CN108178766A - A kind of fluorescent probe molecule of recognizable iron ion and dihydrogen phosphate ions and its preparation method and application - Google Patents
A kind of fluorescent probe molecule of recognizable iron ion and dihydrogen phosphate ions and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of recognizable iron ion, the fluorescent probe molecules and its preparation method and application of dihydrogen phosphate ions, belong to ion detection field.Fluorescent probe molecule its structural formula of the present invention is：, synthesized by highly dilution method, yield is up to 57%.The fluorescent probe molecule is in CH3CN/H2Identification Fe can be selected in the system of O3+, minimum detection limit can reach 4.43 × 10‑6M(0.247 mg/L).In CH3Identification H can be selected in the system of CN2PO4 ‑, H2PO4 ‑Addition so that fluorescence red shift occurs at 434 nm for fluorescent probe molecule, red shift to 515 nm, the fluorescent probe molecule can be used for H2PO4 ‑Fluorescence quickly detect, minimum detection limit can reach 2.89 × 10‑7 M。
Description
Technical field
The invention belongs to ion detection fields, and in particular to a kind of recognizable iron ion, dihydrogen phosphate ions fluorescence
Probe molecule and its preparation method and application.
Background technology
It is the one of supramolecular chemistry research to have the design of the fluorescence chemical sensor of Selective recognition and synthesis to ion
A active area.In metal ion, Fe3+ It is also vital, Fe for human survival and health3+It is in biosystem
One of most important metal ion plays a key effect in many physiology courses, is transported including cell metabolism, enzymatic and oxygen
Defeated and DNA and RNA synthesis.(a)Kim, J. S.; Quang, D. T.Chem. Rev. 2007, 107, 3780–
3799;(b)Duke, R. M.; Veale, E. B.; Pfeffer, F. M.; Kruger, P. E.;
Gunnlaugsson, T. Chem. Soc. Rev.2010, 39, 3936–3953;(c)Aisen P, W.-R. M.;
Leibold, E. A.; Current opinion in chemical biology. 1999, 3, 200–206. Fe3+ It is different
It is often often the mark of 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, therefore 116-124., design to Fe3+Have
The molecule of recognition reaction is especially important.At present, spectrophotometry, atomic absorption spectrography (AAS), voltammetry, atomic emission spectrum
Method and fluorescence analysis have been used for detecting iron ion.However these methods need complicated instrument and cumbersome sample system mostly
Standby process, in contrast, fluorescent technique have many advantages, such as selectively good, high sensitivity, at low cost, simple and efficient, provide one
A easily and efficiently detection mode.(f)Ohashi, A.; Ito, H.; Kanai, C.; Imura, H.; Ohashi,
K. Talanta. 2005, 65, 525–530;(g)Akatsuka, K.; McLaren, J. W.; Lam, J. W.;
Berman, S. S. J. Anal. At. Spectrom.1992, 7, 889–894;(h)Elrod, V. A.;
Johnson, K. S.; Coale, K. H. Anal. Chem.1991, 63, 893–898;(i)Tesfaldet, Z.
O.; van Staden, J. F.; Stefan, R. I. Talanta.2004, 65, 1189–1195;(j)Valeur ,
B.; Leray, I.Coordination Chem. Rev. 2000, 205, 3–40;(k)Petrat, F.; Rauen,
U.; Groot, de H. Hepatology. 1999, 29, 1171–1179;(m)Li, P.; Ji, C.; Ma, H.;
Zhang, M.; Cheng, Y. Chemistry. 2014, 20, 5741–5745;(n)Li, Y.; Gao, Y.; Cao,
Y.; Li, H. Sensors and Actuators B: Chemical.2012, 171, 726–733;(o)Qu, X.;
Liu, Q.; Ji, X.; Chen, H.; Zhou, Z.; Shen, Z. Chem Commun. 2012, 48, 4600–
4602;(p)Wu, X.; Xu, B.; Tong, H.; Wang, L. Macromolecules.2010, 43, 8917–
8923. in recent years, related Fe3+Fluorescent probe molecule be also more and more reported, but fluorescent probe molecule can only be mostly
Selective recognition is carried out in organic solvent, thus cannot be widely used.The identification of selection in aqueous solution Fe related at present3+
Fluorescent probe molecule report it is fewer.
