CN106977437A - A kind of heterocyclic carbamate derivatives fluorescence probe of recognition detection ferric ion and dimercurion and its preparation method and application - Google Patents
A kind of heterocyclic carbamate derivatives fluorescence probe of recognition detection ferric ion and dimercurion and its preparation method and application Download PDFInfo
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Abstract
The invention discloses seven kinds of heterocyclic carbamate derivatives fluorescence probes and its preparation method and application.Heterocyclic carbamate derivatives fluorescence probe prepared by the present invention is using benzoic acid derivative as fluorogen, and the octamethylenediamine of 3,6 dithia 1,8 synthesizes a class and can be used for detecting Fe as the main identification division of metal ion3+And Hg2+Heterocyclic carbamate derivatives fluorescence probe, its method is simple, with low cost；Wherein, fluorescence probe 1b and 1c, respectively to Fe3+And Hg2+There is good selectivity, and to Fe3+And Hg2+, can qualitative and quantitative detection Fe with higher measure sensitivity3+And Hg2+；Available for Fe in water body (III) and Hg (II) identification and detection, with good application prospect.
Description
Technical field
It is on one kind identification specifically the invention belongs to the fluorescent probe technique field for detecting metal ion
Detect Fe3+And Hg2+Heterocyclic carbamate derivatives fluorescence probe with and its preparation method and application.
Background technology
The metal ion being widely present in nature all plays an important role to environment, medical science, biology, chemical science.Its
Middle heavy metal and transition metal ions play critically important effect in vital movement, healthy closely bound up with the mankind, certain
A little contents of the transition metal ions in life entity are too low to give rise to diseases, and not only environment is caused on the contrary, concentration is excessive
Destruction, also greatly threatens the health of the mankind.
Mercury ion is always treated as one of most poisonous metal ion.The characteristics of due to its enrichment and severe toxicity, mercury can cause
Serious health problem, such as antenatal brain damage, cognition and dyskinesia, Minamata disease.Therefore the detection pole of mercury ion content
To be important.
Fe3+It is not only a metal ion species, and it is one of most important trace element in human body, is all life systems
System is essential.It is present in many enzymes and protein, and the confactor reacted as cell metabolism.Fe3+Perform blood
The oxygen carrying capacity of red pigment, iron deficiency can cause people's anaemia, excessive iron content can damage biological system because its oxygen
Generation high activity oxygen can be catalyzed by changing reduction form, and this material can participate in a variety of diseases, such as handkerchief parasol pine syndrome.
Therefore the assay of the iron ion in human body is extremely important.
Compared to traditional detection method, fluorescence probe is because sensitivity is high, selectivity is good, quick analysis the features such as by widely
Detection applied to metal ion in environmental and biological materials.Fe was detected using fluorescence probe in recent years3+And Hg2+Existing a large amount of texts
Offer report, but to there is sensitivity low for most of this kind of fluorescence probe, or poorly water-soluble, main is that existing metal ion is glimmering
Light probe synthesis is relative complex.Therefore designing a simple class synthetic operation, high sensitivity and high selectivity is used to detect Fe3+With
Hg2+Fluorescence probe it is significant.
The content of the invention
There is the problem of low sensitivity or poorly water-soluble for existing fluorescence probe, it is an object of the invention to provide
A kind of heterocyclic carbamate derivatives fluorescence probe of recognition detection ferric ion and dimercurion, the heterocyclic carbamate derivatives are glimmering
Light probe has different degrees of response to Fe (III) and Hg (II), is the benzoic acid derivative and 3 under EDCI and HOBt effects,
What 6- dithia -1,8- octamethylenediamines reacted and obtained.
