CN103865522A - Fluorescence molecular probe and application thereof in hydrogen sulfide detection - Google Patents
Fluorescence molecular probe and application thereof in hydrogen sulfide detection Download PDFInfo
- Publication number
- CN103865522A CN103865522A CN201410071543.2A CN201410071543A CN103865522A CN 103865522 A CN103865522 A CN 103865522A CN 201410071543 A CN201410071543 A CN 201410071543A CN 103865522 A CN103865522 A CN 103865522A
- Authority
- CN
- China
- Prior art keywords
- hydrogen sulfide
- concentration
- nitrine
- detection
- molecular probe
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 CC1(*)C=CC(C(c2ccccc2)=C(C(CC2)=CC=C2I)C2=CC=C*(*)C=C2)=CC=C1 Chemical compound CC1(*)C=CC(C(c2ccccc2)=C(C(CC2)=CC=C2I)C2=CC=C*(*)C=C2)=CC=C1 0.000 description 2
- VWFRTWJSNLGASX-UHFFFAOYSA-N Cc(cc1)ccc1-c1nc(-c2ccccc2)c(-c2ccccc2)nc1-c1ccccc1 Chemical compound Cc(cc1)ccc1-c1nc(-c2ccccc2)c(-c2ccccc2)nc1-c1ccccc1 VWFRTWJSNLGASX-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a fluorescence molecular probe and application thereof in hydrogen sulfide detection. The structure of the fluorescence molecular probe is R1-N3, wherein R1 is a gene with aggregated and induced luminescence property. The principle is as follows: the molecule containing a nitrine functional group does not shine in a solution or an aggregation state due to the quenching effect of nitrine while the molecule containing amino generated after reduction of the nitrine functional group by using hydrogen sulfide displays the characteristics of an adaptive image enhancer (AIE). Thus, detection of the hydrogen sulfide concentration in the aggregation state is achieved. The principle is as follows: the fluorescence quenching of the overall aggregation is caused by azide groups left in the aggregation state. Therefore, luminescence of the probe molecule just can be opened after most of azide groups are reduced. Thus, the detection limit and the effective detection range are regulated and controlled by regulating and controlling the concentration of the probe molecule.
Description
Technical field
The present invention relates to chemical detection and field of biological detection, be specifically related to a kind of novel fluorescent molecular probe and the application in sulfurated hydrogen detection thereof.
Background technology
Hydrogen sulfide (H
2s), as a kind of endogenic gaseous signal molecule, the numerous physiological processs in organism have been participated in, with numerous disease-relateds.Hydrogen sulfide has participated in numerous physiological processs, comprises vasodilation, vasculogenesis, oxygen sensing, apoptosis, tissue inflammation, neuroregulation process and wound and ischemic protection etc.Meanwhile, in human body, hydrogen sulfide levels height, may imply the existence of some diseases in human body, comprises alzheimer's disease, Down's syndrome, diabetes and liver cirrhosis.But hydrogen sulfide effect, the mechanism of action in vivo there is no final conclusion, the definite of the detection to hydrogen sulfide and concentration seems particularly important.Could what kind of the concentration of hydrogen sulfide allow it bring into play due effect within the scope of in organism? conversely, in definite organism, after normal hydrogen sulfide content, also contribute to the concrete mechanism of each physiological process of studying hydrogen sulfide participation.
In the recent period, there is bibliographical information to use Single Walled Carbon Nanotube and quantum dot in abiotic system, to detect hydrogen sulfide as fluorescent probe, detectability divides and has been clipped to 3ppb(specifically referring to Anal.Chem.2010,82,250-257) He 0.15 μ M(is specifically referring to J.Fluoresc.2010,20,243-250).These two kinds of methods all have extraordinary sensitivity and selectivity to sulfurated hydrogen detection, but cannot introduce cell interior.According to same thinking, someone has developed the sulfurated hydrogen detection means based on fluorescence molecule.Reacting with hydrogen sulfide by probe molecule, produce fluorescence and strengthen or quencher, then by the variation of fluorescence intensity, qualitatively or quantitatively determine the hydrogen sulfide in system, is the basic ideas of this detection means.The people such as Xian designed one containing disulfide linkage without fluorescence molecule as probe (specifically referring to Angew Chem.Int.Ed.2011,50,10327-10329), can launch the very molecule of hyperfluorescenceZeng Yongminggaoyingguang with generation after hydrogen sulfide effect, by detecting the variation of glimmering light intensity, can determine hydrogen sulfide content.According to similar principles, the people such as Wang designed one novel, stable without fluorescence molecule---red acid azide (specifically referring to: Angew Chem.Int.Ed.2011,50,9672-9675), after hydrogen reduction, can launch strong fluorescence curing.The fluorescence detection of hydrogen sulfide has simple to operate, responds the advantages such as rapid.
But most of luminous organic materials conventionally can present luminous efficiency and reduce even non-luminous phenomenon in state of aggregation or when solid-state, assemble quenching of fluorescence (ACQ), this has just limited the range of application of luminous organic material greatly.
