CN108752329A - Ag+Fluorescence probe, Ag+Chemical sensor - Google Patents
Ag+Fluorescence probe, Ag+Chemical sensor Download PDFInfo
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- CN108752329A CN108752329A CN201810622317.7A CN201810622317A CN108752329A CN 108752329 A CN108752329 A CN 108752329A CN 201810622317 A CN201810622317 A CN 201810622317A CN 108752329 A CN108752329 A CN 108752329A
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Abstract
Present invention design has synthesized a kind of can detect and has identified Ag+Fluorescence probe, the Ag+Fluorescence probe is Thiacalixarene derivative, and the Ag+The structure of fluorescence probe compound A as follows,Compound with above structure feature is as Ag+When fluorescence probe, highly selective, highly sensitive identification Ag can be selected by fluorescent quenching+I is further added in ion‑After ion, system fluorescence can restore, i.e. Ag+Fluorescence probe solution is with Ag+/I‑Be alternately added, a kind of fluorescence phenomenon that ON-OFF-ON is reversible can be formed, and this reversible process is recycled by multiple switching, fluorescence is almost lossless, environmentally protective it is possible thereby to realize that lasting Reversible Cycle detection uses.In addition, Ag+Fluorescence probe significant solution colour variation, can enable our simplicity by visually can be achieved with to Ag+Detection.
Description
Technical field
The invention belongs to fluorescent probe technique field more particularly to a kind of Ag+Fluorescence probe and preparation method thereof, a kind of Ag+
Green Chemistry sensor.
Background technology
Fluorescence probe due to its it is highly sensitive, highly selective, real-time response, to sample nondestructive evil and be easily manipulated
Feature is widely used in fields such as biochemistry, analytical chemistry, environmental sciences in recent years.It is a kind of abiotic
" molecular device ", usually by recognition group pass through linking arm connect fluorescence signal respond group.Recognition group is by selective knowledge
Object to be analyzed is not detected, this recognition detection behavior, which is then passed to fluorescence signal, by linking arm responds group, and glimmering
Optical signal responds group by the identification information amplification report display with this highly sensitive signal response mode of fluorescence probe.
It is realized to be analyzed to heavy metal ion, organic molecule, large biological molecule etc. by the non-covalent interaction of microscopic fields
Substance specific recognition, is embodied with fluorescence signal, to realize monitoring in real time in situ on a molecular scale.Since it has
The advantages that highly sensitive, highly selective, simple and efficient, it has also become heavy metal, transition metal and Anionic recognition in specific sample
Important method.
Lin etc. is based on g-C3N4Nanometer sheet design has synthesized an Ag+/S2-" On-Off-On " sequence fluorescence probe, when
Ag is added+Afterwards, Ag+With g-C3N4N atoms complexing in nanometer sheet, occurs Photo-induced electron transfer so that the fluorescence of probe solution
Quenching, and S is added2-Afterwards, due to S2-With Ag+The complexing power of bigger generates Ag2S is precipitated, and there is no extra Ag+With g-C3N4
Nanometer sheet acts on, so fluorescence restores, but unique regret of the probe is it to Ag+Identification by Cu2+With Hg2+Interference,
Selectivity is not high.The designs such as Singh have synthesized a four dentation schiff bases, by regulating and controlling Ag+/CN-Addition sequence, present
" On-Off-On " phenomenon, the probe is to Ag+Identification have selectivity, but its identification before and after, the color change difference of solution
It is smaller, and be sepia, it is unfavorable for developing into a kind of open hole detection reagent of simplicity.In addition, CN-High toxicity, to ring
Border harm is big.Wei etc. devises an azophenlyene class fluorescence probe derivative, and the probe is with Ag+Addition, fluorescent quenching is molten
Liquid color becomes dark crocus, I from yellow-The addition of ion can be such that the fluorescence of solution restores, but its fluorescence due to generating AgI
For recovery extent with the increase of cycle-index, fluorescence is lossy, and fluorescence intensity continuously decreases, and is difficult as a kind of heavy therefore
The candidate fluorescence probe recycled again.
Highly selective, high sensitivity is that a fluorescence probe is prerequisite, then as development in recent years, we
It cannot be limited only to this again, nontoxic, environmental protection, it is current theme that green is can be recycled.Current miscellaneous fluorescence is visited
In needle, meet any of the above any, have an a large amount of research work, but whole advantages can be all concentrated together, than
It is less.Therefore, it is highly selective to research and develop a kind of energy, it is highly sensitive, it is nontoxic, and can the environmentally protective reproducible Ag of cycle+Fluorescence is visited
Needle is particularly important.
Invention content
The purpose of the present invention is to provide a kind of Ag+Fluorescence probe and preparation method thereof, it is intended to solve existing Ag+Fluorescence
Probe cannot be taken into account highly selective, highly sensitive simultaneously, and can environmentally protective circulatory problems.
Another object of the present invention is to provide contain Ag of the present invention+The Ag of fluorescence probe+Green Chemistry sensor.
For achieving the above object, the technical solution adopted by the present invention is as follows：
One aspect of the present invention provides a kind of Ag+Fluorescence probe, the Ag+Fluorescence probe is Thiacalixarene derivative, and institute
State Ag+The structure of fluorescence probe compound A as follows,
Another aspect of the present invention provides a kind of Ag+The preparation method of fluorescence probe, includes the following steps：
Under nitrogen or inert gas shielding, addition compound 1 as shown in lower structure in dry reaction bulb, anhydrous third
Ketone, cesium carbonate carry out being heated to reflux processing for the first time；Compound 2 and cesium iodide as shown in lower structure, progress the are added after cooling
Reheating reflow treatment, prepares compound 3 as shown in lower structure, and reaction equation is as follows：
Under nitrogen or inert gas shielding, compound 3, absolute ethyl alcohol, hydrazine hydrate, third are added in dry reaction bulb
Secondary heating reflux reaction filters out white insoluble solids after reaction, and filtrate is recrystallized after being evaporated with chloroform methanol, prepares as follows
Compound 4 shown in structure, reaction equation are as follows：
Under nitrogen or inert gas shielding, compound 4 is added in dry reaction bulb, is dissolved with anhydrous methylene chloride
Afterwards, NBD-Cl and triethylamine is added, reacts at room temperature prepare compound A, reaction equation is as follows：
And further aspect of the present invention provides a kind of Ag+Green Chemistry sensor, the Ag+Green Chemistry sensor contains
Ag of the present invention+Fluorescence probe.
