CN102993207A - Rhodamine B-triazine compounds and preparation method and application thereof - Google Patents
Rhodamine B-triazine compounds and preparation method and application thereof Download PDFInfo
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- CN102993207A CN102993207A CN2012105592410A CN201210559241A CN102993207A CN 102993207 A CN102993207 A CN 102993207A CN 2012105592410 A CN2012105592410 A CN 2012105592410A CN 201210559241 A CN201210559241 A CN 201210559241A CN 102993207 A CN102993207 A CN 102993207A
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- diethanolamine
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Abstract
The invention discloses one kind of Rhodamine B-triazine compounds and a preparation method and application thereof, belonging to the field of organic synthesis and analytical chemistry. The Rhodamine B-triazine compounds have a structure general formula described in the specification, wherein R1 represents a Rhodamine B diaminoethane group, R2 represents a Rhodamine B hydrazide group and R3 represents a diethanol amine group. The preparation method comprises the steps of: in the presence of different acid-binding agents and selective solvents, carrying out step-by-step reaction by using Rhodamine B diaminoethane or Rhodamine B hydrazide for substituting one or two helium atoms on a cyanuric chloride ring, or substituting remained un-substituted helium atoms by using diethanol amine, thus respectively synthesizing series Rhodamine B-triazine compounds. The Rhodamine B-triazine compounds are used as fluorescence or colorimetric reagents of fluorescence spectrum or ultraviolet-visible spectroscopy, and are used for detecting metal ions by an ion probe.
Description
Technical field
The present invention's one class rhodamine B-triaizine compounds and its preparation method and application belongs to organic synthesis and analytical chemistry field.
background technology:metallic element has inseparable contacting with fields such as life science, environmental science, medical science.In vivo, metal ion participates in vital process, in many physiological processs, plays a part extensive and important.The detection by quantitative of trace metal ion is being very important aspect medicine, food, clinical and environment measuring, and the metal-ion fluorescent probe of development highly selective, high sensitivity has great significance.
Fluorescent probe technique as highly sensitive, selectivity good, fast, important means convenient, the visual detection metal ion is widely used in chemical related discipline.Fluorescent probe by with the target substance selectively acting, make to change in conjunction with fluorescence enhancing or the parameters such as quencher, wavelength and peak shape, fluorescence lifetime of front and back, the effect of microscopic fields is showed by optical information, thereby realize that the original position on molecular level detects in real time, reaches the effective identification to metal ion, molecule.Highly sensitive and highly selective due to fluorometric analysis, real-time in-situ detects, equipment is simple, and abundant spectral information can be provided, in the fields such as analytical chemistry, biological chemistry, environmental science, medicine and pharmacology, the aspects such as various ion detection, DNA and protein molecular marker, cell imaging, immunoassay play an important role.
Rhodamine is as classical fluorescence dye, and fluorescence quantum yield is high, and spectrum property is superior, simple in structure, be easy to modify, and is often to select fluorophor in the probe compound design, in the research of metal-ion fluorescent probe, receives much concern.The more fluorescence enhancement type rhodamine probe of bibliographical information mainly concentrates on Hg
2+, Cu
2+, Fe
3+isoionic recognition detection.Aluminium, chromium, copper etc. are as environment and biological coherent element, the detection method research that it is novel, Al particularly simple in structure, highly sensitive, that selectivity is superior
3+and Cr
3+the fluorescent probe design studies is significant.Bibliographical information is introduced triethylene tetramine or diethylenetriamine on the rhodamine molecule, has synthesized respectively Cr
3+or Fe
3+fluorescent probe; Also reported and can make Cr in cell
3+rhodamine probe and the naphthalimide based on resonance energy transfer mechanism-rhodamine fluorescent probe that the ferrocene of imaging replaces.Our study group has reported with rhodamine B and has designed synthetic serial Tripod, calixarene type and the schiff's base type fluorescent probe to special metal ion selective recognition for precursor group.
Highly sensitive, highly selective detection and Identification research in fields such as living things system, physiological process, environment and food safeties to trace metal ion are with a wide range of applications.Discovery is different from traditional organic fluorescent dye molecule, makes that its testing cost is cheap, sample preparation is simple, measuring method is quick, and the fluorescent probe that can simultaneously detect many kinds of metal ions, superior performance has researching value.Fluorescent spectrometry, due to simple to operate, does not need expensive plant and instrument, has more using value.But due to most developer need to pass through the complicated pre-treatment such as extraction, separation could for detection of, crucial is that the sensitivity and the selectivity that detect can not meet more and more higher demand.Fluorescent signal has unrivaled superiority in sensitivity, at present, detects Al
3+the rhodamine fluorescent probe have no report, and Cr
3+fluorescent probe research is very limited, Cu
2+the selectivity of probe and sensitivity need to improve.Development structure is simple, simple synthetic method, cheap, sensitivity and the superior fluorescent probe reagent of selectivity have a using value multi-field.
Cyanuric chloride in compound in triazine class is nitrogenous hexa-member heterocycle, 3 nitrogen-atoms on ring can with metallic ion coordination.Carbon atom very easily reacts with the amine nucleophilic reagent as electrophilic center, utilize the reactive behavior difference of 3 chlorine atoms on the cyanuric chloride ring, control reaction conditions and can realize carrying out the classification substitution reaction, thereby realize that optionally introducing the fluorescence substituting group on triazine ring carries out molecular designing and structural modification.
summary of the invention:the object of the invention is to the rhodamine B that synthetic sensitivity and selectivity are superior-triazine fluorescence or colorimetric reagent, and for the fluorescence of metal ion and colorimetric estimation or as ion probe, by controlling temperature of reaction, using different acid binding agents and selective solvent, with rhodamine B quadrol or rhodamine B hydrazides stepwise reaction, replace 1 or 2 chlorine atoms on the cyanuric chloride ring, or replace again remaining unsubstituted chlorine atom with diethanolamine, synthesize respectively and obtain the different rhodamine-triaizine compounds that replace of series.Under specific ambient condition, utilize fluorescence spectrum and uv-visible absorption spectra, compound can highly sensitive, highly selective detection special metal ion as fluorescence and colorimetric reagent.
Fluorescence or the colorimetric compound structure general formula of preparation are as follows:
In formula, substituent R
1for rhodamine B quadrol base, R
2for rhodamine B hydrazide group, R
3for the di-alcohol amido.