Calendar year 2001, professor Tang Benzhong leader's study group has observed an optical physics phenomenon contrary with traditional ACQ phenomenon: a series of Siloles (silole) molecule is not luminous in solution, and after gathering transmitting very strong fluorescence (specifically referring to Chem.Commun., 2001,1740).Tang is be defined as " aggregation inducing is luminous " (Aggregation-Induced Emission, AIE) by this unique phenomenon.AIE phenomenon has very great academic significance, and people no longer need the generation of removing to avoid the clustering phenomena that is difficult to avoid deliberately, is of value to luminous because assemble.Afterwards, they have found that the molecule much with similar propeller arrangement has same character, when increasing new A IE system is developed, AIE molecule is also widely used in multiple fields such as analyzing and testing, bio-sensing and electroluminescent device (specifically referring to Chem Soc Rev as fluorescent probe and electroluminescent material, 2011,5361; Chem.Commun.2009,4332).
Although can estimate AIE molecule aspect sulfurated hydrogen detection by there being unique advantage, there is not yet at present report.The fluorescent probe molecule of conventional detection hydrogen sulfide shows as the behavior of assembling quench fluorescence, so can only realize the detection to hydrogen sulfide in solution.Contradiction is, organic probe molecule is often water insoluble, and the detection of hydrogen sulfide need to be carried out in water, and in addition, the medium of living things system is generally water.In these media, detect and will greatly reduce the performance of fluorescent probe molecule.And if AIE molecule is used for detecting hydrogen sulfide, even in water, probe molecule has formed state of aggregation, due to its AIE performance, also can emitting fluorescence, realize the highly sensitive detection to hydrogen sulfide.Therefore, adopt the molecule of AIE activity to realize the detection of hydrogen sulfide is had to important scientific meaning and the using value in non-organic solvent system as probe.
Summary of the invention
The invention provides a kind of fluorescent molecular probe and the application in sulfurated hydrogen detection thereof, the principle that this fluorescent molecular probe can regulate based on detectability in non-organic solvent system realizes the simple detection of concentration of hydrogen sulfide.
A kind of fluorescent molecular probe, structure is R
1-N
3, wherein, R
1for thering is the group of aggregation inducing luminescent properties.
In the present invention, R
1-N
3aggregate and hydrogen sulfide react and generate R
1-NH
2, reaction formula is as follows:
Because the fluorescence quenching of nitrine functional group causes molecule R
1-N
3all not luminous in solution or under state of aggregation, and with hydrogen sulfide effect after the R-NH that generates
2molecule can be luminous under state of aggregation, thereby realize the detection of hydrogen sulfide in non-organic solvent system; In addition, because azido group residual under state of aggregation may cause the quenching of fluorescence of whole aggregate, so fluorescence can only just can be " unpacked " after azido group total overall reaction.Like this, just realize the adjusting of sulfurated hydrogen detection limit.
As preferably, described R
1be selected from the one in formula I～formula IV;
In formula I, R
2～R
4independently selected from aryl, alkyl, alkoxyl group or H;
In formula (II), R
5and R
6be selected from C
1～C
5alkyl or aryl;
" * " represents the position of substitution.
As further preferred, described R
1structure suc as formula shown in (I-1):
In formula (I-1), " * " represents the position of substitution.Now, described fluorescent molecular probe has specificity to the detection of hydrogen sulfide, and other negatively charged ion except sulphur hydrogen root are not responded; And this fluorescent molecular probe has freedom from jamming to the detection of hydrogen sulfide, in the time having other negatively charged ion to exist, do not affect its response to sulphur hydrogen radical ion.
The present invention also provides a kind of detection method of concentration of hydrogen sulfide, after being mixed with the fluorescent molecular probe of described different concns, the liquid to be measured of sulfide hydrogen or HS-measures its fluorescence intensity, if emitting fluorescence after mixing, the concentration of hydrogen sulfide or HS-in definite liquid to be measured
Described fluorescent molecular probe is state of aggregation.
As further preferably, the dimethyl sulphoxide solution of described fluorescent molecular probe is added drop-wise to the fluorescent molecular probe that can obtain state of aggregation in the buffered soln that pH is 6.5-8.0;
Described dimethyl sulphoxide solution and the volume ratio of buffered soln are 1～3:9～7.
Be that pH is 7.4 HEPES damping fluid as further preferred, described buffered soln;
The volume ratio of described dimethyl sulphoxide solution and HEPES damping fluid is 2:8.
As preferably, by fluorescent molecular probe, the concentration in state of aggregation regulates the detectability of described hydrogen sulfide;
The detection of described hydrogen sulfide is limited to 0-100 μ M; Within the scope of this, the specificity of detection is good, and response rapidly.
As further preferred, the detectability of described hydrogen sulfide is adjusted within the scope of 10～50 μ M.
