CN108440565A - A kind of luxuriant receptor of acridine imidazoles ring of naphthalene nucleus bridging and preparation method thereof and the identification application to iron ion and dihydrogen phosphate ions - Google Patents
A kind of luxuriant receptor of acridine imidazoles ring of naphthalene nucleus bridging and preparation method thereof and the identification application to iron ion and dihydrogen phosphate ions Download PDFInfo
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- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Abstract
Identification application the invention discloses a kind of preparation method of the luxuriant receptor of imidazoles ring of naphthalene nucleus bridging and its to iron ion and dihydrogen phosphate ions, belongs to ion detection field.The present invention is synthesized by highly dilution method, yield 39%.This receptor molecule is in H2O:CH3CN(3:7,v:V) identification Fe can be selected in system3+, minimum detection limit can reach 1.21 × 10‑5 M(0.678 mg/L).In CH3Identification H may be selected in the system of CN2PO4 −, H is not added2PO4 −The fluorescence emission peak that shows of receptor solution at 451 nm, when 20.0 equiv.H are added2PO4 −Afterwards, fluorescence emission peak is at 518 nm, and the fluorescence intensity after apparent red shift and red shift, which has occurred, in fluorescence emission peak also obviously weakens, and minimum detection limit can reach 4.27 × 10‑7 M (0.041 mg/L), therefore this receptor molecule can be used for Fe3+And H2PO4 −Fluorescence quickly detect.
Description
Technical field
The invention belongs to ion detection fields, and in particular to a kind of luxuriant receptor of imidazoles ring of naphthalene nucleus bridging and its preparation side
Method and identification application to iron ion and dihydrogen phosphate ions.
Background technology
The space structure and rigidity of receptor are an important factor for influencing Receptor recognition performance, due to the spy of the luxuriant receptor structure of ring
The flexibility of different property and combination, the performance of the luxuriant receptor of ring are better than open chain receptor.(a) Zhang D., Jiang X., Yang
H., Martinez A., Feng M., Dong Z., Gao G. Org. Biomol. Chem. 2013, 11, 3375–
3381. Fe3+The trace element most as content in human body, is primarily present in human body hemoglobin and liver, and take part in
The physiology courses such as redox reaction, electronics transfer and oxygen transportation are one of most important metal ions in biosystem,
Key effect is played in many physiology courses.(b) Liu X. J., Zhang M., Yang M. P., et al.Tetrahedron, 2015, 71, 8194-8199; (c) Duke R. M., Veale E. B., Pfeffer F. M.,
Kruger P. E., Gunnlaugsson T. Chem. Soc. Rev.2010, 39, 3936–3953. Fe3+ It is abnormal past
Toward the mark for being disease, such as anaemia, intelligence decline, arthritis, heart failure, diabetes and cancer.(d) Narayanaswamy
N., Govindaraju T. Sensors and Actuators B: Chemical. 2012, 161, 304–310. (e)
Xu J. H., Hou Y. M., Ma Q. J., Wu X. F., Wei X. J. Spectrochim Acta A Mol Biomol Spectrosc.2013, 112, 116–124.
Anion is also extremely important at numerous aspects, such as in life science, H2PO4 −It is considered taking part in metabolic process, letter
Number transduction and energy storage, and as DNA and RNA framework constructions basis.H2PO4 −Due to its unique property, receiving
The extensive concern of scholar.(f) Jadhav J. R., Bae C. H., Kim H. S.Tetrahedron letters.
2011, 52, 1623–1627. (g) Lee G. W., Singh N., Jung H. J., Jang D. O.Tetrahedron Letters.2009, 50, 807–810.
Imidazole ring it is luxuriant can with high selectivity with anion, cation or even bio-molecular interaction.(h) Molina P.,
Tárraga A., Otón F. Organic & Biomolecular Chemistry.2012, 10, 1711-1724. (i)
Zapata F., Caballero A., Tárraga A. The Journal of Organic Chemistry.2009,75, 162-169. (j) Zapata F., Caballero A., Espinosa A.Dalton Transactions.
