CN103159879A - Preparation method of fluorescent molecular thermometer with wide temperature response range and fluorescence intensity heightening as temperature rise - Google Patents
Preparation method of fluorescent molecular thermometer with wide temperature response range and fluorescence intensity heightening as temperature rise Download PDFInfo
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- CN103159879A CN103159879A CN2013100458693A CN201310045869A CN103159879A CN 103159879 A CN103159879 A CN 103159879A CN 2013100458693 A CN2013100458693 A CN 2013100458693A CN 201310045869 A CN201310045869 A CN 201310045869A CN 103159879 A CN103159879 A CN 103159879A
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- XOLVVFSHDULKRS-UHFFFAOYSA-N CC(C)CCCC(C)C(CC1)C(C)(CC2)C1C1C2C(C)(CCC(C2)OC(C(C)Cl)=O)C2=CC1 Chemical compound CC(C)CCCC(C)C(CC1)C(C)(CC2)C1C1C2C(C)(CCC(C2)OC(C(C)Cl)=O)C2=CC1 XOLVVFSHDULKRS-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of a fluorescent molecular thermometer with a wide temperature response range and fluorescence intensity heightening as temperature rise and belongs to the technical field of fluorescence detection. In the prior art, a temperature response range is narrow, fluorescence intensity gradually reduces as the temperature rise. The preparation method is characterized in that at first cholesterol-based is adopted to combine an ATRP initiator; then the initiator is adopted to initiate NIPAM to take place an ATRP polymerization to obtain modified PNIPAM; the third step, the modified PNIPAM is served as a substrate to mutually react with rare earth element europium or rare earth element terbium or rare earth element erbium and micromolecule ligand TTA, and the generated coordination compound is the fluorescent molecular thermometer which is wide in temperature response range and fluorescence intensity heightening as the temperature rise.
Description
Technical field
The present invention relates to a kind of temperature and ring wide ranges fluorescence intensity following temperature rising enhancing fluorescence molecule thermometer preparation method, adopt the ATRP(Transfer Radical Polymerization) by end-functionalization by the PNIPAM(poly N-isopropyl acrylamide) carry out rare earth modified, utilize the fluorescence property of the rare earth elements such as the Thermo-sensitive of modification PNIPAM and europium, terbium, erbium, prepare the fluorescence molecule thermometer by " bonding coordination ", belong to the detection technique of fluorescence field.
Background technology
The advantages such as the fluorescence molecule thermometer is a kind of fluorescence thermometry in the detection technique of fluorescence field, compares with other thermometrys, and that the fluorescence thermometric has is highly sensitive, immunity from interference strong, response is fast, scope is wide.Yet, after the small molecules fluorescent substance enters test soln, owing to can't extracting separation, easily solution to be measured is polluted, can not reuse, water insoluble, and most of small molecules fluorescent substance all has certain toxicity.So should adopt the high molecular fluorescent material as the fluorescence molecule thermometer.
Prior art is all to prepare the high molecular fluorescent material by fluorescence radiation group is introduced to temperature sensitive polymer.Concrete grammar has two kinds: a kind of is that the small molecules fluorescent substance is made to initiator, then causes temperature sensitive monomer polymerization; Another kind is first to synthesize a kind of temperature sensitive polymer, then the small molecules fluorescent substance is reacted with this temperature sensitive polymer.Yet small molecules fluorescent substance solvability is very poor, and because it has certain toxicity meeting contaminated equipment, then have the separating-purifying that causes temperature sensitive monomer polymerization after product also more difficult.Described temperature sensitive polymer is a kind of linear polymer, its polymerization process is emulsion polymerization, the polymer architecture obtained is indefinite, molecular weight distribution is very wide and uncontrollable, and moisture sensitivity is difficult to meet the demands, and this has also limited it as the application for preparing fluorescence molecule thermometer material.
ATRP is a kind of of living polymerization method, and prepared molecular weight distribution is narrower and controlled.
