CN108489970A - Electrochemical luminescence reagent and its application prepared by a kind of macrocyclic compound - Google Patents
Electrochemical luminescence reagent and its application prepared by a kind of macrocyclic compound Download PDFInfo
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Abstract
The electrochemical luminescence reagent prepared the invention discloses a kind of macrocyclic compound and its application, it is simple that this law invents electrochemical luminescence reagent operation prepared by the macrocyclic compound, it takes short, its application can detect polycyclic aromatic hydrocarbon (naphthalene, pyrene, anthracene, it is luxuriant and rich with fragrance, 9.10 benzophenanthrene triphenylenes), it is different from currently used chromatography detection condensed-nuclei aromatics, and the macrocyclic compound has cavity structure, it is different from common electrochemical luminescence substance (such as luminol simultaneously, tris (bipyridine) ruthenium etc.), a kind of new electrochemical luminescence substance is developed, new developing direction is provided for the research and application of big ring host-guest chemistry compound and electrochemical luminescence.
Description
Technical field
The present invention relates to electrochemical luminescence field, electrochemical luminescence reagent prepared by especially a kind of macrocyclic compound and its
Using.
Background technology
Electrochemical luminescence (Electrochemiluminescence, ECL), also known as electrogenerated chemiluminescence, are chemiluminescences
The product be combineding with each other with electrochemical method refers to generating some special substances by electrochemical method, and then these electricity are raw
A kind of luminescence phenomenon for reacting between substance or further and generating between electric biomass and other substances；Electrochemiluminescence analysis
For method other than having many advantages, such as that high sensitivity, the range of linearity are wide possessed by chemiluminometry and device is simple, it can also
The shortcomings that overcoming in the presence of chemiluminometry, if chemical illuminating reagent is not easy to maintain or unstable under given conditions,
It is difficult to realize time and control spatially so that chemical illuminating reagent is difficult to reuse and solution mixes uneven institute
The shortcomings of reproducibility brought is relatively poor, therefore, in recent years, electrochemical luminescence becomes the hot spot of research.
Condensed-nuclei aromatics (PAHs) is a subclass of polycyclc aromatic compound, is the organic compound of generally existing in environment
Object.Condensed-nuclei aromatics be essentially from mankind's activity (such as fossil-fuel-fired, biomass combustion, culinary art and smoking) organic matter not
It is formed when completely burned.It is known they there is carcinogenicity and genotoxicity, and cause angiocardiopathy in zooscopy.At present
Polycyclic aromatic hydrocarbon usually is detected with chromatography, but its sample preparation is difficult, time-consuming, and analysis cost is high.
Invention content
The electrochemical luminescence reagent prepared the object of the present invention is to provide a kind of macrocyclic compound and its application.It is described
Reagent operation is simple, it is short to take, and can to polycyclic aromatic hydrocarbon (naphthalene, pyrene, anthracene, phenanthrene, 9.10- benzophenanthrenes triphenylene) examine
It surveys.A kind of new electrochemical luminescence substance has been developed simultaneously.
Technical scheme of the present invention：A kind of electrochemical luminescence reagent prepared by macrocyclic compound, the macrocyclic compound
Chemical formula is：C60H60N12O6, structural formula is：
The electrochemical luminescence reagent is prepared：Use Al2O3Polishing powder polishing glass-carbon electrode is cleaned, is dried, by big ring
It is compound-modified on the electrode to get.
In electrochemical luminescence reagent prepared by macrocyclic compound above-mentioned, the electrochemical luminescence reagent is prepared：It takes
3-7 μ l a concentration of 1 × 10-5The macrocyclic compound solution of mol/l, coated on the glass-carbon electrode cleaned up, wait for solvent volatilize
Afterwards, then take 3-7 μ l macrocyclic compound solution, coated on the glass-carbon electrode cleaned up, be repeated 10 times to get.
In electrochemical luminescence reagent prepared by macrocyclic compound above-mentioned, polycyclic aromatic hydrocarbon is detected.