The exploitation of chemical sensor probe has great importance with studying in fields such as biology, environment, chemical industry.And fluorescence
Chemical sensor is due to that can realize quick detection, and cost is relatively low, have become very popular detection and analysis means.
From the perspective of biology, dihydrogen phosphate ions be considered in metabolic process be it is essential, dihydrogen phosphate from
Son plays a crucial role in the skeleton of signal transduction, energy storage and structure DNA and RNA.Design synthesis has dihydrogen phosphate ions
The probe molecule tool for having recognition reaction has very important significance.(q)Zhang, D.; Jiang, X.; Yang, H.;
Martinez, A.; Feng, M.; Dong, Z.; Gao, G. Org. Biomol. Chem. 2013, 11, 3375–
3381;(r)Jadhav, J. R.; Bae, C. H.; Kim, H. S.; Tetrahedron letters. 2011, 52,
1623–1627;(s)Lee, G. W.; Singh, N.; Jung, H. J.; Jang, D. O.; Tetrahedron Letters.2009, 50, 807–810;(t)Xu, Z.; Xiao, Y.; Qian, X.; Cui, J.; Cui, D.Org. Lett. 2005, 7, 889-892. and at present most of reports H2PO4 -The fluorescence response of fluorescent optical sensor is mostly glimmering
Optical quenching or enhancing.In fact, in practical applications, some variable factors, such as photobleaching, sensor molecule concentration and sensor
The microenvironment of surrounding molecules may also lead to fluorescent quenching or enhancing.On the contrary, fluorescence red shift can be as the new plan of Anionic recognition
Slightly.(u)Eshghi, H.; Rahimizadeh, M.; Hasanpour, M.; Bakavoli, M.Research on Chemical Intermediates.2014, 41, 4187–4197; (v)Zhang, D.; Cochrane, J. R.;
Martinez, A.; Gao, G. Rsc Adv. 2014, 4, 29735–29749。
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 recognizable iron ion, dihydrogen phosphate from
Fluorescent probe molecule of son and its preparation method and application.Fluorescent probe molecule alternative identification iron ion, biphosphate
Radical ion, to Fe3+Minimum detection limit can reach 4.43 × 10-6 M (0.247 mg/L), to H2PO4 -Minimum detection limit
2.89 × 10 can be reached-7 M。
For achieving the above object, the present invention adopts the following technical scheme that：
First, fluorescent probe molecule and its preparation
Fluorescent probe molecule of the present invention, chemical name are：(12Z,52Z)-11 H,51 H- 8,11- dioxas -3 (4,5)-acridine -1,
The big rings ten three luxuriant -1 of 5 (3,1)-bis- imidazoles -3-3,53Double hexafluorophosphates；Its structural formula is as follows：
Synthesis step：。
The synthetic method of fluorescent probe molecule：It is bis- that 1,2- has been synthesized according to known reference document first（2-（1H- imidazoles -1-
Base）Ethyoxyl）Ethane feed 1 and 4,5- dibromo methylacridine raw material 2,（w）Eshghi, H.; Rahimizadeh, M.;
Hasanpour, M.; Bakavoli, M. Research on ChemicalIntermediates.2014, 41, 4187–
4197；（x）Hasanpour, M.; Eshghi, H.; Bakavoli, M.; Mirzaeia, M.;J. Chi. Chem. Soc. 2015, 62, 412–419；（y）Zhang, D.; Jiang, X.; Yang, H.; Martinez, A.; Feng,
M.; Dong, Z.; Gao, G. Org. Biomol. Chem. 2013, 11, 3375-3381. and then using chloroform to be molten
Agent makes 4,5- dibromos methylacridine and 1,2- bis-（2-（1H- imidazoles -1- bases）Ethyoxyl）Ethane is with 1:1 molar ratio reaction（Such as
Shown in formula 1）, reaction temperature control is at 50 ~ 60 DEG C, and nitrogen protection is lower to react 4 ~ 6 days, the rear ammonium hexafluorophosphate for adding in 3 equivalents,
Solid is precipitated in normal-temperature reaction 20-30h, filters, and washing obtains faint yellow solid.
Formula 1
Wherein：Reactant is slowly dropped into reaction system respectively, by highly dilution method, so as to reduce the generation of side reaction.