2010, 39,5429-5431. imidazole rings are luxuriant can to pass through intermolecular a variety of weak interaction Selective recognition guest molecules
Son, and during Selective recognition object, the cavity size of acceptor molecule is empty to identifying that the type of object has a major impact
Chamber it is of different sizes, the object of identification is also different, when can be only mutually matched between Subjective and Objective, can be only achieved the purpose of identification, because
And the luxuriant receptor of ring is shown than open chain receptor better choice.
Invention content
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of luxuriant receptor of imidazoles ring of naphthalene nucleus bridging
Preparation method and its identification application to iron ion and dihydrogen phosphate ions, this receptor molecule alternative identify Fe3+With
H2PO4 −, to Fe3+Minimum detection limit can reach 1.21 × 10-5 M (0.678 mg/L), to H2PO4 −Minimum detection limit can
To reach 4.27 × 10-7 M (0.041 mg/L)。
For achieving the above object, the present invention adopts the following technical scheme that：
One, fluorescent probe molecule and its preparation
The acceptor molecule of the present invention, chemical name are：(12Z,52Z)-11H,51H-8,10- dioxas -3 (4,5)-acridine -1,5
(3,1)-diimidazole -3- bases -9 (2,7)-naphthalene cyclododecane -13,53Two hexafluorophosphates；Its structural formula is as follows：
。
Synthesis step：
The synthetic method of the luxuriant acceptor molecule of ring：Bis- (imidazoles ethyoxyl) the naphthalene raw materials of 2,7- have been synthesized according to known reference document first
Bis- (bromomethyl) the acridine raw materials 2 of 1 and 4,5-, (a) Zhang D., Jiang X., Yang H., Martinez A., Feng
M., Dong Z., Gao G. Org. Biomol. Chem. 2013, 11, 3375–3381. (k) Yuan W. G.,
Xiong F., Zhang H. L., et al. Crystengcomm, 2014, 16(33):7701-7710. is then with second
Nitrile is solvent, makes bis- (bromomethyl) acridines of 4,5- and 2, bis- (imidazoles ethyoxyl) naphthalenes of 7- are with 1:1 molar ratio reaction（Such as Figure 10 institutes
Show）, reaction temperature control at 40 ~ 60 DEG C, reacted 4 ~ 6 days under nitrogen protection, excessive ammonium hexafluorophosphate be added afterwards, room temperature is anti-
Should solid be precipitated for a period of time, filter, washing obtains faint yellow solid.The present invention is synthesized by highly dilution method,
Under conditions of being stirred continuously, by the isometric reactant of isoconcentration with slow and identical speed from two constant pressure funnels
It instills, to reduce the generation of side reaction as far as possible.
Two, the fluorescence property of acceptor molecule
In spectrofluorimetry experiment, a certain amount of receptor of accurate weighing after being dissolved with spectroscopic pure acetonitrile, then is diluted to concentration
It is 1.0 × 10-5The H of mol/L2O:CH3CN (3:7, v:V) aqueous solution.All metal ions are by its corresponding perchlorate
It is dissolved in H2O:CH3CN (3:7, v:V) it is formulated in aqueous solution, a concentration of 1.0 × 10-2M.Various surveys are carried out at room temperature
Examination, in fluoremetry, excitation wavelength is 355 nm, 5.0 nm of exciting slit, 5.0 nm of transmite slit.
A certain amount of receptor of another accurate weighing, with spectroscopic pure acetontrile at 0.5 × 10-5mol/L.All anion
（F−、Cl−、Br−、I−、AcO−、HSO4 −、H2PO4 −、OH−、ClO4 −）By its corresponding 4-butyl ammonium（TBA+）It is dissolved in spectroscopic pure
It prepares and obtains in acetonitrile solvent, a concentration of 2.5 × 10-3mol/L.Various tests are carried out at room temperature, in fluoremetry, excitation
Wavelength is 355 nm, 5.0 nm of exciting slit, 5.0 nm of transmite slit.