PNIPAM is a kind of polymkeric substance with Thermo-sensitive, and prior art adopts the synthetic PNIPAM hydrogel of ATRP method, then, with the rare earth element coordination such as europium, prepares thus the high molecular fluorescent material, obtains accordingly a kind of PNIPAM of take as basic fluorescence molecule thermometer.But, because this scheme can't overcome the PNIPAM hydrogel at the LCST(lowest critical solution temperature) near strong volume change occurs, make the described PNIPAM of take can't in than large-temperature range, realize temperature response as basic fluorescence molecule thermometer.And, described PNIPAM of take the hydrogel form is the rising of basic fluorescence molecule thermometer along with temperature, fluorescence intensity reduces, and the fluorescence thermometry fluorescence molecule thermometer is required is that rising fluorescence intensity along with temperature raises, this has just limited take the application of PNIPAM as basic fluorescence molecule thermometer.
Summary of the invention
In order to realize temperature response in a big way, and the fluorescence molecule thermometer of the preparation fluorescence intensity of polymkeric substance within the specific limits strengthens gradually along with the rising of temperature, and we have invented a kind of preparation method containing europium modification poly N-isopropyl acrylamide class fluorescence molecule thermometer.
The present invention's temperature is rung wide ranges fluorescence intensity following temperature rising enhancing fluorescence molecule thermometer preparation method and be it is characterized in that, at first adopts cholesteryl to synthesize the ATRP initiator; Next adopts described initiator to cause NIPAM generation ATRP polymerization and obtains modification PNIPAM; The 3rd take modification PNIPAM as matrix, with rare earth elements europium, terbium or erbium and small molecules part TTA, interacts, and the title complex of generation is temperature and rings wide ranges fluorescence intensity following temperature rising enhancing fluorescence molecule thermometer.
Its technique effect of the present invention is, because modification PNIPAM has the hydrophobic end group of cholesteryl, under its impact, the LCST of modification PNIPAM obviously reduces; And modification PNIPAM has various molecular weights, with rare earth element and small molecules part TTA(α-thenoyltrifluoroacetone) after coordination, the LCST of the title complex of generation has multiple and forms a temperature range.Because rare earth element has excellent luminescent properties, introduce again small molecules part TTA, make the title complex of final product there is very strong fluorescence spectral characteristic emission peak, as produced stronger ruddiness under the 365nm ultraviolet lamp, and within 1 year, have no decline.Due to PNIPAM, in the process of temperature rising, occur to change mutually, its form is linearly changed to bulk by hydrophobic, make title complex present the trend that the rising fluorescence intensity along with temperature strengthens gradually, when reaching a certain temperature, fluorescence intensity no longer strengthens, reach a balance, this process is fairly obvious, be with the naked eye considerable finding, the final product that the present invention is described is a kind of fluoroscopic examination that realizes by being separated, and temperature is rung the fluorescence molecule thermometer of wide ranges, the enhancing of fluorescence intensity following temperature rising.
For example, adopt the present invention's method to prepare containing europium modification poly N-isopropyl acrylamide class fluorescence molecule thermometer, modification PNIPAM controllability wherein is good, molecular weight distribution is very narrow, heterogeneity index (PDI) is 1.06 ~ 1.12, much smaller than 1.2, that the LCST of complexes system distributes is wide, luminous intensity is high and stable.
The accompanying drawing explanation
Fig. 1 is NIPAM with the initiator amount of substance than being the modification PNIPAM of 1:50
1h NMR collection of illustrative plates.Fig. 2 ~ Fig. 4 is the fluorescence emission spectrum of the ternary complex (A, B, C) of different molecular weight successively, and wherein Fig. 4 is simultaneously as Figure of abstract.Fig. 5 is that the fluorescence emission spectrum of the ternary complex (A, B, C) of different molecular weight varies with temperature relation curve.
Embodiment
It is as follows that the present invention's temperature is rung wide ranges fluorescence intensity following temperature rising enhancing fluorescence molecule thermometer preparation method concrete scheme:
At first, adopt the synthetic ATRP initiator of cholesteryl.By cholesterol and methylene dichloride, be dissolved in respectively in triethylamine; the volume ratio of methylene dichloride and triethylamine is 7 ~ 8:1; the triethylamine solution of cholesterol, methylene dichloride is mixed; in ice bath, stir 10 ~ 60 minutes; the 2-chlorpromazine chloride that adds afterwards 1/5 ~ 3/5 amount of triethylamine volume; under room temperature, place 8 ~ 12 hours; add 10 ~ 20mL distilled water; after extraction, drying, purification; use the dehydrated alcohol recrystallization; at 35 ~ 45 ℃ of temperature, vacuum-drying is 2 ~ 4 days, obtains ATRP initiator 2-chlorine propionyl cholesterol, and it is stored in moisture eliminator.
