings.In these materials, segment is flexible and the adjustable non-conjugated polymeric object of structure is because of its tool There are important basic meaning and wide application prospect and causes the great interest of people.These polymer usually contain electron rich Hetero atom such as N, O, S etc..Compared with traditional conjugated material, they, which have, prepares simple, environmental-friendly, good biocompatibility etc. Advantage is very suitable to biomedical applications.
Polylactic acid has superior comprehensive performance as ideal Green Polymer Material, and production process is pollution-free, tool There are good biocompatibility and biodegradable, terminal catabolite is mainly water and carbon dioxide, intermediate product lactic acid It is also internal normal sugar metabolism product, there is biological safety.It has been widely used and biological medicine, electronics, daily primary The every field such as sex aids.
In general, longer excitation and launch wavelength make light be easier to penetrate thicker sample, this facilitates in vivo Experiment.Meanwhile longer excitation wavelength is smaller to the adverse effect of cell and tissue in biological sample.However, unconventional Luminescent material is usually in blue and green area transmitting.Although they usually show and excite related luminescence generated by light, several Without finding effective yellow and red emission.Therefore, synthesis can emit the non-traditional of red spectral band under certain condition Fluorescent material is most important for exploring Fluorescence Mechanism fluorescent emission rule.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the above technological deficiencies, and it is poly- to provide a kind of non-conjugated systems transmitting fluorescence Close object preparation and test method.
In order to achieve the above object of the invention, the technical solution adopted by the present invention are as follows: a kind of non-conjugated systems transmitting fluorescence is poly- Object preparation and test method are closed, centered on polyhydroxy compound glucose, connects polyester based polyalcohol polylactic acid, it is a series of poly- Close object organic solution have characteristic fluorescence peak, using glucose be polyhydroxy center polylactic acid synthesize, specifically the preparation method is as follows: Weigh DEXTROSE ANHYDROUS, lactide, stannous octoate Sn (Oct)2In flask, toluene dissolution is added, 140 DEG C of points of water reflux 24 are small When, it instills in anhydrous ether and recrystallizes after reaction solution concentration, filter, obtained solid is dried in vacuo 12 hours, obtains brown solid;
Fluorometric investigation method is as follows: the brown solid of preparation being dissolved in DMF solution, gradually dilution configures each concentration polymerization Object solution, and fluorescence pattern, entrance slit 1.75nm, exit slit 1.25nm, excitation are tested from low concentration to high concentration Wavelength is 380nm, and launch wavelength is 425nm and 485nm.
Further, the DEXTROSE ANHYDROUS, lactide, stannous octoate Sn (Oct)2Feed ratio be (1:70:0.35) or (1:120:0.6) or (1:180:0.9) or (1:240:1.2) or (1:300:1.5).
Further, fluorescence exciting wavelength is in 380nm, and launch wavelength is in 425nm and 485nm, when fluorescence intensity reaches peak After value, as concentration increases, fluorescent emission intensity reduces and red shift of wavelength.
Further, excitation wavelength moves to 600nm from 400nm, and launch wavelength moves to 660nm from 500nm, occur red shift and Fluorescence intensity is reduced with the red shift of excitation wavelength, and fluorescent emission moves to red band by green band.
The invention has the benefit that having been synthesized using different feed ratios a series of using glucose as polyhydroxy center The different polylactic acid of molecular weight tests the change in fluorescence under various concentration using sepectrophotofluorometer, with excitation wavelength Mobile, launch wavelength shows regular variation, provides new test for the detection of ideal green high molecular material polylactic acid Method has especially expanded macromolecular self-assembly medicine-carried system using polylactic acid as the test mode of the Micelle-like Nano-structure of Two of block significantly.
