CN103570736B - Rhodamine-oxadiazole derivative and preparation method and application thereof - Google Patents
Rhodamine-oxadiazole derivative and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a rhodamine-oxadiazole derivative and a preparation method and an application thereof. The specific preparation method comprises the following step: with N-aminoethylpiperazine, rhodamine B, DIPEA (Diisopropyl Ethyl Amine), 4-chloro-7-nitro-2, 1, 3-benzoxepin oxadiazole and K2CO3 with a mol ratio of (1-10): 1: (1-20): (1-1.5): 1 as reactants, preparing a product by a two-step-one-pot method, wherein the product can be used for H<+> ion colorimetry and used as a fluorescent probe. The structure designed and synthesized by the invention is short in synthesis route and mild in reaction conditions, an intermediate is unnecessary to be separated to obtain a target probe with a high yield, and no obvious FRET (fluorescence resonance energy transfer) exists between the oxadiazole and rhodamine fluorophores with matched spectrums in the structure, so that the H<+> can be detected through three channels, and the rhodamine-oxadiazole derivative has high selectivity, high sensitivity and large application potential.
Description
Technical field
The present invention relates to a kind of fluorescent material, be specifically related to a kind of rhodamine-oxadiazole derivative and preparation method thereof and application, belong to organic synthesis field.
Background technology
Hydrogen ion is occurring in nature distribution positively charged ion the most widely, all there is hydrogen ion, and affect the character of the aqueous solution in nearly all aqueous solution.The carrying out of chemical reaction or complete, the many important physiological process of cell and crganelle is all closely related with pH value.Hydrogen ion fluorescent probe can be used for the pH value monitoring in environment and industrial and agricultural production field, and the pH value in the pH value of intraor extracellular and blood measures, for the change of Study of Hydrogen ionic concn provides important information to the impact of environment and vital movement.
Rhodamine because of have fluorescence quantum yield high, excite with emission wavelength in visible region, especially can realize the advantages such as the regulation and control of fluorescence property by forming spirolactams ring or opening spirolactams ring and become one of most widely used reporter group in fluorescent probe and sensor, the fluorescent probe based on rhodamine be widely used in environmental science and life science.
At present, in the synthesis of Rhodamine Derivatives, need first synthetic intermediate, recycling intermediate reaction generates Rhodamine Derivatives.
The people such as Wu J-S utilize rhodamine and reacting ethylenediamine to generate intermediate, and after separating-purifying, intermediate productive rate is 82.1%; Then utilize the Rhodamine Derivatives of intermediate and thiocarbanil reaction production II, productive rate 72.8%, overall yield is 59.8%; The people such as Lee MH utilize rhodamine B and diethylenetriamine reaction to generate intermediate, and after separating-purifying, intermediate productive rate is 83%; Then utilize the Rhodamine Derivatives of intermediate and dansyl chloride reaction production III, productive rate 40%, overall yield is 33.2%; The people such as Zhang X utilize rhodamine B and the reaction of amine bromate to generate intermediate, after separating-purifying, intermediate produces productive rate 37%, then intermediate and azepine-hexaoxacyclooctadecane-6-6 is utilized to react the Rhodamine Derivatives of production IV, productive rate is 20%, and overall yield is only 7.4%(see Wu J-S, Hwang I-C, Kim KS, Kim JS. Rhodamine-Based Hg
2+-Selective Chemodosimeter in Aqueous Solution:Fluorescent OFF-ON. Org Lett 2007; 9:907-910; Lee MH, Kim HJ, Yoon S, Park N, Kim JS. Metal Ion Induced FRET OFF-ON inTren/Dansyl-Appended Rhodamine Org Lett 2008; 10:213-216; Zhang X; Shiraishi Y, Hirai T. Fe (III)-and Hg (II)-selective dual channel fluorescence of a rhodamine – azacrown ether conjugate. Tetrahedron Lett 2008; 49:4178 – 4181).
Aforesaid method can the bright derivative of synthesizing rhodamine; But intermediate carries out subsequent reactions after needing separating-purifying again, causes reaction process loaded down with trivial details; And Rhodamine Derivatives (probe) overall yield is low.Therefore need to design the new Rhodamine Derivatives that preparation method is simple, yield is high.
In addition, when having the fluorophore of Spectral matching to be present in rhodamine fluorescence probe structure, usually there is FRET (fluorescence resonance energy transfer) and obtain Ratiometric fluorescent probe, detecting target compound by giving the Fluorescence Increasing of the quenching of fluorescence of body fluorophore and acceptor fluorescence group; If there is not obvious FRET (fluorescence resonance energy transfer) to body fluorophore and acceptor fluorescence group, and combining target thing all strengthens to the fluorescence of body fluorophore and acceptor fluorescence group later, then can detect target compound by two emission wavelengths simultaneously, namely obtain hyperchannel probe.
