CN110128418A - A kind of near infrared fluorescent probe and its preparation method and application based on half flower cyanines structural derivative - Google Patents
A kind of near infrared fluorescent probe and its preparation method and application based on half flower cyanines structural derivative Download PDFInfo
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Abstract
A kind of near infrared fluorescent probe and its preparation method and application based on half flower cyanines structural derivative, which is C35H32N3O6S2 +, structural formula is as follows:.The probe is to carry out relevant structural modification using half flower cyanines structural derivative as parent, the probe can from generate different fluorescent building-blocks after different response material effects, fluorescence intensity significant changes and adjoint apparent color change, it can be used for benzenethiol, sulphur hydrogen radical ion, the open hole detection of sulfite ion, interfering ion of selection etc. is on detection effect substantially without influence, it realizes to benzenethiol, sulphur hydrogen radical, the identification of inferior sulfate radical responds, the probe is in three kinds of different buffer systems respectively to benzenethiol, hydrogen sulfide, sulfite ion response is rapider, and detection limit is all relatively low, it has good selectivity and higher sensitivity, in biology and the benzenethiol in environmental sample, sulphur hydrogen radical, the detection of inferior sulfate radical has good application prospect.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of near-infrared based on half flower cyanines structural derivative is glimmering
Light probe and its preparation method and application.
Background technique
With the development of society and the requirement of environmental protection, the detection of different ions and small-molecule substance is received more
Carry out the concern of more scientists, while studying small molecule and being concerned in application biological, in chemical and environment.Benzenethiol,
Sulphur hydrogen radical ion, sulfite ion are widely used in pesticide, the preparation of drug and various industrial products, sulphur hydrogen radical ion and sulfurous
Acid ion also performer's important role in Human Physiology level, thus in view of its high toxicity, organism physiology importance and
Caused environmental problem, exploitation is simple, quick, sensitive and can selectively distinguish benzenethiol, sulphur hydrogen radical ion, sulfite ion
Fluorescence probe, be of great significance in environmental protection, food safety and life science.In numerous detection technique means,
Fluorescence probe have easy to operate, high sensitivity, selectivity it is good, it is small to biological sample damage and can directly in living cells or
The advantages that being detected in tissue, thus become one of the hot spot of Recent study.In these numerous detection methods, fluorescence probe
It is researcher's focus of attention since its peculiar advantage forms.Compared with the fluorescence probe of visible light region, it is known that close red
(NIR, 650-900nm) fluorescence probe is more suitable for life system outside, because they generate fluorescence in the near infrared region, to living cells
Damage it is smaller, the least interference of the background auto-fluorescence of biomolecule in the more preferable tissue penetration of effect and biosystem.Hair
Exhibition can be detected effectively especially can detect benzenethiol, sulphur hydrogen radical ion, sulfite ion under the conditions of physiological level
Analysis method is of crucial importance and significant.
In recent years, fluorescent molecular probe technology is due to having the characteristics that high sensitivity, easy to operate, at low cost, at
For the important means for detecting ion and small molecule compound.Fluorescence enhancement sensing material can reduce detection mistake, to complex system
Detection is accurate.Fluorescence probe of the half flower cyanines structural derivative as ON/OFF form, with convieniently synthesized, response time short equal spies
Point obtains more and more extensive attention in ion and small-molecule substance identification field.Therefore, it is proposed that it is a kind of based on half flower cyanines
Fluorescence probe of structural derivative and preparation method thereof.
