CN104449673A - Preparation method of necklace-shaped nitric oxide fluorescent macromolecule probe - Google Patents
Preparation method of necklace-shaped nitric oxide fluorescent macromolecule probe Download PDFInfo
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- CN104449673A CN104449673A CN201410690730.9A CN201410690730A CN104449673A CN 104449673 A CN104449673 A CN 104449673A CN 201410690730 A CN201410690730 A CN 201410690730A CN 104449673 A CN104449673 A CN 104449673A
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Abstract
The invention relates to a preparation method of a necklace-shaped nitric oxide fluorescent macromolecule probe. The method specifically comprises the following steps: using aromatic adjacent diamine containing hydroxyl as a compound capable of introducing a NO (nitric oxide) fluorescent inspection group, using a poly alkyl acrylic acid or poly alkyl acrylic ester as a macromolecule fluorescent probe main chain, introducing the NO fluorescent inspection group into the macromolecule fluorescent probe main chain, and performing an esterification reaction under the existence of a catalyst so as to obtain a macromolecule polymer fluorescent probe of which the main chain is continuously or partially attached to a fluorescent group. Compared with the prior art, the method disclosed by the invention is simple, the cost is lower, many contactable sites of the prepared probe and NO molecules exist, the detection efficiency is high, the detection sensibility is high, and the method has a tremendous application value for efficient home position detection of NO.
Description
Technical field
The invention belongs to macromolecular material, medicine and fluorescent probe technique field, be specifically related to the preparation of the nitrogen protoxide fluorescence polymer probe of a kind of chain.
Background technology
Nitrogen protoxide (nitric oxide, NO) as a kind of gas radicals molecule in organism, have that character is active, the life-span is short, generation chemical reaction is rapid, easily with the feature such as other material or group are combined, play the role of biological messenger molecule, can in biological cells and tissues rapid diffusion, and then to react with biological targets.Based on this, outer detection NO is a challenging job in vivo, a kind of NO detection method efficiently of development, can realize in real time, one of NO detection is fast and accurately study hotspot in recent years.In existing NO detection method, compare the methods such as electrochemical process, ultravioletvisible spectroscopy and electron spin resonance, fluorescent method has the advantages such as highly sensitive, simple to operate and real-time.Because NO molecule itself does not have fluorescent signal, the principle of NO fluorescent probe is by introducing fluorophore reagent and NO reaction bonded, produces the compound larger with fluorescent probe own optical nature difference, carrys out quantitative and qualitative analysis detect NO according to the change of photoluminescent property.
In existing organic molecule NO fluorescent probe, mainly contain O-Phenylene Diamine class and the large class of metal ion match fluorescent molecular probe two.Although these molecular probes all have good selectivity and specificity, but in the NO detection of reality, the fluorescence of probe system is subject to the impact (such as, solvent, pH, temperature, ionic strength etc. cause fluorescent bleach) of himself concentration and acquisition environment.At present, develop and a kind of there is high sensitivity, selectivity and physiologically acceptable and hypotoxicity have become an association area important topic in the NO fluorescent probe of one.
Poly-alkyl acrylic (ester), as conventional high molecular polymer, has potential application at numerous areas, particularly attracts wide attention at the application potential of material and pharmaceutical field.According to photoelectron effect (PET) principle of O-Phenylene Diamine class, design a kind of item chain high molecular fluorescent body and detect for NO, the efficient probe of fluorescence in situ detection can be developed into.Compare conventional NO organic molecule probe, it is high that item chain high molecular fluorescent body has fluorescence intensity, and the site that NO molecule can contact is many, and detection susceptibility is high, has huge using value to the efficient in-situ investigation of NO.
At present, there is not yet a chain high molecular fluorescent body and be combined with NO and form mixture, and the report of the relevant Chinese patent prepared based on the NO fluorescent probe of this mixture.Therefore, prepare a chain high molecular fluorescent body, the detection of development NO fluorescence in situ, these researchs are a significant job predictive of the preparation of this special NO probe, are also key technical problems urgently to be resolved hurrily in current correlative study.
Summary of the invention
Object of the present invention is exactly provide a kind of simple to operate to overcome defect that above-mentioned prior art exists, cost is lower, efficiently can detect NO, have the preparation method of the nitrogen protoxide fluorescence polymer probe of the item chain of applications well prospect at biomedicine field.