To achieve the above object, the present invention uses following technical scheme：
First purpose of the present invention is to provide a kind of heterocyclic carbamate derivatives fluorescence probe, the benzamide derivative
The chemical structural formula of thing fluorescence probe is：
Wherein, R is-H ,-OH ,-NH2、-OCH3,-COOH ,-Br, one kind in-F,
When R is-OH, the heterocyclic carbamate derivatives fluorescence probe spreads out for the benzamide of recognition detection ferric ion
Biological fluorescent labeling 1b；
When R is-NH2When, the heterocyclic carbamate derivatives fluorescence probe is the benzamide of recognition detection ferric ion
Derivatives fluorescent probe 1c；
When R is-H, the heterocyclic carbamate derivatives fluorescence probe is heterocyclic carbamate derivatives fluorescence probe 1a；
When R is-OCH3When, the heterocyclic carbamate derivatives fluorescence probe is heterocyclic carbamate derivatives fluorescence probe 1d；
When R is-COOH, the heterocyclic carbamate derivatives fluorescence probe is heterocyclic carbamate derivatives fluorescence probe 1e；
When R is-Br, the heterocyclic carbamate derivatives fluorescence probe is heterocyclic carbamate derivatives fluorescence probe 1f；
When R is-F, the heterocyclic carbamate derivatives fluorescence probe is heterocyclic carbamate derivatives fluorescence probe 1g.
Second object of the present invention is the preparation method for providing heterocyclic carbamate derivatives fluorescence probe, including following step
Suddenly：
A, benzoic acid is dissolved in dichloromethane；
B, addition EDCI and HOBt, stir-activating under stirring and frozen water cooling；
C, addition 3,6- dithia -1,8- octamethylenediamines；
D, it is stirred overnight at room temperature, reaction is cooled down after terminating, revolving obtains crude product；
E, silica gel column chromatography purifying, dry the heterocyclic carbamate derivatives fluorescence probe described in acquisition.
Further, the stir-activating time of the step B is 0.5-1h.
Further, the benzoic acid is benzoic acid, salicylic acid, ortho-aminobenzoic acid, o-methoxybenzoic acid, adjacent benzene two
One kind in formic anhydride, o-bromobenzoic acid, o-fluorobenzoic acid etc..
Further, the preparation method of 3,6- dithia -1,8- octamethylenediamines of the step C includes：
C1, Mercaptamine and 1,2- Bromofume react 1h in alcohol sodium solution；
C2, room temperature reaction are stayed overnight, and reaction is filtered after terminating, and is rotated, and vacuum drying obtains described 3,6- dithia -1,
8- octamethylenediamines.
Third object of the present invention is that providing the heterocyclic carbamate derivatives fluorescence probe 1a-1g is used for recognition detection
The application of transition metal and heavy metal ion in environment.
Fourth object of the present invention is that providing the heterocyclic carbamate derivatives fluorescence probe 1b is used for recognition detection ring
Fe in border3+Application.
The 5th purpose of the present invention is that providing the heterocyclic carbamate derivatives fluorescence probe 1c is used for recognition detection ring
Hg in border2+Application.
The beneficial effects of the invention are as follows：The present invention is using benzoic acid derivative as fluorogen, 3,6- dithia -1,8- octamethylenediamines
As the main identification division of metal ion, one class of synthesis can be used for detecting Fe3+And Hg2+Heterocyclic carbamate derivatives fluorescence
Probe, its method is simple, with low cost；Fluorescence probe 1b and 1c, respectively to Fe3+And Hg2+There is good selectivity, and to Fe3+
And Hg2+, can qualitative and quantitative detection Fe with higher measure sensitivity3+And Hg2+；Available for Fe in water body (III) and Hg (II)
Identification and detection, with good application prospect.
Brief description of the drawings
Fig. 1 is in DMSO/H2O(5:95, v/v) in solution, fluorescence probe 1a-1g is to different metal (Na+,K+,Mn2+,
Mg2+,Ca2+,Cr3+,Fe3+,Ni2+,Cu2+,Zn2+,Co2+,Ag+,Cd2+,Hg2+,Fe2+And Pb2+) response, wherein, probe 1a-
1g concentration is 10 μM, and the concentration of metal ion is 100 μM.