Detailed description of the invention
Fig. 1 is polylactic acid nuclear-magnetism figure;
Fig. 2 is DEXTROSE ANHYDROUS, lactide, 2 feed ratio of Sn (Oct) are 1:70:0.35 products therefrom in λ ex=380nm Concentration dilution fluorescence pattern;
Fig. 3 is DEXTROSE ANHYDROUS, lactide, Sn (Oct)2Feed ratio is 1:70:0.35 products therefrom in concentration 6mg/mL Excitation wavelength is incremented by fluorescence pattern;
Fig. 4 is DEXTROSE ANHYDROUS, lactide, 2 feed ratio of Sn (Oct) are 1:120:0.6 products therefrom in λ ex=380nm Concentration dilution fluorescence pattern;
Fig. 5 is DEXTROSE ANHYDROUS, lactide, Sn (Oct)2Feed ratio is 1:120:0.6 products therefrom in concentration 10mg/mL Excitation wavelength is incremented by fluorescence pattern.
Fig. 6 is DEXTROSE ANHYDROUS, lactide, 2 feed ratio of Sn (Oct) are 1:180:0.9 products therefrom in λ ex=380nm Concentration dilution fluorescence pattern;
Fig. 7 is DEXTROSE ANHYDROUS, lactide, Sn (Oct)2Feed ratio is 1:180:0.9 products therefrom in concentration 10mg/mL Excitation wavelength is incremented by fluorescence pattern;
Fig. 8 is DEXTROSE ANHYDROUS, lactide, 2 feed ratio of Sn (Oct) are 1:240:1.2 products therefrom in λ ex=380nm Concentration dilution fluorescence pattern;
Fig. 9 is DEXTROSE ANHYDROUS, lactide, Sn (Oct)2Feed ratio is 1:240:1.2 products therefrom in concentration 20mg/mL Excitation wavelength is incremented by fluorescence pattern.
Figure 10 is DEXTROSE ANHYDROUS, lactide, 2 feed ratio of Sn (Oct) are 1:300:1.5 products therefrom in λ ex=380nm Concentration dilution fluorescence pattern;
Figure 11 is DEXTROSE ANHYDROUS, lactide, Sn (Oct)2Feed ratio is 1:300:1.5 products therefrom in concentration 20mg/ ML excitation wavelength is incremented by fluorescence pattern.
Specific embodiment
In order that the present invention can be more clearly and readily understood, following will be combined with the drawings in the embodiments of the present invention, Technical scheme in the embodiment of the invention is clearly and completely described.
Embodiment 1
Fluorescence polylactic acid preparation: DEXTROSE ANHYDROUS, lactide, stannous octoate Sn (Oct) can be emitted2Molar ratio is 1:70: 0.35;DEXTROSE ANHYDROUS, lactide, stannous octoate Sn (Oct) are weighed by above-mentioned molar ratio2In flask, a small amount of toluene is added Dissolution, 140 DEG C of points of water flow back 24 hours.It instills in anhydrous ether and recrystallizes after reaction solution concentration, filter, obtained solid vacuum is dry Dry 12 hours, brown solid is obtained, nuclear-magnetism characterization is shown in Fig. 1.
The 0.1g brown solid prepared is dissolved in 5mLDMF solution, concentration 10mg/mL, gradually dilution configures each concentration Polymer solution, and the test fluorescence pattern from low concentration to high concentration, entrance slit 1.75nm, exit slit 1.25nm, Excitation wavelength is 380nm, and launch wavelength is 425nm and 485nm, determines that fluorescence intensity maximum concentration is 6mg/mL, in the concentration Under, increase with excitation wavelength, launch wavelength red shift and fluorescence intensity reduction are specifically shown in Fig. 2, Fig. 3.
Embodiment 2
Fluorescence polylactic acid preparation: DEXTROSE ANHYDROUS, lactide, stannous octoate Sn (Oct) can be emitted2Molar ratio is 1:120: 0.6, DEXTROSE ANHYDROUS, lactide, stannous octoate Sn (Oct) are weighed by above-mentioned molar ratio2In flask, it is molten that a small amount of toluene is added Solution, 140 DEG C of points of water flow back 24 hours.It instills in anhydrous ether and recrystallizes after reaction solution concentration, filter, obtained solid vacuum drying 12 hours, obtain brown solid.