Compared with prior art, beneficial effect of the present invention is embodied in:
(1) detection of hydrogen sulfide is had to the features such as specificity, freedom from jamming, response be rapid, the present invention also has following special performance:
(2) R
1-N
3aggregate and the R that generates of hydrogen sulfide effect reduction
1-NH
2, because the characteristic of AIE makes its emitting fluorescence, so this detection means can be applied to water, solved traditional probe molecule because its ACQ effect is the not luminous contradiction that need to carry out at water that detects of state of aggregation at water.In addition, because azido group residual under state of aggregation may cause the quenching of fluorescence of whole aggregate, so fluorescence can only just can be " unpacked " after azido group total overall reaction.Like this, just realize the special performance that can regulate and control detectability by the concentration of adjustment probe molecule.
Brief description of the drawings
Fig. 1 is that the probe molecule tetraphenyl ethene nitrine molecule that makes of embodiment 1 is at DMSO-d
6in proton nmr spectra (in figure, " * " represents solvent peak);
Fig. 2 is that the amino tetraphenyl ethylene molecule of the reference substance that makes of embodiment 1 is at CDCl
3in proton nmr spectra (in figure, " * " represents solvent peak);
Fig. 3 is the AIE curve of amino tetraphenyl ethylene molecule, and wherein, A is the luminescent spectrum of amino tetraphenyl ethene in the mixing solutions of the different dimethyl sulfoxide (DMSO)/water of moisture content, and B is the variation with moisture content of luminous peak strength;
Fig. 4 is the existence of tetraphenyl ethene nitrine Molecular Detection hydrogen sulfide;
Fig. 5 is the effect curves of tetraphenyl ethene nitrine molecule and different anions, and A is the luminescent spectrum after tetraphenyl ethene nitrine molecule and different anions and hydrogen sulfide effect; B is luminous peak strength intensification factor after tetraphenyl ethene nitrine molecule and different anions and hydrogen sulfide effect;
Fig. 6 is tetraphenyl ethene nitrine molecule freedom from jamming to sulfurated hydrogen detection under the existence of different anions, and A is under other ions exist, the luminescent spectrum after tetraphenyl ethene nitrine molecule and hydrogen sulfide effect; B is under other ions exist, luminous peak strength intensification factor after tetraphenyl ethene nitrine molecule and hydrogen sulfide effect;
Fig. 7 is tetraphenyl ethene nitrine molecular conecentration detection by quantitative hydrogen sulfide while being 10 μ M;
Fig. 8 is tetraphenyl ethene nitrine molecular conecentration detection by quantitative hydrogen sulfide while being 20 μ M;
Fig. 9 is tetraphenyl ethene nitrine molecular conecentration detection by quantitative hydrogen sulfide while being 50 μ M.
Embodiment
The present invention detects the fluorescent probe molecule of hydrogen sulfide under state of aggregation, and synthetic route is:
The synthetic route of tetraphenyl ethene nitrine molecule: ditane is dissolved in tetrahydrofuran (THF), reacts under nitrogen protection with butyllithium, the solution obtaining drips in the tetrahydrofuran solution of 4-bromine benzophenone, obtains the first intermediate 9; Be dissolved in toluene by 9, add p-methyl benzenesulfonic acid as dewatering agent, after dehydration, obtain bromo tetraphenyl ethene 10; Be dissolved in tetrahydrofuran (THF) 10, after reacting with n-Butyl Lithium under nitrogen protection, drip again Methyl benzenesulfonyl nitrine, obtain tetraphenyl ethene nitrine (1).
Below in conjunction with embodiment, the present invention is described particularly, but protection scope of the present invention is not limited to following examples.
(1) the active tetraphenyl ethene of AIE azido derivant is synthetic:
Take ditane (5.5g, 32.8mmol) add in 500mL twoport round-bottomed flask, be placed in liquid nitrogen acetone bath, vacuumize logical nitrogen three times, adding 100mL newly to steam tetrahydrofuran (THF) dissolves, slowly splash into n-Butyl Lithium (18.75mL, 30mmol), by 4-bromine benzophenone (7.8g, 30mmol) be dissolved in appropriate new steaming tetrahydrofuran (THF), join reaction system, system returns to room temperature, spends the night.Use saturated ammonium chloride termination reaction, after extraction, the crude product of gained intermediate 9 dissolves with appropriate toluene, adds 500mg p-methyl benzenesulfonic acid, and backflow is spent the night.Be spin-dried for solvent, the crude product obtaining after extracting and washing, taking silica gel column chromatogram separating purification (sherwood oil is as eluent), obtains white solid bromo tetraphenyl ethene 10(9.897g, productive rate 80.2%).
By 10(617mg, 1.5mmol) add in 250mL twoport round-bottomed flask, vacuumize and change nitrogen three times, add 50mL tetrahydrofuran (THF) to dissolve, under liquid nitrogen acetone bath, drip n-Butyl Lithium (1.125mL, 1.8mmol), keep low temperature after 1.5 hours, take Methyl benzenesulfonyl nitrine (345.7mg, 1.8mmol), be dissolved in 10mL tetrahydrofuran (THF), join in bottle with two necks.Slowly rise to after room temperature and react and spend the night.The termination reaction that adds water, with dichloromethane extraction, dry organic phase, is spin-dried for, and gained is silica gel column chromatogram separating purification (sherwood oil is eluent) for crude product, obtains yellow solid tetraphenyl ethene nitrine (517mg, productive rate 92.3%).Nucleus magnetic hydrogen spectrum spectrogram is shown in Fig. 1.