Fig. 2 is fluorescence probe 1a-1b fluorescence spectrum block diagram.
Fig. 3 is that other metal ions detect Fe to probe 1b3+Interference；Wherein, probe 1b concentration is 10 μM, other gold
The concentration for belonging to ion is 100 μM, Fe3+Concentration be 100 μM.
Fig. 4 is that other metal ions detect Hg to probe 1c2+Interference；Its middle probe 1c concentration is 10 μM, other gold
The concentration for belonging to ion is 100 μM, Hg2+Concentration be 100 μM.
Fig. 5 is in DMSO/H2O(5:95, v/v) in solution, fluorescence probe 1b fluorescence spectrum is with Fe3+The change of concentration；
Illustration is fluorescence intensity to Fe3+Concentration relationship figure.
Fig. 6 is in DMSO/H2O(5:95, v/v) in solution, fluorescence probe 1c fluorescence spectrum is with Hg2+Concentration change
Figure；Illustration is fluorescence intensity to Hg2+Concentration relationship figure.
Fig. 7 is fluorescence probe 1b and Fe3+Complexing ratio.
Fig. 8 is fluorescence probe 1c and Hg2+Complexing ratio.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.It should be understood that following examples are merely to illustrate this
Invention is not for restriction the scope of the present invention.Various reagents, reaction condition, the detection method arrived used in following examples
Deng unless otherwise stated, being considered as reagent commonly used in the art, reaction condition and detection method.
Embodiment 9-12 detection method reference paper：.Two ' turn-off ' the Schiff such as Bing Zhao base
fluorescence sensors based on phenanthro[9,10-d]imidazole-coumarin
derivatives for Fe3+in aqueous solution.《Tetrahedron Letters》.2016, volume 57,
4417–4423.
The .A novel system for such as Ebru Bozkurt Fe3+ion detection based on
fluorescence resonance energy transfer.《Sensors and Actuators B:Chemical》
.2015, volume 221,136-147.
The preparation of the 3,6- dithia -1,8- octamethylenediamines of embodiment 1
43mmol caustic alcohols are dissolved in 40mL absolute ethyl alcohols, 10 DEG C are cooled to, by 24mmol cysteamine salts under nitrogen protection
Hydrochlorate adds 10mmol 1 after adding above-mentioned solution, reaction 1h, and 2- Bromofumes, room temperature reaction is stayed overnight.Reaction is filtered after terminating,
Revolving, adds the NaOH solution of dilution, refrigerator overnight.Then, CH2Cl2Extraction, is washed three times, anhydrous sodium sulfate drying, revolving,
Be dried in vacuo to obtain 3,6- dithia -1,8- octamethylenediamines, weigh 1.2623g, yield 70.02%, product structure formula by1H NMR、13C
NMR, HRMS are confirmed.
1H NMR(600MHz,CDCl3):2.89 (t, J=6.3Hz, 2H), 2.74 (s, 2H), 2.66 (t, J=6.3Hz,
2H)；13C NMR(147MHz,CD3OD):41.53,35.45,32.71；HRMS(ESI)m/z calcd for C6H16N2S2,[M+
H]+181.08,found 181.0810。
The heterocyclic carbamate derivatives fluorescence probe 1a of embodiment 2 synthesis and appraising datum
5.16mmol benzoic acid is dissolved in 50mL dichloromethane, stirring and frozen water cooling under add EDCI (5mmol) and
HOBt (5mmol), stir-activating 0.5-1h.Then 2mmol 3,6- dithia -1,8- octamethylenediamines are added (to be obtained by embodiment 1
), it is stirred overnight at room temperature.Revolving, CH2Cl2Extraction, uses saturation NaHCO successively3, saturation NaCl, water washing organic phase, anhydrous sulphur
Sour sodium is dried.Revolving, crude product is purified through silica column chromatography, is dried in vacuo to obtain fluorescence probe 1a, weigh 0.4913g, is produced
Rate 63.3%, product structure formula by1H NMR、13C NMR, HRMS are confirmed.