Ag provided by the invention+Fluorescence probe, for the compound A containing Thiacalixarene skeleton structure, meanwhile, describedization
It is 1,3- alternate configurations to close object A, i.e., introduces the chloro- 7- nitrobenzofurazans of 2 4- at 1,3 of Thiacalixarene molecular structure both ends
(NBD), 2,4 introducings, 2 quinoline groups construct the glimmering of the double fluorophors of 1,3- alternating Thiacalixarenes to form molecule jaw type
Light probe.Compound with above structure feature is as Ag+It, can be highly selective, highly sensitive by glimmering when fluorescence probe
Optical quenching selection identification Ag+I is further added in ion-After ion, system fluorescence can restore, i.e. Ag+Fluorescence probe solution with
Ag+/I-Be alternately added, a kind of fluorescence phenomenon that ON-OFF-ON is reversible (fluorescence " ON-OFF-ON " alternation switch) can be formed,
And this reversible process is recycled by multiple switching, fluorescence is almost lossless, it is possible thereby to realize that lasting Reversible Cycle detection makes
With environmentally protective.In addition, Ag+Fluorescence probe significant solution colour variation, can enable our simplicity by naked eyes energy
It realizes to Ag+Detection.To sum up, Ag provided by the invention+Fluorescence probe selectivity higher, it is bright in luster, it is conducive to bore hole colorimetric and examines
It surveys, and can be recycled, fluorescence is reversible lossless.
Ag provided by the invention+The preparation method of fluorescence probe is tried using Thiacalixarene as plateform molecules by template
Agent introduces the chloro- 7- nitrobenzofurazans (NBD) of 2 4- at 1,3 of Thiacalixarene molecule both ends respectively, and 2,4 introduce 2
Quinoline group has constructed a kind of fluorescence probe of 1, the 3- alternating multi-functional double fluorophors of Thiacalixarene of molecule jaw type.Tool
There are the multi-functional double fluorophors of the Thiacalixarene of 1,3- alternate configurations as Ag+When fluorescence probe, fluorescent quenching can be passed through
The highly selective, Ag of selection identification in high sensitivity+I is further added in ion-After ion, system fluorescence can restore, i.e. Ag+Fluorescence
Probe solution is with Ag+/I-Be alternately added, a kind of fluorescence phenomenon that ON-OFF-ON is reversible (fluorescence " ON-OFF- can be formed
ON " alternation switches), and this reversible process is recycled by multiple switching, fluorescence is almost lossless, persistently may be used it is possible thereby to realize
Inverse cycle detection uses, environmentally protective.In addition, Ag+Fluorescence probe significant solution colour variation can enable our simplicity
By visually can be achieved with to Ag+Detection.
Ag provided by the invention+Green Chemistry sensor, due to containing Ag of the present invention+Fluorescence probe, therefore, together
When have the advantages that it is highly selective, highly sensitive and environmentally protective.
Description of the drawings
Fig. 1 is n,N-Dimethylformamide/water provided in an embodiment of the present invention (v/v, 85/15) solution middle probe and metal
The fluorescence spectra of ion；
Fig. 2 is various concentration in n,N-Dimethylformamide/water provided in an embodiment of the present invention (v/v, 85/15) solution
Ag+Curve graph is dripped to the fluorescence spectrum of probe；
Fig. 3 is to detect Ag in n,N-Dimethylformamide/water provided in an embodiment of the present invention (v/v, 85/15) solution+'s
Fluorescent spectrometry correction graph；
Fig. 4 is various concentration in n,N-Dimethylformamide/water provided in an embodiment of the present invention (v/v, 85/15) solution
Ag+After the fluorescence spectroscopic titration of probe, the I of the various concentration of equivalent is added-Fluorescence spectra；
Fig. 5 is alternately added in n,N-Dimethylformamide/water provided in an embodiment of the present invention (v/v, 85/15) solution
The Ag of amount+And I-, the fluorescence intensity level at its 540nm and at 575nm, circulating and reversible variation diagram are surveyed respectively；
Fig. 6 be coexisted in n,N-Dimethylformamide/water provided in an embodiment of the present invention (v/v, 85/15) solution metal from
Son detects Ag to fluorescence probe method+Influence diagram；
Fig. 7 is n,N-Dimethylformamide/water provided in an embodiment of the present invention (v/v, 85/15) solution middle probe and metal
The uv-visible absorption spectra of ion；
Fig. 8 is various concentration Ag in n,N-Dimethylformamide/water provided in an embodiment of the present invention (v/v, 85/15) solution+Figure is titrated to the uv-visible absorption spectra of probe；
Fig. 9 is n,N-Dimethylformamide/water provided in an embodiment of the present invention (v/v, 85/15) solution middle probe detection Ag+UV-Vis Spectrophotometry calibration curve；
Figure 10 is various concentration in n,N-Dimethylformamide/water provided in an embodiment of the present invention (v/v, 85/15) solution
Ag+After the uv-visible absorption spectra titration of probe, the I of the various concentration of equivalent is added-Ultraviolet-ray visible absorbing light
Spectrogram；
Figure 11 is alternately added in n,N-Dimethylformamide/water provided in an embodiment of the present invention (v/v, 85/15) solution
The Ag of equivalent+And I-, its ultraviolet-ray visible absorbing value at 505nm is surveyed, probe can be with circulating and reversible variation diagram；
Figure 12 is that metal coexists in n,N-Dimethylformamide/water provided in an embodiment of the present invention (v/v, 85/15) solution
Ion pair probe UV-Vis Spectrophotometry detects Ag+Fluorescence intensity influence diagram；
Figure 13 is that 365nm is ultraviolet in n,N-Dimethylformamide/water provided in an embodiment of the present invention (v/v, 85/15) solution
Probe in detecting Ag under lamp+Color change photo；
Figure 14 is daylight test in n,N-Dimethylformamide/water provided in an embodiment of the present invention (v/v, 85/15) solution
Needle detects Ag+The color change photo of solution.