R
1or R
2the replacement of cyanuric chloride chlorine in ring atom, by the differential responses temperature, controlledly is made as to monosubstituted or two replacements, twoly is substituted by identical group and replaces.The monosubstituted R that refers to
1or R
2to the replacement of a chlorine on cyanuric chloride, two replacements refer to R
1or R
2or R
3in arbitrary group to the replacement of two chlorine on triazine, R
3replacement refer to after above-mentioned monosubstituted or two replacements the replacement of remaining chlorine on cyanuric chloride obtained to a class rhodamine B-triaizine compounds.
It is raw material that cyanuric chloride, rhodamine B quadrol, rhodamine B hydrazides, diethanolamine are take in the present invention, salt of wormwood, cesium carbonate, N, the N-diisopropylethylamine is acid binding agent, anhydrous tetrahydro furan, dioxane are solvent, control temperature of reaction, select different acid binding agents and solvent, through stepwise reaction, synthetic making.Synthetic route is as follows:
（1）
Control temperature of reaction, with rhodamine B hydrazides or rhodamine B quadrol, replace a chlorine on the cyanuric chloride ring, carry out monosubstituted;
（2）
Aforementioned (1) reaction product of take is raw material, then replaces remaining two chlorine on the cyanuric chloride ring with diethanolamine, carries out three replacements;
（3）
Aforementioned (1) reaction product of take is raw material, then uses identical substituting group (rhodamine B hydrazides or rhodamine B quadrol) to replace another chlorine on the cyanuric chloride ring, carries out two the replacement;
（4）
Aforementioned (3) reaction product of take is raw material, then replaces a remaining chlorine on the cyanuric chloride ring with diethanolamine, carries out three replacements;
According to said synthesis route, the preparation method of each compound is as follows:
Compound
1-a(the chloro-6-rhodamine B of 2,4-bis-hydrazides--1,3,5-triazines
)synthetic
At N
2under protection, cyanuric chloride, salt of wormwood and anhydrous tetrahydro furan are mixed, control temperature, stir the lower anhydrous tetrahydrofuran solution that drips the rhodamine B hydrazides, stirring and refluxing, reaction finishes, and filters, and filtrate is spin-dried for, and silica gel chromatographic column separates, and obtains the white object product
1-a:
Time for adding: 30min
Temperature of reaction: 0 ~ 5 ℃
Reaction times: 9h
Acid binding agent: salt of wormwood
Reaction solvent: anhydrous tetrahydro furan, add-on can have been dissolved corresponding solute
Eluent: sherwood oil: ethyl acetate: chloroform (
v:V:
v=3:1:4)
Mol ratio: cyanuric chloride: salt of wormwood: rhodamine B hydrazides=1: 4～5: 1
Compound
1-b(the chloro-6-of 2,4-bis-(N-amine ethyl rhodamine B acid amides)-1,3,5-triazines
)synthetic
At N
2under protection, cyanuric chloride, salt of wormwood and anhydrous tetrahydro furan are mixed, control temperature, stir the lower anhydrous tetrahydrofuran solution that drips the rhodamine B quadrol, stirring and refluxing, reaction finishes, and filters, and filtrate is spin-dried for, and silica gel chromatography separates, and obtains the white object compound
1-b:
Time for adding: 30min
Temperature of reaction: 0 ~ 5 ℃
Reaction times: 9h
Acid binding agent: salt of wormwood
Reaction solvent: anhydrous tetrahydro furan, add-on can have been dissolved corresponding solute
Eluent: sherwood oil: ethyl acetate (
v:V=3:2)
Mol ratio: cyanuric chloride: salt of wormwood: rhodamine B quadrol=1～1.2: 4～4.5: 1
Compound
2-a(the two diethanolamine of 2,4--6-rhodamine B hydrazides-1,3,5-triazines
)synthetic
At N
2under protection, diethanolamine and DIPEA are dissolved in to anhydrous tetrahydro furan, control temperature, drip compound
1-aanhydrous tetrahydrofuran solution, stirring and refluxing, reaction finishes, and filters, filtrate is spin-dried for, silica gel chromatographic column separates, and obtains the white object compound
2-a:
Time for adding: 30min
Temperature of reaction: 50 ℃ of the first step reactions, 66 ℃ of second step reactions
Reaction times: 9 ~ 10h
Acid binding agent: DIPEA
Reaction solvent: anhydrous tetrahydro furan, add-on can have been dissolved corresponding solute
Eluent: ethanol: chloroform (
v:V=1:4)
Mol ratio: diethanolamine: DIPEA: compound
1-a=10: 4～5: 1
Compound
2-b(two diethanolamine-the 6-(N-amine ethyl rhodamine B acid amides) of 2,4--1,3,5-triazines
)synthetic
At N
2under protection, diethanolamine and DIPEA are dissolved in to dioxane, compound
1-bbe dissolved in dioxane, control dropping temperature, stirring and refluxing, reaction finishes, and filters, and filtrate is spin-dried for silica gel chromatographic column separates, and obtains the white object compound
2-b:
Time for adding: 30min
Temperature of reaction: 50 ℃ of the first step reactions, 101 ℃ of second step reactions
Reaction times: 8h
Acid binding agent: DIPEA
Reaction solvent: dioxane, add-on can have been dissolved corresponding solute
Eluent: ethanol: chloroform (
v:V=1:4)
Mol ratio: diethanolamine: DIPEA: compound
1-b=10: 1.5～2: 1
Compound
3-b(2-is chloro-4, two (N-amine ethyl rhodamine B the acid amides)-1,3,5-triazines of 6-
)synthetic
By rhodamine B quadrol and compound
1-bbe dissolved in anhydrous tetrahydro furan, then add cesium carbonate, stirring and refluxing, cooling, to filter, after filtrate is spin-dried for, silica gel chromatographic column separates, and obtains target compound
3-b:
Temperature of reaction: 66 ℃
Reaction times: 6h
Acid binding agent: cesium carbonate
Reaction solvent: anhydrous tetrahydro furan, add-on can have been dissolved corresponding solute
Eluent: sherwood oil: ethyl acetate (
v:V=1:1)
Mol ratio: rhodamine B quadrol: cesium carbonate: compound
1-b=1: 5～6: 1
In patent of the present invention, the gordian technique of building-up reactions is to utilize the reactive behavior difference of 3 chlorine atoms on the cyanuric chloride ring, control reaction conditions and realize the classification substitution reaction, react and can obtain the different serial rhodamine-triaizine compounds that replace by one-step or two-step, productive rate is all more than 60%.