Summary of the invention
The object of this invention is to provide a kind of rhodamine-oxadiazole derivative and preparation method thereof; The method is simple, and without the need to separating-purifying intermediate, obtained rhodamine-oxadiazole derivative has H
+the spectrum property of the uniqueness of response, and its absorption spectrum and fluorescence spectrum are to H
+all there is excellent selectivity and sensitivity, fast response speed.
For achieving the above object, the technical solution used in the present invention is: a kind of rhodamine-oxadiazole derivative with structure shown in formula I:
Formula I.
The preparation method of above-mentioned rhodamine-oxadiazole derivative, comprises the steps:
(1) at N
2under protective condition, N-aminoethyl piperazine, DIPEA are joined in acetonitrile and dissolve, after stirring, adds the acetonitrile solution of rhodamine B again; Stirred at ambient temperature 30 minutes, then back flow reaction 12 ~ 24h; Be cooled to room temperature, removing acetonitrile, resistates is washed, and obtains salmon coloured solid;
(2) above-mentioned salmon coloured solid is dissolved in solvent, after stirring, adds K
2cO
3and 4-chloro-7-nitro-2,1,3-Ben Yang Za oxadiazole solution, room temperature reaction 30 ~ 120 minutes; Except desolventizing, resistates is separated by silicagel column, obtains Orange red solid, is described rhodamine-oxadiazole derivative; Wherein 4-chloro-7-nitro-2,1,3-Ben solvent in Yang Za oxadiazole solution is consistent with the solvent dissolving salmon coloured solid;
Described N-aminoethyl piperazine, rhodamine B, DIPEA, 4-chloro-7-nitro-2,1,3-Ben Yang Za oxadiazole and K
2cO
3mol ratio be (1 ~ 10): 1: (1 ~ 20): (1 ~ 1.5): 1.
In preferred technical scheme, described N-aminoethyl piperazine, rhodamine B, DIPEA, 4-chloro-7-nitro-2,1,3-Ben Yang Za oxadiazole and K
2cO
3mol ratio be 7: 1: 12: 1: 1.
In technique scheme, the described method except desolventizing is that rotary evaporation desolventizes method.
In technique scheme, eluent when silicagel column is separated in described step (2) is ethyl acetate and sherwood oil mixed solution, wherein V
ethyl acetate: V
sherwood oil=2: 1.
In technique scheme, in described step (2), solvent is acetonitrile, ethanol or methylene dichloride.
The invention also discloses above-mentioned rhodamine-oxadiazole derivative as H
+fluorescent probe and H
+the application of colorimetric probe.
In technique scheme, when rhodamine-oxadiazole derivative uses as probe adopt solvent system be: acetonitrile and Bloomsbury smooth-Robison's buffered soln; Wherein acetonitrile and Bloomsbury smooth-volume ratio of Robison's buffered soln is 1: 1.
Above-mentioned preparation method can be expressed as follows:
。
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. the present invention utilizes N-aminoethyl piperazine for raw material, its two ends have primary amino and the secondary amine of differential responses activity, can accomplish that when reacting with rhodamine B primary amino reacts and secondary amine retains, decrease side reaction, utilize DIPEA to facilitate the reaction of N-aminoethyl piperazine and rhodamine B simultaneously; So reaction efficiency disclosed by the invention is high, impurity is few, reaction conditions is gentle, and intermediate does not need separating-purifying just directly can carry out next step reaction;
2. the own solution of product that prepared by the present invention is yellow, and basic unstressed configuration, in conjunction with H
+rear solution becomes orange red, and fluorescence significantly strengthens, and under different excitation light irradiation, can show green and red two kinds of fluorescence respectively, has H
+the spectrum property of the uniqueness of response, as H
+fluorescent probe and colorimetric probe have highly selective, highly sensitive when using, and can avoid FRET (fluorescence resonance energy transfer) phenomenon especially, thus triple channel can detect H
+, have a good application prospect.