In electrochemical luminescence reagent prepared by macrocyclic compound above-mentioned, the polycyclic aromatic hydrocarbon be naphthalene, pyrene, anthracene, phenanthrene,
Or 9.10- benzophenanthrene triphenylenes.
The application of electrochemical luminescence reagent prepared by macrocyclic compound above-mentioned, it is described that polycyclic aromatic hydrocarbon is examined
It surveys, specifically includes following steps：
1. with acetontrile at a concentration of 1.0 × 10-15mol/L-1.0×10-5Mol/L to polycyclic aromatic hydrocarbon solution；
2. by electrochemical luminescence reagent and step 1. in polycyclic aromatic hydrocarbon solution stirring at normal temperature 20-30min, dry,
Obtain for use electrode；
3. by step 2. in for use electrode measured in electrochemical luminescence tester, you can, electrochemical luminescence
The detection parameters of tester are：Potential range is 0-1.6V, sweep speed 50mv/s.
In the application of electrochemical luminescence reagent prepared by macrocyclic compound above-mentioned, the macrocyclic compound is mainly by pressing weight
1-3 parts of 2- hydroxybenzimidazoles, 0.1-0.5 parts of the tetrabutylammonium bromide that part calculates are measured, and the toluene 40- calculated by parts by volume
1-3 parts of 60 parts, 10-30 parts of 40% sodium hydroxide solution and iodomethane are made in the steps below：
(1) 2- hydroxybenzimidazoles, tetrabutylammonium bromide, toluene, 40% sodium hydroxide solution and iodomethane are mixed,
It is heated 19 hours at 60-80 DEG C, obtains A product；
(2) A product, hydrochloric acid solution and pure formic acid are mixed, obtains B product；
(3) formalin of a concentration of 30-50% is added into B product, stirs evenly, obtains C product；
(4) C product stir 4-6 hours under room temperature, white precipitate occur, obtain D product；
(5) D product filter, washed successively with methanol, dichloromethane, dry, obtain white solid to get.
In the application of electrochemical luminescence reagent prepared by macrocyclic compound above-mentioned, in step (2), the hydrochloric acid solution is dense
Degree is 4-8mol/L, adds 10-15ml hydrochloric acid solutions and the pure formic acid of 3-6ml per 300mg 2- hydroxybenzimidazoles.
In the application of electrochemical luminescence reagent prepared by macrocyclic compound above-mentioned, in step (3), the 30-50%'s
The addition of formalin is with the molar ratio of A product and formaldehyde for 1:10-12 is calculated.
In the application of electrochemical luminescence reagent prepared by macrocyclic compound above-mentioned, the macrocyclic compound is mainly by pressing weight
Measure part calculate 2 parts of 2- hydroxybenzimidazoles, 0.24 part of tetrabutylammonium bromide, and by parts by volume calculate 50 parts of toluene,
2 parts of 40% 20 parts of sodium hydroxide solution and iodomethane are made.
Compared with prior art, this law invents that electrochemical luminescence reagent operation prepared by the macrocyclic compound is simple, consumption
When it is short, application can detect polycyclic aromatic hydrocarbon (naphthalene, pyrene, anthracene, phenanthrene, 9.10- benzophenanthrenes triphenylene), be different from common at present
Chromatography detect condensed-nuclei aromatics, and the macrocyclic compound has cavity structure, while being different from common electrochemical luminescence
Substance (such as luminol, tris (bipyridine) ruthenium) has developed a kind of new electrochemical luminescence substance, is big ring host-guest chemistry chemical combination
The research and application of object and electrochemical luminescence provide new developing direction.
Description of the drawings：
Fig. 1 (a) is the cyclic voltammogram of macrocyclic compound, and Fig. 1 (b) is its electrochemical luminescence figure；
Fig. 2 (a) is the electrochemical luminescence figure for being modified with object 9.10- benzophenanthrene triphenylenes；(b) it is ECL intensity and object
9.10- benzophenanthrenes Sanya benzene concentration bears logarithmic curve chart.
With reference to embodiment and Figure of description, the present invention is further illustrated.