Summary of the invention
Present invention aims to overcome that prior art defect, it is glimmering to provide a kind of near-infrared based on half flower cyanines structural derivative
Light probe and its preparation method and application, the probe have good selectivity with higher sensitivity, be applicable to test sample
The fluorescence detection, visually qualitative of benzenethiol in product, sulphur hydrogen radical ion, sulfite ion content.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of near infrared fluorescent probe based on half flower cyanines structural derivative, the near infrared fluorescent probe molecular formula are
C35H32N3O6S2 +, structural formula is as follows:
。
The preparation method of the above-mentioned near infrared fluorescent probe based on half flower cyanines structural derivative comprising following steps:
1) seven methine Hua Jingyu compounds 1 reaction obtains compound 2；
2) compound 2 reacts to obtain near-infrared fluorescent of the target product based on half flower cyanines structural derivative with 2,4- dinitrofluorobenzene
Probe；
Wherein, the structural formula of compound 1 and compound 2 difference is as follows:
。
Further, step 1) specifically: under nitrogen protection, by compound 1 and K2CO3It is dissolved in acquisition solution a in acetonitrile, it will
Seven methines flower cyanines are dissolved in acquisition solution b in acetonitrile, react 10-15h, reaction knot in 50 DEG C of heating after solution a and solution b is mixed
Shu Hou, evaporating solvent under reduced pressure, and through silica gel column chromatogram separating purification, gained blue-green solid is compound 2, wherein seven first
River Hua Jing, compound 1 and K2CO3Molar ratio be 1:(2.0 ~ 2.1): (2.0 ~ 2.1).
Step 2 specifically: under nitrogen protection, by compound 2 and K2CO3It is dissolved in acquisition solution a in acetonitrile, by 2,4- bis-
Fluoronitrobenzene is dissolved in acquisition solution b in acetonitrile, reacts 5-15h in 50 DEG C of heating after solution a and solution b is mixed, and reaction terminates
Afterwards, evaporating solvent under reduced pressure, and through silica gel column chromatogram separating purification, obtained solid is that target product is based on half flower cyanines derivative knot
The near infrared fluorescent probe of structure, wherein the K of the 2,4-dinitrofluorobenzene, 2 sum of compound2CO3Molar ratio be 1:(2.5 ~
2.6): (3.0 ~ 3.1).
The present invention also provides it is above-mentioned based on half flower cyanines structural derivative near infrared region detect benzenethiol, sulphur hydrogen radical from
The application of son, sulfite ion, the probe is for benzenethiol, sulphur hydrogen radical ion, inferior sulfate radical in the environmental system of near infrared region
The content of ion and carry out fluorescence detection, visual qualitative detection.The near infrared fluorescent probe is respectively in DMSO/HEPES
(v/v=5/5, pH=7.4), DMSO/Tris-HCl (v/v=7/3, pH=7.4), DMSO/PB (v/v=9/1, pH=7.4) are mixed
It closes and benzenethiol, sulphur hydrogen is detected with ion, sulfite ion respectively in solution.
Various raw materials used in the present invention are ordinary commercial products, or by well known to a person skilled in the art
Method disclosed in method or the prior art obtains.
It is the relevant structural modification of parent progress that the probe, which is using half flower cyanines structural derivative, the probe can from it is different
Different fluorescent building-blocks, fluorescence intensity significant changes and adjoint apparent color change are generated after response material effect, it will
The present invention is surveyed in benzenethiol, hydrogen sulfide, the analysis performance of sulfite ion near infrared fluorescent probe and pertinent literature report and is reported
Other selective fluorescence probes in road are compared, the results showed that this near infrared fluorescent probe effect is fine.Near-infrared excitation and
Transmitting effectively reduces the light injury of biological sample and avoids the autofluorescence from n cell species.The present invention passes through1HNMR
、13CNMR phenetic analysis, the probe can with DMSO/HEPES (v/v=5/5, pH=7.4), DMSO/Tris-HCl (v/v=7/3,
PH=7.4), it is fast to benzenethiol, hydrogen sulfide, sulfite ion respectively in DMSO/PB (v/v=9/1, pH=7.4) mixed solution
Speed response.
Compared to the prior art, beneficial effects of the present invention:
The probe is to carry out relevant structural modification using half flower cyanines structural derivative as parent, which can be from different responses
Different fluorescent building-blocks, fluorescence intensity significant changes and adjoint apparent color change are generated after material effect, can be used for
The open hole detection of benzenethiol, sulphur hydrogen radical ion, sulfite ion, interfering ion of selection etc. is to detection effect substantially without shadow
It rings, realizes the response of the identification to benzenethiol, hydrogen sulfide, sulfite ion, the probe is in three kinds of different buffer systems
It is rapider to benzenethiol, hydrogen sulfide, sulfite ion response respectively, and detection limit is all relatively low, has good selection
Property and higher sensitivity, biology and benzenethiol, hydrogen sulfide, sulfite ion in environmental sample detection have it is good
Application prospect.
