CN104449673B - The preparation method of the nitric oxide fluorescence polymer probe of item chain - Google Patents
The preparation method of the nitric oxide fluorescence polymer probe of item chain Download PDFInfo
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- CN104449673B CN104449673B CN201410690730.9A CN201410690730A CN104449673B CN 104449673 B CN104449673 B CN 104449673B CN 201410690730 A CN201410690730 A CN 201410690730A CN 104449673 B CN104449673 B CN 104449673B
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Abstract
The present invention relates to the preparation method of the nitric oxide fluorescence polymer probe of a chain, the method specifically includes following steps: utilize the adjacent diamines of the fragrance containing hydroxyl as the compound that can introduce 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, it is thus achieved that main chain is continuously or part mounts the high molecular polymer fluorescence probe of fluorogen.Compared with prior art, the inventive method is simple, and cost is relatively low, and it is many that the probe of preparation can contact site with NO molecule, and detection efficiency is high, and detection sensitiveness is high, and the efficient in-situ investigation for NO has huge using value.
Description
Technical field
The invention belongs to macromolecular material, medicine and fluorescent probe technique field, be specifically related to an oxygen of a kind of chain
Change the preparation of nitrogen fluorescence polymer probe.
Background technology
Nitric oxide (nitric oxide, NO), as a kind of gas radicals molecule in organism, has character and lives
Sprinkle, the life-span short, occur chemical reaction rapid, easily with the feature such as other material or group are combined, play biology messenger molecule
Role, it is possible to quickly spread in cell and tissue, and then react with biological targets.Based on this, outer spy in vivo
Surveying NO is a challenging job, a kind of efficient NO detection method of development, it is possible to realize in real time, fast and accurately
NO detection is one of study hotspot in recent years.In existing NO detection method, compare electrochemical process, ultraviolet-visible spectrum
The method such as method and electron spin resonance, fluorescence method has the advantages such as highly sensitive, simple to operate and real-time.Due to NO
Molecule itself does not have fluorescence signal, and the principle of NO fluorescence probe is by introducing fluorogen reagent and NO reaction bonded, produces
The compound bigger with fluorescence probe own optical nature difference, carrys out qualitative and quantitative detection NO according to the change of photoluminescent property.
In existing organic molecule NO fluorescence probe, o-phenylenediamine class and metal ion match fluorescence is mainly had to divide
The sub-big class of probe two.Although these molecular probes all have good selectivity and selectivity, but in actual NO detection, visit
The fluorescence of needle body system is easily affected by himself concentration and detection environment, and (such as, solvent, pH, temperature, ionic strength etc. cause glimmering
Photobleaching).At present, develop a kind of have high sensitivity, selectivity and bio-compatible and hypotoxicity in one NO fluorescence probe
Become an important topic of association area.
Poly-alkyl acrylic (ester), as conventional high molecular polymer, has potential application at numerous areas, especially
It is to have attracted wide attention at the application potential of material and pharmaceutical field.Photoelectron effect according to o-phenylenediamine class
(PET) principle, a kind of item chain high molecular fluorescent body of design detects for NO, can develop into the efficient spy of fluorescence in situ detection
Pin.Comparing conventional NO organic molecule probe, it is high that item chain high molecular fluorescent body has fluorescence intensity, the position that NO molecule can contact
Point is many, and detection sensitiveness is high, and the efficient in-situ investigation of NO is had huge using value.
At present, there is not yet a chain high molecular fluorescent body and be combined formation compound, and NO based on this compound with NO
The report of relevant Chinese patent prepared by fluorescence probe.Therefore, prepare a chain high molecular fluorescent body, develop NO fluorescence in situ
Detection, these researchs are a significant job predictive of the preparation of this special NO probe, are also currently associated research
In key technical problem urgently to be resolved hurrily.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and provide a kind of simple to operate, cost
Relatively low, can efficiently detect NO, have the nitric oxide fluorescence high score of the item chain of applications well prospect at biomedicine field
The preparation method of sub-probe.
The purpose of the present invention can be achieved through the following technical solutions: the nitric oxide fluorescence polymer probe of item chain
Preparation method, it is characterised in that the method specifically includes following steps: utilize the adjacent diamines of the fragrance containing hydroxyl as drawing
Enter the compound of NO fluoroscopic examination group, using poly-alkyl acrylic or polyalkyl acrylate as high molecular fluorescent probe master
Chain, introduces high molecular fluorescent probe main chain by NO fluoroscopic examination group, carries out esterification in the presence of a catalyst, it is thus achieved that main chain
Continuously or partly mount the high molecular polymer fluorescence probe of fluorogen.
The compound of described introduced NO fluoroscopic examination group is first dissolved in alcoholic solution before participating in esterification, is configured to
It is the solution of 0.01g/ml for mass concentration, during with polyalkyl acrylate for high molecular fluorescent probe main chain, uses hydroxide
The alcoholic solution of this compound is regulated to alkalescence by sodium；During with poly-alkyl acrylic for high molecular fluorescent probe main chain, use sulfuric acid
The alcoholic solution of this compound is regulated to acid.