1, acceptor molecule is studied in the fluorescence property of the different acetonitrile in the mixed solvent of moisture ratio
Acceptor molecule is configured to a concentration of 1.0 × 10 in the different acetonitrile in the mixed solvent of moisture ratio-5The detection of mol/L
Liquid.Using 355 nm as excitation wavelength, transmitting spectrogram of the scanning receptor in different solutions.Such as Fig. 1, in H2O:CH3CN (3:7,
v:V) in aqueous solution and in pure CH3Fluorescence intensity in CN solution is almost the same.Therefore select H2O:CH3CN (3:7, v:V)
Aqueous solution carries out subsequent test.
2, acceptor molecule is to Fe3+Fluorescence identifying
A certain amount of receptor is weighed, after being dissolved with spectroscopic pure acetonitrile, then is diluted to a concentration of 1.0 × 10-5The H of mol/L2O:
CH3CN (3:7, v:V) aqueous solution.Different metal ions (the Al of 150 equivalents is added into the aqueous solution of receptor3+、Cd2+、Co2 +、Cr3+、Cu2+、Fe3+、Hg2+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+), other cations（Al3+、Cd2+、Co2+、Cr3+、Cu2 +、Hg2+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+）Addition fluorescence spectrum is not caused to change, when in receptor solution plus
Enter Fe3+When, fluorescent quenching is caused, as shown in Fig. 2, illustrating that acceptor molecule can highly selective identification Fe in acetonitrile solution3 +。
3, acceptor molecule is to H2PO4 −Fluorescence identifying
Acceptor molecule is separately configured to a concentration of 0.5 × 10 in acetonitrile-5The solution of mol/L.Acetonitrile to acceptor molecule is molten
Different anions (the F of 20 equivalents is added in liquid−、Cl−、Br−、I−、HSO4 −、AcO−、OH−、ClO4 −、H2PO4 −), as shown in figure 3,
When H is added into receptor solution2PO4 −When, red shift has occurred in fluorescence spectrum, and instills other anion（F−、Cl−、Br−、I−、
HSO4 −、AcO−、OH−、ClO4 −）When, the fluorescence spectrum of acceptor molecule does not change substantially, thus illustrates that acceptor molecule is molten in acetonitrile
It can highly selective identification H in liquid2PO4 −。
4, Receptor recognition Fe3+Anti-interference test
In practical applications, the interference free performance of acceptor molecule is most important, in order to examine it as Fe3+Acceptor molecule resists
Interference, to there are other competitive metal ions（Zn2+、Al3+、Cd2+、Co2+、Cr3+、Cu2+、Hg2+、Mg2+、Mn2+、Na+、Ni2 +、Pb2+）In the case of interference experiment be tested.As shown in figure 4, it can be appreciated that the aqueous acetonitrile of receptor from figure
After being separately added into the interfering ion of 150 equiv. in liquid, there is no significant changes for the fluorescence intensity of system, then again to each survey
The Fe of 150 equiv. is added in examination solution3+, fluorescent quenching occurs rapidly, other competitive metal ions are to Fe3+Detection
It is a good Fe it is possible thereby to illustrate that the anti-interference ability of acceptor molecule is very strong almost without interference3+Fluorescent receptor point
Son.
5, Receptor recognition H2PO4 −Anti-interference test
In order to examine it as H2PO4 −The anti-interference of acceptor molecule, to there are other competition anions（F−、Cl−、Br−、I−、AcO−、HSO4 −、OH−、ClO4 −）In the case of interference experiment be tested.As shown in figure 5, from figure it can be appreciated that
The CH of receptor3After being separately added into the interfering ion of 20 equiv. in CN solution, the fluorescence emission peak of system does not occur red
It moves, 20 equiv. H then is added into each test solution again2PO4 −, red shift occurs rapidly, other competition anions pair
H2PO4 −Detection interference it is smaller, only the fluorescence intensity after red shift can be had an impact, acceptor molecule thus can be explained
Anti-interference ability is more satisfactory.