Specific implementation mode
In order to make technical problems, technical solutions and advantageous effects to be solved by the present invention be more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only explaining this
Invention, is not intended to limit the present invention.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indicating or implies relative importance or implicitly indicate the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more this feature.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
One aspect of the present invention provides a kind of Ag+Fluorescence probe, the Ag+Fluorescence probe is Thiacalixarene derivative, and institute
State Ag+The structure of fluorescence probe compound A as follows,
Ag provided in an embodiment of the present invention+Fluorescence probe, for the compound A containing Thiacalixarene skeleton structure, meanwhile,
The compound A is 1,3- alternate configurations, i.e., introduces the chloro- 7- nitros of 2 4- at 1,3 of Thiacalixarene molecular structure both ends
Benzene furazan (NBD), 2,4 introducings, 2 quinoline groups construct the double fluorescent bases of 1,3- alternating Thiacalixarenes to form molecule jaw type
The fluorescence probe of group.Compound with above structure feature is as Ag+When fluorescence probe, fluorescent quenching high selection can be passed through
Property, highly sensitive selection identification Ag+I is further added in ion-After ion, system fluorescence can restore, i.e. Ag+Fluorescence probe solution
With Ag+/I-Be alternately added, can forming a kind of fluorescence phenomenon that ON-OFF-ON is reversible, (fluorescence " ON-OFF-ON " is alternately opened
Close), and this reversible process is recycled by multiple switching, fluorescence is almost lossless, it is possible thereby to realize lasting Reversible Cycle inspection
It surveys and uses, it is environmentally protective.In addition, Ag+The significant solution colour variation of fluorescence probe, can enable we are easy to pass through visually
It can be achieved with to Ag+Detection.
To sum up, Ag provided in an embodiment of the present invention+Fluorescence probe selectivity higher, it is bright in luster, it is conducive to bore hole colorimetric and examines
It surveys, and can be recycled, fluorescence is reversible lossless.
Ag provided in an embodiment of the present invention+Fluorescence probe can be prepared by following methods.
Correspondingly, on the other hand the embodiment of the present invention provides a kind of Ag+The preparation method of fluorescence probe, including following step
Suddenly：
S01. under nitrogen or inert gas shielding, compound 1 as shown in lower structure is added in dry reaction bulb, it is anhydrous
Acetone, cesium carbonate carry out being heated to reflux processing for the first time；Compound 2 and cesium iodide as shown in lower structure are added after cooling, carries out
It is heated to reflux processing for the second time, prepares compound 3 as shown in lower structure, reaction equation is as follows：
S02. under nitrogen or inert gas shielding, compound 3 is added in dry reaction bulb, water is added in absolute ethyl alcohol
Hydrazine is closed, third time heating reflux reaction filters out white insoluble solids after reaction, and filtrate is tied after being evaporated with chloroform methanol again
Crystalline substance, prepares compound 4 as shown in lower structure, and reaction equation is as follows：
S03. under nitrogen or inert gas shielding, compound 4 is added in dry reaction bulb, it is molten with anhydrous methylene chloride
NBD-Cl and triethylamine is added in Xie Hou, reacts at room temperature prepare compound A, and reaction equation is as follows：
Ag provided in an embodiment of the present invention+The preparation method of fluorescence probe passes through mould using Thiacalixarene as plateform molecules
Plate reagent introduces the chloro- 7- nitrobenzofurazans (NBD) of 2 4-, 2,4 introducings at 1,3 of Thiacalixarene molecule both ends respectively
2 quinoline groups have constructed a kind of fluorescence probe of 1, the 3- alternating multi-functional double fluorophors of Thiacalixarene of molecule jaw type.
The multi-functional double fluorophors of Thiacalixarene with 1,3- alternate configurations are as Ag+It, can be sudden by fluorescence when fluorescence probe
Go out the highly selective, Ag of selection identification in high sensitivity+I is further added in ion-After ion, system fluorescence can restore, i.e. Ag+It is glimmering
Light probe solution is with Ag+/I-Be alternately added, a kind of fluorescence phenomenon that ON-OFF-ON is reversible (fluorescence " ON- can be formed
OFF-ON " alternation switches), and this reversible process is recycled by multiple switching, fluorescence is almost lossless, is held it is possible thereby to realize
Continuous Reversible Cycle detection uses, environmentally protective.In addition, Ag+The significant solution colour variation of fluorescence probe, can enable our letters
Just by visually can be achieved with to Ag+Detection.
Due to the present embodiments relate to chemical reaction influence factor it is more, reaction sensitivity is high, therefore, prepares the Ag+When fluorescence probe, that is, compound A, all chemical reactions carry out in an inert atmosphere, to avoid drawing for other gases
Enter, causes chemical reaction direction to be deviateed, cannot get the target compound A of the embodiment of the present invention.Specifically, the indifferent gas
Atmosphere can be nitrogen atmosphere, or inert gas atmosphere, including but not limited to helium, argon gas.
In the embodiment of the present invention, in order to avoid the introducing of water, oxygen interferes reaction, reaction bulb is selected dry abundant
Reaction bulb.
In above-mentioned steps S01, using compound 1 as initial reaction raw materials, solvent is made with anhydrous propanone.Described anhydrous third
Ketone has suitable boiling point and polarity, and compound 1 is used as when particularly suitable for pressing the method prepare compound 2 of the embodiment of the present invention
Solvent.It is worth noting that, the present invention implements for the acetone of dissolved compound 1 to be anhydrous propanone, draw to avoid water, oxygen
Enter, lead to the generation of hydrolysis and other miscellaneous side reactions, influences the progress of reaction, lead to that target product cannot be obtained, or
Obtained products collection efficiency is low.Preferably, it is 4.5~5.5mg according to compound 1 and anhydrous propanone mass volume ratio:The ratio of 1mL
Anhydrous propanone is added, it is specific preferred, it is 5mg according to compound 1 and anhydrous propanone mass volume ratio:The ratio of 1mL adds nothing
Water acetone.