Detailed description of the invention
Fig. 1 is that the present invention is based on the synthetic route charts of the near infrared fluorescent probe of half flower cyanines structural derivative；
Fig. 2 is that the present invention is based on the nucleus magnetic hydrogen spectrums of the near infrared fluorescent probe of half flower cyanines structural derivative；
Fig. 3 is that the present invention is based on the nuclear-magnetism carbon spectrums of the near infrared fluorescent probe of half flower cyanines structural derivative；
Fig. 4 be it is ultraviolet after the near infrared fluorescent probe (10 μM) that benzenethiol is surveyed in based on half flower cyanines structural derivative is added-
Visible absorption spectra changes with time trend；Illustration is after the color of probe and probe and benzenethiol have reacted under ultraviolet lamp
Color change；
Fig. 5 is that fluorescence light after benzenethiol to the near infrared fluorescent probe (10 μM) surveyed based on half flower cyanines structural derivative is added
Compose the trend that changes with time；
Fig. 6 is that the solution for the near infrared fluorescent probe (10 μM) surveyed the present invention is based on half flower cyanines structural derivative is dense with benzenethiol
The increase of degree and present uv-visible absorption spectra variation；
Fig. 7 is that the solution for the near infrared fluorescent probe (10 μM) surveyed the present invention is based on half flower cyanines structural derivative is dense with benzenethiol
The increase of degree and present fluorescence spectrum variation；
Fig. 8 is the solution for the near infrared fluorescent probe (10 μM) surveyed the present invention is based on half flower cyanines structural derivative with different ions
Uv-visible absorption spectra variation；
Fig. 9 is the solution for the near infrared fluorescent probe (10 μM) surveyed the present invention is based on half flower cyanines structural derivative with different ions
Fluorescence spectrum variation；
Figure 10 is purple after NaHS to the near infrared fluorescent probe (10 μM) surveyed based on half flower cyanines structural derivative is added
Outside-visible absorption spectra changes with time trend；Illustration is that the color of probe and probe and NaHS are anti-under ultraviolet lamp
Color change after having answered；
Figure 11 is that fluorescence after NaHS to the near infrared fluorescent probe (10 μM) surveyed based on half flower cyanines structural derivative is added
Spectrum changes with time trend；
Figure 12 is the solution for the near infrared fluorescent probe (10 μM) surveyed the present invention is based on half flower cyanines structural derivative with NaHS
The increase of concentration and present uv-visible absorption spectra variation；
Figure 13 is the solution for the near infrared fluorescent probe (10 μM) surveyed the present invention is based on half flower cyanines structural derivative with NaHS
The increase of concentration and present fluorescence spectrum variation；
Figure 14 is the solution for the near infrared fluorescent probe (10 μM) surveyed the present invention is based on half flower cyanines structural derivative with different ions
Uv-visible absorption spectra variation；
Figure 15 is purple after sodium sulfite to the near infrared fluorescent probe (10 μM) surveyed based on half flower cyanines structural derivative is added
Outside-visible absorption spectra changes with time trend；Illustration is that the color of probe and probe and sodium sulfite are anti-under ultraviolet lamp
Color change after having answered；
Figure 16 is the solution for the near infrared fluorescent probe (10 μM) surveyed the present invention is based on half flower cyanines structural derivative with sodium sulfite
The increase of concentration and present uv-visible absorption spectra variation.
Specific embodiment
Below by way of preferred embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited to
This.
Embodiment 1:
A kind of near infrared fluorescent probe based on half flower cyanines structural derivative, the near infrared fluorescent probe molecular formula are
C35H32N3O6S2 +, structural formula is as follows:
。
The above-mentioned preparation method based on the near infrared fluorescent probe based on half flower cyanines structural derivative, synthetic route are shown in figure
1, specifically includes the following steps:
1) preparation of compound 2
Under nitrogen protection, by compound 1(70 mg, 0.33 mmol) and K2CO3(45 mg, 0.33 mmol) is added to 25
In mL acetonitrile, 30 min are stirred at room temperature and obtain solution a.Seven methines flower cyanines (100 mg, 0.16 mmol) is dissolved in 10 mL
Acetonitrile obtains solution b.Solution b is added in above-mentioned solution a by syringe, then heating reflux reaction under the conditions of 50 DEG C
10 hours.After reaction, evaporating solvent under reduced pressure passes through silica gel column chromatography (eluant, eluent, VMethylene chloride:VMethanol=50:1) further divide
From purifying, 57 mg of blue-green solid, as compound 2(yield are obtained, 71%).