6, acceptor molecule identifies Fe3+Fluorescence titration
In order to further probe into Fe3+To the effect trend of acceptor molecule, We conducted fluorescence emission spectrum titration experiments.It moves
Take 2 mL acceptor molecules (c=1.0 × 10-5Mol/L H)2O:CH3CN (3:7, v:V) aqueous solution is in 4 mL centrifuge tubes, respectively
The Fe of different equivalents is added3+, stand, carry out fluorometric investigation.As shown in fig. 6, with Fe3+Addition, fluorescence spectrum is in 455nm
The fluorescence intensity at place gradually weakens, and when dropwise addition reaches 120 equiv., fluorescence intensity becomes very faint at 455 nm, several
No longer change, is quenched completely, it is initial 1/16 to be quenched.
7, acceptor molecule identifies H2PO4 −Fluorescence titration
Receptor is to H2PO4 −Fluorescence titration：The acetonitrile solution of 2 mL receptors is pipetted in 4 mL centrifuge tubes, is separately added into different equivalents
H2PO4 −, stand, fluorometric investigation carried out, as shown in fig. 7, with H2PO4 −Addition, the gradual red shift of fluorescence emission peak of receptor
And fluorescence intensity first weakens and enhances afterwards, and when dropwise addition reaches 5.0 equiv., fluorescence emission peak almost no longer red shift, fluorescent emission
Peak by 451 nm red shifts to 518 nm at, red shift 67 nm, fluorescence intensity also no longer change.
8, acceptor molecule is to Fe3+And H2PO4 -Fluorescence minimum detection limit
The relationship of fluorescence intensity and ion concentration in being tested according to fluorescence titration carries out data point within the scope of a certain concentration
Linear fit obtains a linear good curve and is continuously swept to blank sample under the conditions of same test as shown in Figure 8 and Figure 9
Ten times, standard deviation is thus calculated to obtain, further according to 3 σ of detection limit formula/k, acquires receptor to Fe3+And H2PO4 −Fluorescence spectrum most
Low detection limit is respectively 0.678 mg/L and 0.041 mg/L.
The remarkable advantage of the present invention：The present invention is synthesized by highly dilution method, yield 39%.This receptor molecule exists
H2O:CH3CN (3:7, v:V) identification Fe can be selected in system3+, minimum detection limit can reach 1.21 × 10-5 M
(0.678 mg/L).In CH3Identification H may be selected in the system of CN2PO4 −, H is not added2PO4 −Receptor solution show fluorescence hair
Peak is penetrated at 451 nm, as 20.0 equiv. H of addition2PO4 −Afterwards, at 518 nm, fluorescence emission peak occurs fluorescence emission peak
Fluorescence intensity after apparent red shift and red shift also obviously weakens, and minimum detection limit can reach 4.27 × 10-7 M
(0.041 mg/L), therefore this receptor molecule can be used for Fe3+And H2PO4 −Fluorescence quickly detect.