Cesium carbonate is added in the acetone soln for the compound 1 that dissolving obtains, on the one hand the cesium carbonate is used as alkali, another
Aspect is as template reagent so that the 2 of compound 1 can generate 1,3- alternate configurations after introducing compound 2 on 4 phenolic hydroxyl groups
Compound 3, after configuration is fixed, it is follow-up introduce the reactions such as fluorophor and can be based on this special 1,3- alternate configurations maintain reaction
The fluorescence probe for going down to obtain the double fluorophors of 1, the 3- for finally obtaining molecule jaw type alternating Thiacalixarenes, to obtain Gao Xuan
Selecting property, highly sensitive Ag+Fluorescence probe, i.e. compound A.Mole additive amount of the cesium carbonate is not less than the compound 1
Mole additive amount, to be conducive to holding 1,3- alternate configurations.Preferably, mole of the compound 1 and the cesium carbonate
Than being 1:1~1:10, concretely 1:1,1:2,1:3,1:4,1:10.If the too high levels of the cesium carbonate, not only bad for
Cost is reduced, can also cause trouble to post-processing.
The effect that the embodiment of the present invention makes the cesium carbonate play template reagent by being heated to reflux processing so that describedization
Object 1 is closed to be formed during the reaction and maintain 1,3- alternate configurations.The temperature that the first time is heated to reflux processing is no more than institute
State the boiling point of anhydrous propanone.Preferably, the reaction temperature that the first time is heated to reflux processing is 50-55 DEG C, when reaction
Between be 55-65 minutes, to be conducive to realize 1,3- alternate configurations under uniform and stable environment.
It will carry out being heated to reflux that treated for the first time that reaction system carries out cooling treatment, reaction raw materials compound 2 is added,
Cesium iodide is added.The cesium iodide promotes phenolic hydroxyl group to lose hydrogen ion as catalyst, forms negative oxygen ion, anti-to accelerate
The generation answered, prepare compound 3.In the step of preparing the compound 3, the molar ratio of the compound 1 and the cesium iodide
It is 1:0.8~1:1.2, be conducive to the progress for economically and quickly promoting reaction.
The embodiment of the present invention is realized by the reaction of 2 prepare compound 3 of compound 1 and compound by being heated to reflux processing.
The temperature for being heated to reflux processing for the second time is no more than the boiling point of the anhydrous propanone.Preferably, add for described second
The reaction temperature of hot reflow treatment is 50-55 DEG C, and the reaction time is 5.5-6.5 hours, to be conducive to the preparation of compound 3.
In the step of further preparing the compound 3, it is described be heated to reflux processing for the second time after, further include following
Processing：
By reaction system solvent evaporated, organic phase is extracted and collected using chloroform, is had using described in saturated common salt water washing
Processing is dried using drier such as anhydrous magnesium sulfate, anhydrous sodium sulfate etc. after machine phase, after decompression removes chloroform, by sample into
Row silica gel column chromatography carries out separating-purifying, and silica gel column chromatography separation proposes in step, with volume ratio for 100:2 chloroform, methanol
It is eluted as mobile phase, purification enrichment compound 3.
In above-mentioned steps S02, making solvent using absolute ethyl alcohol has suitable boiling point and polarity, particularly suitable for pressing the present invention
Dissolution solvent as compound 3 when embodiment the method prepare compound 4.It is worth noting that, present invention implementation is used for
The ethyl alcohol of dissolved compound 3 is absolute ethyl alcohol, to avoid the introducing of water, oxygen, leads to hydrolysis and other miscellaneous side reactions
Occur, influences the progress of reaction, lead to that target product cannot be obtained, or obtained products collection efficiency is low.Using absolute ethyl alcohol to changing
It closes object 3 to be dissolved, is preferably performed under heating conditions dissolving, heating temperature is no more than the boiling point of absolute ethyl alcohol.
Reaction raw materials hydrazine hydrate is added in the ethanol solution of compound 3 upon dissolution, is carried out third time and is heated back
Stream heating reaction.The reaction temperature of the third time heating reflux reaction is no more than the boiling point of the absolute ethyl alcohol.It is preferred that
, the temperature of the third time heating reflux reaction is 65-75 DEG C, 10-16 hours, is conducive to the preparation of compound 4.
Reaction generates a large amount of white precipitate (phthalylhydrazine), the white insoluble solids of filtering removal.Further, will
It after obtained filtrate is evaporated out, is recrystallized with chloroform methanol, obtains lurid compound 4.
In above-mentioned steps S03, compound 4 is dissolved with anhydrous methylene chloride, the anhydrous methylene chloride is to the chemical combination
Object 4 has good dissolubility good, and has suitable boiling point and polarity, is suitable for preparing by the method for the embodiment of the present invention
Dissolution solvent as compound 4 when compound A.It is worth noting that, the present invention implements the dichloromethane for dissolved compound 4
Alkane is anhydrous methylene chloride, to avoid the introducing of water, oxygen, leads to the generation of hydrolysis and other miscellaneous side reactions, is influenced anti-
The progress answered leads to that target product cannot be obtained, or obtained products collection efficiency is low.Preferably, according to compound 4 and anhydrous dichloro
Methane mass volume ratio is 3.5~4.5mg:The ratio of 1ml adds anhydrous methylene chloride, specific preferred, according to compound 4 with
Anhydrous methylene chloride mass volume ratio is 4mg:The ratio of 1ml adds anhydrous methylene chloride.Using anhydrous methylene chloride to chemical combination
Object 4 is dissolved, and stir process rush may be used and make it dissolve.
Reaction raw materials NBD-Cl is added in the anhydrous methylene chloride solution of compound 4 upon dissolution, adds triethylamine.Institute
Triethylamine is stated as acid binding agent, to which driving a reaction is carried out to positive direction, to promote for reacting with the acidic materials for reacting generation
The generation of target product compound A.Preferably, in the step of preparing the compound A, the additive amount of the triethylamine meets：
The mass volume ratio of the compound 4 and the triethylamine is 100mg：1.00~1.50ml is conducive to obtain good reflection
Effect, yield is 60% or more.Specific preferred, the additive amount of the triethylamine meets：The compound 4 and the triethylamine
Mass volume ratio be 100mg：1.25ml.