The characterization data of tetraphenyl ethene nitrine is: IR (KBr), v (cm
-1): 3083,2124,1498,1287,823,755,695.
1h NMR (400MHz, DMSO-d
6), δ (TMS, ppm): 7.10-7.14 (m, 9H), 6.96-7.00 (m, 8H), 6.89 (d, 2H).
13cNMR (400MHz, DMSO-d
6), δ (TMS, ppm): 143.5,143.4,141.3,140.5,140.1,137.9,132.8,131.1,128.3,127.1.Anal.Calcd for C
26h
19n
3: C, 83.62; H, 5.13; N, 11.25; Found:C, 83.85; H, 5.11; N, 10.99.
(2) the amino tetraphenyl ethene of reference substance is synthetic:
Zinc powder (9.6g, 144mmol) adds in 250mL twoport round-bottomed flask, vacuumizes logical nitrogen three times, adds 60mL tetrahydrofuran (THF), under ice bath, drips TiCl
4(7.8mL, 72mmol), slowly being back to room temperature post-heating refluxes 2.5 hours, again use ice bath cooling, add pyridine (6mL, 36mmol), stir and after 10 minutes, take 4-aminobenzophenone (2.84g, 14.4mmol) and benzophenone (3.15g, 17.28mmol) add reaction system after being dissolved in together appropriate tetrahydrofuran (THF).Slowly returning to room temperature post-heating refluxes 12 hours.Reaction solution cold filtration.Gained crude product is with silica gel column chromatogram separating purification (sherwood oil/methylene dichloride=5:1 mixed solvent does eluent), obtain the amino tetraphenyl ethene of faint yellow solid (2.56g, productive rate 51.2%), reference substance when the amino tetraphenyl ethene obtaining detects hydrogen sulfide as tetraphenyl ethene nitrine.Nucleus magnetic hydrogen spectrum figure is shown in Fig. 2.
Amino tetraphenyl ethene characterization data is: IR (KBr), v (cm
-1): 3385,3044,1617,1513,1277,820,739,698.
1hNMR (400MHz, DMSO-d
6), δ (TMS, ppm): 6.97-7.11 (m, 17H), 6.80 (d, 2H), 6.43 (d, 2H).
13c NMR (400MHz, DMSO-d
6), δ (TMS, ppm): 144.2,144.1,144.0,140.8,139.4,134.5,132.5,131.4,127.5,126.3,126.0,114.6.Anal.Calc d for C
26h
21n:C, 89.88; H, 6.09; N, 4.03; Found:C, 90.09; H, 6.09; N, 3.97.
(3) drafting of amino tetraphenyl ethene fluorescence curve:
Amino tetraphenyl ethene is the molecule generating after probe molecule tetraphenyl ethene nitrine and hydrogen sulfide effect in theory, it has typical aggregation inducing luminescent properties, the AIE fluorescence curve of amino tetraphenyl ethene is as shown in Figure 3: in the time that water-content is 0, concentration is that the dimethyl sulphoxide solution of the amino tetraphenyl ethene of 10 μ M does not have fluorescence completely; Until water-content is while being increased to 80%, amino tetraphenyl ethene starts to assemble, and fluorescence starts obvious enhancing.
(4) detection of tetraphenyl ethene nitrine to hydrogen sulfide:
The qualitative detection process of hydrogen sulfide is as follows: preparation 10
-4the dimethyl sulphoxide solution of the tetraphenyl ethene nitrine of M, getting 1mL adds in 10mL volumetric flask, getting 1mL dimethyl sulfoxide (DMSO) adds in volumetric flask again, adjust to 7.4 HEPES(4-hydroxyethyl piperazine ethanesulfonic acid with pH) buffered soln is settled to 10mL, the solution that the aqueous phase content that obtains the tetraphenyl ethene nitrine of 10 μ M is 80%, its fluorescence spectrum of Fast Measurement, as blank reference.
The mixing solutions of preparation tetraphenyl ethene nitrine and NaHS, operation is basic identical with the preparation of blank reference, and difference adds 10 of 50 μ L before constant volume
-2naHS (a kind of conventional hydrogen sulfide donor) aqueous solution of M, having obtained tetraphenyl ethene nitrine concentration is 10 μ M, NaHS concentration is the mixing solutions that the aqueous phase content of 50 μ M is 80%, measures its fluorescence spectrum, obtains test curve.