2nd, the fluorescence property of fluorescent probe molecule
Fluorescent probe molecule is configured to 1.0 × 10-5The aqueous solution of mol/L carries out the fluorescent spectroscopic properties survey to metal ion
Examination.Exciting slit width is 2.5 nm, and transmite slit 5.0nm, voltage is 700 V, carries out fluorescence emission spectrum scanning.It separately will be glimmering
Light probe molecule is configured to 0.5 × 10-5The acetonitrile solution of mol/L carries out fluorescent spectroscopic properties test to anion.Exciting slit
Width is 5.0 nm, and transmite slit 5.0nm, voltage is 700 V, carries out fluorescence emission spectrum scanning.
1st, fluorescent probe molecule is in the fluorescence intensity research of the acetonitrile in the mixed solvent of different moisture content
Acetonitrile in the mixed solvent of the fluorescent probe molecule in different moisture content is configured to a concentration of 1.0 × 10-5The inspection of mol/L
Survey liquid.Using 360 nm as excitation wavelength, the transmitting spectrogram of fluorescent probe molecule is scanned.Such as Fig. 1, as the ratio for adding in water is gradual
First increases and then decreases is presented in increase, fluorescence intensity.When in CH3CN:H2O (V:V=1:49) during system, fluorescence intensity reaches maximum,
Therefore with CH3CN:H2O (V:V=1:49) mixed solvent carries out subsequent cations recognition test.
2nd, fluorescent probe molecule is to Fe3+And H2PO4 -Fluorescence identifying
By fluorescent probe molecule in CH3CN:H2O (V:V=1:49) a concentration of 1.0 × 10 are configured under mixed solvent-5 mol/L。
Different metal ions (the Al of 100 equivalents is added in into fluorescent probe molecule solution3+、Cd2+、Co2+、Cr3+、Cu2+、Fe3+、Hg2+、
Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+).When adding in Fe into fluorescent probe molecule solution3+When, fluorescence intensity is quenched
It goes out；And instill other cations（Al3+、Cd2+、Co2+、Cr3+、Cu2+、Hg2+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+）When, it is glimmering
The fluorescence of light probe does not change substantially.As shown in Figure 2.It is clear that only Fe3+Addition, fluorescent probe molecule
Fluorescence intensity is quenched, and illustrates that fluorescent probe molecule can identify Fe in acetonitrile solution with efficient selective3+。
Fluorescent probe molecule is separately configured to a concentration of 0.5 × 10 in acetonitrile-5mol/L.To fluorescent probe molecule solution
Middle different anions (the F for adding in 10 equivalents-、Cl-、Br-、I-、HSO4 -、AcO-、OH-、ClO4 -、H2PO4 -).When to fluorescence probe
H is added in molecular solution2PO4 -When, red shift has occurred in fluorescence spectrum；And instill other anion（F-、Cl-、Br-、I-、HSO4 -、
AcO-、OH-、ClO4 -）When, the fluorescence spectrum of acceptor molecule does not change substantially.As shown in Figure 4.It is clear that only
H2PO4 -Addition, the fluorescence spectrum of fluorescent probe molecule has occurred red shift, illustrates that fluorescent probe molecule can be efficient in acetonitrile
Selective recognition H2PO4 -。
3rd, fluorescent probe molecule is to Fe3+And H2PO4 -The anti-interference of identification
For the receptor of ion identification, interference free performance is a very important index, in order to study fluorescent probe molecule
To Fe3+The interference free performance of identification, we have done following interference--free experiments：By the different metal ions (Al of 100 equivalents3+、
Cd2+、Co2+、Cr3+、Cu2+、Hg2+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+) be separately added into fluorescent probe molecule (c=1.0 ×