1H NMR(600MHz,DMSO-d6):12.48 (s, J=6.24Hz, 2H), 2.73 (s, 4H), 2.66 (t, J=
6.24Hz,4H)；13C NMR(150MHz,CDCl3):167.54,134.08,131.38,128.37,126.79,39.19,
31.33,31.14；HRMS(ESI)m/z calcd for C20H24N2O2S2,[M+H]+389.13,found 389.1340.Structure
Formula is：
Wherein, R is-H.
The heterocyclic carbamate derivatives fluorescence probe 1b of embodiment 3 synthesis and appraising datum
2.8mmol salicylic acids are dissolved in 50mL dichloromethane, stirring and frozen water cooling under add EDCI (4mmol) and
HOBt (4mmol), stir-activating 0.5-1h.Then 1mmol 3,6- dithia -1,8- octamethylenediamines are added (to be obtained by embodiment 1
), it is stirred overnight at room temperature.Revolving, CH2Cl2Extraction, uses saturation NaHCO successively3, saturation NaCl, water washing organic phase, anhydrous sulphur
Sour sodium is dried.Revolving, crude product is purified through silica column chromatography, is dried in vacuo to obtain fluorescence probe 1b, yield 46.9%, product
Structural formula by1H NMR、13C NMR, HRMS are confirmed.
1H NMR(600MHz,DMSO-d6):12.48 (s, 2H), 8.95 (t, J=5.6Hz, 2H), 7.82 (d, J=
7.9Hz, 2H), 7.39 (t, J=8.1Hz, 2H), 6.93-6.85 (m, 4H), 3.48 (q, J=6.6Hz, 4H), 2.78 (s, 4H),
2.74 (t, J=7.1Hz, 4H)；13C NMR(150MHz,DMSO-d6):169.47,160.56,134.34,128.43,
119.25,118.03,115.89,40.61,40.47,40.32,40.18,40.04,31.73,30.87；HRMS(ESI)m/z
calcd for C20H24N2O4S2,[M+H]+421.12,found 421.1208.General structure is：
Wherein, R is-OH.
The heterocyclic carbamate derivatives fluorescence probe 1c of embodiment 4 synthesis and appraising datum
By 2.8mmol ortho-aminobenzoic acids in 50mL dichloromethane, EDCI (4mmol) is added under stirring and frozen water cooling
With HOBt (4mmol), stir-activating 0.5-1h.Then 1mmol 3,6- dithia -1,8- octamethylenediamines are added (by embodiment 1
Obtain), it is stirred overnight at room temperature.Revolving, CH2Cl2Extraction, uses saturation NaHCO successively3, saturation NaCl, water washing organic phase is anhydrous
Sodium sulphate is dried.Revolving, crude product is purified through silica column chromatography, is dried in vacuo to obtain fluorescence probe 1c, yield 51.2%, production
Thing structural formula by1H NMR、13C NMR, HRMS are confirmed.