With the amino tetraphenyl vinyl solution of above-mentioned similar operations preparation same concentrations, its fluorescence spectrum of Fast Measurement, as a comparison.Can obtain detected result as shown in Figure 4, only have the solution of tetraphenyl ethene nitrine luminous hardly, and the luminescent spectrum of the amino tetraphenyl ethene of the mixing solutions of tetraphenyl ethene nitrine and NaHS and same concentrations is almost identical, be that tetraphenyl ethene nitrine can detect hydrogen sulfide under state of aggregation, its mechanism is to obtain amino tetraphenyl ethene after tetraphenyl ethene nitrine and hydrogen sulfide effect.
(5) tetraphenyl ethene nitrine specificity test to sulfurated hydrogen detection under state of aggregation:
Specificity qualification process to sulfurated hydrogen detection is as follows: preparation 10
-4the dimethyl sulphoxide solution of the tetraphenyl ethene nitrine of M, getting 1mL adds in 10mL volumetric flask, getting 1mL dimethyl sulfoxide (DMSO) adds in volumetric flask again, adjust to 7.4 HEPES buffered soln with pH and be settled to 10mL, the solution that the aqueous phase content that obtains the tetraphenyl ethene nitrine of 10 μ M is 80%, its fluorescence spectrum of Fast Measurement, as blank reference.
The mixing solutions of preparation tetraphenyl ethene nitrine and NaHS and other negatively charged ion, operation is basic identical with the preparation of blank reference, and difference adds respectively 10 of 50 μ L before constant volume
-2the aqueous solution of a series of negatively charged ion of M, having obtained tetraphenyl ethene nitrine concentration is 10 μ M, anion concentration is a series of mixing solutionss that the aqueous phase content of 50 μ M is 80%, measures its fluorescence spectrum, obtains test curve.Can obtain detected result as shown in Figure 5, can find out, tetraphenyl ethene nitrine molecule only has response to hydrogen sulfide, to other negatively charged ion all without responding.
(6) tetraphenyl ethene nitrine detection to hydrogen sulfide under state of aggregation of the present embodiment has freedom from jamming.
Freedom from jamming qualification process to sulfurated hydrogen detection is as follows: preparation 10
-4the dimethyl sulphoxide solution of the tetraphenyl ethene nitrine of M, getting 1mL adds in 10mL volumetric flask, getting 1mL dimethyl sulfoxide (DMSO) adds in volumetric flask again, adjust to 7.4 HEPES buffered soln with PH and be settled to 10mL, the solution that the aqueous phase content that obtains the tetraphenyl ethene nitrine of 10 μ M is 80%, its fluorescence spectrum of Fast Measurement, as blank reference.
Prepare other negatively charged ion and have lower tetraphenyl ethene nitrine molecule and the mixing solutions of NaHS, the preparation of operation and blank reference is basic identical, and difference adds respectively 10 of 50 μ L before constant volume
-2the NaHS (a kind of conventional hydrogen sulfide donor) of M and the mixed aqueous solution of other negatively charged ion, having obtained tetraphenyl ethene nitrine concentration is 10 μ M, other anion concentrations are 50 μ M, NaHS concentration is also a series of mixing solutionss that the aqueous phase content of 50 μ M is 80%, measure its fluorescence spectrum, obtain test curve.Can obtain detected result as shown in Figure 6, can find out, under the condition that tetraphenyl ethene nitrine molecule exists at other negatively charged ion, hydrogen sulfide be had to response, and be not subject to the impact of other negatively charged ion, illustrate that it has good freedom from jamming.
(7) tetraphenyl ethene nitrine detection by quantitative hydrogen sulfide under state of aggregation.
The detection by quantitative process of hydrogen sulfide is as follows: preparation 10
-4the dimethyl sulphoxide solution of the tetraphenyl ethene nitrine of M, gets 1mL and adds in 10mL volumetric flask, then gets 1mL dimethyl sulfoxide (DMSO) and add in volumetric flask, draws 10 of different volumes with liquid-transfering gun
-2the NaHS aqueous solution of M adds in volumetric flask, adjust to 7.4 HEPES buffered soln with pH and be settled to 10mL, having obtained tetraphenyl ethene nitrine concentration is 10 μ M, and NaHS concentration is a series of mixing solutionss that the aqueous phase content of 2-50 μ M is 80%, tests its fluorescence spectrum.In order to reduce error, in triplicate, the fluorescence that obtains detection hydrogen sulfide as shown in Figure 7 strengthens curve to aforesaid operations.In the time that concentration of hydrogen sulfide is 0, the tetraphenyl ethene nitrine solution of water-content 80% is luminous hardly; In the time that concentration of hydrogen sulfide is less than tetraphenyl ethene nitrine concentration, fluorescence does not obviously strengthen; When concentration of hydrogen sulfide exceedes after tetraphenyl ethene nitrine concentration, fluorescence starts phenomenal growth; After concentration of hydrogen sulfide exceedes three times of tetraphenyl ethene nitrine concentration, fluorescence intensity tends towards stability again.Be that fluorescence intensity increases along with the growth of concentration of hydrogen sulfide within the specific limits, the lower limit of its valid analysing range and response is determined by the concentration of probe molecule tetraphenyl ethene nitrine.