It is 1 in molar ratio that described high molecular fluorescent probe main chain can introduce the compound of NO fluoroscopic examination group: (1～
5) esterification is carried out.
The structural formula of the described adjacent diamines of the fragrance containing hydroxyl includes:
Wherein CxHy should be conjugated system with the aromatic ring at adjacent diamines place.
Described poly-alkyl acrylic or the structural formula of polyalkyl acrylate are 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 catalyst is sulfuric acid or NaOH, and consumption is poly-alkyl acrylic or polyalkyl acrylate weight
0～2%.
The temperature of described esterification is 15～100 DEG C, and the reaction time is 10～96h.
Prepared high molecular polymer fluorescence probe is reacted with NO, obtains the fluorescence in backbone portion esterification unit
The adjacent diamine groups of fragrance of group generates BTA with NO, and due to PET effect, this high molecular polymer fluorescence probe is combined with NO
After, Fluorescence Increasing or excitation wavelength generation red shift；
Reaction equation is as follows:
Compared with prior art, the present invention comprises the adjacent diaminourea aromatic of active organic group and poly-alkyl
Acid (ester), is combined by organic reaction, builds the item chain Polymer Systems containing multiple adjacent diaminourea groups, measures this body
It it is the relation between fluorescence intensity and NO concentration, it is thus achieved that NO fluorescence probe based on this system.Compared with prior art, the present invention
Method is simple, and cost is relatively low, and it is high that the probe of preparation has fluorescence intensity, and it is many that NO molecule can contact site, and detection sensitiveness is high, right
Efficient in-situ investigation in NO has huge using value.
Detailed description of the invention
Preparation method based on the high molecular nitric oxide fluorescent probe of item chain, enters the present invention below in conjunction with specific embodiment
Row describes in detail.
Embodiment 1
In 500ml there-necked flask, polymethyl methacrylate 12.1g is dissolved in 200ml ethyl acetate wiring solution-forming, keeps
Temperature 60-80 DEG C is also stirred vigorously.The 50ml methyl alcohol that ortho-diaminobenzene phenol 0.5g is dissolved in is made solution, regulates with NaOH
PH is slowly added dropwise to the ethyl acetate solution of alkaline backward polymethyl methacrylate, reacts 48-96h, obtains polymethyl
Acid methyl esters and the block polymer of ortho-diaminobenzene phenolic ester.In this polymer, it is passed through NO solution, measures under different NO concentration
The fluorescence intensity of this system, thus build based on this chain high molecular NO fluorescence probe.
Embodiment 2
In 500ml there-necked flask, polymethylacrylic acid 12.1g is dissolved in 200ml ethyl acetate wiring solution-forming, keeps temperature
60-80 DEG C and be stirred vigorously.The 50ml methyl alcohol that ortho-diaminobenzene phenol 0.5g is dissolved in is made solution, with concentrated sulfuric acid regulation pH to acid
It is slowly added dropwise to the ethyl acetate solution of polymethyl methacrylate after property, reacts 48-96h, obtain polymethylacrylic acid with adjacent
The block polymer of diaminophenol esterification.Being passed through NO solution in this polymer, under the different NO concentration of mensuration, this system is glimmering
Luminous intensity, thus build based on this chain high molecular NO fluorescence probe.
Embodiment 3
In 500ml there-necked flask, PMA 12.1g is dissolved in 200ml ethyl acetate wiring solution-forming, keeps temperature
60-80 DEG C and be stirred vigorously.The 50ml methyl alcohol that ortho-diaminobenzene phenol 0.5g is dissolved in is made solution, with NaOH regulation pH extremely
The ethyl acetate solution of the backward PMA of alkalescence is slowly added dropwise, and reacts 48-96h, obtains PMA and adjacent two
The block polymer of amino-phenol esterification.In this polymer, it is passed through NO solution, measures the fluorescence of this system under different NO concentration
Intensity, thus build based on this chain high molecular NO fluorescence probe.
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 be stirred vigorously.The 50ml methyl alcohol that ortho-diaminobenzene phenol 0.5g is dissolved in is made solution, after concentrated sulfuric acid regulation pH to acidity
It is slowly added dropwise to polyacrylic ethyl acetate solution, reacts 48-96h, obtain polyacrylic acid and ortho-diaminobenzene phenolic ester
Block polymer.In this polymer, it is passed through NO solution, measures the fluorescence intensity of this system under different NO concentration, thus build base
In this chain high molecular NO fluorescence probe.