1H NMR(600MHz,DMSO-d6):8.35 (t, J=5.8Hz, 2H), 7.45 (d, J=8.1Hz, 2H), 7.13 (t,
J=7.6Hz, 2H), 6.68 (d, J=8.2Hz, 2H), 6.50 (t, J=7.5Hz, 2H), 6.41 (s, 5H), 3.38 (q, J=
6.6Hz, 4H), 2.77 (s, 4H), 2.70 (t, J=7.2Hz, 4H)；13C NMR(150MHz,DMSO-d6):168.94,
168.83,149.62,149.59,131.71,131.66,128.00,127.95,116.34,114.52,114.42,39.93,
38.95,38.82,38.38,37.20,31.04,30.42.HRMS(ESI)m/z calcd for C20H26N4O2S2,[M+H]+
419.15,found 419.1530.General structure is：
Wherein, R is-NH2。
The heterocyclic carbamate derivatives fluorescence probe 1d of embodiment 5 synthesis and appraising datum
By 3mmol o-methoxybenzoic acids in 20mL dichloromethane, HBTU is added under stirring and frozen water cooling
(4.5mmol) and DIPEA (1mL), stir-activating 0.5-1h.Then add 1mmol 3,6- dithia -1,8- octamethylenediamines (by
Embodiment 1 is obtained), 40 DEG C are stirred overnight.With a large amount of water diluted mixtures, CH2Cl2Extraction, uses saturation NaHCO successively3, saturation
NaCl washs organic phase, anhydrous sodium sulfate drying.Revolving, crude product is purified through silica column chromatography, is dried in vacuo to obtain yield
49.5%, product structure formula by1H NMR、13C NMR, HRMS are confirmed.
1H NMR(600MHz,CDCl3):8.33 (s, 2H), 8.19 (d, J=7.6Hz, 2H), 7.45 (d, J=8.4Hz,
2H), 7.07 (dt, J=11.0,5.6Hz, 2H), 6.97 (dd, J=8.2,3.7Hz, 2H), 3.98 (d, J=3.5Hz, 6H),
3.83–3.66(m,4H),2.99–2.77(m,8H).13C NMR(150MHz,CDCl3):165.37,157.53,132.87,
132.16,121.23,111.31,55.99,39.05,38.33,38.00,31.82.HRMS(ESI)m/z calcd for
C22H28N2O4S2,[M+H]+449.15,found 449.1549.General structure is：
Wherein, R is-OCH3。
The heterocyclic carbamate derivatives fluorescence probe 1e of embodiment 6 synthesis and appraising datum
By 3mmol phthalic anhydrides in 30mL chloroforms, 1.3mmol 3,6- dithia -1,8- octamethylenediamines are then added
(being obtained by embodiment 1), is heated to reflux 3h.Ice bath cools, and filters and uses chloroform：N-hexane=6:1 washing, solid vacuum drying
Yield 42.6%, product structure formula by1H NMR、13C NMR, HRMS are confirmed.
1H NMR(584MHz,DMSO-d6):8.45 (t, J=5.9Hz, 2H), 7.75 (d, J=7.6Hz, 2H), 7.55 (t,
J=7.5Hz, 2H), 7.50 (t, J=7.6Hz, 3H), 7.40 (d, J=7.4Hz, 2H), 3.36 (d, J=7.0Hz, 4H), 2.78
(s, 4H), 2.70 (t, J=7.4Hz, 4H)；13C NMR(150MHz,DMSO-d6):169.22,168.57,138.97,
131.81,131.40,129.84,129.82,128.18,40.59,31.73,30.68.HRMS(ESI)m/z calcd for
C22H24N2O6S2,[M+H]+477.11,found 477.1160.General structure is：
Wherein, R is-COOH.
The heterocyclic carbamate derivatives fluorescence probe 1f of embodiment 7 synthesis and appraising datum
By 3mmol o-bromobenzoic acids in 20mLDMF, HBTU (4.5mmol) and DIPEA is added under stirring and frozen water cooling
(1mL), stir-activating 0.5-1h.Then 1mmol 3 is added, 6- dithias -1,8- octamethylenediamine (is obtained) by embodiment 1,40
DEG C it is stirred overnight.With a large amount of water diluted mixtures, CH2Cl2Extraction, uses saturation NaHCO successively3, saturation NaCl washing organic phases,
Anhydrous sodium sulfate drying.Revolving, crude product is purified through silica column chromatography, is dried in vacuo to obtain yield 59.1%, product structure
Formula by1H NMR、13C NMR, HRMS are confirmed.