The synthetic route of compound 2 is as follows:
。
2) preparation of near infrared fluorescent probe of the target compound based on half flower cyanines structural derivative
Under nitrogen protection, by compound 2(200 mg, 0.41 mmol) and K2CO3(68 mg, 0.49 mmol) is added to 25
In mL acetonitrile, 30 min are stirred at room temperature and obtain solution a.By compound 2,4-dinitrofluorobenzene (100 mg, 0.16 mmol)
It is dissolved in 10 mL acetonitriles and obtains solution b.Solution b is added in above-mentioned solution a by syringe, it is then anti-at room temperature
It answers 15 hours.After reaction, evaporating solvent under reduced pressure passes through silica gel column chromatography (eluant, eluent, VMethylene chloride:VMethanol=30:1) further
It isolates and purifies, obtains 185 mg of solid, as target compound (is received based on the near infrared fluorescent probe of half flower cyanines structural derivative
Rate, 69%).
To preparation gained target compound based on the near infrared fluorescent probe of half flower cyanines structural derivative carry out nucleus magnetic hydrogen spectrum,
Nuclear-magnetism carbon spectrum analysis, as a result following (being detailed in Fig. 2 and 3):
1H NMR (400 MHz, CDCl3) δ 8.92 (d, J = 2.7 Hz, 1H), 8.56 (d, J = 15.2 Hz,
1H), 8.45 (dd, J = 9.2, 2.8 Hz, 1H), 7.89 (s, 1H), 7.50 (d, J = 2.2 Hz, 2H),
7.43 (dd, J = 4.1, 1.9 Hz, 2H), 7.18 (d, J = 9.3 Hz, 1H), 7.02 (d, J = 6.9
Hz, 2H), 6.96 (d, J = 6.3 Hz, 1H), 5.84 (s, 1H), 4.27 (s, 3H), 3.51 – 3.39
(m, 2H), 3.39 – 3.29 (m, 2H), 2.90 (t, J = 6.0 Hz, 2H), 2.73 (t, J = 6.0 Hz,
2H), 1.99 – 1.89 (m, 2H), 1.72 (s, 6H). 13C NMR (100 MHz, CDCl3) δ 179.37,
152.85, 152.03, 146.32, 142.33, 142.06, 141.96, 139.46, 131.34, 131.22,
129.44, 129.35, 128.49, 128.30, 122.35, 122.24, 120.68, 119.15, 116.32,
113.59, 108.09, 107.95, 51.13, 48.28, 39.97, 34.76, 29.69, 27.72, 24.55,
20.21.
The synthetic route of target compound is as follows:
。
Fluorescence detection application test
Hereinafter, easy for description, the present invention is prepared into gained target compound and " surveys benzenethiol, hydrogen sulfide, sulfite ion
Near infrared fluorescent probe " be together simply referred to as " probe 2SFB ".
1) preparation of stand-by storage liquid is detected:
A. probe 2SFB sample solution (1.00 × 10-3 mol·L-1) preparation:
0.00654 g (M=654.78) probe 2SFB is taken to be dissolved in 10 mL acetonitriles, being made into concentration is 1.00 × 10-3
mol·L-1Solution.
B. it is 1.00 × 10 that various ions, which are configured as concentration with deionized water,-3 mol·L-1Or 1.00 × 10-2 mol·L-1Solution
C. HEPES buffer solution (0.01 molL-1, pH=7.4) preparation:
It takes 119.15g 4- hydroxyethyl piperazineethanesulfonic acid to be dissolved in 400 mL deionized waters, adds 1 mol L-1Sodium hydroxide
Aqueous solution is adjusted to required pH (pH=7.4), is then settled to 500 mL in saving in refrigerator with deionized water.