Description of the drawings
Fluorescence emission spectrogram of compound of Fig. 1 receptors in the different aqueous solution of moisture ratio；
Fig. 2 acceptor molecules (1.0 × 10-5Mol/L H)2O:CH3CN (3:7, v:V) in aqueous solution, 150 are added
Equiv. different cation (Al3+、Cd2+、Co2+、Cr3+、Cu2+、Fe3+、Hg2+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+, c=
1.0×10-2Mol/L fluorescence emission spectrogram of compound)；
Fig. 3 acceptor molecules (0.5 × 10-5Mol/L in acetonitrile solution), 20 equiv. different anions (F are added−、Cl−、
Br−、I−、HSO4 −、AcO−、OH−、ClO4 −、H2PO4 −, c=2.5×10-3Mol/L fluorescence emission spectrogram of compound)；
Fig. 4 acceptor molecules (1.0 × 10-5Mol/L H)2O:CH3CN (3:7, v:V) in aqueous solution, 150 are added
Equiv. different cation (Al3+、Cd2+、Co2+、Cr3+、Cu2+、Hg2+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+, c=1.0×
10-2Mol/L after) testing, then the Fe of 150 equiv. is added into each test solution3+, to there are other competitive metals from
Interference experiment under subcase is tested, and Fe is added in comparison3+The variation of front and back fluorescence intensity；
Fig. 5 acceptor molecules (0.5 × 10-5Mol/L in acetonitrile solution), 20 equiv. different anions (F are added−、Cl−、
Br−、I−、HSO4 −、AcO−、OH−、ClO4 −, c=2.5×10-3Mol/L after) testing, then 20 are added into each test solution
Equiv. H2PO4 −, to there are the interference experiments in the case of other competition anions to be tested, H is added in comparison2PO4 −
The variation of front and back fluorescence spectrum；
Fig. 6 acceptor molecules (1.0 × 10-5Mol/L H)2O:CH3CN (3:7, v:V) to Fe in aqueous solution3+Fluorescence drop
Fixed figure；
Fig. 7 acceptor molecules (0.5 × 10-5Mol/L) in CH3To H in CN solution2PO4 −Fluorescence titration figure；
Fluorescence intensity and Fe of Fig. 8 acceptor molecules at 455 nm3+Concentration relationship；
Fluorescence intensity and H of Fig. 9 acceptor molecules at 450 nm2PO4 −Concentration relationship；
Figure 10 is the building-up process of the luxuriant acceptor molecule of acridine imidazoles ring of naphthalene nucleus bridging.
Specific implementation mode
Below by specific implementation mode to the synthesis of acceptor molecule of the present invention, structure and to iron ion and dihydrogen phosphate
The method of ion identification is described in detail.
1, the preparation of acceptor molecule
By highly dilution method, using acetonitrile as solvent, make bis- (bromomethyl) acridines of 4,5- and 2, bis- (imidazoles ethyoxyl) naphthalenes of 7- with
1:1 molar ratio reaction, reaction temperature control at 40 ~ 60 DEG C, are reacted 4 ~ 6 days under nitrogen protection, excessive hexafluoro phosphorus is added afterwards
Sour ammonium, room temperature reaction a period of time, is precipitated solid, filters, and washing obtains faint yellow solid.Yield is 39%, mp:209~
210 ℃。
2, the structural characterization of acceptor molecule
NMR, HRMS, IR data of acceptor molecule are as follows：
1H NMR (400 MHz, CD3CN) δ: 9.17 (s, 1H, Py-H), 8.80 (s, 2H, N=CH), 8.26
(d, J = 8.8 Hz, 2H, Ar-H), 7.72 (s, 2H, Ar-H), 7.70 (s, 2H, Ar-H), 7.49 (s,
2H, C=CH), 7.38 (s, 2H, C=CH), 7.06 (d, J = 2.5 Hz, 2H, Ar-H), 7.03 (d, J =
1.5 Hz, 2H, Ar-H), 7.01 (d, J = 1.0 Hz, 2H, Ar-H), 6.03 (s, 4H, Ar-CH 2 ), 4.66
(t, J = 5.4 Hz, 4H, C-CH 2 ), 4.60 (t, J = 5.0 Hz, 4H, C-CH 2 ).
13C NMR (101 MHz, CD3CN) δ: 156.43, 145.78, 138.44, 136.49, 135.39 131.51,
131.16, 130.23, 129.66, 126.78, 125.90, 125.17, 123.57, 122.78, 116.04,
108.11, 66.28, 49.83, 49.14.
HRMS (ESI): C35H31N5O2P2F12, (3a+PF6 −) requires 698.2120, found 698.2119; M/
2 requires 276.6239, found 276.6237.
IR (neat): νmax (cm-1) = 1507, 1157, 821, 554.