10-5Mol/L CH)3CN:H2O (V:V=1:49) after aqueous solution, then the Fe by 100 equivalents3+It is separately added into above-mentioned system
In, carry out fluorometric investigation.Experimental result is with only adding in Fe3+The phenomenon that be identical.It chooses glimmering at 455 nm in fluorescence spectrum
Light intensity data does block diagram.As shown in Fig. 2, we are, it is clear that other are cationic to Fe3+Identification it is not dry
It disturbs.Therefore, fluorescent probe molecule can identify Fe with efficient selective3+。
In order to study fluorescent probe molecule to H2PO4 -The interference free performance of identification, we have done following interference--free experiments：
By the different anions (F of 10 equivalents-、Cl-、Br-、I-、HSO4 -、AcO-、OH-、ClO4 -) be separately added into fluorescent probe molecule (c=
0.5×10-5Mol/L after in acetonitrile solution), then the H by 10 equivalents2PO4 -It adds in above-mentioned system, carries out fluorometric investigation.It is real
Result is tested with only adding in H2PO4 -The phenomenon that be identical.As shown in figure 4, we are, it is clear that other anion pair
H2PO4 -Identification do not interfere with.Therefore, fluorescent probe molecule can identify H with efficient selective2PO4 -。
4th, fluorescent probe molecule is to Fe3+And H2PO4 -Fluorescence titration
In order to further probe into fluorescent probe molecule to Fe3+And H2PO4 -Effect trend, We conducted fluorescence emission spectrums
Titration experiments.Fluorescent probe molecule is to Fe3+Fluorescence titration：Pipette 2 mL fluorescent probe molecules (c=1.0 × 10-5 mol/L)
CH3CN:H2O (V:V=1:49) aqueous solution is sequentially added into the Fe of different equivalents in 4 mL centrifuge tubes3+Aqueous solution,
It stands, carries out fluorometric investigation.As shown in Figure 3a, with Fe3+Addition, fluorescence intensity of the fluorescence spectrum at 455nm gradually subtract
It is weak；As 150 equivalent Fe of addition3+When, fluorescence intensity is quenched completely.Fluorescent probe molecule is to H2PO4 -Fluorescence titration：Pipette 2 mL
Fluorescent probe molecule (c=0.5 × 10-5Mol/L acetonitrile solution) is sequentially added into different equivalents in 4 mL centrifuge tubes
H2PO4 -Acetonitrile solution, stand, carry out fluorometric investigation.As shown in Figure 5 a, with H2PO4 -Addition, fluorescence spectrum is in 434 nm
Fluorescence intensity gradually weaken, gradually enhance in the fluorescence intensity of 515 nm, significantly red shift has occurred in fluorescence spectrum.
5th, fluorescent probe molecule is to Fe3+And H2PO4 -Fluorescence minimum detection limit
Fluorescent probe molecule is calculated to Fe according to 3 σ/k methods3+And H2PO4 -Fluorescence spectrum minimum detection limit can reach respectively
4.43×10-6 M (0.247 mg/L) and 2.89 × 10-7M.As shown in fig. 6, therefore, the fluorescent probe molecule is to Fe3+With
H2PO4 -Detection have higher sensitivity.
6th, fluorescent probe molecule is to Fe3+And H2PO4 -Binding constant measure
Fluorescent probe molecule can be calculated to Fe according to Job ' splots equations and Benesi-Hildebrand equations3+Combination
Constant and combine than.With Fe3+The inverse of concentration is abscissa, with (F0- F) inverse for ordinate map (such as Fig. 7 and 8).
(F0- F) inverse and Fe3+Linear relationship, R is presented in the reciprocal of concentration2It is 0.99.Therefore show fluorescent probe molecule and Fe3+'s
With reference to than being 1:1, binding constant is 3.094 × 103 M-1.Fluorescent probe molecule pair can be calculated according to Job ' splots equations
H2PO4 -Combination ratio (such as Fig. 7), the results showed that fluorescent probe molecule and H2PO4 -Combination ratio be 1: 1.With H2PO4 -Concentration