(1) tetraphenyl ethene nitrine and amino tetraphenyl ethene is synthetic with embodiment 1
(2) existence of tetraphenyl ethene nitrine qualitative detection hydrogen sulfide is with embodiment 1
(3) specificity of tetraphenyl ethene nitrine detection to hydrogen sulfide under state of aggregation and freedom from jamming are identified with embodiment 1.
(4) different tetraphenyl ethene nitrine concentration detection by quantitative hydrogen sulfide under state of aggregation.
The detection by quantitative process of hydrogen sulfide is as follows: preparation 2 × 10
-4the dimethyl sulphoxide solution of the tetraphenyl ethene nitrine of M, gets 1mL and adds in 10mL volumetric flask, then gets 1mL dimethyl sulfoxide (DMSO) and add in volumetric flask, draws 2 × 10 of different volumes with liquid-transfering gun
-2the NaHS aqueous solution of M adds in volumetric flask, adjust to 7.4 HEPES buffered soln with PH and be settled to 10mL, having obtained tetraphenyl ethene nitrine concentration is 20 μ M, and NaHS concentration is a series of mixing solutionss that the aqueous phase content of 4-100 μ M is 80%, tests its fluorescence spectrum.In order to reduce error, in triplicate, the fluorescence that obtains detection hydrogen sulfide as shown in Figure 8 strengthens curve to aforesaid operations.Fluorescence intensification factor and hydrogen sulfide with respect to the relation of the equivalent of tetraphenyl ethene nitrine with embodiment 1.Be that fluorescence intensity increases along with the growth of concentration of hydrogen sulfide within the specific limits, the lower limit of its valid analysing range and response is determined by the concentration of probe molecule tetraphenyl ethene nitrine.
(1) tetraphenyl ethene nitrine and amino tetraphenyl ethene is synthetic with embodiment 1
(2) existence of tetraphenyl ethene nitrine qualitative detection hydrogen sulfide is with embodiment 1
(3) specificity of the present embodiment tetraphenyl ethene nitrine detection to hydrogen sulfide under state of aggregation and freedom from jamming are identified with embodiment 1.
(4) tetraphenyl ethene nitrine detection by quantitative hydrogen sulfide under state of aggregation.
The detection by quantitative process of hydrogen sulfide is as follows: preparation 5 × 10
-4the dimethyl sulphoxide solution of the tetraphenyl ethene nitrine of M, gets 1mL and adds in 10mL volumetric flask, then gets 1mL dimethyl sulfoxide (DMSO) and add in volumetric flask, draws 5 × 10 of different volumes with liquid-transfering gun
-2the NaHS aqueous solution of M adds in volumetric flask, adjust to 7.4 HEPES buffered soln with PH and be settled to 10mL, having obtained tetraphenyl ethene nitrine concentration is 50 μ M, and NaHS concentration is a series of mixing solutionss that the aqueous phase content of 10-250 μ M is 80%, tests its fluorescence spectrum.In order to reduce error, in triplicate, the fluorescence that obtains the detection hydrogen sulfide as shown in 9 strengthens curve to aforesaid operations.Fluorescence intensification factor and hydrogen sulfide with respect to the relation of the equivalent of tetraphenyl ethene nitrine with embodiment 1.Be that fluorescence intensity increases along with the growth of concentration of hydrogen sulfide within the specific limits, the lower limit of its valid analysing range and response is determined by the concentration of probe molecule tetraphenyl ethene nitrine.
Claims (8)
1. a fluorescent molecular probe, is characterized in that, structure is R
1-N
3, wherein, R
1for thering is the group of aggregation inducing luminescent properties.
2. fluorescent molecular probe according to claim 1, is characterized in that, described R
1be selected from the one in formula I～formula IV;
In formula I, R
2～R
4independently selected from aryl, alkyl, alkoxyl group or H;
In formula (II), R
5and R
6be selected from C
1～C
5alkyl or aryl;
" * " represents the position of substitution.
3. fluorescent molecular probe according to claim 2, is characterized in that, described R
1structure suc as formula shown in (I-1):
In formula (I-1), " * " represents the position of substitution.
4. the detection method of a concentration of hydrogen sulfide, it is characterized in that, after being mixed with the fluorescent molecular probe of the different concns described in claim 1～3 any one, the liquid to be measured of sulfide hydrogen or HS-measures its fluorescence intensity, if mix rear emitting fluorescence, determine the concentration of hydrogen sulfide or HS-according to the concentration of fluorescent probe molecule;
Described fluorescent molecular probe is state of aggregation.
5. the detection method of concentration of hydrogen sulfide according to claim 4, is characterized in that, the dimethyl sulphoxide solution of described fluorescent molecular probe is added drop-wise to the fluorescent molecular probe that can obtain state of aggregation in the buffered soln that pH is 6.5-8.0;
Described dimethyl sulphoxide solution and the volume ratio of buffered soln are 1～3:9～7.