The equation of the reaction occurred in said process is:
Secondly, adopt described initiator to cause NIPAM generation ATRP polymerization and obtain modification PNIPAM.Purification process NIPAM; for 1:25,1:50,1:400, NIPAM monomer and 2-chlorine propionyl cholesterol initiator are put into to W type Guan Yiduan by the amount of substance ratio respectively; be dissolved in DMF(N, dinethylformamide) in, initiator concentration now is respectively 41.7,20.8,2.6mg/mL.Then add the CuCl(cuprous chloride identical with the initiator amount of substance at middle pipe), in the DMF that to be dissolved in volume ratio be 1:1 and the mixing solutions of water, CuCl concentration now is respectively 25.0,12.5,1.6mg/mL, tightness system, logical nitrogen-freezing-twice of vacuumize-Tong nitrogen-thaw cycles.Inject the Me with initiator amount of substance same amount in middle pipe
6tREN part (three-(N, N-dimethylaminoethyl) amine), continue logical nitrogen 10 ~ 20 minutes, stirs, and logical nitrogen-freezing-vacuumize-Tong nitrogen-thaw.Solution in first pipe is poured in middle pipe, stirred, react 2 ~ 4 hours at 20 ~ 30 ℃ of temperature.Open W type pipe, the solution ingress of air finishes reaction.Solution is crossed to neutral alumina column, collect colourless solution, rotary evaporation is to a small amount of liquid is still arranged, this liquid slowly is added drop-wise in hexane solution, obtains precipitate, remove normal hexane, vacuum-drying, obtain modification PNIPAM, be respectively Ch-PNIPAM (A), Ch-PNIPAM (B), Ch-PNIPAM (C), molecular weight is about respectively 2550,6600,31600.A on curve in Fig. 1, b, c, d, e, f each point are consistent with corresponding chemical shift, confirm successful synthesis modification PNIPAM.
The equation of the reaction occurred in said process is:
The 3rd take modification PNIPAM as matrix, with rare earth element and small molecules part TTA, interacts, and the title complex of generation is temperature and rings wide ranges fluorescence intensity following temperature rising enhancing fluorescence molecule thermometer.Ch-PNIPAM (A), Ch-PNIPAM (B), Ch-PNIPAM (C) are placed in to tool plug bottle, respectively according to mass ratio Eu
3+: PNIPAM=0.07:1, mol ratio TTA:Eu
3+=2:1 pipettes respectively the EuCl of calculated amount with transfer pipet
3ethanolic soln and TTA ethanolic soln are to tool plug bottle, add the dehydrated alcohol constant volume, tool plug bottle is put into to 20 ~ 25 ℃ of water-bath stirring reactions 40 ~ 50 hours, after purified, vacuum-drying orange-yellow powdered product, be Eu (III)-Ch-PNIPAM (A)-TTA, Eu (III)-Ch-PNIPAM (B)-TTA, Eu (III)-Ch-PNIPAM (C)-TTA, product presents red fluorescence under the 365nm UV-irradiation, sees shown in Fig. 2 ~ Fig. 4.Described rare earth elements europium replaces with terbium or erbium is also content of the present invention.
Below illustrate the present invention's method.
Get the 5.17mmol cholesterol and be dissolved in the 15mL methylene dichloride, after all dissolving, add the 2.0mL triethylamine solution, stir half an hour in ice bath, inject the 8mmol2-chlorpromazine chloride with syringe, dropwise drip, the solution flavescence, start to have the yellow mercury oxide deposits yields, after dripping off, after question response heat is all emitted, move under room temperature, place an evening, in reaction process, color deepens gradually, has insolubles to occur simultaneously.After reaction finishes, add distilled water 20mL to dissolve, use twice of dichloromethane extraction; Add again the saturated sodium bicarbonate extracting twice; Again with saturated sodium chloride solution extraction; Finally use anhydrous sodium sulfate drying.Cross chromatography column and purify, solvent is methylene dichloride; Finally use twice, 40 ℃ of vacuum-drying of dehydrated alcohol recrystallization 3 days, obtain ATRP initiator 2-chlorine propionyl cholesterol, it is stored in moisture eliminator.