Temperature is controlled: temperature of reaction is controlled at 0-5 C, prepares the triaizine compounds that single rhodamine group replaces; Temperature of reaction is controlled at 50-66 C(solvent boiling point), the triaizine compounds that the two rhodamine groups of preparation replace; Temperature of reaction is controlled at 66-101 ℃ (solvent boiling point), prepares the triaizine compounds of three replacements (rhodamine group and diethanolamine).
Acid binding agent: the acid binding agent carried out when monosubstituted is salt of wormwood; Acid binding agent while carrying out two the replacement is cesium carbonate; Acid binding agent while carrying out three replacements is DIPEA.
Solvent: adopt different reaction solvents during different substitution reaction, reaction times and productive rate differ greatly.Compound
2-bsynthetic, with the organic bases DIPEA, be acid binding agent, dioxane is solvent, while with tetrahydrofuran (THF), being solvent, compares, the reaction times shortens to 8h by 38h, productive rate is increased to 79.4% from 65.7%.Compound
3-bsynthetic, with the inorganic salt cesium carbonate, be acid binding agent, tetrahydrofuran (THF) is reaction solvent, while with dioxane, being solvent, compares, the reaction times shortens to 6h by 44h, productive rate brings up to 67.2% by 30.8%.
The proton nmr spectra data of its chemical structure of part rhodamine-triaizine compounds that the present invention is synthetic are listed in table 2, the carbon-13 nmr spectra data of compound are listed in table 3, the mass-spectrometric data of compound is listed in table 4, and the infrared signature peak spectroscopic data of compound is listed in table 5.
The proton nmr spectra data of table 2 compound
The above-claimed cpd that the inventive method is synthetic, with fluorescence spectrum or uv-visible absorption spectra as detecting Al
3+, Cr
3+, Cu
2+fluorescence or colorimetric reagent in the special metal ion.The detection working method is easy, highly sensitive, selectivity is superior.The compound of different structure can detect respectively Al
3+, Cr
3+, Cu
2+in the different metal ion, 2 orders of magnitude of Fluorometric assay concentration linearity range Da Keda, detectability is low to moderate 10
-8mol
.l
-1 .
Because reagent of the present invention has very high selectivity, sensitivity and low detectability to metal ion, can be used for ion probe, detect metal ion.
the accompanying drawing explanation:
Fig. 1 concentration is 1.00 * 10
-5mol
.l
-1compound
1-bethanolic soln, in Tutofusin tris-hydrochloric acid pH ~ 4 buffered soln, do not add respectively metal ion or add 2.00 * 10
-4mol
.l
-1metal ion Al
3+, Cr
3+, Fe
3+, Hg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ag
+, K
+, Na
+after fluorescence spectrum.Al
3+add fluorescence significantly strengthened, be secondly Cr
3+.Excitation wavelength is 556, and emission wavelength is 578 nm.Ordinate zou means fluorescence intensity, and X-coordinate means wavelength.M
n+the metal ion that means experiment.
Fig. 2 concentration is 1.00 * 10
-5mol
.l
-1compound
1-bethanolic soln, in Tutofusin tris-hydrochloric acid pH ~ 4 buffered soln, do not add respectively metal ion or add 2.00 * 10
-4mol
.l
-1metal ion Al
3+, Cr
3+, Fe
3+, Hg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ag
+, K
+, Na
+after visible absorption spectra.Al
3+add absorbancy significantly strengthened, be secondly Cr
3+.Ordinate zou means absorbancy, and X-coordinate means wavelength.M
n+the metal ion that means experiment.
Fig. 3 concentration is 1.00 * 10
-5mol
.l
-1compound
3-bethanolic soln, in Tutofusin tris-hydrochloric acid pH ~ 4 buffered soln, do not add respectively metal ion or add 2.00 * 10
-4mol
.l
-1metal ion Al
3+, Cr
3+, Fe
3+, Hg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ag
+, K
+, Na
+after fluorescence spectrum.Al
3+add fluorescence significantly strengthened, be secondly Cr
3+.Excitation wavelength is 556, and emission wavelength is 578 nm.Ordinate zou means fluorescence intensity, and X-coordinate means wavelength.M
n+the metal ion that means experiment.
Fig. 4 concentration is 1.00 * 10
-5mol
.l
-1compound
3-bethanolic soln, in Tutofusin tris-hydrochloric acid pH ~ 4 buffered soln, do not add respectively metal ion or add 2.00 * 10
-4mol
.l
-1metal ion Al
3+, Cr
3+, Fe
3+, Hg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ag
+, K
+, Na
+after visible absorption spectra.Al
3+add and make to absorb remarkable enhancing, be secondly Cr
3+.Ordinate zou means absorbancy, and X-coordinate means wavelength.M
n+the metal ion that means experiment.
Fig. 5 coexistent metallic ion is to compound
3-
bfluorometric assay Al
3+impact
In concentration, be 1.00 * 10
-5mol
.l
-1fluorescence or colorimetric compound
3-bethanolic soln in, Tutofusin tris-hydrochloric acid buffer solution is controlled pH ~ 4, adds 2.00 * 10
-4molL
-1al
3+after solution, fluorescence significantly strengthens.Again respectively to
3-b-al
3+other metal ions that add isodose in solution: Cr
3+, Fe
3+, M
3+(La
3+, Ce
3+, Pr
3+, Eu
3+, Gd
3+, Dy
3+, Er
3+, Yb
3+, Lu
3+), Hg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, K
+, Na
+after fluorescence intensity change.White bars is illustrated in compound
3-bin add the emissive porwer of different metal ion.Black bar is illustrated in
3-b-al
3+solution adds the fluorescence intensity change after other coexistent metallic ions again.Show compound
3-bdetect Al
3+fluorescence be not subject to Cr
3+and the impact of other common coexistent metallic ions.Ordinate zou means fluorescence intensity, and X-coordinate means metal ion.M
n+the metal ion that means experiment.
Fig. 6 coexistent metallic ion is to compound
3-
babsorption spectroscopy detects Al
3+impact.