D. Tris-HCl buffer solution (0.05 mol L-1, pH=7.4) preparation:
It takes 1.51425g trishydroxymethylaminomethane to be dissolved in 100 mL deionized waters, adds 0.1 mol L-1Hydrochloric acid it is water-soluble
Liquid is adjusted to required pH (pH=7.4), is then settled to 250 mL in saving in refrigerator with deionized water.
E. PB buffer solution (0.2 mol L-1, pH=7.4) preparation:
0.2 mol•L-1PBS mother liquor (pH=7.4): the 0.2 mol L of 19 mL is taken-1KH2PO4, 0.2 mol L of 81mL-1
K2HPO4?.Then 50 mL0.2 mol L are taken-1 PBS solution is diluted with water to 1000 mL.
Experimental water used in experiment is deionized water herein.
2) it tests and analyzes
A. benzenethiol
Take 3 mL DMSO/HEPES (0.10 mol L-1, v/v=5/5, pH=7.4) and mixed solution, 30 μ L probe 2SFB are added
Sample solution (1.00 × 10-3 mol·L-1) and 30 μ L benzenethiols (1.00 × 10-3 mol·L-1), it is reacted in 25 DEG C, so
After carry out ultraviolet detection, as a result as shown in Figure 4.As seen from Figure 4: as time increases, probe 2SFB and benzenethiol are anti-
It answers, gradually increases absorbance.Absorbance as shown in the figure was to increase at 713nm with the growth of time in wavelength, at 3 minutes
Absorbance reaches maximum afterwards, it can thus be appreciated that the reaction time completes in 3 minutes in later test.Fig. 4 illustration is before reacting
Photo afterwards, the visible benzenethiol of naked eyes can make near infrared fluorescent probe solution occur apparent color change in figure, color by
Purple becomes green.
Take 3 mL DMSO/HEPES (0.10 mol L-1, v/v=5/5, pH=7.4) and mixed solution, 30 μ L probes are added
2SFB sample solution (1.00 × 10-3 mol·L-1), add benzenethiol (1.00 × 10-3 mol·L-1) 30 μ L, in 25
It is reacted under the conditions of DEG C, then carries out fluorescence detection, excitation wavelength 713nm, slit: 2.5/2.5nm, as a result as shown in Figure 5.By
Fig. 5 is it can be seen that as time increases, release fluorescence after probe 2SFB and benzenethiol reaction, fluorescence intensity gradually increases
Add.
Take 3 mL DMSO/HEPES (0.10 mol L-1, v/v=5/5, pH=7.4) and mixed solution, 30 μ L probes are added
2SFB sample solution (1.00 × 10-3 mol·L-1), 5 μ L benzenethiols are added every 3min, reacts in 25 DEG C, then carries out
Ultraviolet detection, until absorbance reaches maximum when 30 μ L benzenethiol is added.As a result as shown in fig. 6, as seen from Figure 6: with
It is to release fluorescence at 713nm that the increase of equivalent, probe 2SFB and benzenethiol, which is added, in wavelength in benzenethiol, makes absorbance gradually
Increase.
Take 3 mL DMSO/HEPES (0.10 mol L-1, v/v=5/5, pH=7.4) and mixed solution, 30 μ L probes are added
2SFB sample solution (1.00 × 10-3 mol·L-1), 5 μ L benzenethiols (1.00 × 10 are added every 3min-3 mol·L-1),
It is reacted under the conditions of 25 DEG C, then carries out fluorescence detection, excitation wavelength 713nm, slit: 2.5/2.5nm, as a result such as Fig. 7 institute
Show.As seen from Figure 7: as the increase of equivalent is added in benzenethiol, probe 2SFB and benzenethiol release fluorescence, make fluorescence
Intensity gradually increases.