Specific implementation mode
The chemical formula of a kind of macrocyclic compound, the macrocyclic compound is C60H60N12O6, structural formula is：
Embodiment 1
The chemical formula of a kind of macrocyclic compound, the macrocyclic compound is C60H60N12O6, structural formula is：
The synthetic method of the macrocyclic compound, is synthesized in the steps below：
(1) by 2- hydroxybenzimidazoles (2g, 0.015mol), tetrabutylammonium bromide (0.24g, 0.75mmol), toluene
50mL, 40% sodium hydroxide solution 20mL and iodomethane (2mL, 0.032mol) heat 19 hours at 60-80 DEG C, obtain A product；
(2) A product, hydrochloric acid solution and formic acid are mixed, obtains B product；
(3) a concentration of 40% formalin is added into B product, stirs evenly, obtains C product；
(4) C product stir 5 hours under room temperature, white precipitate occur, obtain D product；
(5) D product filter, washed successively with methanol, dichloromethane, dry, obtain white solid to get.
The concentration of hydrochloric acid solution is 6mol/L, adds 10ml hydrochloric acid solutions and 5ml pure per 300mg 2- hydroxybenzimidazoles
Formic acid；The addition of described 40% formalin is with the molar ratio of A product and formaldehyde for 1:11 amount calculates.
The electrochemical luminescence reagent prepared with above-mentioned macrocyclic compound, specifically includes：
(1) Al is used2O3Polishing powder polishing glass-carbon electrode is cleaned, is dried, and takes 5ul a concentration of 1.0 × 10-5The big ring of mol/l
Compound solution then takes 5ul macrocyclic compound solution, dries coated on the glass-carbon electrode cleaned up, waiting for that solvent volatilizees,
It is repeated 10 times, obtains modified glassy carbon electrode；
(2) it is to electrode with platinum filament using conventional three-electrode system, glass-carbon electrode (GCE, Φ=3mm) is working electrode,
For Ag/AgCl as reference electrode, buffer solution is 0.1mol/l 4- hydroxyethyl piperazineethanesulfonic acids and 0.1mol/l sodium hydroxides
Volume ratio is 1:1 mixed solution, pH=12.0；
(3) the result is shown in Figure 1 observes at+1.1v there is oxidation peak appearance, and is generated along with electrochemical luminescence phenomenon.
Embodiment 2：
(1) acetontrile 1.0 × 10 is used-5mol/l、1.0×10-6mol/l…1.0×10-14mol/l、1.0×10- 15Above-mentioned each polycyclic aromatic hydrocarbon solution of mol/l isoconcentrations；
(2) by the glass-carbon electrode for being modified with macrocyclic compound and each polycyclic aromatic hydrocarbon stirring at normal temperature in above-mentioned steps (1)
25min dries, for use；
(3) for use electrode in above-mentioned steps (2) is measured in electrochemical luminescence tester；
(4) data completed will be measured to map, as a result sees Fig. 2, wherein Fig. 2 (b), find 9.10- benzophenanthrenes triphenylene visitor
The electrochemical luminescence of the macrocyclic compound is not quenched in body completely, remaining object is quenched completely.
Claims (9)
1. electrochemical luminescence reagent prepared by a kind of macrocyclic compound, it is characterised in that：The chemical formula of the macrocyclic compound is：
C60H60N12O6, structural formula is：
The electrochemical luminescence reagent is prepared：Use Al2O3Polishing powder polishing glass-carbon electrode is cleaned, is dried, and will be cyclized conjunction greatly
Object modification on the electrode to get.
2. electrochemical luminescence reagent prepared by macrocyclic compound as described in claim 1, it is characterised in that：The electrochemistry hair
Light reagent is prepared：Take 3-7 μ l a concentration of 1 × 10-5The macrocyclic compound solution of mol/l, coated in the glass carbon cleaned up
On electrode, after the solvent is volatilized, then 3-7 μ l macrocyclic compound solution is taken, coated on the glass-carbon electrode cleaned up, repeats 10
It is secondary to get.