Object of the present invention can be achieved through the following technical solutions: the preparation method of the nitrogen protoxide fluorescence polymer probe of item chain, it is characterized in that, the method specifically comprises the following steps: utilize the adjacent diamines of the fragrance containing hydroxyl as the compound introducing NO fluoroscopic examination group, using poly-alkyl acrylic or polyalkyl acrylate as high molecular fluorescent probe main chain, NO fluoroscopic examination group is introduced high molecular fluorescent probe main chain, carry out esterification in the presence of a catalyst, obtain main chain high molecular polymer fluorescent probe that is continuous or partly mounting fluorophore.
First be dissolved in alcoholic solution before the compound participation esterification of described introduced NO fluoroscopic examination group, preparation becomes the solution that mass concentration is 0.01g/ml, when taking polyalkyl acrylate as high molecular fluorescent probe main chain, adopt sodium hydroxide that the alcoholic solution of this compound is adjusted to alkalescence; During with poly-alkyl acrylic for high molecular fluorescent probe main chain, adopt sulfuric acid that the alcoholic solution of this compound is adjusted to acidity.
The compound that described high molecular fluorescent probe main chain can introduce NO fluoroscopic examination group is 1 in molar ratio: (1 ~ 5) carries out esterification.
The structural formula of the adjacent diamines of the described fragrance containing hydroxyl comprises:
Wherein the aromatic ring at CxHy and adjacent diamines place should be conjugated system.
Described poly-alkyl acrylic or the structural formula of polyalkyl acrylate as follows:
Wherein, R is alkyl, R '=alkyl or hydrogen.
Described poly-alkyl acrylic or polyalkyl acrylate concentration are 10 ~ 50wt%, and molecular weight is 500 ~ 5000.
Described catalyzer is sulfuric acid or sodium hydroxide, and consumption is 0 ~ 2% of poly-alkyl acrylic or polyalkyl acrylate weight.
The temperature of described esterification is 15 ~ 100 DEG C, and the reaction times is 10 ~ 96h.
Obtained high molecular polymer fluorescent probe and NO are reacted, the adjacent diamine groups of fragrance and the NO that obtain the fluorophore in backbone portion esterification unit generate benzotriazole, due to PET effect, after this high molecular polymer fluorescent probe is combined with NO, Fluorescence Increasing or excitation wavelength generation red shift;
Reaction formula is as follows:
Compared with prior art, the present invention comprises adjacent diamino aromatic compound and the poly-alkyl acrylic (ester) of active organic group, combined by organic reaction, build the item chain Polymer Systems containing multiple adjacent diamino group, measure the relation between this system fluorescence intensity and NO concentration, obtain the NO fluorescent probe based on this system.Compared with prior art, the inventive method is simple, and cost is lower, and it is high that the probe of preparation has fluorescence intensity, and it is many that NO molecule can contact site, and detection susceptibility is high, and the efficient in-situ investigation for NO has huge using value.
Embodiment
Based on the method for making of the high molecular nitric oxide fluorescent probe of item chain, below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
In 500ml there-necked flask, polymethylmethacrylate 12.1g is dissolved in 200ml ethyl acetate wiring solution-forming, keeps temperature 60-80 DEG C and vigorous stirring.The 50ml methyl alcohol that ortho-diaminobenzene phenol 0.5g is dissolved in is made solution, pH is regulated slowly to drip to the ethyl acetate solution of alkaline backward polymethylmethacrylate with sodium hydroxide, reaction 48-96h, obtains the block polymer of polymethylmethacrylate and ortho-diaminobenzene phenolic ester.In this polymkeric substance, pass into NO solution, the fluorescence intensity of this system under mensuration different N O concentration, thus build based on the high molecular NO fluorescent probe of this chain.
Embodiment 2
In 500ml there-necked flask, polymethyl acrylic acid 12.1g is dissolved in 200ml ethyl acetate wiring solution-forming, keeps temperature 60-80 DEG C and vigorous stirring.The 50ml methyl alcohol that ortho-diaminobenzene phenol 0.5g is dissolved in is made solution, pH is regulated slowly to drip to the ethyl acetate solution of acid backward polymethylmethacrylate with the vitriol oil, reaction 48-96h, obtains the block polymer of polymethyl acrylic acid and ortho-diaminobenzene phenolic ester.In this polymkeric substance, pass into NO solution, the fluorescence intensity of this system under mensuration different N O concentration, thus build based on the high molecular NO fluorescent probe of this chain.