In NIPAM: the ratio that initiator equals 1:25,1:50,1:400 respectively by 100,50, the DMF of the NIPAM of 6.25mg initiator and 0.6g and 2.4mL is positioned over an end of W type pipe, fully stirring and dissolving, form white suspension.Middle pipe adds 20,10, the DMF of CuCl, the 0.4mL of 1.25mg and the H of 0.4mL
2o, stirring and dissolving.After sealing, under liquid nitrogen, vacuumize, rush nitrogen, circulate 2 times; Then add respectively 50,25,3.13 μ L part Me at middle pipe
6tREN, stir 10 minutes, and it is fully dissolved.Then vacuumize again, rush nitrogen, catalyzer, part are mixed with the two ends test tube of monomer, initiator.25 ℃ of lower polyase 13 h, then stop polymerization, by mixture THF(tetrahydrofuran (THF)) dilution, then peroxidation aluminium chromatography column is to remove copper complex.Finally revolve to steam and remove THF and DMF, then with a small amount of THF, dissolve, in normal hexane, precipitate twice, then polymkeric substance is placed on to vacuum-drying in 40 ℃ of vacuum drying ovens and obtains white solid Ch-PNIPAM (A), Ch-PNIPAM (B), Ch-PNIPAM (C) to constant weight in three days.
By Ch-PNIPAM (A), Ch-PNIPAM (B), Ch-PNIPAM (C) and EuCl
3and TTA coordination synthesizing series ternary complex.The Ch-PNIPAM that takes respectively the 50mg different molecular weight is placed in tool plug bottle, pipettes respectively the EuCl of 2.4mL with transfer pipet
3the TTA ethanolic soln of ethanolic soln and 4.1mL, to tool plug bottle, finally adds dehydrated alcohol to be settled to 10ml.Bottle is put into to 25 ℃ of water-bath stirring reactions 48 hours, after purified, vacuum-drying orange-yellow powder Eu (III)-Ch-PNIPAM (A)-TTA, Eu (III)-Ch-PNIPAM (B)-TTA, Eu (III)-Ch-PNIPAM (C)-TTA.
Finally the serial ternary complex of each 5mg is dissolved in respectively to the 5mL deionized water, is placed on magnetic stirring apparatus and is stirred to dissolving, be mixed with the aqueous solution of 1mg/mL, utilize the UV-1240 ultraviolet-visible pectrophotometer to survey its LCST.And heat up gradually in certain temperature range, take 352nm as excitation wavelength, record the fluorescence emission spectrum of Different Complex, see shown in Fig. 2 ~ Fig. 4, draw complex fluorescent emmission spectrum variation with temperature curve, as shown in Figure 5.
Claims (2)
1. a temperature is rung wide ranges fluorescence intensity following temperature rising enhancing fluorescence molecule thermometer preparation method, it is characterized in that, at first adopts cholesteryl to synthesize the ATRP initiator; Next adopts described initiator to cause NIPAM generation ATRP polymerization and obtains modification PNIPAM; The 3rd take modification PNIPAM as matrix, with rare earth elements europium, terbium or erbium and small molecules part TTA, interacts, and the title complex of generation is temperature and rings wide ranges fluorescence intensity following temperature rising enhancing fluorescence molecule thermometer.