1H NMR(600MHz,DMSO-d6):8.58 (d, J=5.9Hz, 2H), 7.65 (dd, J=8.0,3.9Hz, 2H),
7.39 (ddd, J=25.7,13.4,6.6Hz, 4H), 3.40 (q, J=6.4Hz, 4H), 2.80 (d, J=4.3Hz, 4H), 2.72
(t, J=6.8Hz, 4H)13C NMR(150MHz,DMSO-d6)δ167.94,167.86,139.64,139.60,134.34,
133.33,131.50,129.38,128.33,128.17,119.54,40.59,31.72,30.93.HRMS(ESI)m/z
calcd for C20H22Br2N2O2S2,[M]+546.95,found 546.9542.General structure is：
Wherein, R is-Br.
The heterocyclic carbamate derivatives fluorescence probe 1g of embodiment 8 synthesis and appraising datum
By 3mmol o-fluorobenzoic acids in 20mLDMF, HBTU (4.5mmol) and DIPEA is added under stirring and frozen water cooling
(1mL), stir-activating 0.5-1h.Then 1mmol 3 is added, 6- dithias -1,8- octamethylenediamine (is obtained) by embodiment 1,40
DEG C it is stirred overnight.With a large amount of water diluted mixtures, CH2Cl2Extraction, uses saturation NaHCO successively3, saturation NaCl washing organic phases,
Anhydrous sodium sulfate drying.Revolving, crude product is purified through silica column chromatography, is dried in vacuo to obtain yield 60.8%, product structure
Formula by1H NMR、13C NMR, HRMS are confirmed.
1H NMR(600MHz,DMSO-d6):8.44 (s, 2H), 7.63 (t, J=7.7Hz, 2H), 7.53 (q, J=7.2Hz,
2H), 7.28 (q, J=8.2,7.2Hz, 2H), 3.43 (q, J=6.8Hz, 4H), 2.78 (s, 4H), 2.72 (t, J=7.3Hz,
4H).13C NMR(150MHz,CDCl3):163.28,163.26,161.24,159.55,133.16,133.10,131.68,
124.58,124.56,120.81,120.72,115.92,115.75,76.88,76.66,39.16,38.62,37.42,
31.59,31.33.HRMS(ESI)m/z calcd for C20H22F2N2O2S2,[M+H]+425.11,found 425.1135.Knot
Structure formula is：
Wherein, R is-F.
Selective enumeration method of the fluorescence probe of embodiment 9 to metal ion
The heterocyclic carbamate derivatives fluorescence probe 1a-1g that embodiment 2-- embodiments 8 are obtained is to different metal ions (Na+,K+,Mn2+,Mg2+,Ca2+,Cr3+,Fe3+,Ni2+,Cu2+,Zn2+,Co2+,Ag+,Cd2+,Hg2+,Fe2+And Pb2+) fluorescence titration it is bent
Line, as shown in Figure 1.The different metal ions of 10 equivalents are added into 10 μM of fluorescence probe test solution, its fluorescence light is determined
Spectrum.It will be seen from figure 1 that adding 10 equivalent Fe3+Afterwards, a certain degree of quenching all occurs for fluorescence probe 1a-1g fluorescence.Compare
Other probes, Fe3+It is best to probe 1b fluorescent quenching effects.Compared to Fe3+Identification, probe 1c is to Hg2+Show more highly sensitive
Degree identification.Figure it is seen that seven kinds of fluorescence probe 1a-1g have different degrees of selectivity to metal ion.
Conclusion：Seven kinds of fluorescence probe 1a-1g are to Fe3+And Hg2+There is certain quenching effect, wherein, visited for fluorescence
Pin 1b, as 10 equivalent Fe of addition3+Afterwards, its fluorescence is almost quenched, thus fluorescence probe 1b can as Fe3+High selectivity is visited
Pin.Similarly, fluorescence probe 1c can as Hg2+High selectivity probe.