For abscissa, with (F-F0)/ (Fmax-F0) map for ordinate.(F-F0)/ (Fmax-F0) and H2PO4 -Concentration present it is linear
Relationship (such as Fig. 9), R2It is 0.99.Be computed binding constant be 5.37 × 104 M-1。
Description of the drawings
Fig. 1 fluorescent probe molecules (c=1.0 × 10-5Mol/L) the fluorescent emission in the acetonitrile solution containing different water
Spectrum (λex=360 nm) and fluorescence intensity block diagram of the wavelength at 455 nm；
Fig. 2 fluorescent probe molecules (1.0 × 10-5Mol/L CH)3CN:H2O (V:V=1:49) in aqueous solution, 100 are added in
Equiv. different cation (Al3+、Cd2+、Co2+、Cr3+、Cu2+、Fe3+、Hg2+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+, c=
10.0×10-3Mol/L fluorescence emission spectrogram of compound)；Fluorescent probe molecule (1.0 × 10-5Mol/L CH)3CN:H2O (V:V
=1:49) to Fe in aqueous solution3+(c=10.0×10-3Mol/L) the anti-interference block diagram of identification；
Fig. 3 a fluorescent probe molecules (1.0 × 10-5Mol/L CH)3CN:H2O (V:V=1:49) to Fe in aqueous solution3+'s
Fluorescence titration figure；Fig. 3 b are the figure of fluorescence intensity changes at 455 nm；
Fig. 4 fluorescent probe molecules (0.5 × 10-5Mol/L in acetonitrile solution), 10 equiv. different anions (F are added in-、
Cl-、Br-、I-、HSO4 -、AcO-、OH-、ClO4 -、H2PO4 -, c=5.0×10-3Mol/L fluorescence emission spectrogram of compound and fluorescence) is visited
Needle molecule (0.5 × 10-5Mol/L to H in acetonitrile solution)2PO4 - (c=5.0×10-3Mol/L) the anti-interference figure of identification；
Fig. 5 a fluorescent probe molecules (0.5 × 10-5Mol/L to H in acetonitrile solution)2PO4 -Fluorescence titration figure；Fig. 5 b are
Figure of fluorescence intensity changes at 434 and 515nm；
Fig. 6 fluorescent probe molecules respectively with Fe3+And H2PO4 -Linear correlation curve；
Fig. 7 fluorescent probe molecules are to Fe3+And H2PO4 -Job ' splots working curves；
Fig. 8 fluorescent probe molecules (1.0 × 10-5Mol/L CH)3CN:H2O (V:V=1:49) aqueous solution is to Fe3+'s
Benesi-Hildebrand curves；
Fig. 9 fluorescent probe molecules (0.5 × 10-5Mol/L CH)3CN solution is to H2PO4 -Binding constant figure.
Specific embodiment
Below by specific embodiment to the synthesis of fluorescent probe molecule of the present invention, structure and to iron ion and di(2-ethylhexyl)phosphate
The method of hydrogen radical ion identification is described in detail.
1st, the preparation of fluorescent probe molecule
Using chloroform as solvent, make 4,5- dibromos methylacridine and 1,2- bis-（2-（1H- imidazoles -1- bases）Ethyoxyl）Ethane is with 1:1
Molar ratio reaction, reaction temperature control is at 50 ~ 60 DEG C, the lower reaction of nitrogen protection 4 ~ 6 days, the rear hexafluorophosphoric acid for adding in 3 equivalents
Solid is precipitated in ammonium, normal-temperature reaction 20-30h, filters, and washing obtains faint yellow solid.Yield is 57%, mp>250 ℃.
2nd, the structural characterization of fluorescent probe molecule
NMR, HRMS, IR data of fluorescent probe molecule are as follows：1H NMR (400 MHz, CD3CN) δH 3.64 (s, 4H,
C-CH 2 ), 3.79-3.77 (m, 4H, C-CH 2 ), 4.26-4.24 (m, 4H, N-CH 2 ), 5.97 (s, 4H, Ar-
CH 2 ), 7.26 (s, 2H, C=CH), 7.37 (s, 2H, C=CH), 7.76-7.72 (m, 2H, Ar-H), 7.98
(d, 2H, J = 6.7 Hz, Ar-H), 8.31 (d, 2H, J = 8.6 Hz, Ar-H), 8.55 (s, 2H, N=CH
), 9.20 (s, 1H, Py-H). 13C NMR (101 MHz, CH3CN) δ 49.36, 49.66, 68.00, 69.62,
121.98, 123.18, 126.02, 126.93, 130.46, 130.74, 133.22, 135.87, 138.39,
146.19. HRMS (ESI): C27H29N5O2P2F12, (3+PF6 -) measured value 600.1957, actual value 600.1979; M/2
Measured value 227.6155, actual value 227.6163. IR (neat): νmax (cm-1) = 837, 557.