The reaction of prepare compound A of the present invention carries out at ambient temperature, and present invention meaning room temperature is 10-35 DEG C.
Further, in the step of preparing the compound A, further include after the room temperature reaction：Decompression boils off organic molten
After agent, sample is subjected to silica gel column chromatography and carries out separating-purifying, silica gel column chromatography separation proposes in step, with volume ratio for 10:1
Chloroform, ethyl acetate eluted as mobile phase.
And another further aspect of the embodiment of the present invention provides a kind of Ag+Green Chemistry sensor, the Ag+Green Chemistry senses
Device contains Ag of the present invention+Fluorescence probe.
Ag provided in an embodiment of the present invention+Green Chemistry sensor, due to containing Ag of the present invention+Fluorescence probe, because
This, while having the advantages that highly selective, highly sensitive, nontoxic and environmentally protective.
It is illustrated with reference to specific embodiment.
In the embodiment of the present invention, ultraviolet-visible spectrophotometer model UV-1800 used, Japanese Shimadzu Corporation's production；
Sepectrophotofluorometer model Cary Eclipse sepectrophotofluorometers, the production of VARIAN companies of the U.S.；Microwave synthesis system
The production of system model Discover SP, U.S. CE M companies.
Embodiment 1
A kind of Ag+The preparation method of fluorescence probe (following abbreviation probes), includes the following steps：
S11. compound 3 is synthesized
Under nitrogen protection, compound 1 (500mg, 0.48mmol) is added in dry 250ml three-necked flasks, 100mL is dry
Acetone stirs to dissolve, and cesium carbonate (1.56g, 4.8mmol) is added, is heated to reflux 1h.After its cooling, compound 2 is added
(264mg, 1.2mmol), cesium iodide (124mg, 0.48mmol), is heated to reflux 6h.Reaction finishes, solvent evaporated, chloroform extraction
(3 × 100mL), organic phase are washed with saturated salt solution 200mL, and anhydrous magnesium sulfate is dried overnight, and decompression boils off solvent.Silicagel column
Chromatography purifies chloroform/methanol (100/:2) 0.46g yellow solid compounds 3, yield 67.3%, are obtained.
The nuclear magnetic data of compound 3 is as follows：
1H NMR(500MHz,CDCl3,ppm)δ:10.76 (s, 1H ,-NH-), 8.92 (d, J=5Hz, 1H, ArH), 8.79
(d, J=10Hz, 1H, ArH), 8.24 (d, J=5Hz, 1H, ArH), 7.95 (s, 2H, ArH), 7.91 (q, J=5Hz, 2H,
ArH), 7.76 (q, J=5Hz, 2H, ArH), 7.60 (m, 2H, ArH), 7.52 (m, 3H, ArH), 4.41 (s, 2H ,-O-CH2-
CO-), 4.33 (t, J=7.5Hz, 2H ,-O-CH2), 4.05 (t, J=10Hz, 2H, CH2- N), 1.93 [s, 9H, (- C-
(CH3)3], 0.82 [s, 9H, (- C- (CH3)3]。
S12. compound 4 is synthesized
Under nitrogen protection, the addition intermediate 3 (1.5g, 1.45mmol) in 250ml three-necked flasks, absolute ethyl alcohol 100mL,
Heating is allowed to that hydrazine hydrate (3.63g, 72.5mmol) is added after dissolving, and flow back 12h, generates a large amount of white precipitates.Filter off white
Insoluble solids are evaporated filtrate, are recrystallized with chloroform methanol, obtain 0.72g light yellow solids 4, yield 61.5%.
The nuclear magnetic data of compound 4 is as follows：
1H NMR(500MHz,CDCl3,ppm)δ:9.04(s,4H,-NH2), 7.66 (s, 4H, ArH), 7.31 (s, 4H,
ArH), 4.67 (t, J=5Hz, 4H ,-OCH2), 3.87 (t, J=5Hz, 4H ,-CH2- N), 1.33 [s, 9H, (- C- (CH3)3],
0.99[s,9H,(-C-(CH3)3]。
S13. target-probe compound is synthesized
In the there-necked flask of 250ml, intermediate 4 (400mg, 0.34mmol), CH dry 100mL is added2Cl2, stirring makes it
It dissolves, then addition NBD-Cl (160mg, 0.40mmol), 5mL triethylamines, is reacted at room temperature for 24 hours under nitrogen protection.Decompression boils off
Solvent, silica gel column chromatography separating-purifying chloroform/ethyl acetate (10:1, v/v) 0.224g bright yellow solid target-probes, are obtained, are produced
Rate 43.8%.
The fusing point of compound A, infrared data, nuclear-magnetism (hydrogen spectrum, carbon spectrum) data are as follows：
m.p.196-198℃。
IR(KBr,νcm-1):3432,1589,1355,1178,999,784,625.
1H NMR(500MHz,DMSO,ppm)δ:10.54 (s, 2H ,-NH-), 8.92 (d, J=5Hz, 2H, ArH), 8.73
(d, J=10Hz, 2H, ArH), 8.75 (d, J=10Hz, 2H, ArH), 7.78 (d, J=5Hz, 2H, ArH), 7.75 (d, J=
10Hz, 2H, ArH), 7.65-7.70 (m, 6H, ArH), 7.55 (s, 4H, ArH), 7.40 (s, 2H, ArH), 4.38 (t, J=
7.5Hz,4H,-O-CH2), 4.21 (t, J=7.5Hz, 4H ,-CH2-N),4.01(s,4H,O-CH2-CO),1.29[s,18H,(-
C-(CH3)3],1.18[s,18H,(-C-(CH3)3]。
13C-NMR(500MHz,CDCl3)δ(ppm):166.94,156.60,155.60,148.40,144.71,139.04,
136.06,134.61,129.74,128.78,128.03,127.77,127.12,123.22,121.92,121.55,120.51,
118.88,128.02,117.50,34.23,31.26,30.99,30.55.