In concentration, be 1.00 * 10
-5mol
.l
-1compound
3-bethanolic soln in, Tutofusin tris-hydrochloric acid buffer solution is controlled pH ~ 4, adds 2.00 * 10
-4molL
-1al
3+absorb significantly and strengthen after solution.Again respectively to
3-b-al
3+other metal ions that add isodose in solution: Cr
3+, Fe
3+, M
3+(La
3+, Ce
3+, Pr
3+, Eu
3+, Gd
3+, Dy
3+, Er
3+, Yb
3+, Lu
3+), Hg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, K
+, Na
+after absorbancy change.White bars is illustrated in compound
3-bin add the absorbancy of different metal ion.Black bar is illustrated in
3-b-al
3+solution adds the absorbancy after other coexistent metallic ions to change again.Show compound
3-bdetect Al
3+absorption be not subject to Cr
3+and the impact of other common coexistent metallic ions.Ordinate zou means absorbancy, and X-coordinate means metal ion.M
n+the metal ion that means experiment.
Fig. 7 coexistent metallic ion is to compound
3-
bfluorometric assay Cr
3+impact
In concentration, be 1.00 * 10
-5mol
.l
-1compound
3-bethanolic soln in, Tutofusin tris-hydrochloric acid buffer solution is controlled pH ~ 4, adds 2.00 * 10
-4molL
-1cr
3+after solution, fluorescence significantly strengthens.Again respectively to
3-b-cr
3+other metal ions that add isodose in solution: Al
3+, Fe
3+, M
3+(La
3+, Ce
3+, Pr
3+, Eu
3+, Gd
3+, Dy
3+, Er
3+, Yb
3+, Lu
3+), Hg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, K
+, Na
+after fluorescence intensity change.White bars is illustrated in compound
3-bin add the emissive porwer of different metal ion.Black bar is illustrated in
3-b-cr
3+solution adds the fluorescence intensity change after other coexistent metallic ions again.Show compound
3-bdetect Cr
3+fluorescence be not subject to other common coexistent metallic ions (except Al
3+impact outward).Ordinate zou means fluorescence intensity, and X-coordinate means metal ion.M
n+the metal ion that means experiment.
Fig. 8 coexistent metallic ion is to compound
3-
babsorption spectroscopy detects Cr
3+impact.
In concentration, be 1.00 * 10
-5mol
.l
-1compound
3-bethanolic soln in, Tutofusin tris-hydrochloric acid buffer solution is controlled pH ~ 4, adds 2.00 * 10
-4molL
-1cr
3+absorb significantly and strengthen after solution.Again respectively to
3-b-cr
3+other metal ions that add isodose in solution: Al
3+, Fe
3+, M
3+(La
3+, Ce
3+, Pr
3+, Eu
3+, Gd
3+, Dy
3+, Er
3+, Yb
3+, Lu
3+), Hg
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, K
+, Na
+after absorbancy change.White bars is illustrated in compound
3-bin add the absorbancy of different metal ion.Black bar is illustrated in
3-b-cr
3+solution adds the absorbancy after other coexistent metallic ions to change again.Show compound
3-bdetect Cr
3+absorption be not subject to other common coexistent metallic ions (except Al
3+impact outward).Ordinate zou means fluorescence intensity, and X-coordinate means metal ion.M
n+the metal ion that means experiment.
Fig. 9 concentration is 1.00 * 10
-5mol
.l
-1compound
2-aacetonitrile-water (3:7) solution, in Tutofusin tris-hydrochloric acid pH ~ 6 buffered soln, do not add respectively metal ion or add 2.00 * 10
-4mol
.l
-1metal ion Cu
2+, Al
3+, Cr
3+, Fe
3+, Hg
2+, Co
2+, Ni
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, K
+, Na
+after fluorescence spectrum.Cu
2+add fluorescence significantly strengthened, other metal ions are without response.Excitation wavelength is 553, and emission wavelength is 578 nm.Ordinate zou is fluorescence intensity, and X-coordinate is wavelength.M
n+the metal ion that means experiment.
Figure 10 is 1.00 * 10
-5mol
.l
-1compound
2-aacetonitrile-water (3:7) solution, in Tutofusin tris-hydrochloric acid pH ~ 6 buffered soln, do not add respectively metal ion or add 2.00 * 10
-4mol
.l
-1metal ion
Cu
2+, Al
3+, Cr
3+, Fe
3+, Hg
2+, Co
2+, Ni
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, K
+, Na
+after visible absorption spectra.Cu
2+add visible absorbance significantly strengthened, other metal ions are without response.Ordinate zou is absorbancy, and X-coordinate is wavelength.M
n+the metal ion that means experiment.
Figure 11 coexistent metallic ion is to compound
2-afluorometric assay Cu
2+impact
In concentration, be 1.00 * 10
-5mol
.l
-1fluorescence or colorimetric compound
2-aacetonitrile-water (3:7) solution in, Tutofusin tris-hydrochloric acid buffer solution is controlled pH ~ 6, adds 2.00 * 10
-4molL
-1cu
2+after solution, fluorescence significantly strengthens.Again respectively to
2-a-cu
2+other metal ions that add isodose in solution: Al
3+, Cr
3+, Fe
3+, Hg
2+, Co
2+, Ni
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, K
+, Na
+after fluorescence intensity change.White bars is illustrated in compound
2-ain add the emissive porwer of different metal ion.Black bar is illustrated in
2-a-cu
2+solution adds the fluorescence intensity change after other coexistent metallic ions again.Show compound
3-adetect Cu
2+fluorescence be not subject to the impact of other common coexistent metallic ions.Ordinate zou means fluorescence intensity, and X-coordinate means metal ion.M
n+the metal ion that means experiment.
Figure 12 coexistent metallic ion is to compound
2-aabsorption spectroscopy detects Cu
2+impact.
In concentration, be 1.00 * 10
-5mol
.l
-1fluorescence or colorimetric compound
2-aacetonitrile-water (3:7) solution in, Tutofusin tris-hydrochloric acid buffer solution is controlled pH ~ 6, adds 2.00 * 10
-4molL
-1cu
2+absorb significantly and strengthen after solution.Again respectively to
2-a-cu
2+other metal ions that add isodose in solution: Al
3+, Cr
3+, Fe
3+, Hg
2+, Co
2+, Ni
2+, Zn
2+, Cd
2+, Pb
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, K
+, Na
+after absorbancy change.White bars is illustrated in compound
2-ain add the absorbancy of different metal ion.Black bar is illustrated in
2-a-cu
2+solution adds the absorbancy after other coexistent metallic ions to change again.Show compound
3-adetect Cu
2+absorption be not subject to the impact of other common coexistent metallic ions.Ordinate zou means absorbancy, and X-coordinate means metal ion.M
n+the metal ion that means experiment.