The 0.3g brown solid prepared is dissolved in 5mLDMF solution, concentration 60mg/mL, gradually dilution configures each concentration Polymer solution, and the test fluorescence pattern from low concentration to high concentration, entrance slit 1.75nm, exit slit 1.25nm, Excitation wavelength is 380nm, and launch wavelength is 425nm and 485nm, determines that fluorescence intensity maximum concentration is 10mg/mL, in the concentration Under, increase with excitation wavelength, launch wavelength red shift and fluorescence intensity reduction are specifically shown in Fig. 4, Fig. 5.
Embodiment 3
Fluorescence polylactic acid preparation: DEXTROSE ANHYDROUS, lactide, stannous octoate Sn (Oct) can be emitted2Molar ratio is 1:180: 0.9, DEXTROSE ANHYDROUS, lactide, stannous octoate Sn (Oct) are weighed by above-mentioned molar ratio2In flask, it is molten that a small amount of toluene is added Solution, 140 DEG C of points of water flow back 24 hours.It instills in anhydrous ether and recrystallizes after reaction solution concentration, filter, obtained solid vacuum drying 12 hours, obtain brown solid.
The 0.3g brown solid prepared is dissolved in 5mLDMF solution, concentration 60mg/mL, gradually dilution configures each concentration Polymer solution, and the test fluorescence pattern from low concentration to high concentration, entrance slit 1.75nm, exit slit 1.25nm, Excitation wavelength is 380nm, and launch wavelength is 425nm and 485nm, determines that fluorescence intensity maximum concentration is 10mg/mL, in the concentration Under, increase with excitation wavelength, launch wavelength red shift and fluorescence intensity reduction are specifically shown in Fig. 6, Fig. 7.
Embodiment 4
Fluorescence polylactic acid preparation: DEXTROSE ANHYDROUS, lactide, stannous octoate Sn (Oct) can be emitted2Molar ratio is 1:240: 1.2, DEXTROSE ANHYDROUS, lactide, stannous octoate Sn (Oct) are weighed by above-mentioned molar ratio2In flask, it is molten that a small amount of toluene is added Solution, 140 DEG C of points of water flow back 24 hours.It instills in anhydrous ether and recrystallizes after reaction solution concentration, filter, obtained solid vacuum drying 12 hours, obtain brown solid.
The 0.5g brown solid prepared is dissolved in 5mLDMF solution, concentration 100mg/mL, gradually dilution configuration is each dense Polymer solution is spent, and tests fluorescence pattern, entrance slit 1.75nm from low concentration to high concentration, exit slit is 1.25nm, excitation wavelength 380nm, launch wavelength are 425nm and 485nm, determine that fluorescence intensity maximum concentration is 20mg/mL, Under the concentration, increase with excitation wavelength, launch wavelength red shift and fluorescence intensity reduction are specifically shown in Fig. 8, Fig. 9.
Embodiment 5
Fluorescence polylactic acid preparation: DEXTROSE ANHYDROUS, lactide, stannous octoate Sn (Oct) can be emitted2Molar ratio is 1:300: 1.5, DEXTROSE ANHYDROUS, lactide, stannous octoate Sn (Oct) are weighed by above-mentioned molar ratio2In flask, it is molten that a small amount of toluene is added Solution, 140 DEG C of points of water flow back 24 hours.It instills in anhydrous ether and recrystallizes after reaction solution concentration, filter, obtained solid vacuum drying 12 hours, obtain brown solid.
The 0.5g brown solid prepared is dissolved in 5mLDMF solution, concentration 100mg/mL, gradually dilution configuration is each dense Polymer solution is spent, and tests fluorescence pattern, entrance slit 1.75nm from low concentration to high concentration, exit slit is 1.25nm, excitation wavelength 380nm, launch wavelength are 425nm and 485nm, determine that fluorescence intensity maximum concentration is 20mg/mL, Under the concentration, increase with excitation wavelength, launch wavelength red shift and fluorescence intensity reduction are specifically shown in Figure 10, Figure 11.