Embodiment 2
The preparation method of various reagents in analysis method of the present invention：
(1) preparation of probe storing solution：The probe reagent prepared in 75.1mg embodiments 1 is weighed, uses N, N- diformazans respectively
Base formamide and acetonitrile dissolving, are configured to Ag+N,N-dimethylformamide solution (N, the N- diformazan of a concentration of 1mM of fluorescence probe
Base formamide probe storing solution) 50mL, Ag+Acetonitrile solution (acetonitrile probe storing solution) 50mL of a concentration of 1mM of fluorescence probe.
(2)Ag+Storing solution is prepared：A perchloric acid hydrate silver 90.4mg is weighed to be configured to a concentration of with ultrapure water dissolution
The solution 10mL of 20mM.
(3) other metal ions Li+, Na+, K+, Mg2+, Ca2+, Ba2+-, Hg2+, Sr2+, Zn2+, Al3+, Fe3+,Co2+, Ni2+,
Cu2+, Zn2+, Pb2+, Cd2+, Mn2+The preparation of storing solution：The perchlorate of respective metal ion is taken respectively.Cr3+Ion corresponds to
Nitrate water dissolution and be configured to the metal ion storing solution of 20mM.
(4)I-Storing solution is prepared：Tetrabutylammonium iodide 73.9mg is weighed, is dissolved with n,N-Dimethylformamide, is configured to
The solution 10mL of a concentration of 20mM.
(5)F-Lay in liquid making method：Tetrabutyl ammonium fluoride 63.0mg is weighed, is dissolved with acetonitrile, is configured to a concentration of
The solution 10mL of 20mM.
(6) preparation of other counter anion solution：Corresponding anion 4-butyl ammonium is taken respectively, simultaneously with acetonitrile dissolving
It is configured to the anion acetonitrile storing solution of 2mM.
Embodiment 3
Fluorescent spectrometry is to Ag+Detection
(1) setting fluorescence exciting wavelength is 472nm, and n,N-Dimethylformamide probe deposit is added in 10mL volumetric flasks
After liquid (1mM, 0.1mL), it is diluted to scale with n,N-Dimethylformamide/aqueous solution, makes N in probe test solution, N- diformazans
Base formamide/water is 85/15 (v/v), shakes up, probe solution is made, take solution 3mL middle carry out fluorescence in the cuvette of 1cm
Spectroscopic assay.After being separately added into n,N-Dimethylformamide probe storing solution (1mM, 0.1mL) in a series of 10mL volumetric flasks,
It is separately added into metal ion Li again+, Na+, K+, Mg2+, Ca2+, Ba2+-, Hg2+, Sr2+, Zn2+, Al3+, Fe3+,Cr3+,Co2+, Ni2+,
Ag+, Cu2+, Zn2+, Pb2+, Cd2+, Mn2+Storing solution (20mM, 0.1mL).
In N,N-dimethylformamide/H2In O (v/v, 85/15) solution, a concentration of 10 μM of probe solution, in 472nm
Under wavelength excitation, emit the strong yellow fluorescence of 540nm；It is separately added into 200 μM of metal ion Li+, Na+, K+, Mg2+, Ca2+, Ba2 +-, Hg2+, Sr2+, Zn2+, Al3+, Fe3+,Cr3+,Co2+, Ni2+, Ag+, Cu2+, Zn2+, Pb2+, Cd2+, Mn2+Afterwards, only Ag+Keep its glimmering
Light emitting peak red shift 35nm, Fluorescent peal move at 575nm, and fluorescence is obviously reduced, there is faint enhancing, shape at 625nm
At ratio fluorescent, there is a ratio in 600nm and absorb point, the fluorescence light of probe is not observed in the addition of remaining metal ion
Spectrum has significant change (being specifically shown in Fig. 1), the addition of other metal ions not to change the fluorescence spectrum of probe solution, show at this
Probe solution is to Hg under part2+There is fluorescence identifying detection effect.
(2) in N,N-dimethylformamide/H2In O (85/15, v/v) solution, using 472nm as fluorescence exciting wavelength, Ag is taken+
Storing solution is configured to the Ag of various concentration+Solution, and be added in 10 μM of probe solutions, obtain fluorescence spectroscopic titration curve (tool
Body is shown in Fig. 2), with Ag+It is added, the red shift of the emission spectra of probe is to 575nm, and fluorescence intensity is weakened；When addition exists
Occur a ratio at 600nm and absorb point, therefore forms ratio fluorescent.
(3) in a concentration of 10 μM of N,N-dimethylformamide/H2In O (85/15, v/v) solution, various concentration is added
Ag+, using 472nm as fluorescence exciting wavelength, with the addition fluorescence intensity linear taper of Ag+, measure Ag+Probe when concentration changes
Fluorescence intensity of the solution at 540nm obtains Correction of the fluorescent spectrum song (being specifically shown in Fig. 3), by the slope and measurement of calibration curve
The standard deviation of 10 blank values measures and fluorescence probe method detection Ag is calculated+The concentration range of linearity and detection limit row
In table 1.When be further continued for be added Ag+When ion, when fluorescence probe intensity and wavelength no longer change, the addition of equivalent is added not at this time
With the I of concentration-Survey the fluorescence intensity (being specifically shown in Fig. 4) that its fluorescent spectrum curve can be such that fluorescence is restored at 540nm.Fig. 4 shows,
With I-The addition of ion, the gradual blue shift of fluorescence spectrum and enhances, when the amount and Ag of addition+Concentration it is equal when, fluorescence can be made
Be restored to original wavelength and with original fluorescence intensity.The Ag of addition equivalent alternately and repeatedly+And I-, survey respectively at its 540nm
With the fluorescent value at 575nm, fluorescence is hardly lost, and probe can be with circulating and reversible, (being specifically shown in Fig. 5), that is to say, that probe
A kind of green probe can be used as to recycle.