3. the application of electrochemical luminescence reagent prepared by macrocyclic compound as claimed in claim 1 or 2, it is characterised in that：It is right
Polycyclic aromatic hydrocarbon is detected.
4. the application of electrochemical luminescence reagent prepared by macrocyclic compound as claimed in claim 3, it is characterised in that：Described
Polycyclic aromatic hydrocarbon is naphthalene, pyrene, anthracene, phenanthrene or 9.10- benzophenanthrene triphenylenes.
5. the application of electrochemical luminescence reagent prepared by macrocyclic compound as claimed in claim 3, it is characterised in that：Described
Polycyclic aromatic hydrocarbon is detected, following steps are specifically included：
1. with acetontrile at a concentration of 1.0 × 10-15mol/L-1.0×10-5Mol/L to polycyclic aromatic hydrocarbon solution；
2. by electrochemical luminescence reagent and step 1. in polycyclic aromatic hydrocarbon solution stirring at normal temperature 20-30min, dry, must wait for
Use electrode；
3. by step 2. in for use electrode measured in electrochemical luminescence tester, you can, electrochemical luminescence test
The detection parameters of instrument are：Potential range is 0-1.6V, sweep speed 50mv/s.
6. the application of electrochemical luminescence reagent prepared by macrocyclic compound as claimed in claim 5, it is characterised in that：It is described big
Cycle compound mainly by calculate by weight 1-3 parts of 2- hydroxybenzimidazoles, 0.1-0.5 parts of tetrabutylammonium bromide, and press
1-3 parts of 40-60 parts of toluene, 10-30 parts of 40% sodium hydroxide solution and the iodomethane that parts by volume calculates are made in the steps below：
(1) 2- hydroxybenzimidazoles, tetrabutylammonium bromide, toluene, 40% sodium hydroxide solution and iodomethane are mixed, in 60-
It is heated 19 hours at 80 DEG C, obtains A product；
(2) A product, hydrochloric acid solution and pure formic acid are mixed, obtains B product；
(3) formalin of a concentration of 30-50% is added into B product, stirs evenly, obtains C product；
(4) C product stir 4-6 hours under room temperature, white precipitate occur, obtain D product；
(5) D product filter, washed successively with methanol, dichloromethane, dry, obtain white solid to get.
7. the application of electrochemical luminescence reagent prepared by macrocyclic compound as claimed in claim 6, it is characterised in that：Step
(2) in, the concentration of hydrochloric acid solution is 4-8mol/L, adds 10-15ml hydrochloric acid solutions and 3- per 300mg 2- hydroxybenzimidazoles
The pure formic acid of 6ml.
8. the application of electrochemical luminescence reagent prepared by macrocyclic compound as claimed in claim 6, it is characterised in that：Step
(3) in, the addition of the formalin of the 30-50% is with the molar ratio of A product and formaldehyde for 1:10-12 is calculated.
9. the application of electrochemical luminescence reagent prepared by macrocyclic compound as claimed in claim 6, it is characterised in that：It is described big
Cycle compound mainly by calculate by weight 2 parts of 2- hydroxybenzimidazoles, 0.24 part of tetrabutylammonium bromide, and press parts by volume
2 parts of 50 parts of toluene, 20 parts of 40% sodium hydroxide solution and the iodomethane of calculating are made.
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2018
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| US6284756B1 (en) * | 1998-04-30 | 2001-09-04 | Eli Lilly And Company | Antithrombotic agents |
| JP2005298483A (en) * | 2004-03-17 | 2005-10-27 | National Institute Of Advanced Industrial & Technology | Iridium complex and luminous material using the same |
| CN1950958A (en) * | 2004-05-04 | 2007-04-18 | 默克专利有限公司 | Organic electronic devices |
| CN102040562A (en) * | 2010-11-18 | 2011-05-04 | 南京信息工程大学 | Macrocyclic aromatic-amine structured compound as well as preparation method and application thereof |
| CN103808781A (en) * | 2014-01-24 | 2014-05-21 | 宁波大学 | Method for fixing electrochemical luminophor on surface of electrode |
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