Mechanism of the present invention is: when polymer is excited in weak solution, emitted energy is consumed by internal molecular motion, is caused glimmering Luminous intensity is weaker, even without fluorescence.With the increase of concentration, polymer chain is close to each other, and intertwine with each other, and greatly increases The aggregation of carbonyl.Assemble lone pair electrons and pi-electron interaction and overlapping in cluster, generates spatial conjugation, fluorescence intensity is big Big enhancing.When concentration further increases, strand is gradually fixed, and carbonyl aggregation cannot effectively occur, and fluorescence intensity is gradually Weaken.The result is that fluorescence intensity, which presents, first enhances the trend weakened afterwards with the increase of polyester liquid concentration.Since multi-arm is poly- Lactic acid structure, the generation of spatial conjugation depends on the aggregation between molecular end carbonyl, identical when polymer molecular weight is smaller Molecular number is more under mass concentration, therefore mass concentration needed for reaching identical fluorescence intensity is smaller.
The present invention and its embodiments have been described above, this description is no restricted, only reality of the invention One of mode is applied, actual embodiment is not limited thereto.All in all if those skilled in the art are opened by it Show, without departing from the spirit of the invention, not inventively designs structure side similar with the technical solution Formula and embodiment, are within the scope of protection of the invention.

Claims (4)

1. a kind of non-conjugated systems transmitting fluorescent polymer preparation and test method, it is characterised in that: with polyol Portugal Centered on grape sugar, polyester based polyalcohol polylactic acid is connected, a series of organic solution of polymer has characteristic fluorescence peak, with grape Sugar is that polyhydroxy center polylactic acid synthesizes, it is specific the preparation method is as follows:
Weigh DEXTROSE ANHYDROUS, lactide, stannous octoate Sn (Oct)2In flask, toluene dissolution is added, 140 DEG C of points of water flow back It 24 hours, instills in anhydrous ether and recrystallizes after reaction solution concentration, filter, obtained solid is dried in vacuo 12 hours, obtains brown Solid;
Fluorometric investigation method is as follows: the brown solid of preparation being dissolved in DMF solution, gradually it is molten to configure each concentration polymer for dilution Liquid, and fluorescence pattern, entrance slit 1.75nm, exit slit 1.25nm, excitation wavelength are tested from low concentration to high concentration For 380nm, launch wavelength is 425nm and 485nm.
2. a kind of non-conjugated systems transmitting fluorescent polymer preparation according to claim 1 and test method, feature exist In: the DEXTROSE ANHYDROUS, lactide, stannous octoate Sn (Oct)2Feed ratio be (1:70:0.35) or (1:120:0.6) or (1:180:0.9) or (1:240:1.2) or (1:300:1.5).
3. a kind of non-conjugated systems transmitting fluorescent polymer preparation according to claim 1 and test method, feature exist In: fluorescence exciting wavelength is in 380nm, and launch wavelength is in 425nm and 485nm, after fluorescence intensity reaches peak value, as concentration increases Greatly, fluorescent emission intensity reduction and red shift of wavelength.
4. a kind of non-conjugated systems transmitting fluorescent polymer preparation according to claim 1 and test method, feature exist In: excitation wavelength moves to 600nm from 400nm, and launch wavelength moves to 660nm from 500nm, and red shift occurs and fluorescence intensity is with sharp It sends out the red shift of wavelength and reduces, fluorescent emission moves to red band by green band.
CN201910624630.9A 2019-07-11 2019-07-11 Preparation and test method of non-conjugated system emission fluorescent polymer Expired - Fee Related CN110358064B (en)

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CN114736363A (en) * 2022-05-17 2022-07-12 常州大学 Fluorescent polymer and method for regulating and controlling luminescent color of fluorescent polymer

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