Embodiment 3
In 500ml there-necked flask, polymethyl acrylate 12.1g is dissolved in 200ml ethyl acetate wiring solution-forming, keeps temperature 60-80 DEG C and vigorous stirring.The 50ml methyl alcohol that ortho-diaminobenzene phenol 0.5g is dissolved in is made solution, pH is regulated slowly to drip to the ethyl acetate solution of alkaline backward polymethyl acrylate with sodium hydroxide, reaction 48-96h, obtains the block polymer of polymethyl acrylate and ortho-diaminobenzene phenolic ester.In this polymkeric substance, pass into NO solution, the fluorescence intensity of this system under mensuration different N O concentration, thus build based on the high molecular NO fluorescent probe of this chain.
Embodiment 4
In 500ml there-necked flask, polyacrylic acid 12.1g is dissolved in 200ml ethyl acetate wiring solution-forming, keeps temperature 60-80 DEG C and vigorous stirring.The 50ml methyl alcohol that ortho-diaminobenzene phenol 0.5g is dissolved in is made solution, and regulate pH slowly to drip to acid backward polyacrylic ethyl acetate solution with the vitriol oil, reaction 48-96h, obtains the block polymer of polyacrylic acid and ortho-diaminobenzene phenolic ester.In this polymkeric substance, pass into NO solution, the fluorescence intensity of this system under mensuration different N O concentration, thus build based on the high molecular NO fluorescent probe of this chain.
The preparation method of the item chain nitrogen protoxide fluorescence polymer probe being main chain with poly-alkyl acrylic, the method specifically comprises the following steps:
(1) utilize the adjacent diamines of the fragrance containing hydroxyl as the compound can introducing NO fluoroscopic examination group, be dissolved in preparation in methyl alcohol and become the solution that mass concentration is 0.01g/ml, then acidity is adjusted to sulfuric acid, using poly-alkyl acrylic as high molecular fluorescent probe main chain, be catalyst sulfuric acid exist under carry out esterification at 1: 1 in molar ratio by adjacent to high molecular fluorescent probe main chain and fragrance diamines, the consumption of sulfuric acid is 2% of poly-alkyl acrylic weight.The temperature of esterification is 60 ~ 100 DEG C, and the reaction times is 70 ~ 96h.Obtain main chain high molecular polymer fluorescent probe that is continuous or partly mounting fluorophore.
The structural formula of the adjacent diamines of the described fragrance containing hydroxyl comprises:
Wherein the aromatic ring at CxHy and adjacent diamines place should be conjugated system.
The structural formula of described poly-alkyl acrylic is as follows:
Wherein, R is alkyl, and its concentration is 10wt%, and molecular weight is 500 ~ 1000.
(2) obtained high molecular polymer fluorescent probe and NO are reacted, the adjacent diamine groups of fragrance and the NO that obtain the fluorophore in backbone portion esterification unit generate benzotriazole, due to PET effect, after this high molecular polymer fluorescent probe is combined with NO, Fluorescence Increasing or excitation wavelength generation red shift.
The preparation method of the item chain nitrogen protoxide fluorescence polymer probe being main chain with poly-alkyl acrylic acid ester, the method specifically comprises the following steps:
(1) utilize the adjacent diamines of the fragrance containing hydroxyl as the compound can introducing NO fluoroscopic examination group, be dissolved in preparation in methyl alcohol and become the solution that mass concentration is 0.01g/ml, then alkalescence is adjusted to sodium hydroxide, using poly-alkyl acrylic acid ester as high molecular fluorescent probe main chain, be catalyzer sodium hydroxide exist under carry out esterification at 1: 5 in molar ratio by adjacent to high molecular fluorescent probe main chain and fragrance diamines, the consumption of sodium hydroxide is 1% of poly-alkyl acrylic acid ester weight.The temperature of esterification is 90 ~ 100 DEG C, and the reaction times is 10 ~ 30h.Obtain main chain high molecular polymer fluorescent probe that is continuous or partly mounting fluorophore.
The structural formula of the adjacent diamines of the described fragrance containing hydroxyl comprises:
Wherein the aromatic ring at CxHy and adjacent diamines place should be conjugated system.
Described poly-alkyl acrylic or the structural formula of polyalkyl acrylate as follows:
Wherein, R is alkyl, and R ' is alkyl, and its concentration is 50wt%, and molecular weight is 4000 ~ 5000.