The hybrid ionic of embodiment 10 is to fluorescence probe 1b specific recognitions Fe3+Hg is recognized with fluorescence probe 1c2+Interference inspection
Survey
The interfering ion of 10 equivalents is added dropwise into 10 μM of fluorescence probe 1b test solution, fluorescence spectrum is tested, then
Add the Fe of 10 equivalents3+, detection probe 1b identifications Fe in the presence of different metal ions3+Antijamming capability.As Fig. 3 can be with
Find out, fluorescence probe 1b is to Fe3+Identification do not disturbed by other ions.
The interfering ion of 10 equivalents is added dropwise into 10 μM of fluorescence probe 1c test solution, fluorescence spectrum is tested, then
Add the Hg of 10 equivalents2+, detection probe 1c identifications Hg in the presence of different metal ions2+Antijamming capability.As Fig. 4 can be with
Find out, fluorescence probe 1c is to Hg2+Identification do not disturbed by other ions.
Conclusion：Fluorescence probe 1b and fluorescence probe 1c are respectively to Fe3+And Hg2+Identification process have it is good anti-interference
Ability.
The fluorescence probe 1b of embodiment 11 and fluorescence probe 1c sensitivity test
(1) detection fluorescence probe 1b and Fe3+The relation of concentration
Fixed fluorescence probe 1b concentration is 10 μM, Fe3+Concentration increases successively.Work as Fe as Fig. 5 can be seen that3+Reach that 1 works as
During amount, 1b fluorescence intensity no longer increases, and gradually tends to balance.Simultaneously fluorescence intensities of the fluorescence probe 1b at 426nm with
Fe3+There is preferable linear relationship between concentration, linear formula is y=-0.01044+1.13487x, can be obtained by linear formula
The detection for going out fluorescence probe 1b is limited to 0.216 μM.Pass through (the F of Benesi-Hildebrand formula 1/ simultaneously0- F)=1/ { Ka*
(F0-Fmax)*[Fe3+]}+1/(F0-Fmax), binding constant 1.48 × 10 can be calculated4M-1。
(2) detection fluorescence probe 1c and Hg2+The relation of concentration
Fixed fluorescence probe 1c concentration is 10 μM, Hg2+Concentration increases successively.Work as Hg as Fig. 6 can be seen that2+Reach that 2 work as
During amount, 1c fluorescence intensity change is slow.Fluorescence intensities of the fluorescence probe 1c at 419nm is with Hg simultaneously2+Exist between concentration
Preferable linear relationship, its linear formula y=0.00115+0.30578x can draw fluorescence probe 1c's by linearly disclosing
Detection is limited to 0.481 μM.Pass through (the F of Benesi-Hildebrand formula 1/ simultaneously0- F)=1/ { Ka*(F0-Fmax)*[Hg2+]2}+
1/(F0-Fmax) binding constant 1.90 × 10 can be calculated10M-2。
Conclusion：Fluorescence probe 1b and fluorescence probe 1c are respectively to Fe3+And Hg2+With preferable linear relationship and higher
Sensitivity is determined, Fe in quantitative detection environment is may be respectively used for3+And Hg2+Content.
Embodiment 12 probe 1b and Fe3+Complexing compare and probe 1c and Hg2+Complexing ratio
The working curve that probe interacts with metal ion is done by fluorescence spectrum, selected probe and metal is studied
The combination ratio of the interaction of ion.Fixed probe 1b and Fe3+Total concentration and for 10 μM, by changing Fe3+Percentage composition
Than being measured.As shown in Figure 7, maximum molar fraction correspondence numerical value is 0.5, i.e. probe 1b and Fe3+Form 1:1 complex.
Fixed probe 1c and Hg2+Total concentration and for 10 μM, by changing Hg2+Percentage composition ratio be measured.As schemed
8 understand, maximum molar fraction correspondence numerical value is 0.6, i.e. probe 1c and Hg2+Form 1:2 complex.