3 mL DMSO/HEPES (0.10 mol L is taken in parallel-1, v/v=5/5, pH=7.4) and 20 parts of mixed solution, every part
30 μ L probe 2SFB sample solutions (1.00 × 10 are added-3 mol·L-1), then it is separately added into (1) blank；(2)30μL F-；
(3)30μL Br-；(4)30μL Cl-；(5)30μL SO4 2-；(6)30μL HCO3 -；(7)30μL CO3 2-；(8)30μL NO2 -；
(9)30μL CH3COO-；(10)30μL H2O2；(11)30μL H2PO4 -；(12)30μL PhOH；(13)30μL ClO-；(14)30
μL K+；(15)30μL Na+；(16)30μL Cys；(17)30μL GSH； (18)30μL HS-；(19)30μL SO3 2-；(20)
30 μ L PhSH carry out UV-Vis spectra and fluorescent scanning after reaction 3 minutes, as a result as shown in Figure 8 and Figure 9 respectively.By
Fig. 8 and Fig. 9 increases absorbance and fluorescence intensity, sulphur hydrogen radical ion and sulfurous it can be seen that probe 2SFB and benzenethiol reaction
Acid ion is decline with this condition, and other ions are strong without apparent absorbance and fluorescence with this condition with probe
Degree variation.
B. NaHS
Take 3 mL DMSO/Tris-HCl (0.10 mol L-1, v/v=7/3, pH=7.4) and mixed solution, 30 μ L probes are added
2SFB sample solution (1.00 × 10-3 molL-1), 30 μ L NaHSs (1.00 × 10 are added-3 mol·L-1), in 25
DEG C reaction, every 1min then carry out ultraviolet detection, the results are shown in Figure 10.As seen from Figure 10: as time increases,
Probe 2SFB and NaHS reaction, gradually increase absorbance.Absorbance as shown in the figure increases with the growth of time, but
Absorbance reaches maximum after 11 minutes, it can thus be appreciated that the reaction time completes in 11 minutes in later test.Figure 10 is inserted
Figure is the photo of reaction front and back, and the visible NaHS of naked eyes can make near infrared fluorescent probe solution that apparent color occur in figure
Variation, color become bright green from purple.
Take 3 mL DMSO/Tris-HCl (0.10 mol L-1, v/v=7/3, pH=7.4) and mixed solution, 30 μ L are added and visit
Needle 2SFB sample solution (1.00 × 10-3 molL-1), add NaHS (1.00 × 10-3 mol·L-1) 30μ
L is reacted in 25 DEG C, every 1min and then carries out fluorescence detection, excitation wavelength 718nm, slit: 1.5/5nm, as a result such as Figure 11
It is shown.As seen from Figure 11: as time increases, probe 2SFB and NaHS release fluorescence, make fluorescence intensity
It gradually increases.
Take 3 mL DMSO/Tris-HCl (0.10 mol L-1, v/v=7/3, pH=7.4) and mixed solution, 30 μ L are added and visit
Needle 2SFB sample solution (1.00 × 10-3 mol·L-1), 5 μ L NaHSs are added every 11min, are reacted in 25 DEG C, so
After carry out ultraviolet detection, until absorbance reaches maximum when 12 μM of NaHSs are added.It as a result as shown in figure 12, can by Figure 12
To find out: as the increase of equivalent is added in NaHS, probe 2SFB and NaHS release fluorescence, make absorbance gradually
Increase.
Take 3mL DMSO/Tris-HCl (0.10 mol L-1, v/v=7/3, pH=7.4) and mixed solution, 30 μ L are added and visit
Needle 2SFB sample solution (1.00 × 10-3 mol·L-1), 5 μ L are added every 11min, NaHS (1.00 × 10 is added-3
mol·L-1), it is reacted under the conditions of 25 DEG C, then carries out fluorescence detection, excitation wavelength 718nm, slit: 1.5/5nm, as a result
As shown in figure 13.As seen from Figure 13: as the increase of equivalent is added in NaHS, probe 2SFB and NaHS are released
Carry out fluorescence, gradually increases fluorescence intensity.
Take 3 mL DMSO/Tris-HCl (0.10 mol L-1, v/v=7/3, pH=7.4) and 20 parts of mixed solution, every part adds
Enter 30 μ L probe 2SFB sample solutions (1.00 × 10-3 mol·L-1), then it is separately added into (1) blank；(2)30μL F-；(3)
30μL Br-；(4)30μL Cl-；(5)30μL SO4 2-；(6)30μL HCO3 -；(7)30μL CO3 2-；(8)30μL NO2 -；(9)30
μL CH3COO-；(10)30μL H2O2；(11)30μL H2PO4 -；(12)30μL PhOH；(13)30μL ClO-；(14)30μL K+；(15)30μL Na+；(16)30μL Cys；(17)30μL GSH (18)30μL SO3 2-；(19)30μL PhSH；(20)30μL
HS-, UV, visible light spectrum scanning is carried out after reaction 11 minutes, it is as a result as shown in figure 14 respectively.As seen from Figure 14: probe 2SFB
And HS-Reaction increases absorbance and fluorescence intensity, and benzenethiol and sulfite ion have a fraction interference, and other ions
With probe with this condition without apparent absorbance and fluorescence intensity change.