Embodiment
Embodiment mono-: compound
1-a(the chloro-6-rhodamine B of 2,4-bis-hydrazides-1,3,5-triazines
)synthetic
At N
2in the there-necked flask of the 250ml of protection, add 323mg (1.75mmol) cyanuric chloride, 604mg (4.38mmol) K
2cO
3with the 10ml anhydrous tetrahydro furan, control 0 ~ 5 ℃ of temperature, dropwise add 800mg(1.75mmol under stirring) solution of rhodamine B hydrazides (being dissolved in the 50ml anhydrous tetrahydro furan), in 30min, add, continue to stir 9h (thin-layer chromatography tracking).Reaction finishes, and filters, and filtrate is spin-dried for, and silica gel chromatographic column separates, and developping agent is: sherwood oil: ethyl acetate: chloroform (
v:
v:
v=3:1:4) obtain 0.81g white object product
1-a, productive rate 76.6%.m.p.?>300 C;?
1H?NMR(400MHz,?CDCl
3)?δ:1.16?(t,?12H,?J=7.0Hz,?NCH
2CH
3),?3.33(q,?8H,?J=7.0Hz,?NCH
2CH
3),?6.31-6.29(m,?4H,?ArH),?6.66-6.63(m,?2H,?ArH),?7.20(d,?1H,?J=8Hz,?ArH),?7.61-7.53(m,?2H,?ArH),?8.01(d,?1H,?J=8Hz,?ArH);?MS?(ESI)
?m/z:?604.5(M
+-1)。
Embodiment bis-: compound
1-b(the chloro-6-of 2,4-bis-(N-amine ethyl rhodamine acid amides)-1,3,5-triazines
)synthetic
At N
2in the there-necked flask of the 250ml of protection, add 365mg (1.98mmol) cyanuric chloride, 568mg (4.11mmol) K
2cO
3with the 10ml anhydrous tetrahydro furan, control 0 ~ 5 ℃ of temperature, dropwise add 800mg(1.65mmol under stirring) solution of rhodamine B quadrol (being dissolved in the 50ml anhydrous tetrahydro furan), in 30min, add, continue to stir 5h (thin-layer chromatography tracking).Reaction finishes, and filters, and filtrate is spin-dried for, and silica gel chromatography separates, and developping agent is: sherwood oil: ethyl acetate (
v:V=3:2), obtain 0.66g white object compound
1-b, productive rate 63.3%.m.p.?148.4-150.3 C;
?1H?NMR(400MHz,?CDCl
3)?δ:1.17?(t,?12H,?J=6.8Hz,?NCH
2CH
3),?3.26-3.22(m,?2H,?NCH
2CH
2N),?3.34(q,?8H,?J=6.8Hz,?NCH
2CH
3),?3.42-3.39(m,?2H,?NCH
2CH
2N),?6.41-6.22(m,?12H,?ArH),?7.11-7.09(m,?1H,?ArH),?7.49-7.47(m,?2H,?ArH),?7.93-7.91(m,?1H,?ArH);?MS?(ESI)
?m/z:?632.2(M
+-1)。
Embodiment tri-: compound
2-a(the two diethanolamine of 2,4--6-rhodamine B hydrazides-1,3,5-triazines
)synthetic
At N
2in the there-necked flask of 250ml of protection, by 1.22g(11.6mmol) diethanolamine and 599mg(4.64mmol) DIPEA is dissolved in 20ml anhydrous tetrahydro furan, 700mg(1.16mmol) compound
1-abe dissolved in the 70ml anhydrous tetrahydro furan, and, dropwise add there-necked flask in the time of 50 ℃ in, drip complete stirring and refluxing 9h (thin-layer chromatography tracking).Reaction finishes, and filters, and filtrate is spin-dried for, and silica gel chromatographic column separates, developping agent: ethanol: chloroform (
v:V=1:4), obtain the 0.79g product, productive rate 91.9%.m.p.?73.6-75.5 C;?
1H?NMR(400MHz,?CDCl
3)?δ:1.25-1.08?(m,?12H,?NCH
2CH
3),?3.39-3.28(m,?8H,?NCH
2CH
3),?3.78-3.64(m,?20H,?NCH
2CH
2N?and?CH
2CH
2OH),?6.39-6.27(m,?6H,?ArH),?7.10-7.06(m,?1H,?ArH),?7.48-7.44(m,?2H,?ArH),?7.92-7.88(m,?1H,?ArH);?MS?(ESI)
?m/z:?742.5(M
+-1)。
Embodiment tetra-: compound
2-b(two diethanolamine-the 6-(N-amine ethyl rhodamine acid amides) of 2,4--1,3,5-triazines
)synthetic
At N
2in the there-necked flask of 250ml of protection, by 504mg (4.80mmol) diethanolamine and 248mg(1.92mmol) DIPEA is dissolved in 10ml dioxane (molecular sieve drying), 300mg (0.48mmol) compound
1-bbe dissolved in 30ml dioxane (molecular sieve drying), and, dropwise add there-necked flask in the time of 50 ℃ in, drip complete stirring and refluxing 8h (thin-layer chromatography tracking).Reaction finishes, and filters, and filtrate is spin-dried for.Silica gel chromatographic column separates (ethanol: chloroform=1:4 wash-out), obtain the 0.29g product, productive rate 79.4%.m.p.?94.3-95.5 C;?