The preparation method of the item chain nitric oxide fluorescence polymer probe with poly-alkyl acrylic as main chain, the method has
Body comprises the following steps:
(1) utilize the adjacent diamines of fragrance containing hydroxyl as the compound of NO fluoroscopic examination group can be introduced, it is molten
In methyl alcohol, preparation becomes the solution that mass concentration is 0.01g/ml, then with sulfuric acid regulation to acid, with poly-alkyl acrylic
As high molecular fluorescent probe main chain, it is 1: 1 at catalyst in molar ratio by high molecular fluorescent probe main chain and fragrance neighbour's diamines
Carrying out esterification in the presence of sulfuric acid, the consumption of sulfuric acid is the 2% of poly-alkyl acrylic weight.The temperature of esterification be 60～
100 DEG C, the reaction time is 70～96h.Continuously or part mounts the high molecular polymer fluorescence probe of fluorogen to obtain main chain.
The structural formula of the described adjacent diamines of the fragrance containing hydroxyl includes:
Wherein CxHy should be conjugated system with the aromatic ring at adjacent diamines place.
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) prepared high molecular polymer fluorescence probe is reacted with NO, obtain in backbone portion esterification unit
The adjacent diamine groups of fragrance of fluorogen generates BTA, due to PET effect, this high molecular polymer fluorescence probe and NO with NO
After in conjunction with, Fluorescence Increasing or excitation wavelength generation red shift.
The preparation method of the item chain nitric oxide fluorescence polymer probe with poly-alkyl acrylic acid ester as main chain, the method
Specifically include following steps:
(1) utilize the adjacent diamines of fragrance containing hydroxyl as the compound of NO fluoroscopic examination group can be introduced, it is molten
In methyl alcohol, preparation becomes the solution that mass concentration is 0.01g/ml, then with NaOH regulation to alkalescence, with poly-alkyl third
Diluted acid ester as high molecular fluorescent probe main chain, by high molecular fluorescent probe main chain and fragrance neighbour's diamines be in molar ratio 1: 5
Carrying out esterification in the presence of catalyst NaOH, the consumption of NaOH is the 1% of poly-alkyl acrylic acid ester weight.Esterification
The temperature of reaction is 90～100 DEG C, and the reaction time is 10～30h.Continuously or part mounts the macromolecule of fluorogen to obtain main chain
Polymer fluorescent probe.
The structural formula of the described adjacent diamines of the fragrance containing hydroxyl includes:
Wherein CxHy should be conjugated system with the aromatic ring at adjacent diamines place.
Described poly-alkyl acrylic or the structural formula of polyalkyl acrylate are as follows:
Wherein, R is alkyl, and R ' is alkyl, and its concentration is 50wt%, and molecular weight is 4000～5000.
(2) prepared high molecular polymer fluorescence probe is reacted with NO, obtain in backbone portion esterification unit
The adjacent diamines fluorophor of fragrance generates BTA with NO, and due to PET effect, this high molecular polymer fluorescence probe is combined with NO
After, Fluorescence Increasing or excitation wavelength generation red shift.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should be regarded as
Protection scope of the present invention.
Claims (5)
1. the preparation method of the nitric oxide fluorescence polymer probe of a chain, it is characterised in that the method specifically includes following
Step: utilize ortho-diaminobenzene phenol as the compound of NO fluoroscopic examination group can be introduced, with poly-alkyl acrylic or poly-alkane
NO fluoroscopic examination group, as high molecular fluorescent probe main chain, is introduced high molecular fluorescent probe main chain, is urging by base acrylate
Esterification is carried out, it is thus achieved that main chain is continuously or part mounts the high molecular polymer fluorescence probe of fluorogen in the presence of agent.
The preparation method of the nitric oxide fluorescence polymer probe of the most according to claim 1 chain, it is characterised in that
Described poly-alkyl acrylic or the structural formula of polyalkyl acrylate are as follows:
Wherein, R is alkyl, R '=alkyl or hydrogen.
The preparation method of the nitric oxide fluorescence polymer probe of the most according to claim 1 and 2 chain, its feature exists
In, described poly-alkyl acrylic or polyalkyl acrylate concentration are 10～50wt%, and molecular weight is 500～5000.
The preparation method of the nitric oxide fluorescence polymer probe of the most according to claim 1 chain, it is characterised in that
Described catalyst is sulfuric acid or NaOH, and consumption is poly-alkyl acrylic or the 0 of polyalkyl acrylate weight～2%.
The preparation method of the nitric oxide fluorescence polymer probe of the most according to claim 1 chain, it is characterised in that
The temperature of described esterification is 15～100 DEG C, and the reaction time is 10～96h.
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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 |
-
2014
- 2014-11-25 CN CN201410690730.9A patent/CN104449673B/en not_active Expired - Fee Related
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 |
|---|
| Reactions of Nitric Oxide with Amines in the Presence of Dioxygen;Tetsuo Nagano et al.;《Tetrahedron Letters》;19951230;第36卷(第45期);8239-8242 * |
| 一氧化氮荧光分子探针;张灯青等;《化学进展》;20080930;第20卷(第9期);1396-1405 * |
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