C. sodium sulfite
Take 3mL DMSO/PB (0.10 mol L-1, v/v=9/1, pH=7.4) and mixed solution, 30 μ L probe 2SFB samples are added
Solution (1.00 × 10-3 mol·L-1) and 30 μ L sodium sulfites response time, in 25 DEG C react, then carry out ultraviolet inspection
It surveys, as a result as shown in figure 15.As seen from Figure 15: as time increases, probe 2SFB and sodium sulfite reaction make extinction
Degree gradually increases.Absorbance as shown in the figure increases with the growth of time, but absorbance reaches maximum after 30 minutes, thus
It knows in later test, the reaction time completes in 30 minutes.Figure 15 illustration is the photo of reaction front and back, and naked eyes can in figure
See that sodium sulfite can make near infrared fluorescent probe solution that apparent color change occur, color becomes light green color from purple.
Take 3 mL DMSO/PB (0.10 mol L-1, v/v=9/1, pH=7.4) and mixed solution, 30 μ L probe 2SFB are added
Sample solution (1.00 × 10-3 mol·L-1) every 30min 5 μ L sodium sulfites of addition, it is reacted under the conditions of being often inferior to 25 DEG C,
Then ultraviolet detection is carried out, until absorbance reaches maximum when 30 μ L sodium sulfite is added.As a result as shown in figure 16, by Figure 16
It can be seen that probe 2SFB and sodium sulfite release fluorescence as the increase of equivalent is added in sodium sulfite, make absorbance by
It is cumulative to add.
3) detection limit
A. benzenethiol
Take 3 mL DMSO/HEPES (0.10 mol L-1, v/v=5/5, pH=7.4) and mixed solution, 30 μ are added every time respectively
L probe 2SFB sample acetonitrile solution (1.00 × 10-3 mol·L-1), ultraviolet-visible spectrum is carried out after each reaction 3 minutes
Scanning, until photon absorbing intensity does not have significant change, using concentration as abscissa, absorbance be ordinate carry out doing figure, obtain as
Linear equation described in attached drawing in Fig. 6.Separately take 3 mL DMSO/HEPES (0.10 mol L-1, v/v=5/5, pH=7.4) and mixed
Solution is closed, 30 μ L probe 2SFB sample solutions (1.00 × 10 are added-3 mol·L-1), continuously survey 20 photon absorbing intensities, meter
Standard variance is calculated, it again can divided by the slope of linear equation in Fig. 6 multiplied by 3 by the result of the standard variance according to detection limit formula
The detection for obtaining fluorescence probe of the present invention is limited to 0.26 μM.
B. NaHS
Take 3 mL DMSO/Tris-HCl (0.10 mol L-1, v/v=7/3, pH=7.4) and mixed solution, it is added every time respectively
30 μ L probe 2SFB sample acetonitrile solutions (1.00 × 10-3 mol·L-1), UV, visible light is carried out after each reaction 11 minutes
Light spectral scan, until photon absorbing intensity does not have significant change, using concentration as abscissa, absorbance is that ordinate is done
Figure, obtains the linear equation as described in the attached drawing in Figure 12.Separately take 3 mL DMSO/Tris-HCl (0.10 mol L-1,v/v=7/
3, pH=7.4) 30 μ L probe 2SFB sample solutions (1.00 × 10 are added in mixed solution-3 mol·L-1), it is continuous to survey 20 times
Photon absorbing intensity calculates standard variance, according to detection limit formula by the result of the standard variance multiplied by 3 again divided by linear in Figure 12
The detection that the slope of equation can obtain fluorescence probe of the present invention is limited to 0.45 μM.