1H?NMR(400MHz,?CDCl
3)?δ:1.17?(t,?12H,?J=6.8Hz,NCH
2CH
3),?3.34-2.82?(m,?12H,?NCH
2CH
3?and?NCH
2CH
2N),?3.78-3.64(m,16H,CH
2CH
2OH),?6.46-6.27(m,?6H,?ArH),?7.10-7.07(m,?1H,?ArH),?7.48-7.44(m,?2H,?ArH),?7.90-7.88(m,?1H,?ArH);?MS?(ESI)
?m/z:?770.5(M
+-1)。
Embodiment five: compound
3-b(2-is chloro-4, two (N-amine ethyl rhodamine the acid amides)-1,3,5-triazines of 6-
)synthetic
In the there-necked flask of 100ml, by 1.14g (1.80mmol) rhodamine B quadrol and 875mg(1.80mmol) compound
1-bbe dissolved in the 50ml anhydrous tetrahydro furan, then add 1.76g(5.4mmol) Cs
2cO
3, stirring and refluxing 6h (thin-layer chromatography tracking).Cooling, to filter, after filtrate is spin-dried for, silica gel chromatographic column separates, developping agent: sherwood oil: ethyl acetate (
v:V=1:1 wash-out), obtain the 1.31g product, productive rate 67.2%.m.p.?164.2-166.1 C;
?1H?NMR(400MHz,?CDCl
3)?δ:1.17-1.11(m,?24H,?NCH
2CH
3),?3.14-3.10(q,?4H,?NCH
2CH
2N),?3.32-3.28(m,?20H,?NCH
2CH
2N?and?NCH
2CH
3),?6.42-6.15(m,?12H,?ArH),?7.09-7.00(m,?2H,?ArH),?7.45-7.42(m,?4H,?ArH),?7.90-7.86(m,?2H,?ArH);?MS?(ESI)
?m/z:?1081.3(M
+-2)。
Embodiment six:
Add compound in 10.0 mL volumetric flasks
1b-1(or
3b-1) ethanol storing solution (1.00 * 10
-4molL
-1, 0-3.0mL), add Tutofusin tris-hydrochloric acid buffer solution (5.00 * 10
-2molL-1, pH 4.0,1.0 mL), metal ion Al
3+(2.00 * 10
-3molL-1,0-3.75 mL) or Cr
3+(2.00 * 10
-3molL
-1, 0-4.25 mL).Be diluted to scale with ethanolic soln, shake up, at 40 C constant temperature 2h, the quartz colorimetric utensil that moves into 1cm carries out fluorescence spectrum and uv-visible absorption spectra mensuration.Excite and the emission wavelength of fluorescence spectrometry are 556/578 nm.
Agents useful for same is analytical reagent, and test water is redistilled water.
Spectrophotofluorometer model used is Cary Eclipse spectrophotofluorometer, and U.S. VARIAN company manufactures.The ultraviolet-visible spectrophotometer model is UV – vis TU-1901, and Beijing Pu Xi general instrument Corp. manufactures.
Regulate compound with Tutofusin tris-hydrochloric acid buffer solution
1-b(or
3-b) ethanolic soln pH in 4 ~ 6 scopes, not observing compound itself has obvious fluorescent emission and ultraviolet-ray visible absorbing.Add metal ion Al
3+(or Cr
3+) after, take 556nm as excitation wavelength, observe significant fluorescent emission, the fluorescence intensity maximum at 578 nm places, Al
3+and Cr
3+make respectively compound fluorescence significantly strengthen that (Fig. 1 is compound
1-b, Fig. 3 is compound
3-b), solution, by the colourless pink that becomes, is observed emission safran fluorescence under the 365nm ultraviolet lamp.Simultaneously, (Fig. 2 is compound all to observe very strong visible absorbance at 556nm wavelength place
1-b, Fig. 4 is compound
3-b).Except Fe
3+add and have outside feeble signal increases, other experiment metal ions all without obvious response signal, show that these two kinds of compounds are to Al to compound
3+and Cr
3+there is the recognition detection performance.
Compound
3-bdetect Al
3+fluorescence (Fig. 5) and absorption intensity (Fig. 6) be not subject to Cr
3+the impact coexisted.And Al
3+while coexisting to compound
3-bdetect Cr
3+fluorescence (Fig. 7) and absorption intensity (Fig. 8) certain influence is arranged.Other common coexistent metallic ions when concentration is suitable with test ion, on the relative deviation of the fluorescence intensity that detects and absorbancy impact all in 5%.Equal interference measurements not.
Control in the ethanolic soln of pH ~ 4 at Tutofusin tris-hydrochloric acid, take 556/578nm as fluorescence excitation and emission wavelength, take 556nm as maximum absorption wavelength, measure respectively Al
3+and Cr
3+change in concentration and compound
1-b(or
3-b) fluorescent emission and the working curve that strengthens of absorbancy.Slope by calibration curve and measure the standard deviation of 10 blank values, measure and calculate linearity range and detection limit is listed in table 6.
Table 6 compound detects the analytical parameters of metal ion as fluorescence or colorimetric reagent
Embodiment seven:
Add compound in 10.0 mL volumetric flasks
2-aacetonitrile storing solution (1.00 * 10
-4molL
-1, 0-3.0mL), add Tutofusin tris-hydrochloric acid buffer solution (5.00 * 10
-2molL-1, pH ~ 6,1.0 mL), metal ion Cu
2+(2.00 * 10
-3molL-1,0-1.0 mL).(make acetonitrile in solution: water=3:7), shake up, in room temperature, place 2h, the quartz colorimetric utensil that moves into 1cm carries out fluorescence spectrum and uv-visible absorption spectra mensuration to be diluted to scale with acetonitrile-aqueous solution.Excite and the emission wavelength of fluorescence spectrometry are 553/578 nm.
Regulate compound with Tutofusin tris-hydrochloric acid buffer solution
2-aacetonitrile-aqueous solution (acetonitrile: water=3:7) pH is in 3 ~ 7 scopes, and compound itself does not have obvious fluorescent emission and ultraviolet-ray visible absorbing.Add metal ion Cu
2+after, take 553nm as excitation wavelength, observe significant fluorescent emission, the fluorescence intensity maximum at 578 nm places, Cu
2+make compound fluorescence significantly strengthen (Fig. 9), solution, by the colourless pink that becomes, is observed emission safran fluorescence under the 365nm ultraviolet lamp.Simultaneously, observe very strong visible absorbance (Figure 10) at 553nm wavelength place.Other experiment metal ions all without obvious response signal, show that these two kinds of reagent are to Cu to compound
2+there is the recognition detection performance.
Compound in embodiments of the invention
2-adetect Cu as fluorescence or colorimetric reagent
2+the time, when in concentration, other suitable common coexistent metallic ions exist, the relative deviation that the fluorescence intensity (Figure 11) that detects and absorbancy (Figure 12) are affected is all in 5%.Equal interference measurements not.
Control in the ethanolic soln of pH ~ 6.0 at Tutofusin tris-hydrochloric acid, take 553/578nm as fluorescence excitation and emission wavelength, take 553nm as maximum absorption wavelength, measure respectively Cu
2+change in concentration and compound
2-afluorescent emission and the working curve that strengthens of absorbancy.Slope by calibration curve and measure the standard deviation of 10 blank values, measure and calculate linearity range and detection limit is listed in table 7.