6. the detection method of concentration of hydrogen sulfide according to claim 5, is characterized in that, described buffered soln is that pH is 7.4 HEPES damping fluid;
The volume ratio of described dimethyl sulphoxide solution and HEPES damping fluid is 2:8.
7. the detection method of concentration of hydrogen sulfide according to claim 5, is characterized in that, by fluorescent molecular probe, the concentration in state of aggregation regulates the detectability of described hydrogen sulfide;
The detection of described hydrogen sulfide is limited to 0-100 μ M.
8. the detection method of concentration of hydrogen sulfide according to claim 7, is characterized in that, the detectability of described hydrogen sulfide is adjusted within the scope of 10～50 μ M.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410071543.2A CN103865522B (en) | 2014-02-28 | 2014-02-28 | A kind of fluorescent molecular probe and the application in sulfurated hydrogen detection thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410071543.2A CN103865522B (en) | 2014-02-28 | 2014-02-28 | A kind of fluorescent molecular probe and the application in sulfurated hydrogen detection thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103865522A true CN103865522A (en) | 2014-06-18 |
| CN103865522B CN103865522B (en) | 2015-12-02 |
Family
ID=50904548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410071543.2A Active CN103865522B (en) | 2014-02-28 | 2014-02-28 | A kind of fluorescent molecular probe and the application in sulfurated hydrogen detection thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103865522B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104263353A (en) * | 2014-09-11 | 2015-01-07 | 华南理工大学 | Ratiometric fluorescent probe for detection of hydrogen sulfide and preparation method of ratio-dependent fluorescent probe |
| WO2016078603A1 (en) * | 2014-11-21 | 2016-05-26 | The Hong Kong University Of Science And Technology | Aie luminogens for bacteria imaging, killing, photodynamic therapy and antibiotics screening, and their methods of manufacturing |
| WO2016165487A1 (en) * | 2015-04-13 | 2016-10-20 | The Hong Kong University Of Science And Technology | Real-time monitoring mitophagy process by fluorescent photostable mitochondrial specific bioprobe with aie characteristics |
| CN106279278B (en) * | 2016-08-09 | 2018-09-14 | 济南大学 | It is a kind of that there is Mitochondrially targeted and two-phpton property hydrogen sulfide molecule fluorescence probe and its preparation method and application |
| CN109280033A (en) * | 2017-07-21 | 2019-01-29 | 香港科技大学 | The preparation and application of the AIE molecule of itrile group vinyl functionalization based on tetraphernl pyrazine |
| CN109422667A (en) * | 2017-08-23 | 2019-03-05 | 北京工商大学 | A kind of naphthonitrile class hydrogen sulfide fluorescence probe |
| CN110687086A (en) * | 2019-10-14 | 2020-01-14 | 浙江工业大学上虞研究院有限公司 | Method for colorimetric detection of sulfide ions and concentration and preparation of detection test paper thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850272A (en) * | 2012-09-26 | 2013-01-02 | 华东理工大学 | Azido-containing naphthalimide compound and applications thereof in detecting hydrogen sulfide |
| WO2013029340A1 (en) * | 2011-09-01 | 2013-03-07 | The Hong Kong University Of Science And Technology | Biocompatible nanoparticles with aggregation induced emission characteristics as fluorescent bioprobes and methods of using the same for in vitro and in vivo imaging |
-
2014
- 2014-02-28 CN CN201410071543.2A patent/CN103865522B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013029340A1 (en) * | 2011-09-01 | 2013-03-07 | The Hong Kong University Of Science And Technology | Biocompatible nanoparticles with aggregation induced emission characteristics as fluorescent bioprobes and methods of using the same for in vitro and in vivo imaging |
| CN102850272A (en) * | 2012-09-26 | 2013-01-02 | 华东理工大学 | Azido-containing naphthalimide compound and applications thereof in detecting hydrogen sulfide |
Non-Patent Citations (1)
| Title |
|---|
| 赵国生 等: "聚集诱导发光应用研究进展", 《有机化学》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104263353B (en) * | 2014-09-11 | 2016-07-06 | 华南理工大学 | A kind of Ratiometric fluorescent probe for sulfurated hydrogen detection and preparation method thereof |
| CN104263353A (en) * | 2014-09-11 | 2015-01-07 | 华南理工大学 | Ratiometric fluorescent probe for detection of hydrogen sulfide and preparation method of ratio-dependent fluorescent probe |
| WO2016078603A1 (en) * | 2014-11-21 | 2016-05-26 | The Hong Kong University Of Science And Technology | Aie luminogens for bacteria imaging, killing, photodynamic therapy and antibiotics screening, and their methods of manufacturing |
| CN107001927A (en) * | 2014-11-21 | 2017-08-01 | 香港科技大学 | AIE illuminophores and its production method for bacterium imaging, killing, photodynamic therapy and antibiotic-screening |
| CN107922834B (en) * | 2015-04-13 | 2020-04-14 | 香港科技大学 | Real-time monitoring of mitochondrial autophagy process using fluorescent photostable mitochondrial-specific bioprobes with AIE properties |