C. sodium sulfite
Take 3 mL DMSO/PB (0.10 mol L-1, v/v=9/1, pH=7.4) and mixed solution, 30 μ L are added every time respectively and visit
Needle 2SFB sample acetonitrile solution (1.00 × 10-3 mol·L-1), ultraviolet-visible spectrum is carried out after each reaction 30 minutes to be swept
It retouches, until photon absorbing intensity does not have significant change, using concentration as abscissa, absorbance is that ordinate carries out doing figure, is obtained such as figure
Linear equation described in attached drawing in 16.Separately take 3 mL DMSO/PB (0.10 mol L-1, v/v=9/1, pH=7.4) mixing it is molten
30 μ L probe 2SFB sample solutions (1.00 × 10 are added in liquid-3 mol·L-1), 20 photon absorbing intensities are continuously surveyed, mark is calculated
Quasi- variance can obtain the result of the standard variance multiplied by 3 according to detection limit formula divided by the slope of linear equation in Figure 16 again
The detection of fluorescence probe of the present invention is limited to 0.32 μM.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of near infrared fluorescent probe based on half flower cyanines structural derivative, which is characterized in that the near infrared fluorescent probe point
Minor is C35H32N3O6S2 +, structural formula is as follows:
。
2. the preparation method of the near infrared fluorescent probe according to claim 1 based on half flower cyanines structural derivative, feature
It is, comprising the following steps:
1) seven methine Hua Jingyu compounds 1 reaction obtains compound 2；
2) compound 2 reacts to obtain near-infrared fluorescent of the target product based on half flower cyanines structural derivative with 2,4- dinitrofluorobenzene
Probe；
Wherein, the structural formula of compound 1 and compound 2 difference is as follows:
。
3. the preparation method of the near infrared fluorescent probe according to claim 2 based on half flower cyanines structural derivative, feature
It is, step 1) specifically: under nitrogen protection, by compound 1 and K2CO3It is dissolved in acquisition solution a in acetonitrile, by seven methines flower
Cyanines are dissolved in acetonitrile acquisition solution b, in stirring to after reaction after solution a and solution b is mixed, evaporating solvent under reduced pressure, and
Through silica gel column chromatogram separating purification to get compound 2.
4. the preparation method of the near infrared fluorescent probe according to claim 3 based on half flower cyanines structural derivative, feature
It is, seven methines flower cyanines, compound 1 and K2CO3Molar ratio be 1:(2.0 ~ 2.1): (2.0 ~ 2.1), solution a and solution b mixing
Reaction temperature is 50 DEG C afterwards.
5. the preparation method of the near infrared fluorescent probe according to claim 2 based on half flower cyanines structural derivative, feature
It is, step 2 specifically: under nitrogen protection, by compound 2 and K2CO3It is dissolved in acquisition solution a in acetonitrile, by 2,4- dinitro
Base fluorobenzene is dissolved in acquisition solution b in acetonitrile, molten to after reaction, removing under reduced pressure in stirring after solution a and solution b is mixed
Agent, and through silica gel column chromatogram separating purification, obtained solid is target product.
6. the preparation method of the near infrared fluorescent probe according to claim 5 based on half flower cyanines structural derivative, feature
It is, the K of the 2,4-dinitrofluorobenzene, 2 sum of compound2CO3Molar ratio be 1:(2.5 ~ 2.6): (3.0 ~ 3.1).
7. the near infrared fluorescent probe based on half flower cyanines structural derivative described in claim 1 is applied in compound test,
It is characterized in that, for detecting benzenethiol, sulphur hydrogen radical, one or any of several in inferior sulfate radical.
8. utilizing the compound test side of the near infrared fluorescent probe based on half flower cyanines structural derivative described in claim 1
Method, which is characterized in that the compound is benzenethiol, sulphur hydrogen radical, one or any of several in inferior sulfate radical；Specific detection method
Are as follows:
In near infrared spectrum:
Measuring samples are dissolved in the DMSO/HEPES mixed solution of pH=7.4, benzenethiol in measuring samples is detected；
Measuring samples are dissolved in the DMSO/Tris-HCl mixed solution of pH=7.4, sulphur hydrogen radical ion in measuring samples is carried out
Detection；
Measuring samples are dissolved in the DMSO/PB mixed solution of pH=7.4, measuring samples sulfite radical ion is detected.
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