Table 7 compound detects Cu as fluorescence or colorimetric reagent
2+analytical parameters
Claims (8)
1. a class rhodamine B-triaizine compounds, it is characterized in that by controlling temperature of reaction, using different acid binding agents and selective solvent, with rhodamine B quadrol or rhodamine B hydrazides stepwise reaction, replace 1 or 2 chlorine atoms on the cyanuric chloride ring, or with diethanolamine, residue is not replaced the chlorine atom and replaces, syntheticly respectively obtaining serial rhodamine-triaizine compounds, compound is as fluorescence or colorimetric reagent, energy is highly sensitive, highly selective detects the special metal ion, and its general structure is:
2. a class rhodamine B-triaizine compounds according to claim 1, is characterized in that R
1, R
2can be monosubstitutedly, also can be two the replacement, substituent R
1for rhodamine B quadrol base, R
2for rhodamine B hydrazide group, R
3for the di-alcohol amido.
3. a class rhodamine B-triaizine compounds according to claim 1, R while it is characterized in that two the replacement
1, R
2identical substituting group, R
3replacement be at R
1or R
2complete the described monosubstituted R that refers to after replacing
1or R
2to the replacement of a chlorine on the cyanuric chloride ring, two replacements refer to R
1or R
2or R
3in arbitrary group to the replacement of two chlorine on the cyanuric chloride ring, R
3replacement refer to after above-mentioned monosubstituted or two replacements the replacement to remaining chlorine on the cyanuric chloride ring.
4. according to the preparation method of claim 1 or 2 or 3 described class rhodamine B-triaizine compounds, by controlling temperature of reaction, select acid binding agent and solvent, with rhodamine B quadrol or rhodamine B hydrazides or diethanolamine, cyanuric chloride chlorine in ring atom is controlled to substituted in reaction step by step and make, synthetic route is as follows:
（1）
Control temperature of reaction, with rhodamine B hydrazides or rhodamine B quadrol, replace a chlorine on the cyanuric chloride ring, carry out monosubstituted;
（2）
Aforementioned (1) reaction product of take is raw material, then replaces remaining two chlorine on the cyanuric chloride ring with diethanolamine, carries out three replacements;
（3）
Aforementioned (1) reaction product of take is raw material, then uses identical substituting group (rhodamine B hydrazides or rhodamine B quadrol) to replace another chlorine on the cyanuric chloride ring, carries out two the replacement;
（4）
Aforementioned (3) reaction product of take is raw material, then replaces a remaining chlorine on the cyanuric chloride ring with diethanolamine, carries out three replacements.
5. according to the preparation method of claim 1 or 2 or 3 described class rhodamine B-triaizine compounds, it is characterized in that take that cyanuric chloride, rhodamine B quadrol, rhodamine B hydrazides, diethanolamine are raw material, salt of wormwood, cesium carbonate, N, the N-diisopropylethylamine is acid binding agent, anhydrous tetrahydro furan, dioxane are solvent, control temperature of reaction, select different acid binding agents and solvent, through stepwise reaction, synthetic making:
Compound
1-a(the chloro-6-rhodamine B of 2,4-bis-hydrazides-1,3,5-triazines
)synthetic
At N
2under protection, cyanuric chloride, salt of wormwood and anhydrous tetrahydro furan are mixed, control temperature, stir the lower anhydrous tetrahydrofuran solution that drips the rhodamine B hydrazides, stirring and refluxing, reaction finishes, and filters, and filtrate is spin-dried for, and silica gel chromatographic column separates, and obtains the white object product
1-a:
Time for adding: 30min
Temperature of reaction: 0 ~ 5 ℃
Reaction times: 9h
Acid binding agent: salt of wormwood
Reaction solvent: anhydrous tetrahydro furan, add-on can have been dissolved corresponding solute
Eluent: sherwood oil: ethyl acetate: chloroform (
v:V:
v=3:1:4)
Mol ratio: cyanuric chloride: salt of wormwood: rhodamine B hydrazides=1: 4～5: 1
Compound
1-b(the chloro-6-of 2,4-bis-(N-amine ethyl rhodamine B acid amides)-1,3,5-triazines
)synthetic
At N
2under protection, cyanuric chloride, salt of wormwood and anhydrous tetrahydro furan are mixed, control temperature, stir the lower anhydrous tetrahydrofuran solution that drips the rhodamine B quadrol, stirring and refluxing, reaction finishes, and filters, and filtrate is spin-dried for, and silica gel chromatography separates, and obtains the white object compound
1-b:
Time for adding: 30min
Temperature of reaction: 0 ~ 5 ℃
Reaction times: 9h
Acid binding agent: salt of wormwood
Reaction solvent: anhydrous tetrahydro furan, add-on can have been dissolved corresponding solute
Eluent: sherwood oil: ethyl acetate (
v:V=3:2)
Mol ratio: cyanuric chloride: salt of wormwood: rhodamine B quadrol=1～1.2: 4～4.5: 1
Compound
2-a(the two diethanolamine of 2,4--6-rhodamine B hydrazides-1,3,5-triazines
)synthetic
At N
2under protection, diethanolamine and DIPEA are dissolved in to anhydrous tetrahydro furan, control temperature, drip compound
1-aanhydrous tetrahydrofuran solution, stirring and refluxing, reaction finishes, and filters, filtrate is spin-dried for, silica gel chromatographic column separates, and obtains the white object compound
2-a:
Time for adding: 30min
Temperature of reaction: 50 ℃ of the first step reactions, 66 ℃ of second step reactions
Reaction times: 9 ~ 10h
Acid binding agent: DIPEA
Reaction solvent: anhydrous tetrahydro furan, add-on can have been dissolved corresponding solute
Eluent: ethanol: chloroform (
v:V=1:4)
Mol ratio: diethanolamine: DIPEA: compound
1-b=10: 4～5: 1
Compound
2-b(two diethanolamine-the 6-(N-amine ethyl rhodamine B acid amides) of 2,4--1,3,5-triazines
)synthetic
At N
2under protection, diethanolamine and DIPEA are dissolved in to dioxane, compound
1-bbe dissolved in dioxane, control dropping temperature, stirring and refluxing, reaction finishes, and filters, and filtrate is spin-dried for silica gel chromatographic column separates, and obtains the white object compound
2-b:
Time for adding: 30min
Temperature of reaction: 50 ℃ of the first step reactions, 101 ℃ of second step reactions
Reaction times: 8h
Acid binding agent: DIPEA
Reaction solvent: dioxane, add-on can have been dissolved corresponding solute
Eluent: ethanol: chloroform (
v:V=1:4)
Mol ratio: diethanolamine: DIPEA: compound
1-b=10: 1.5～2: 1
Compound
3-b(2-is chloro-4, two (N-amine ethyl rhodamine B the acid amides)-1,3,5-triazines of 6-
)synthetic
By rhodamine B quadrol and compound
1-bbe dissolved in anhydrous tetrahydro furan, then add cesium carbonate, stirring and refluxing, cooling, to filter, after filtrate is spin-dried for, silica gel chromatographic column separates, and obtains target compound
3-b:
Temperature of reaction: 66 ℃
Reaction times: 6h
Acid binding agent: cesium carbonate
Reaction solvent: anhydrous tetrahydro furan, add-on can have been dissolved corresponding solute
Eluent: sherwood oil: ethyl acetate (
v:V=1:1)
Mol ratio: rhodamine B quadrol: cesium carbonate: compound
1-b=1: 5～6: 1.