3rd, the recognition performance research of fluorescence probe acceptor molecule
In spectrum analysis experiment, a certain amount of receptor of accurate weighing after being dissolved with order of spectrum acetonitrile, adds second distillation
Water is configured to a concentration of 1.0 × 10-5The CH of mol/L3CN:H2O (V:V=1:49) solution.The various gold for detection and analysis
Belong to ion and be made into 10.0 × 10 with redistilled water-3mol/L.Various tests, in fluoremetry, excitation wave are carried out at room temperature
A length of 360 nm, 2.5 nm of exciting slit, 5.0 nm of transmite slit；A certain amount of receptor of another accurate weighing, with order of spectrum acetonitrile
Dissolving, is configured to concentration 0.5 × 10-5The solution of mol/L.The various anion for detection and analysis are matched with spectroscopic pure acetonitrile
Into 5.0 × 10-3mol/L.Carry out various tests at room temperature, in fluoremetry, excitation wavelength be 365 nm, exciting slit 5.0
Nm, 5.0 nm of transmite slit.
4th, fluorescence probe acceptor molecule identification Fe3+Selection Journal of Sex Research
In fluorometric investigation experiment, the fluorescent probe molecule (1.0 × 10 of 2.0 mL is pipetted with liquid-transfering gun-5Mol/L CH)3CN:
H2O (V:V=1:49) aqueous solution pipettes the difference of equivalent to each centrifuge tube respectively to numbered 4mL centrifuge tubes
Metal cation (Al3+、Cd2+、Co2+、Cr3+、Cu2+、Fe3+、Hg2+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+, c=10.0×
10-3Mol/L), fluorescence spectrum test is carried out.
5th, fluorescence probe acceptor molecule identification Fe3+Titration
In fluorescence titration experiment, the fluorescent probe molecule (1.0 × 10 of 2.0 mL is pipetted with liquid-transfering gun-5Mol/L CH)3CN:
H2O (V:V=1:49) aqueous solution pipettes the three of different equivalents to each centrifuge tube respectively to numbered 4mL centrifuge tubes
Valency iron ion (eq of 0.00 eq ~ 200.0, c=10.0 × 10-3Mol/L), fluorescence spectrum test is carried out.
6th, fluorescence probe acceptor molecule identification Fe3+Anti-interference research
The fluorescence acceptor molecules (1.0 × 10 of 2 mL are added in 4 mL centrifuge tubes-5Mol/L CH)3CN:H2O (V:V=1:
49) aqueous solution is separately added into 100 equivalent others metal ion (Al3+、Cd2+、Co2+、Cr3+、Cu2+、Hg2+、Mg2+、Mn2+、
Na+、Ni2+、Pb2+、Zn2+, c=10.0×10-3Mol/L after), 100 equivalent Fe are added3+, its fluorescence intensity is measured respectively, is painted
Fluorescence intensity block diagram of the different metal cation processed at 455 nm, the results show that other metal cations not interference system
To Fe3+Detection.
7th, fluorescence probe acceptor molecule identification H2PO4 -Selection Journal of Sex Research
In fluorometric investigation experiment, the fluorescent probe molecule (0.5 × 10 of 2.0 mL is pipetted with liquid-transfering gun-5Mol/L acetonitrile)
Solution pipettes the different anions (F of equivalent to each centrifuge tube respectively to in numbered 4mL centrifuge tubes-、Cl-、
Br-、I-、HSO4 -、AcO-、OH-、ClO4 -、H2PO4 -, c=5.0×10-3Mol/L), fluorescence spectrum test is carried out.
8th, fluorescence probe acceptor molecule identification H2PO4 -Titration
In fluorescence titration experiment, the fluorescent probe molecule (0.5 × 10 of 2.0 mL is pipetted with liquid-transfering gun-5Mol/L acetonitrile)
Solution pipettes the H of different equivalents to each centrifuge tube respectively to in numbered 4mL centrifuge tubes2PO4 -Ion (0.00 eq
~10.0 eq, c=5.0×10-3Mol/L), fluorescence spectrum test is carried out.
9th, fluorescence probe acceptor molecule identification H2PO4 -Anti-interference research
The fluorescence acceptor molecules (0.5 × 10 of 2 mL are added in 4 mL centrifuge tubes-5Mol/L acetonitrile solution) adds respectively
Enter 10 equivalent others anion (F-、Cl-、Br-、I-、HSO4 -、AcO-、OH-、ClO4 -, c=5.0×10-3Mol/L after), then
Add in 10 equivalent H2PO4 -, respectively carry out fluorescence spectrum test, the results show that other anion not interference system to H2PO4 -Inspection
It surveys.