3, the recognition performance research of acceptor molecule
Various tests are carried out at room temperature, and in fluoremetry, excitation wavelength is 355 nm, 5.0 nm of exciting slit, transmite slit
5.0 nm.In being tested to the spectrofluorimetry of metal ion, a certain amount of receptor of accurate weighing is dissolved with spectroscopic pure acetonitrile
Afterwards, a concentration of 1.0 × 10 are diluted to then-5The H of mol/L2O:CH3CN (3:7, v:V) aqueous solution.All metal ions are equal
H is dissolved in by its corresponding perchlorate2O:CH3CN (3:7, v:V) it is formulated in aqueous solution, a concentration of 1.0 × 10-2 M。
In being tested to the spectrofluorimetry of anion, another a certain amount of receptor of accurate weighing is molten with order of spectrum acetonitrile
Solution, is configured to concentration 0.5 × 10-5The solution of mol/L, all anion（F−、Cl−、Br−、I−、AcO−、HSO4 −、H2PO4 −、
OH−、ClO4 −）By its corresponding 4-butyl ammonium（TBA+）It is dissolved in spectroscopic pure acetonitrile solvent and prepares and obtain, a concentration of 2.5 ×
10-3 mol/L。
4, the selection Journal of Sex Research of acceptor molecule identification metal ion
2.0 mL acceptor molecules (1.0 × 10 are pipetted with liquid-transfering gun-5Mol/L H)2O:CH3CN (3:7, v:V) aqueous solution is extremely
With numbered 4 mL centrifuge tubes, the different metal cation (Al of 150 equivalents is added to each centrifuge tube respectively3+、Cd2+、
Co2+、Cr3+、Cu2+、Fe3+、Hg2+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+, c=1.0×10-2Mol/L), fluorescence light is carried out
Spectrum test.
5, acceptor molecule identifies Fe3+Anti-interference research
2 mL acceptor molecules (1.0 × 10 are added in 4 mL centrifuge tubes-5Mol/L H)2O:CH3CN (3:7, v:V)
Aqueous solution is separately added into 150 equivalent others metal ion (Al3+、Cd2+、Co2+、Cr3+、Cu2+、Hg2+、Mg2+、Mn2+、Na+、
Ni2+、Pb2+、Zn2+, c=10.0×10-3Mol/L after), 150 equivalent Fe are added3+, measure Fe is added respectively3+Front and back is glimmering
Optical emission spectroscopy, the fluorescence intensity block diagram being plotted at 455 nm.
6, acceptor molecule identifies Fe3+Fluorescence titration
In fluorescence titration experiment, 2.0 mL acceptor molecules (1.0 × 10 are pipetted with liquid-transfering gun-5Mol/L H)2O:CH3CN
(3:7, v:V) Fe of different equivalents is added to numbered 4 mL centrifuge tubes in aqueous solution into each centrifuge tube respectively3+
(0.0 eq~150.0 eq, c=1.0×10-2Mol/L), fluorescence spectrum test is carried out.
7, acceptor molecule identifies H2PO4 -Selection Journal of Sex Research
2.0 mL acceptor molecules (0.5 × 10 are pipetted with liquid-transfering gun-5Mol/L acetonitrile solution) is centrifuged to numbered 4 mL
In test tube, the different anions (F of 20 equivalents is added to each centrifuge tube respectively−、Cl−、Br−、I−、AcO−、HSO4 −、H2PO4 −、OH−、ClO4 −, c=2.5×10-3Mol/L), fluorescence spectrum test is carried out.
8, acceptor molecule identifies H2PO4 -Anti-interference research
2 mL acceptor molecules (0.5 × 10 are added in 4 mL centrifuge tubes-5Mol/L acetonitrile solution) is separately added into 20 and works as
Other anion (the F of amount−、Cl−、Br−、I−、AcO−、HSO4 −、OH−、ClO4 −, c=2.5×10-3Mol/L after), 20 are added
Equivalent H2PO4 −, measure H is added respectively2PO4 −Front and back fluorescence emission spectrum.