6. according to claim 1 or 2 or 3 described class rhodamine B-triaizine compounds, it is characterized in that the compound of partial synthesis is as follows:
Compound
1-a(the chloro-6-rhodamine B of 2,4-bis-hydrazides-1,3,5-triazines
)
Molecular formula: C
31h
33cl
2n
7o
2
Structural formula:
Molecular weight
:605
Fusing point: > 300 C
Solvability: can be dissolved in chloroform, methylene dichloride, acetone, ethanol
Spectral quality: the fluorescence exciting wavelength in ethanolic soln is 557nm, and emission wavelength is 578nm, and maximum absorption wavelength is 557nm
Compound
1-b(the chloro-6-of 2,4-bis-(N-amine ethyl rhodamine B acid amides)-1,3,5-triazines
)
Molecular formula: C
33h
37cl
2n
7o
2
Structural formula:
Molecular weight
:633
Fusing point: 148.4-150.3 C
Solvability: can be dissolved in chloroform, methylene dichloride, acetone, ethanol
Spectral quality: the fluorescence exciting wavelength in ethanolic soln is 556nm, and emission wavelength is 578nm, and maximum absorption wavelength is 556nm
Compound
2-a(the two diethanolamine of 2,4--6-rhodamine B hydrazides-1,3,5-triazines
)
Molecular formula: C
39h
53n
9o
6
Structural formula:
Molecular weight
:743
Fusing point: 73.6-75.5 C
Solvability: can be dissolved in chloroform, methylene dichloride, acetone, ethanol, water
Spectral quality: the fluorescence exciting wavelength in ethanolic soln is 553nm, and emission wavelength is 578nm, and maximum absorption wavelength is 553nm
Compound
2-b(two diethanolamine-the 6-(N-amine ethyl rhodamine B acid amides) of 2,4--1,3,5-triazines
)
Molecular formula: C
41h
57n
9o
6
Structural formula:
Molecular weight
:771
Fusing point: 94.3-95.5 C
Solvability: can be dissolved in chloroform, methylene dichloride, acetone, ethanol
Spectral quality: the fluorescence exciting wavelength in ethanolic soln is 557nm, and emission wavelength is 578nm, and maximum absorption wavelength is 557nm
Compound
3-b(2-is chloro-4, two (N-amine ethyl rhodamine B the acid amides)-1,3,5-triazines of 6-
)
Molecular formula: C
63h
74clN
11o
4
Structural formula:
Molecular weight
:1083
Fusing point: 164.2-166.1 C
Solvability: can be dissolved in chloroform, methylene dichloride, acetone, ethanol
Spectral quality: the fluorescence exciting wavelength in ethanolic soln is 556nm, and emission wavelength is 578nm, and maximum absorption wavelength is 556nm.
7. according to the application of a class rhodamine B-triaizine compounds described in claim 1 or 2 or 3, it is characterized in that with fluorescence spectrum or uv-visible absorption spectra as detecting Al
3+, Cr
3+, Cu
2+fluorescence or colorimetric reagent in the special metal ion.
8. according to the application of the described class rhodamine B-triaizine compounds of claim 7, it is characterized in that the compound of different structure can detect respectively Al
3+, Cr
3+, Cu
2+metal ion, 2 orders of magnitude of Fluorometric assay concentration linearity range Da Keda, detectability is low to moderate 10
-8mol
.l
-1 ,compound detects metal ion for ion probe.
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| CN103913441B (en) * | 2014-04-01 | 2016-07-06 | 南京理工大学 | The fluorescent optical sensor of a kind of rhodamine B, preparation and application thereof |
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| CN105482812A (en) * | 2015-12-18 | 2016-04-13 | 贵州大学 | Fluorescent probe reagent for concurrent selection and determination of multiple metal ions, and preparation and appliance |
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| CN107501284A (en) * | 2017-08-09 | 2017-12-22 | 贵州大学 | A kind of probe and application the probe simultaneously detect micro Cu2+And/or Hg2+Method |
| CN107501284B (en) * | 2017-08-09 | 2019-06-28 | 贵州大学 | A kind of probe and the application probe detect micro Cu simultaneously2+And/or Hg2+Method |
| CN107501285A (en) * | 2017-09-08 | 2017-12-22 | 中国地质大学（武汉） | A kind of water-soluble rhodamine base ionic liquid probe of bimetallic ion selectivity Division identification and preparation method, application |
| CN113637027A (en) * | 2021-07-22 | 2021-11-12 | 海南师范大学 | Phenyl triazole dicarboxylic acid-rhodamine B derivative fluorescent probe and preparation method and application thereof |
| CN113637027B (en) * | 2021-07-22 | 2022-04-05 | 海南师范大学 | Phenyl triazole dicarboxylic acid-rhodamine B derivative fluorescent probe and preparation method and application thereof |
| CN114456375A (en) * | 2022-01-21 | 2022-05-10 | 武汉工程大学 | Polyhydroxy triazine-based charring agent and preparation method and application thereof |
| CN114456375B (en) * | 2022-01-21 | 2024-04-23 | 武汉工程大学 | Polyhydroxy triazine charring agent and preparation method and application thereof |
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