(4) probe in detecting Ag+Fluorescence intensity at 540nm is in Li+, Na+, K+, Mg2+, Ca2+, Ba2+-, Hg2+, Sr2+,
Zn2+, Al3+, Fe3+,Cr3+,Co2+, Ni2+, Ag+, Cu2+, Zn2+, Pb2+, Cd2+, Mn2+Ion is present in respectively as coexisting ion
Probe-Ag+In mixed solution, when the coexistent metallic ion concentration and Ag of addition+When concentration is identical, other metal ions are to probe
Detect Ag+Fluorescence intensity influence it is smaller, do not interfere Ag+Measurement, (being specifically shown in Fig. 6), when concentration and Ag+ concentration phases is added
Meanwhile other metal ions influence the fluorescence intensity of probe in detecting Ag+ smaller, not interference measurement, the i.e. selectivity of probe
It is high.
Embodiment 4
UV-Vis Spectrophotometry is to Ag+Detection
(1) after n,N-Dimethylformamide probe storing solution (1mM, 0.2mL) being added in 10mL volumetric flasks, with N, N- bis-
Methylformamide/aqueous solution is diluted to scale, makes n,N-Dimethylformamide/water (85/15, v/v) in probe test solution.It shakes
It is even, probe solution is made, takes solution 3mL in the cuvette of 1cm, carries out uv-visible absorption spectra measurement.A series of
After being separately added into n,N-Dimethylformamide probe storing solution (1mM, 0.2mL) in 10mL volumetric flasks, then be separately added into metal from
Sub- Li+, Na+, K+, Mg2+, Ca2+, Ba2+-, Hg2+, Sr2+, Zn2+, Al3+, Fe3+,Cr3+,Co2+, Ni2+, Cu2+, Zn2+, Pb2+, Cd2 +, Mn2+Storing solution (20mM, 0.2mL), with n,N-Dimethylformamide/H2O is diluted to scale, make n,N-Dimethylformamide/
H2O is (85/15, v/v), shakes up, solution about 3mL is taken to carry out uv-visible absorption spectra measurement in the cuvette of 1cm.
(2) in N,N-dimethylformamide/H2O is in 2/3 (v/v) solution, and a concentration of 20 μM of probe solution is in 472nm
There is absorption peak at place；It is separately added into 400 μM of metal ion Li+, Na+, K+, Mg2+, Ca2+, Ba2+-, Hg2+, Sr2+, Zn2+, Al3+, Fe3+,
Cr3+,Co2+, Ni2+, Ag+, Cu2+, Zn2+, Pb2+, Cd2+, Mn2+Afterwards, only Ag+Make the 505nm of the absorption peak red shift at its 472nm
Place, and occur new absorption peak at 388nm, two ratios occur at 412nm and at 482nm absorbs point, (is specifically shown in figure
7), the addition of other metal ions does not change the uv-visible absorption spectra of probe solution, shows that probe is to Ag with this condition+There is highly selective recognition detection to act on.
(3) Ag is taken+Storing solution is configured to the Ag of various concentration+Solution, and be added in a concentration of 20 μM of probe solution, it obtains
To uv-visible absorption spectra titration curve, with Ag+ the one new ultraviolet absorption peak of appearance being added at 388nm and
Constantly enhancing, the absorption peak at 472nm gradually weakens, and the absorption peak at 505nm gradually increases, at 412nm and 482nm
There are two ratios and absorbs point.This chart is bright, and probe shows typical ratiometer property (being specifically shown in Fig. 8).Measure Ag+Concentration
Ratio absorbance value of the probe solution at 505nm and at 482nm when variation, it is (specific to obtain ultraviolet-ray visible absorbing calibration curve
See Fig. 9).By the standard deviation of 10 blank values of slope and measurement of calibration curve, measures and probe ratios absorption is calculated
Method detects Ag+The concentration range of linearity and detection limit be listed in table 1.
(4) when be further continued for be added Ag+When probe absorbance value and wavelength no longer change when ion, equivalent is added at this time
The I of various concentration-Survey its ultraviolet-ray visible absorbing shading value I-Probe can be made to be restored to initial uv-visible absorption spectra, (tool
Body is shown in Figure 10).With I-The increase of concentration can make probe gradually be restored to initial uv-visible absorption spectra.Alternately and repeatedly
Addition equivalent Ag+And I-, uv-visible absorption spectra value at its 505nm is surveyed respectively, and absorbance is almost unchanged, that is, visits
Needle can be with circulating and reversible (being specifically shown in Figure 11).
(6) probe in detecting Ag+UV, visible light absorbance spectrum at 505nm is in Li+, Na+, K+, Mg2+, Ca2+, Ba2+-,
Hg2+, Sr2+, Zn2+, Al3+, Fe3+,Cr3+,Co2+, Ni2+, Ag+, Cu2+, Zn2+, Pb2+, Cd2+, Mn2+Ion respectively as coexist from
Son is present in probe-Ag+In mixed solution, when the coexistent metallic ion concentration and Ag of addition+When concentration is identical, other metals from
Son is to probe in detecting Ag+Fluorescence intensity influence can almost ignore, interference measurement (is not specifically shown in Figure 12, the suction at 505nm
Receive peak value such as white histogram).
Table 1
5 visual method of embodiment is to Ag+Ion detection：
(1) under 365nm ultraviolet lamps, in n,N-Dimethylformamide/H2O is in (85/15, v/v) solution a concentration of 10
μM probe solution, probe solution be in very strong yellow fluorescence；10 μM of Ag is added+Afterwards, probe solution is in Chinese red fluorescence；Point
It Jia Ru not equal other metal ions Li of concentration+, Na+, K+, Mg2+, Ca2+, Ba2+-, Hg2+, Sr2+, Zn2+, Al3+, Fe3+,Cr3 +,Co2+, Ni2+, Cu2+, Zn2+, Pb2+, Cd2+, Mn2+Afterwards, probe solution still yellow fluorescence (being specifically shown in Figure 13), the probe
Can be visually equal to the Ag more than 10 μM with detectable concentration+。
(2) in the sunlight, in n,N-Dimethylformamide/H2O is a concentration of 20 μM of spy in (85/15, v/v) solution
Needle solution, probe solution yellow；20 μM of Ag is added+Afterwards, probe solution is in Chinese red；It is separately added into equal other of concentration
Metal ion Li+, Na+, K+, Mg2+, Ca2+, Ba2+-, Hg2+, Sr2+, Zn2+, Al3+, Fe3+,Cr3+,Co2+, Ni2+, Cu2+, Zn2+,
Pb2+, Cd2+, Mn2+Afterwards, probe solution still yellow (being specifically shown in Figure 14) illustrates that probe can be examined by visual observation under fluorescent light
Survey the Ag that concentration is more than or equal to 20 μM+Ion.
By embodiment 5 it is found that we, which can simply identify according to color, judges detection Ag+Presence or absence.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (10)
1. a kind of Ag+Fluorescence probe, which is characterized in that the Ag+Fluorescence probe is Thiacalixarene derivative, and the Ag+It is glimmering
The structure of light probe compound A as follows,
2. a kind of Ag+The preparation method of fluorescence probe, which is characterized in that include the following steps：
Under nitrogen or inert gas shielding, compound 1 as shown in lower structure, anhydrous propanone, carbon are added in dry reaction bulb
Sour caesium carries out being heated to reflux processing for the first time；Compound 2 and cesium iodide as shown in lower structure are added after cooling, carries out second
It is heated to reflux processing, prepares compound 3 as shown in lower structure, reaction equation is as follows：
Under nitrogen or inert gas shielding, compound 3, absolute ethyl alcohol are added in dry reaction bulb, hydrazine hydrate adds for the third time
Hot back flow reaction filters out white insoluble solids after reaction, and filtrate is recrystallized after being evaporated with chloroform methanol, prepares such as lower structure
Shown compound 4, reaction equation is as follows：
Under nitrogen or inert gas shielding, compound 4 is added in dry reaction bulb, after being dissolved with anhydrous methylene chloride, adds
Enter NBD-Cl and triethylamine, react at room temperature prepare compound A, reaction equation is as follows：
3. Ag as claimed in claim 2+The preparation method of fluorescence probe, which is characterized in that the first time is heated to reflux processing
Reaction temperature be 50-55 DEG C, the reaction time be 55-65 minutes.
4. Ag as claimed in claim 2+The preparation method of fluorescence probe, which is characterized in that described to be heated to reflux processing for the second time
Reaction temperature be 50-55 DEG C, the reaction time be 5.5-6.5 hours.
5. Ag as claimed in claim 2+The preparation method of fluorescence probe, which is characterized in that the third time heating reflux reaction
Temperature be 65-75 DEG C, 10-16 hours.
6. such as claim 2-5 any one of them Ag+The preparation method of fluorescence probe, which is characterized in that prepare the compound
In 3 the step of, the molar ratio of the compound 1 and the cesium carbonate is 1:2~1:10；And/or
In the step of preparing the compound 3, the molar ratio of the compound 1 and the cesium iodide is 1:0.8~1:1.2.
7. such as claim 2-5 any one of them Ag+The preparation method of fluorescence probe, which is characterized in that prepare the compound
In the step of A, the additive amount of the triethylamine meets：The mass volume ratio of the compound 4 and the triethylamine is 100mg：
1.00~1.50ml.
8. such as claim 2-5 any one of them Ag+The preparation method of fluorescence probe, which is characterized in that prepare the compound
In 3 the step of, it is described be heated to reflux processing for the second time after, further include following processing：
By reaction system solvent evaporated, organic phase is extracted and collected using chloroform, using organic phase described in saturated common salt water washing
It uses desiccant dryness to handle afterwards, after decompression removal chloroform, sample is subjected to silica gel column chromatography and carries out separating-purifying, silica gel column layer
Analysis separation proposes in step, with volume ratio for 100:2 chloroform, methanol are eluted as mobile phase.
9. such as claim 2-5 any one of them Ag+The preparation method of fluorescence probe, which is characterized in that prepare the compound
In the step of A, further include after the room temperature reaction：After decompression boils off organic solvent, sample progress silica gel column chromatography is divided
From purification, silica gel column chromatography separation proposes in step, with volume ratio for 10:1 chloroform, ethyl acetate are washed as mobile phase
It is de-.
10. a kind of Ag+Green Chemistry sensor, which is characterized in that the Ag+Green Chemistry sensor contains described in claim 1
Ag+Fluorescence probe.
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| CN110672574A (en) * | 2019-11-06 | 2020-01-10 | 湖北师范大学 | For detecting Cu2+Ratiometric fluorescent sensor, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002265467A (en) * | 2001-03-12 | 2002-09-18 | Cosmo Research Inst | Optically active thiacalixarene derivative and method for producing the same |
| CN104177351A (en) * | 2014-08-05 | 2014-12-03 | 贵州大学 | Fluorescent probe reagent for measuring Ag<+>, F<-> or AcO<-> by use of ratio method, and preparation method and application of fluorescent probe reagent |
| CN107936953A (en) * | 2017-11-23 | 2018-04-20 | 深圳先进技术研究院 | A kind of fluorescence probe and its preparation method and application |
-
2018
- 2018-06-15 CN CN201810622317.7A patent/CN108752329A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002265467A (en) * | 2001-03-12 | 2002-09-18 | Cosmo Research Inst | Optically active thiacalixarene derivative and method for producing the same |
| CN104177351A (en) * | 2014-08-05 | 2014-12-03 | 贵州大学 | Fluorescent probe reagent for measuring Ag<+>, F<-> or AcO<-> by use of ratio method, and preparation method and application of fluorescent probe reagent |
| CN107936953A (en) * | 2017-11-23 | 2018-04-20 | 深圳先进技术研究院 | A kind of fluorescence probe and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 吴玉田: "基于杂原子桥联杯芳烃荧光探针的合成及性质研究", 《中国优秀硕士学位论文全文数据库（电子期刊） 工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110672574A (en) * | 2019-11-06 | 2020-01-10 | 湖北师范大学 | For detecting Cu2+Ratiometric fluorescent sensor, and preparation method and application thereof |
| CN110672574B (en) * | 2019-11-06 | 2021-10-15 | 湖北师范大学 | For detecting Cu2+Ratiometric fluorescent sensor, and preparation method and application thereof |
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