In summary, the fluorescence probe 1b and fluorescence probe 1c of the present embodiment design, is with this good, sensitivity of selectivity
Height, and there is stronger antijamming capability to other common metal ions, can be in qualitative and quantitative detection environment
Fe3+And Hg2+.Therefore to the Fe in environment3+And Hg2+Detection has potential application value.
General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, various changes and modifications of the present invention are possible without departing from the spirit and scope of the present invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent is defined.
Claims (8)
1. a kind of heterocyclic carbamate derivatives fluorescence probe, it is characterised in that the chemistry of the heterocyclic carbamate derivatives fluorescence probe
Structural formula is：
Wherein, R is-H ,-OH ,-NH2、-OCH3,-COOH ,-Br, one kind in-F,
When R is-OH, the heterocyclic carbamate derivatives fluorescence probe is the heterocyclic carbamate derivatives of recognition detection ferric ion
Fluorescence probe 1b；
When R is-NH2When, the heterocyclic carbamate derivatives fluorescence probe is the heterocyclic carbamate derivatives of recognition detection ferric ion
Fluorescence probe 1c；
When R is-H, the heterocyclic carbamate derivatives fluorescence probe is heterocyclic carbamate derivatives fluorescence probe 1a；
When R is-OCH3When, the heterocyclic carbamate derivatives fluorescence probe is heterocyclic carbamate derivatives fluorescence probe 1d；
When R is-COOH, the heterocyclic carbamate derivatives fluorescence probe is heterocyclic carbamate derivatives fluorescence probe 1e；
When R is-Br, the heterocyclic carbamate derivatives fluorescence probe is heterocyclic carbamate derivatives fluorescence probe 1f；
When R is-F, the heterocyclic carbamate derivatives fluorescence probe is heterocyclic carbamate derivatives fluorescence probe 1g.
2. a kind of preparation method of heterocyclic carbamate derivatives fluorescence probe as claimed in claim 1, it is characterised in that including such as
Lower step：
A, benzoic acid is dissolved in dichloromethane；
B, addition EDCI and HOBt, stir-activating under stirring and frozen water cooling；
C, addition 3,6- dithia -1,8- octamethylenediamines；
D, it is stirred overnight at room temperature, reaction is cooled down after terminating, revolving obtains crude product；
E, silica gel column chromatography purifying, dry the heterocyclic carbamate derivatives fluorescence probe described in acquisition.
3. the preparation method of heterocyclic carbamate derivatives fluorescence probe as claimed in claim 2, it is characterised in that the step B
The stir-activating time be 0.5-1h.
4. the preparation method of heterocyclic carbamate derivatives fluorescence probe as claimed in claim 2, it is characterised in that the benzoic acid
For benzoic acid, salicylic acid, ortho-aminobenzoic acid, o-methoxybenzoic acid, phthalic anhydride, o-bromobenzoic acid, adjacent fluorobenzene first
One kind in acid.
5. the preparation method of heterocyclic carbamate derivatives fluorescence probe as claimed in claim 2, it is characterised in that the step C
The preparation methods of 3,6- dithia -1,8- octamethylenediamines include：
C1, Mercaptamine and 1,2- Bromofume react 1h in alcohol sodium solution；
C2, room temperature reaction are stayed overnight, and reaction is filtered after terminating, and is rotated, and vacuum drying obtains described 3,6- dithias -1,8- pungent
Diamines.
6. a kind of heterocyclic carbamate derivatives fluorescence probe 1a-1g as claimed in claim 1 is used for transition in recognition detection environment
The application of metal and heavy metal ion.
7. the Fe that a kind of heterocyclic carbamate derivatives fluorescence probe 1b as claimed in claim 1 is used in recognition detection environment3+'s
Using.
8. the Hg that a kind of heterocyclic carbamate derivatives fluorescence probe 1c as claimed in claim 1 is used in recognition detection environment2+'s
Using.
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