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 fluorescent probe molecule of recognizable iron ion, dihydrogen phosphate ions, it is characterised in that：Its structural formula is as follows：
。
2. a kind of preparation side of the fluorescent probe molecule of recognizable iron ion as described in claim 1, dihydrogen phosphate ions
Method, it is characterised in that：It is using chloroform as solvent, 4,5- dibromos methylacridine and 1,2- is bis-（2-（1H- imidazoles -1- bases）Ethyoxyl）
Ethane is with 1:1 molar ratio reaction, at 50 ~ 60 DEG C, the lower reaction of nitrogen protection 4 ~ 6 days is rear to add in 3 equivalents for reaction temperature control
Ammonium hexafluorophosphate, react at room temperature 20-30h, be precipitated solid, filter, washing, obtain faint yellow solid.
3. preparation method according to claim 2, it is characterised in that：It is by highly dilution method, reactant is slow simultaneously
It instills in reaction system, so as to reduce the generation of side reaction.
4. a kind of fluorescent probe molecule as described in claim 1 Selective recognition Fe in acetonitrile solution3+Application, it is special
Sign is：Fluorescent probe molecule is dissolved in acetonitrile solution, is separately added into Al3+、Cd2+、Co2+、Cr3+、Cu2+、Fe3+、Hg2 +、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+, Fe3+Addition cause fluorescent probe molecule that fluorescent quenching has occurred at 455 nm,
And the addition of other cations, fluorescence spectrum do not change.
5. fluorescent probe molecule according to claim 4 Selective recognition Fe in acetonitrile solution3+Application, feature
It is：Fe3+At a concentration of 0 ~ 900 μM, fluorescence intensity level and Fe3+Concentration value has good linear correlation, to Fe3+Minimum inspection
Survey is limited to 4.43 × 10-6 M, i.e. 0.247mg/L.
6. a kind of fluorescent probe molecule as described in claim 1 in acetonitrile Selective recognition dihydrogen phosphate ions should
With, it is characterised in that：Fluorescent probe molecule is dissolved in acetonitrile, is separately added into F-、Cl-、Br-、I-、HSO4 -、AcO-、OH-、
ClO4 -、H2PO4 -, H2PO4 -Addition cause fluorescent probe molecule that fluorescence red shift has occurred at 434nm, red shift to 515nm, and
The addition of other anion fails that its fluorescence spectrum is made to change.
7. the application of fluorescent probe molecule according to claim 6 Selective recognition dihydrogen phosphate ions in acetonitrile,
It is characterized in that：H2PO4 -At a concentration of 0 ~ 20 μM, fluorescence intensity level and H2PO4 -Concentration value has good linear correlation, right
H2PO4 -Lowest detection is limited to 2.89 × 10-7 M。
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| CN108440565A (en) * | 2018-05-08 | 2018-08-24 | 福州大学 | 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 |
| CN108822130A (en) * | 2018-07-30 | 2018-11-16 | 天津师范大学 | Benzimidazole ring kind and the preparation method and application thereof |
| CN109535129A (en) * | 2018-12-14 | 2019-03-29 | 北京工业大学 | A kind of fluorescent probe molecule and its preparation and application |
| CN109884014A (en) * | 2019-03-07 | 2019-06-14 | 济南大学 | A kind of organosilicon imidazoles polymer detecting iron ion |
| 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 |
| 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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| CN108822130A (en) * | 2018-07-30 | 2018-11-16 | 天津师范大学 | Benzimidazole ring kind and the preparation method and application thereof |
| CN108822130B (en) * | 2018-07-30 | 2021-03-23 | 天津师范大学 | Benzimidazole cyclophane and preparation method and application thereof |
| CN109535129A (en) * | 2018-12-14 | 2019-03-29 | 北京工业大学 | A kind of fluorescent probe molecule and its preparation and application |
| CN109884014A (en) * | 2019-03-07 | 2019-06-14 | 济南大学 | A kind of organosilicon imidazoles polymer detecting iron ion |
| CN109884014B (en) * | 2019-03-07 | 2021-07-23 | 济南大学 | Organic silicon imidazole polymer for detecting iron ions |
| 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 |
| 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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