2. temperature according to claim 1 is rung wide ranges fluorescence intensity following temperature rising enhancing fluorescence molecule thermometer preparation method, it is characterized in that, adopt the detailed process of the synthetic ATRP initiator of cholesteryl to be, by cholesterol and methylene dichloride, be dissolved in respectively in triethylamine, the volume ratio of methylene dichloride and triethylamine is 7 ~ 8:1, by cholesterol, the triethylamine solution of methylene dichloride mixes, in ice bath, stir 10 ~ 60 minutes, the 2-chlorpromazine chloride that adds afterwards 1/5 ~ 3/5 amount of triethylamine volume, under room temperature, place 8 ~ 12 hours, add 10 ~ 20mL distilled water, through extraction, dry, after purification, use the dehydrated alcohol recrystallization, at 35 ~ 45 ℃ of temperature, vacuum-drying is 2 ~ 4 days, obtain ATRP initiator 2-chlorine propionyl cholesterol, the equation of the reaction occurred in said process is:
The detailed process that adopts described initiator initiation NIPAM generation ATRP polymerization to obtain modification PNIPAM is, purification process NIPAM, press respectively amount of substance than being 1:25, 1:50, 1:400 puts into W type Guan Yiduan by NIPAM monomer and 2-chlorine propionyl cholesterol initiator, be dissolved in DMF, initiator concentration now is respectively 41.7, 20.8, 2.6mg/mL, add the CuCl identical with the initiator amount of substance at middle pipe, in the DMF that to be dissolved in volume ratio be 1:1 and the mixing solutions of water, CuCl concentration now is respectively 25.0, 12.5, 1.6mg/mL, tightness system, logical nitrogen-freezing-twice of vacuumize-Tong nitrogen-thaw cycles, inject the Me with initiator amount of substance same amount in middle pipe
6the TREN part, continue logical nitrogen 10 ~ 20 minutes, stir, logical nitrogen-freezing-vacuumize-Tong nitrogen-thaw, solution in first pipe is poured in middle pipe, stir, at 20 ~ 30 ℃ of temperature, react 2 ~ 4 hours, open W type pipe, the solution ingress of air finishes reaction, solution is crossed to neutral alumina column, collect colourless solution, rotary evaporation is to a small amount of liquid is still arranged, by this liquid, slowly be added drop-wise in hexane solution, obtain precipitate, remove normal hexane, vacuum-drying, obtain modification PNIPAM, be respectively Ch-PNIPAM (A), Ch-PNIPAM (B), Ch-PNIPAM (C), the equation of the reaction occurred in said process is:
The modification PNIPAM of take be matrix and rare earth element and small molecules part TTA interact the title complex that generates be temperature ring detailed process that wide ranges fluorescence intensity following temperature rising strengthens the fluorescence molecule thermometer as, Ch-PNIPAM (A), Ch-PNIPAM (B), Ch-PNIPAM (C) are placed in to tool plug bottle, respectively according to mass ratio Eu
3+: PNIPAM=0.07:1, mol ratio TTA:Eu
3+=2:1 pipettes respectively the EuCl of calculated amount with transfer pipet
3ethanolic soln and TTA ethanolic soln are to tool plug bottle, add the dehydrated alcohol constant volume, tool plug bottle is put into to 20 ~ 25 ℃ of water-bath stirring reactions 40 ~ 50 hours, after purified, vacuum-drying orange-yellow powdered product, be Eu (III)-Ch-PNIPAM (A)-TTA, Eu (III)-Ch-PNIPAM (B)-TTA, Eu (III)-Ch-PNIPAM (C)-TTA, the equation of the reaction occurred in said process is:
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| CN106432348A (en) * | 2016-09-05 | 2017-02-22 | 南京邮电大学 | Visible light excitable ratio fluorescence thermosensitive probe based on europium complex and preparation method and application of probe |
| CN109187449A (en) * | 2018-07-26 | 2019-01-11 | 中认英泰检测技术有限公司 | Environmental response type Intelligent sensing device and the preparation method and application thereof |
| CN109540331A (en) * | 2018-11-08 | 2019-03-29 | 中国科学院理化技术研究所 | A kind of wide-range fluorescence nano thermometer and preparation method thereof based on cocktail type Nanoscale assemblies |
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| WO2020019238A1 (en) * | 2018-07-26 | 2020-01-30 | 中认英泰检测技术有限公司 | Environmental-responsive smart sensing device and preparation method and use thereof |
| CN109540331A (en) * | 2018-11-08 | 2019-03-29 | 中国科学院理化技术研究所 | A kind of wide-range fluorescence nano thermometer and preparation method thereof based on cocktail type Nanoscale assemblies |
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Application publication date: 20130619 |