9, acceptor molecule identifies H2PO4 −Titration
In fluorescence titration experiment, 2.0 mL acceptor molecules (0.5 × 10 are pipetted with liquid-transfering gun-5Mol/L acetonitrile solution) is extremely
With in numbered 4 mL centrifuge tubes, the H of different equivalents is added into each centrifuge tube respectively2PO4 −Ion (0.00 eq ~
20.0 eq, c=2.5×10-3Mol/L), fluorescence spectrum test is carried out.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (7)
1. a kind of luxuriant acceptor molecule of acridine imidazoles ring of naphthalene nucleus bridging, it is characterised in that：Its structural formula is as follows：
。
2. a kind of preparation method of the luxuriant acceptor molecule of acridine imidazoles ring of naphthalene nucleus bridging as described in claim 1, feature
It is：Using acetonitrile as solvent, by bis- (bromomethyl) acridines of 4,5- and 2, bis- (imidazoles ethyoxyl) naphthalenes of 7- are with 1:1 molar ratio is anti-
It answers, reaction temperature is controlled at 40 ~ 60 DEG C, is reacted 4 ~ 6 days under nitrogen protection, excessive ammonium hexafluorophosphate is added afterwards, is reacted at room temperature
For a period of time, solid is precipitated, filters, washing obtains faint yellow solid.
3. preparation method according to claim 2, it is characterised in that：By highly dilution method, in the condition being stirred continuously
Under, the isometric reactant of isoconcentration is instilled from two constant pressure funnels with slow and identical speed, to reduce
The generation of side reaction.
4. a kind of acceptor molecule as described in claim 1 Selective recognition Fe in acetonitrile solution3+Application, feature exists
In：Acceptor molecule is dissolved in acetonitrile solution, 150 equivalent Al are separately added into3+、Cd2+、Co2+、Cr3+、Cu2+、Fe3+、Hg2+、
Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+, the addition of other metal ions, fluorescence response has almost no change, Fe3+Addition but
So that fluorescent quenching has occurred at 455 nm in acceptor molecule.
5. acceptor molecule according to claim 4 Selective recognition Fe in acetonitrile solution3+Application, feature exists
In：Fe3+Concentration is at 0 ~ 500 μM, fluorescence intensity level and Fe3+There is good linear correlation, to Fe between concentration value3+Most
Low detection is limited to 1.21 × 10-5 M, i.e. 0.678 mg/L.
6. a kind of acceptor molecule as described in claim 1 Selective recognition dihydrogen phosphate ions in acetonitrile solution are answered
With, it is characterised in that：Acceptor molecule is dissolved in acetonitrile, 20 equivalent F are separately added into−、Cl−、Br−、I−、AcO−、HSO4 −、OH−、
ClO4 −、H2PO4 −, H2PO4 −Addition make acceptor molecule that fluorescence red shift have occurred at 451 nm, red shift to 518 nm, and its
He does not cause fluorescence spectrum to change at the addition of anion.
7. the application of acceptor molecule according to claim 6 Selective recognition dihydrogen phosphate ions in acetonitrile solution,
It is characterized in that：H2PO4 −Concentration is at 0 ~ 25 μM, fluorescence intensity level and H2PO4 −There is good linear phase between concentration value
It closes, to H2PO4 −Lowest detection is limited to 4.27 × 10-7 M, i.e. 0.041 mg/L.
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| CN113278011A (en) * | 2021-06-01 | 2021-08-20 | 湖北师范大学 | Fluorescent probe for identifying bimetallic ions and preparation and application methods thereof |
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| CN113880851A (en) * | 2021-11-12 | 2022-01-04 | 广东科学技术职业学院 | Trifluorene bridged hexaimidazole macrocyclic compound and preparation method and application thereof |
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| CN113278011A (en) * | 2021-06-01 | 2021-08-20 | 湖北师范大学 | Fluorescent probe for identifying bimetallic ions and preparation and application methods thereof |
| CN113603709A (en) * | 2021-08-18 | 2021-11-05 | 南方科技大学 | Macrocyclic molecules, methods of preparation and uses thereof |
| CN113880851A (en) * | 2021-11-12 | 2022-01-04 | 广东科学技术职业学院 | Trifluorene bridged hexaimidazole macrocyclic compound and preparation method and application thereof |
| CN113880851B (en) * | 2021-11-12 | 2022-07-29 | 广东科学技术职业学院 | Trifluorene bridged hexaimidazole macrocyclic compound and preparation method and application thereof |
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