(2) obtained high molecular polymer fluorescent probe and NO are reacted, obtain the adjacent diamines fluorophor of fragrance in backbone portion esterification unit and NO generates benzotriazole, due to PET effect, after this high molecular polymer fluorescent probe is combined with NO, Fluorescence Increasing or excitation wavelength generation red shift.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (7)
1. the preparation method of the nitrogen protoxide fluorescence polymer probe of a chain, it is characterized in that, the method specifically comprises the following steps: utilize the adjacent diamines of the fragrance containing hydroxyl as the compound can introducing NO fluoroscopic examination group, using poly-alkyl acrylic or polyalkyl acrylate as high molecular fluorescent probe main chain, NO fluoroscopic examination group is introduced high molecular fluorescent probe main chain, carry out esterification in the presence of a catalyst, obtain main chain high molecular polymer fluorescent probe that is continuous or partly mounting fluorophore.
2. the preparation method of the nitrogen protoxide fluorescence polymer probe of according to claim 1 chain, is characterized in that, the structural formula of the adjacent diamines of the described fragrance containing hydroxyl comprises:
Wherein the aromatic ring at CxHy and adjacent diamines place should be conjugated system.
3. the preparation method of the nitrogen protoxide fluorescence polymer probe of according to claim 1 chain, is characterized in that, described poly-alkyl acrylic or the structural formula of polyalkyl acrylate as follows:
Wherein, R is alkyl, R '=alkyl or hydrogen.
4. the preparation method of the nitrogen protoxide fluorescence polymer probe of the item chain according to claim 1 or 3, it is characterized in that, described poly-alkyl acrylic or polyalkyl acrylate concentration are 10 ~ 50wt%, molecular weight is 500 ~ 5000.
5. the preparation method of the nitrogen protoxide fluorescence polymer probe of according to claim 1 chain, is characterized in that, described catalyzer is sulfuric acid or sodium hydroxide, and consumption is 0 ~ 2% of poly-alkyl acrylic or polyalkyl acrylate weight.
6. the preparation method of the nitrogen protoxide fluorescence polymer probe of according to claim 1 chain, is characterized in that, the temperature of described esterification is 15 ~ 100 DEG C, and the reaction times is 10 ~ 96h.
7. the preparation method of the nitrogen protoxide fluorescence polymer probe of according to claim 1 chain, it is characterized in that, obtained high molecular polymer fluorescent probe and NO are reacted, the adjacent diamine groups of fragrance and the NO that obtain the fluorophore in backbone portion esterification unit generate benzotriazole, due to PET effect, after this high molecular polymer fluorescent probe is combined with NO, Fluorescence Increasing or excitation wavelength generation red shift;
Reaction formula is as follows:
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302425A (en) * | 2008-05-26 | 2008-11-12 | 天津理工大学 | Fluorescent probe for detecting generation of nitric oxide and use thereof |
| CN102516606A (en) * | 2011-11-25 | 2012-06-27 | 上海交通大学 | Preparation method of nitrogen oxide donor - quantum dots compound |
| CN102585417A (en) * | 2012-01-04 | 2012-07-18 | 武汉理工大学 | Quantum dot/polymer composite nitric oxide fluorescent probe and preparation method thereof |
| CN103760143A (en) * | 2014-01-17 | 2014-04-30 | 上海交通大学 | Manufacture method of nitrogen oxide fluorescent probe based on necklace type gold nanoparticle self-assembling system |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302425A (en) * | 2008-05-26 | 2008-11-12 | 天津理工大学 | Fluorescent probe for detecting generation of nitric oxide and use thereof |
| CN102516606A (en) * | 2011-11-25 | 2012-06-27 | 上海交通大学 | Preparation method of nitrogen oxide donor - quantum dots compound |
| CN102585417A (en) * | 2012-01-04 | 2012-07-18 | 武汉理工大学 | Quantum dot/polymer composite nitric oxide fluorescent probe and preparation method thereof |
| CN103760143A (en) * | 2014-01-17 | 2014-04-30 | 上海交通大学 | Manufacture method of nitrogen oxide fluorescent probe based on necklace type gold nanoparticle self-assembling system |
Non-Patent Citations (2)
| Title |
|---|
| TETSUO NAGANO ET AL.: "Reactions of Nitric Oxide with Amines in the Presence of Dioxygen", 《TETRAHEDRON LETTERS》 * |
| 张灯青等: "一氧化氮荧光分子探针", 《化学进展》 * |
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