| WO2016165487A1 (en) * | 2015-04-13 | 2016-10-20 | The Hong Kong University Of Science And Technology | Real-time monitoring mitophagy process by fluorescent photostable mitochondrial specific bioprobe with aie characteristics |
| CN107922834A (en) * | 2015-04-13 | 2018-04-17 | 香港科技大学 | Stablize mitochondria specific biological probe with the fluorescence light with AIE characteristics and monitor Mitochondrial autophagy process in real time |
| CN106279278B (en) * | 2016-08-09 | 2018-09-14 | 济南大学 | It is a kind of that there is Mitochondrially targeted and two-phpton property hydrogen sulfide molecule fluorescence probe and its preparation method and application |
| CN109280033A (en) * | 2017-07-21 | 2019-01-29 | 香港科技大学 | The preparation and application of the AIE molecule of itrile group vinyl functionalization based on tetraphernl pyrazine |
| CN109280033B (en) * | 2017-07-21 | 2021-11-16 | 香港科技大学 | Preparation and application of tetraphenylpyrazine-based nitrile vinyl functionalized AIE molecule |
| CN109422667A (en) * | 2017-08-23 | 2019-03-05 | 北京工商大学 | A kind of naphthonitrile class hydrogen sulfide fluorescence probe |
| CN109422667B (en) * | 2017-08-23 | 2021-10-08 | 北京工商大学 | Naphthalocyanine hydrogen sulfide fluorescent probe |
| CN110687086A (en) * | 2019-10-14 | 2020-01-14 | 浙江工业大学上虞研究院有限公司 | Method for colorimetric detection of sulfide ions and concentration and preparation of detection test paper thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103865522B (en) | 2015-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103865522A (en) | Fluorescence molecular probe and application thereof in hydrogen sulfide detection | |
| Gunnlaugsson et al. | Dual responsive chemosensors for anions: the combination of fluorescent PET (Photoinduced Electron Transfer) and colorimetric chemosensors in a single molecule | |
| Tan et al. | Determination of tetracycline in milk by using nucleotide/lanthanide coordination polymer-based ternary complex | |
| CN102942537B (en) | Benzothiazole-aniline compound used as pH fluorescent probe and preparation method thereof | |
| Sun et al. | Tetraphenylethene-substituted benzothiadiazoles: AIE and TICT properties, tunable intramolecular conjugation and application in detecting trace water in organic solvents | |
| CN103214428B (en) | Benzothiazole-cyanophenyl compound serving as hydrazine fluorescence probe as well as preparation method and application method of benzothiazole-cyanophenyl compound | |
| CN106496067B (en) | Buzane base azine structural compounds and its preparation method and application based on meta position link | |
| CN107188876B (en) | It is a kind of for detecting the synthesis and application of the near infrared fluorescent probe of hydrogen polysulfide | |
| CN106432041A (en) | Preparation and application of ratio type near infrared hydrazine fluorescent probe compound | |
| Cao et al. | Multifunctional fluorescent naphthalimide self-assembly system for the detection of Cu 2+ and K+ and continuous sensing of organic amines and gaseous acids | |
| CN105524612A (en) | Isophorone fluorescence probe, and preparation method and application thereof | |
| CN107602417B (en) | A kind of fluorescence probe and the preparation method and application thereof that zinc ion can be quickly detected based on aggregation-induced emission mechanism | |
| CN112098484B (en) | Sensor for detecting acetamiprid based on electrochemical luminescence method, and preparation method and application thereof | |
| Okutan et al. | Colorimetric fluorescent sensors for hemoglobin based on BODIPY dyes | |
| CN104357044A (en) | Fluorescent probe as well as preparation method and application thereof | |
| Song et al. | Aptamer-based fluorescent platform for ultrasensitive adenosine detection utilizing Fe 3 O 4 magnetic nanoparticles and silver nanoparticles | |
| Zuo et al. | Near-infrared fluorescent amphiphilic Aza-BODIPY dye: Synthesis, solvatochromic properties, and selective detection of Cu2+ | |
| Chopra et al. | Fluorescent organic nanoparticles as chemosensor for nanomolar detection of Cs+ in aqueous medium | |
| CN106543226A (en) | A kind of preparation and application for positioning mitochondrial ATP fluorescent probes | |
| Wang et al. | ACQ-to-AIE conversion by regio-isomerization of rofecoxib analogues for developing new multi-functional aggregation-induced emission luminogens | |
| CN104845611A (en) | Novel fluorinion rate fluorescent probe and application | |
| Li et al. | Highly sensitive determination of ssDNA and real-time sensing of nuclease activity and inhibition based on the controlled self-assembly of a 9, 10-distyrylanthracene probe | |
| CN110308124A (en) | Application of the fluorescence probe containing benzothiazole compound in detection bacterium messenger molecule c-di-GMP | |
| CN103937487A (en) | Phosphorescent fluorinion probe, preparation and applications thereof | |
| CN105319194A (en) | Method for continuously detecting I<-> and Hg<2+> by using aggregation-induced emission type fluorescent sensing molecule |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |