CN107501285B - A kind of the water-soluble rhodamine base ionic liquid probe and preparation method, application of bimetallic ion selectivity Division identification - Google Patents
A kind of the water-soluble rhodamine base ionic liquid probe and preparation method, application of bimetallic ion selectivity Division identification Download PDFInfo
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Abstract
The invention discloses water-soluble rhodamine base ionic liquid probes of a kind of bimetallic ion selectivity Division identification and preparation method thereof, and are applied to independent and selective Division identification copper ion and aluminium ion in pure water phase.The rhodamine base ionic liquid probe is formed by salicylide imidazoles chlorination ionic liquid and rhodamine B hydrazides dehydrating condensation, the advantages such as, preparation simplicity cheap and easy to get with raw material and water solubility are good, the efficient detection to copper trace and aluminium can not only be realized in pure water environment, and the selective Division identification under copper aluminium coexisted environment may be implemented using the significant difference on copper ion and aluminium ion response time.
Description
Technical field
The present invention relates to more metal ion detection fields more particularly to a kind of water of bimetallic ion selectivity Division identification
Dissolubility rhodamine base ionic liquid probe and preparation method, application.
Background technique
In recent years, the optochemical sensor based on organic probes molecule has evolved into a hot topic in heavy metal analysis field
Method.Wherein, detected simultaneously using single probe multiple object ions (i.e. " one-to-many " detection) because its with high efficiency, it is low at
This outstanding advantages of and paid close attention to by people.And it is this it is " one-to-many " detection to developer molecule logic gate, molecule keypad lock, point
Sub- experimental facilities etc. provides a possibility that new.
Although " one-to-many " detection possesses many advantages, different responses in reported all kinds of " one-to-many " sensing systems
Often exist between ion and significantly interfere with each other, single probe is caused to be difficult to realize the detection of the difference to multiple object ions.
In order to break through the bottleneck problem, the solution generallyd use at present is that solvent environment locating for modulation probe molecule (uses
The solvent pairs such as methanol/water, the acetonitrile/water of different ratio) so that solvent burden ratio item of the different target ion in each self-optimizing
The effect of difference detection is finally reached with probe response respectively under part.
However, the method for this modulation solvent is necessarily required to using organic solvent, and due to organic probes molecule (such as sieve
Red bright class) usually there is strong-hydrophobicity, so that used organic solvent ratio is generally more than 30%, it is clear that do not meet current
The green idea that analysis industry is advocated, and be difficult to meet the detection needs of many biological samples.In addition to this, it is using
When water-organic phase cosolvent system, with the addition of water phase, it is likely to result in the aggregation of organic probes molecule, to influence to examine
Survey effect.
Therefore, it develops a kind of highly-water-soluble and is capable of the novel probe of the more metal ions of selective Division identification, for
Realize that the selective more metal ions of Division identification have great practical application value in pure water.
Summary of the invention
In view of this, the embodiment provides a kind of spies with highly-water-soluble, highly selective, highly sensitive
Point, can selective Division identification copper ion and aluminum ions water-soluble rhodamine base ionic liquid probe and preparation in pure water phase
Method, application.
The embodiment of the present invention provides a kind of water-soluble rhodamine base ionic liquid of bimetallic ion selectivity Division identification
Body probe, structural formula are as follows:
A kind of preparation method of the water-soluble rhodamine base ionic liquid probe of bimetallic ion selectivity Division identification, sieve
Red bright B hydrazides arrives rhodamine base ionic liquid probe with salicylide imidazoles chlorination ionic liquid dehydration condensation.
Further, the mass ratio of the rhodamine B hydrazides and salicylide imidazoles chlorination ionic liquid is (0.9-2.3) g:
(0.5-1.3)g。
Further, the condition of the dehydration condensation are as follows: rhodamine B hydrazides and salicylide imidazoles chlorination ionic liquid
For raw material, absolute methanol solution is as solvent, heating reflux reaction under an inert atmosphere.
Further, the temperature being heated to reflux is 68-75 DEG C, and the time being heated to reflux is 6-12h.
A kind of application of the water-soluble rhodamine base ionic liquid probe of bimetallic ion selectivity Division identification, sieve
Dan Mingji ionic liquid is used as in water phase copper ion and aluminium ion probe application.
A kind of application of the water-soluble rhodamine base ionic liquid probe of bimetallic ion selectivity Division identification, sieve
Dan Mingji ionic liquid is used as in water phase copper ion and aluminium ion selectivity Division identification probe application.
Compared with prior art, the invention has the following advantages:
1. rhodamine base ionic liquid IMI-SARhBH of the invention has the characteristics that highly-water-soluble, can be in pure water phase
It realizes to copper ion and aluminum ions detection, and there is high sensitivity, detection limit is respectively 0.08 μM of (Cu2+) and 0.13 μM
(Al3+), far below 31 μM of (Cu as defined in the World Health Organization (WHO)2+) and 7.4 μM of (Al3+)。
2. rhodamine base ionic liquid IMI-SARhBH of the invention can not use organic solvent under the conditions of (i.e. pure water
Phase environment), utilize Cu2+And Al3+It identifies the greatest differences of response time, realizes bimetallic ion (Cu2+And Al3+) selectivity
Division identification.
3. rhodamine base ionic liquid IMI-SARhBH of the invention has highly selective and excellent anti-interference ability,
Ba2+、Ca2+、Cd2+、Co2+、Cr3+、Cu2+、K+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+Under plasma concurrent conditions, Ke Yishi
Now to copper ion and aluminum ions specific recognition, other coexistent metallic ions nothing is significantly interfered with.
4. raw material needed for rhodamine base ionic liquid IMI-SARhBH of the invention is synthesized is cheap and easy to get, synthesis technology is simple
Fast, simple, at low cost, the suitable large-scale production of equipment, and detection efficiency is high, detection process is environmentally protective, application prospect is wide
It is wealthy.
Detailed description of the invention
Fig. 1 is the synthetic route of rhodamine base ionic liquid IMI-SARhBH of the present invention.
Fig. 2 is IMI-SARhBH probe centering Cu2+And Al3+The UV-vis spectrogram of different time detection；IMI- when 1min
SARhBH probe in detecting Cu2+Cu in solution coexists with copper aluminium2+The histogram of photon absorbing intensity at 561nm.
Fig. 3 is UV-vis spectrogram when different metal ions 1min and 5h is added in IMI-SARhBH probe.
Fig. 4 be disturbance metal ion in the presence of, Cu is added in prepared IMI-SARhBH probe2+And Al3+Front and back
The histogram of photon absorbing intensity at 561 and 554nm.
Fig. 5 is that various concentration Cu is added in prepared IMI-SARhBH probe2+And Al3+UV-vis spectrogram afterwards.
Fig. 6 be prepared IMI-SARhBH probe at 561 and 554nm photon absorbing intensity with Cu2+And Al3+The change of concentration
Change curve and linear relationship.
Fig. 7 is prepared IMI-SARhBH probe under the conditions of copper ions, and various concentration Al is added3+UV-vis afterwards
Spectrogram.
Fig. 8 is prepared IMI-SARhBH probe under the conditions of copper ions, and photon absorbing intensity is with Al at 554nm3+Concentration
Change curve and linear relationship.
Fig. 9 is prepared IMI-SARhBH probe at various ph values to Cu2+And Al3+Detection absorbance broken line
Figure.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is further described.
The embodiment provides a kind of water-soluble rhodamine base ions of bimetallic ion selectivity Division identification
Liquid probe, abbreviation notation IMI-SARhBH, structural formula are as follows:
A kind of preparation method of the water-soluble rhodamine base ionic liquid probe of bimetallic ion selectivity Division identification, sieve
Red bright B hydrazides and salicylide imidazoles chlorination ionic liquid dehydration condensation (as shown in Figure 1)；
The preparation method of rhodamine B hydrazides (RhBH) can be with are as follows: using rhodamine B (RhB) and hydrazine hydrate as raw material, anhydrous second
Alcohol is cooled to room temperature as solvent, heating reflux reaction, rotary evaporation, then plus water and is adjusted pH to 8-9, is filtered and purify,
Vacuum drying obtains rhodamine B hydrazides (RhBH).
Preferably, the mass ratio of the RhB and hydrazine hydrate is (3-5) g:(7.5-12.5) mL.
Preferably, the reaction temperature is 78-85 DEG C, reaction time 1-3h.
Preferably, the ratio of the solvent and RhB are (80-150) mL:(3-5) g.
According to the above scheme, the preparation method of the salicylide imidazoles chlorination ionic liquid (IMI-SA) can be with are as follows: with 5-
Chloromethyl salicylaldehyde and 1- methylimidazole are raw material, and acetonitrile is cooled to room temperature as solvent, heating reflux reaction, filters and mention
Pure, vacuum drying obtains salicylide imidazoles chlorination ionic liquid (IMI-SA).
Preferably, the mass ratio of the 5- chloromethyl salicylaldehyde and 1- methylimidazole is (1.5-3) g:(0.7-1.4) mL.
Preferably, the reaction temperature is 82-90 DEG C, reaction time 6-12h.
Preferably, the ratio of the solvent and 5- chloromethyl salicylaldehyde is (20-40) mL:(1.5-3) g.
According to the above scheme, the preparation method of the 5- chloromethyl salicylaldehyde can be with are as follows: with salicylide and paraformaldehyde is original
Material, concentrated hydrochloric acid react under room temperature as solvent, and suction filtration obtains solid, are then dissolved in anhydrous ether and use saturated sodium-chloride
Solution is washed till pH=6-7, and anhydrous sodium sulfate dries, filters solid and rotary evaporation removes a certain amount of ether, is cooled to room temperature, and takes out
It filters and is recrystallized with petroleum ether and purified, vacuum drying obtains 5- chloromethyl salicylaldehyde.
Preferably, the ratio of the salicylide and paraformaldehyde is (4-20) mL:(3-15) g.
Preferably, the room temperature reaction temperature is 15-25 DEG C, reaction time 18-24h.
Preferably, the solvent usage and the ratio of salicylide are (40-200) mL:(4-20) mL.
The mass ratio of rhodamine B hydrazides and salicylide imidazoles chlorination ionic liquid is (0.9-2.3) g:(0.5-1.3) g.
The condition of dehydration condensation are as follows: rhodamine B hydrazides is raw material with salicylide imidazoles chlorination ionic liquid, anhydrous
Methanol solution is as solvent, and heating reflux reaction, the temperature being heated to reflux are 68-75 DEG C under an inert atmosphere, is heated to reflux
Time is 6-12h, and rotary evaporation, washing purification, in one embodiment, washing purification solvent for use are followed successively by ice water and dichloromethane
Alkane is dried in vacuo to get rhodamine base ionic liquid probe is arrived.
A kind of application of the water-soluble rhodamine base ionic liquid probe of bimetallic ion selectivity Division identification, sieve
Dan Mingji ionic liquid is used as in water phase copper ion and aluminium ion probe application；The rhodamine base ionic liquid is used as in water phase
Copper ion and aluminium ion selectivity Division identification probe application.
Rhodamine base ionic liquid both can pass through colorimetric or ultraviolet detection in copper ion and the non-coexisted environment of aluminium ion
Copper ion or aluminium ion concentration out；It can also be responded in copper ion and aluminium ion coexisted environment using copper ion and aluminium ion
Temporal difference detection copper ion and aluminium ion concentration.
In one embodiment, the water-soluble rhodamine base ionic liquid probe of a kind of bimetallic ion selectivity Division identification
Preparation method specifically:
1) the bright B hydrazides (RhBH) of synthesizing rhodamine: 4.8g rhodamine B (RhB) and 12mL hydrazine hydrate are dissolved in the anhydrous second of 130mL
Alcohol, heats 80 DEG C of reflux, reacts and is cooled to room temperature after 2.5h, rotary evaporation, then plus water and adjusts pH to 8 or so, filters simultaneously
It is washed with distilled water purification, vacuum drying obtains RhBH, yield: 90.1%；
2) synthesize 5- chloromethyl salicylaldehyde: 6g paraformaldehyde and 8mL salicylide are dissolved in 80mL concentrated hydrochloric acid, under room temperature instead
20h is answered, suction filtration obtains solid, is then dissolved in anhydrous ether and is washed till pH=6-7 with saturated sodium chloride solution, anhydrous sodium sulfate is dry
It is dry, it crosses filter solid and rotary evaporation removes a certain amount of ether, be cooled to room temperature, filter and purified with petroleum ether recrystallization, vacuum
It is dried to obtain 5- chloromethyl salicylaldehyde, yield: 61.6%；
3) salicylide imidazoles chlorination ionic liquid (IMI-SA) is synthesized: 1.5g 5- chloromethyl salicylaldehyde and 0.7mL1- first
Base imidazoles is dissolved in 20mL acetonitrile, heats 85 DEG C of reflux, is cooled to room temperature after reacting 6h, filters and wash purification with anhydrous ether,
Vacuum drying obtains IMI-SA, yield: 93.2%；
4) the bright base ionic liquid probe (IMI-SARhBH) of synthesizing rhodamine: 2.3g RhBH and 1.3g IMI-SA are dissolved in 80mL
Anhydrous methanol, 70 DEG C of reflux of heating, react 12h under condition of nitrogen gas, and rotary evaporation is successively washed with ice water and methylene chloride and mentioned
Pure, vacuum drying obtains IMI-SARhBH, yield: 70.1%.
The nuclear magnetic resonance data of IMI-SARhBH:1H NMR(400MHz,DMSO)δ(ppm):10.61(s,1H),9.11
(s, 1H), 8.91 (s, 1H), 7.92 (d, J=7.0Hz, 1H), 7.74-7.49 (m, 5H), 7.29 (d, J=8.2Hz, 1H),
7.09 (d, J=7.3Hz, 1H), 6.84 (d, J=8.4Hz, 1H), 6.45-6.32 (m, 6H), 5.27 (s, 2H), 3.80 (s,
3H), 3.33-3.24 (m, 8H), 1.06 (t, J=6.8Hz, 12H)；
13C NMR(101MHz,DMSO)δ(ppm):164.21,157.99,153.04,151.82,149.04,136.86,
134.65,132.49,129.99,129.39,128.58,128.05,125.97,124.30,123.59,122.59,119.60,
117.56,108.67,104.94,97.80,65.76,51.70,44.11,36.26,12.88。
Application examples 1
Rhodamine base ionic liquid IMI-SARhBH detects Cu2+And Al3+Time
Rhodamine base ionic liquid IMI-SARhBH synthesized by the present invention is dissolved in deionized water, 25 μM of IMI- is made into
SARhBH stock solution.
The sample bottle for taking 2 10mL is separately added into 4mL IMI-SARhBH stock solution, then is separately added into 50 μM of Cu of 1mL2+
And Al3+, so that rhodamine base ionic liquid IMI-SARhBH and ion (Cu2+And Al3+) ultimate density is respectively 20 μM and 10 μ
M.In different times point in carries out spectrophotometry test respectively to solution therein, with investigate rhodamine base from
Sub- liquid IMI-SARhBH is to Cu2+And Al3+The individually time needed for detection.In addition, take the sample bottle of 2 10mL again, respectively plus
Enter 4mL IMI-SARhBH stock solution, then is separately added into 50 μM of Cu of 1mL2+With 1mL copper aluminium mixed solution (Cu2+And Al3+Concentration
It is 50 μM).Spectrophotometry test is carried out to solution therein in 1min, respectively to investigate the moment, Al3+
Presence to rhodamine base ionic liquid IMI-SARhBH detect Cu2+Influence.
As a result as shown in Fig. 2, showing: rhodamine base ionic liquid IMI-SARhBH is exceedingly fast to copper ion detection, in 1min
It inside just can reach balance；And rhodamine base ionic liquid IMI-SARhBH is slower to aluminium ion detection, requiring more than 5h just can reach
Balance.In addition, detecting copper aluminium in 1min coexists the copper ion in solution, discovery solution absorbance with do not contain it is aluminum ions identical
Concentration copper ion solution absorbance is identical, illustrates the moment, aluminum ions to there is the detection that will not influence copper ion.It is based on
This, may infer that rhodamine base ionic liquid IMI-SARhBH synthesized by the present invention not only may be implemented to Cu-Al bimetal from
The independent detection of son, and can use the difference on the response time, realize the Division identification of Cu-Al bimetal ion.
Application examples 2
Rhodamine base ionic liquid IMI-SARhBH is to Cu2+And Al3+The selectivity of colorimetric detection
Rhodamine base ionic liquid IMI-SARhBH synthesized by the present invention is dissolved in deionized water, is made into 12.5 μM
IMI-SARhBH stock solution.
The sample bottle for taking 15 10mL is separately added into 4mL IMI-SARhBH stock solution, then is separately added into 50 μM of Al of 1mL3 +、Ba2+、Ca2+、Cd2+、Co2+、Cr3+、Cu2+、K+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+And H2O, finally, rhodamine base ion
The concentration of liquid IMI-SARhBH and ion is 10 μM.Ultraviolet-visible is carried out respectively to solution therein in 1min and 5h
Spectrophotometric test, to verify rhodamine base ionic liquid IMI-SARhBH to copper ion and detecting and selecting property of aluminium ion.
As a result as shown in figure 3, showing: in 1min, rhodamine base ionic liquid IMI-SARhBH only has copper ion bright
Aobvious response has apparent ultraviolet absorption peak at 561nm, remaining color and ultraviolet absorption peak have no significant change.Further
In 5h, rhodamine base ionic liquid IMI-SARhBH has apparent response to aluminium ion, there is apparent ultraviolet suction at 554nm
Peak is received, remaining color and ultraviolet absorption peak are still without significant change.Therefore, the rhodamine base ionic liquid IMI- synthesized by the present invention
SARhBH shows the selectivity of height to copper ion and aluminium ion.
Application examples 3
Rhodamine base ionic liquid IMI-SARhBH is to Cu2+And Al3+The interference of colorimetric detection
Rhodamine base ionic liquid IMI-SARhBH synthesized by the present invention is dissolved in deionized water, is made into 12.5 μM
IMI-SARhBH stock solution.
The sample bottle for taking 14 10mL is separately added into 4mL IMI-SARhBH stock solution, then is separately added into 50 μM of Al of 1mL3 +、Ba2+、Ca2+、Cd2+、Co2+、Cr3+、K+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+And H2O is finally separately added into 50 μM again
Cu2+, final solution is containing 10 μM of rhodamine base ionic liquid IMI-SARhBH, 10 μM of Cu2+With 10 μM of interfering ions.In addition, taking
The sample bottle of 13 10mL is separately added into 4mL IMI-SARhBH stock solution, then is separately added into 50 μM of Ba of 1mL2+、Ca2+、Cd2 +、Co2+、Cr3+、K+、Mg2+、Mn2+、Na+、Ni2+、Pb2+、Zn2+And H2O is finally separately added into 50 μM of Al again3+, final solution contains
10 μM of rhodamine base ionic liquid IMI-SARhBH, 10 μM of Al3+With 10 μM of interfering ions.When 1min, to copper ions sample bottle
In solution successively carry out spectrophotometry test；When 5h, purple is successively carried out to the solution in sample bottle containing aluminium ion
Outside-visible spectrophotometric test.To verify rhodamine base ionic liquid IMI-SARhBH to copper ion and aluminium ion detection interference
Property.
As a result as shown in figure 4, showing: in 1min, there is no obviously change other coexistent metallic ions (including aluminium ion)
Become rhodamine base ionic liquid IMI-SARhBH of the present invention to the detection effect of copper ion.It is other that gold coexists further in 5h
Belong to ion (except copper ion) and does not substantially change rhodamine base ionic liquid IMI-SARhBH of the present invention to aluminum ions inspection
Survey effect.It is good anti-dry to reflect that this rhodamine base ionic liquid IMI-SARhBH all has detection copper ion and aluminium ion
Immunity energy.
Application examples 4
Rhodamine base ionic liquid IMI-SARhBH is to Cu2+And Al3+Colorimetric detection
Rhodamine base ionic liquid IMI-SARhBH synthesized by the present invention is dissolved in deionized water, is made into 12.5 μM
IMI-SARhBH stock solution.
The sample bottle for taking 23 10mL is separately added into 4mL IMI-SARhBH stock solution, then is separately added into 1mL various concentration
Cu2+(0.75-150 μM), final solution contain 10 μM of rhodamines base ionic liquid IMI-SARhBH and 0.15-30 μM of Cu2+.Separately
Outside, the sample bottle for taking 23 10mL is separately added into 4mL IMI-SARhBH stock solution, then is separately added into the Al of 1mL various concentration3+
(0.75-150 μM), final solution contain 10 μM of rhodamines base ionic liquid IMI-SARhBH and 0.15-30 μM of Al3+.It is right when 1min
Solution in copper ions sample bottle successively carries out spectrophotometry test；When 5h, in sample bottle containing aluminium ion
Solution successively carries out spectrophotometry test.
Rhodamine base ionic liquid IMI-SARhBH detects uv-visible absorption spectra such as Fig. 5 to copper ion and aluminium ion
It is shown, with Cu2+And Al3+Increase, nearby absorbance gradually increases at 560nm, until copper ion and aluminium ion concentration reach
Absorbance is substantially saturated at 10 μM.Rhodamine base ionic liquid IMI-SARhBH is to copper ion and aluminium ion detection trend and linearly
Detection is as shown in Figure 6, the results showed that: in [Cu2+Within the scope of]=0.15-4 μM, a good linear relationship straight line can be made
(R2=0.99875), detection is limited to 0.8 × 10-7mol/L；In [Al3+Within the scope of]=0.15-3.5 μM, can make one it is good
Good linear relationship straight line (R2=0.9961), detection is limited to 1.3 × 10-7mol/L.Copper ion and aluminum ions ultraviolet-visible
The detection limit of light absorption spectrogram quantitative detection is far below as defined in the World Health Organization (WHO) 31 μM and 7.4 μM, illustrates Luo Dan
Bright base ionic liquid IMI-SARhBH can be applied to pure water Environmental Trace copper ion and aluminum ions efficient detection.
Application examples 5
In the case where system coexists in copper aluminium, rhodamine base ionic liquid IMI-SARhBH is to Cu2+And Al3+Difference detection
The result of application examples 1 is it can be shown that due to rhodamine base ionic liquid IMI-SARhBH and Cu2+And Al3+Response
There are greatest differences on time, it may be implemented to detect copper aluminium in 1min Cu in solution coexist2+, to further determine that copper aluminium is total
Deposit the Al in solution3+, we have carried out following experiment.
Rhodamine base ionic liquid IMI-SARhBH synthesized by the present invention is dissolved in deionized water, 50 μM of Cu are added2+Match
At 25 μM of IMI-SARhBH+2.5 μM of Cu2+Stock solution.
The sample bottle for taking 20 10mL is separately added into 4mL IMI-SARhBH+Cu2+Stock solution, then difference is added in 1mL respectively
The Al of concentration3+(0.75-150 μM) and H2O, final solution contain 20 μM of rhodamine base ionic liquid IMI-SARhBH, 2 μM of Cu2+With
0.15-30μMAl3+.When 5h, with 20 μM of rhodamine base ionic liquid IMI-SARhBH and 2 μM of Cu2+Sample bottle solution is back
Scape successively carries out spectrophotometry test to the solution in sample bottle containing aluminium ion.
Solution (2 μM of Cu coexist in copper aluminium2+) in, rhodamine base ionic liquid IMI-SARhBH to aluminium ion detection it is ultraviolet-
Visible absorption spectra is as shown in fig. 7, with Al3+Increase, absorbance gradually increases at 554nm, until aluminium ion concentration reaches
Absorbance is substantially saturated at 15 μM.(2 μM of Cu coexist in copper aluminium2+) in, rhodamine base ionic liquid IMI-SARhBH is to aluminium ion
Detection trend and linearity test are as shown in Figure 8, the results showed that: in [Al3+Within the scope of]=0.5-4.5 μM, can make one it is good
Good linear relationship straight line (R2=0.99516), detection is limited to 2.0 × 10-7mol/L.Under this condition, aluminium ion detection limit is same
7.4 μM are provided far below the World Health Organization (WHO), illustrate to coexist in solution in copper aluminium, rhodamine base ionic liquid IMI-
SARhBH still can be applied to the aluminum ions efficient detection of pure water Environmental Trace.The common table of the result of connected applications example 1 and 4
Bright: rhodamine base ionic liquid IMI-SARhBH can use it to Cu2+And Al3+Response time on greatest differences, realize
The Cu in pure water phase2+And Al3+Selectivity distinguish detection.Application examples 6
Rhodamine base ionic liquid IMI-SARhBH is to Cu2+And Al3+The influence of colorimetric detection working environment
Rhodamine base ionic liquid IMI-SARhBH synthesized by the present invention is dissolved in deionized water, 25 μM of IMI- is made into
SARhBH stock solution.
The sample bottle for taking 33 20mL is separately added into 4mL IMI-SARhBH stock solution, three one group of sample, adjusts respectively
PH be 2,3,4,5,6,7,8,9,10,11 and 12, while ensure rhodamine base ionic liquid IMI-SARhBH concentration be 12.5 μM,
Volume is 8mL.50 μM of Cu that 2mL corresponds to pH are added in every group in headpin2+, 50 μM of Al that 2mL corresponds to pH are added in No. 2 bottles3 +, be added the aqueous solution that 2mL correspond to pH in No. 3 bottles, it is every group final in headpin containing 10 μM of rhodamine base ionic liquid IMI-
SARhBH and 10 μM of Cu2+, No. 2 bottles contain 10 μM of rhodamine base ionic liquid IMI-SARhBH and 10 μM of Al in every group3+, every group
In No. 3 bottles contain 10 μM of rhodamine base ionic liquid IMI-SARhBH.Ultraviolet-visible is carried out to the solution in every group of sample bottle respectively
Spectrophotometric test.
As a result as shown in figure 9, showing: in the presence of no copper ion and aluminium ion, rhodamine base ionic liquid IMI-
SARhBH probe absorbance between pH=2-12 has almost no change, as addition Cu2+And Al3+Afterwards, solution absorbance is obvious
Increase, absorbance is in highest level between pH=5-9 and pH=5-8 respectively, illustrates rhodamine base ionic liquid of the present invention
Body IMI-SARhBH probe is to detection Cu2+And Al3+With wider pH adaptation range, have applied to the latent of environmental and biological materials
It is being worth.
In conclusion a kind of water-soluble rhodamine base of bimetallic ion selectivity Division identification provided by the present invention from
Sub- liquid probe and preparation method thereof, this is the difference for utilizing the metal ion response time for the first time, realizes selectivity in pure water phase
The research report of bimetallic " one-to-many " the detection organic probes molecule of Division identification.Changed using imidazoles chlorination ionic liquid
Property, hydrophobicity probe molecule water solubility is improved, can be realized in pure water phase to copper ion and aluminum ions detection, and have
High sensitivity, detection limit are respectively 0.08 μM of (Cu2+) and 0.13 μM of (Al3+), it is provided far below the World Health Organization (WHO)
31 μM of (Cu2+) and 7.4 μM of (Al3+).Moreover, to copper ion and aluminium ion detection have excellent selectivity, hardly by appoint
The what interference of its coexistent metallic ion.Importantly, there is copper ion and aluminium ion response time in pure water phase in it
Greatest differences (Cu2+<1min；Al3+>=5h), to realize bimetallic ion (Cu2+And Al3+) selectivity distinguish identification.
In the absence of conflict, the feature in embodiment and embodiment herein-above set forth can be combined with each other.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of water-soluble rhodamine base ionic liquid probe of bimetallic ion selectivity Division identification, which is characterized in that knot
Structure formula is as follows:
2. a kind of preparation method of the water-soluble rhodamine base ionic liquid probe of bimetallic ion selectivity Division identification, special
Sign is that rhodamine B hydrazides arrives rhodamine base ionic liquid with salicylide imidazoles chlorination ionic liquid dehydration condensation
Body probe；The salicylide imidazoles chlorination ionic liquid the preparation method comprises the following steps: with 5- chloromethyl salicylaldehyde and 1- methylimidazole
For raw material, acetonitrile is cooled to room temperature as solvent, heating reflux reaction, filters and purifies, and vacuum drying obtains salicylide imidazoles
Chlorination ionic liquid.
3. the water-soluble rhodamine base ionic liquid probe of bimetallic ion selectivity Division identification according to claim 2
Preparation method, which is characterized in that the mass ratio of the rhodamine B hydrazides and salicylide imidazoles chlorination ionic liquid is
(0.9-2.3) g:(0.5-1.3) g.
4. the water-soluble rhodamine base ionic liquid probe of bimetallic ion selectivity Division identification according to claim 2
Preparation method, which is characterized in that the condition of the dehydration condensation are as follows: rhodamine B hydrazides and salicylide imidazoles chlorate
Ionic liquid is raw material, and absolute methanol solution is as solvent, heating reflux reaction under an inert atmosphere.
5. the water-soluble rhodamine base ionic liquid probe of bimetallic ion selectivity Division identification according to claim 4
Preparation method, which is characterized in that the temperature being heated to reflux be 68-75 DEG C, the time being heated to reflux be 6-12h.
6. a kind of water-soluble rhodamine base ionic liquid of bimetallic ion selectivity Division identification according to claim 1
The application of probe, which is characterized in that the rhodamine base ionic liquid is used as in water phase copper ion and aluminium ion probe application.
7. a kind of water-soluble rhodamine base ionic liquid of bimetallic ion selectivity Division identification according to claim 1
The application of probe, which is characterized in that the rhodamine base ionic liquid is used as selectively to be distinguished in water phase copper ion and aluminium ion
Identify probe application.
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| CN111766277B (en) * | 2020-06-09 | 2022-06-28 | 安徽大学 | Distinguish metal ion Fe3+And Cu2+Method (2) |
| CN112079847B (en) * | 2020-09-14 | 2022-09-27 | 贵州大学 | Rhodamine imidazole-containing six-membered ring compound and preparation method and application thereof |
| CN114656476A (en) * | 2022-02-18 | 2022-06-24 | 晋中学院 | Lysosome targeting rhodamine B hydrazide fluorescent probe as well as preparation method and application thereof |
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| CN102219789A (en) * | 2011-04-08 | 2011-10-19 | 山东大学 | Chromone acylhydrazone derivative of rhodamine B, and preparation method and application thereof |
| CN102321093A (en) * | 2011-07-06 | 2012-01-18 | 山东大学 | A kind of is the chloro chromone acyl hydrazone derivative of parent and as the application of fluorescent probe with the rhodamine B |
| CN104262351B (en) * | 2012-09-04 | 2016-06-08 | 国家地质实验测试中心 | The preparation method of N-(dinitrophenyl group)-rhodamine B hydrazides and the application of detection Cu (II) thereof |
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| CN106083897B (en) * | 2016-05-24 | 2019-02-22 | 泰山医学院 | Imidazopyridine rhodamine salicylide Cu-like ion ratio fluorescent probe and its application |
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