Accompanying drawing explanation
Fig. 1 is pure RPBD, RPBD/H in embodiment nine
+with the ultraviolet-visible absorption spectroscopy of RPBD/ metal ion;
Fig. 2 is pure RPBD, RPBD/H in embodiment nine
+with the fluorescence spectrum figure of RPBD/ metal ion;
Fig. 3 be in embodiment ten coexisting ion to RPBD/H
+the effect diagram of solution absorbance and fluorescence intensity.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the invention will be further described:
Embodiment one: H
+the preparation of probe rhodamine-oxadiazole derivative (RPBD)
N-aminoethyl piperazine (AEP), rhodamine B (RB), DIPEA, 4-chloro-7-nitro-2,1,3-Ben Yang Za oxadiazole (NBD-Cl), K
2cO
3mol ratio be: 1: 1: 1: 1: 1.At N
2under protection, AEP and DIPEA is dissolved in acetonitrile in 100 mL there-necked flasks, RB is dissolved in acetonitrile and is added drop-wise in above-mentioned solution; at room temperature stir 30 min, then heating reflux reaction 12 h, then cools; rotary evaporation removing acetonitrile, residuum washes rear acetonitrile with water and dissolves, and adds K
2cO
3, then NBD-Cl is dissolved in homogeneous solvent and is added drop-wise in above-mentioned solution, at room temperature react 30 min, rotary evaporation is except desolventizing, and resistates is separated by silica gel column chromatography, developping agent: ethyl acetate/petroleum ether (volume ratio 2/1), obtain Orange red solid target product RPBD, productive rate 14.6 %.
1H NMR (CDCl
3, 400 MHz) δ 1.16 (t,
J=6.8 Hz, 12H, CH
3), 2.17 (t,
J=6.8 Hz, 2H, CH
2), 2.50 (t,
J=7.2 Hz, 4H, CH
2), 3.33 (m, 2H, j; 8H, CH
2), 3.97 (t,
J=6.8 Hz, 4H, CH
2), 6.26 (m,2H, ArH; 1H, ArH ), 6.39 (d,
J=8.0 Hz, 2H, ArH), 6.45 (d,
J=8.8 Hz, 2H, ArH), 7.10 (t,
J=7.6 Hz,1H, ArH), 7.44 (m, 1H, ArH; 1H, ArH), 7.90 (d,
J=8.2 Hz, 1H, ArH), 8.40 (d,
J=8.8 Hz, 1H, ArH).
13C NMR (CDCl
3,300 MHz) δ 168.30, 153.51, 148.38, 145.15, 144.74, 135.16, 132.38, 131.17, 129.09, 128.04, 123.79, 123.06, 122.64, 108.40, 105.65, 102.18, 97.53, 64.79, 55.10, 52.38, 49.26, 44.22,37.21, 12.70. IR (KBr) cm
-1: 2971, 2927 (CH
3,CH
2), 1688 (C=O), 1620, 1514, 1436 (benzene ring), 1541 (NO
2), 1235, 1301 (C=N), 1118 (C-O-C). LC-MS
m/z calcd. For C
40H
44N
8O
5:717.83 (M+H
+), found: 717.3; Anal.Calcd. For C
40H
44N
8O
5(716.83): C, 67.02; H, 6.19; N, 15.63; found: C, 67.00; H,6.21; N, 15.30。
Embodiment two: H
+the preparation of probe RPBD
N-aminoethyl piperazine (AEP), rhodamine B (RB), DIPEA, 4-chloro-7-nitro-2,1,3-Ben Yang Za oxadiazole (NBD-Cl), K
2cO
3mol ratio be: 7:1: 12: 1: 1.At N
2under protection, AEP and DIPEA is dissolved in acetonitrile in 100 mL there-necked flasks, RB is dissolved in acetonitrile and is added drop-wise in above-mentioned solution; at room temperature stir 30 min, then heating reflux reaction 12 h, then cools; rotary evaporation removing acetonitrile, residuum washes rear acetonitrile with water and dissolves, and adds K
2cO
3, then NBD-Cl is dissolved in homogeneous solvent and is added drop-wise in above-mentioned solution, at room temperature react 30 min, rotary evaporation is except desolventizing, and resistates is separated by silica gel column chromatography, developping agent: ethyl acetate/petroleum ether (volume ratio 2/1), obtain Orange red solid target product RPBD, productive rate 82.5%.
Embodiment three: H
+the preparation of probe RPBD
N-aminoethyl piperazine (AEP), rhodamine B (RB), DIPEA, 4-chloro-7-nitro-2,1,3-Ben Yang Za oxadiazole (NBD-Cl), K
2cO
3mol ratio be: 10:1: 20: 1: 1.At N
2under protection, AEP and DIPEA is dissolved in acetonitrile in 100 mL there-necked flasks, RB is dissolved in acetonitrile and is added drop-wise in above-mentioned solution; at room temperature stir 30 min, then heating reflux reaction 12 h, then cools; rotary evaporation removing acetonitrile, residuum washes rear acetonitrile with water and dissolves, and adds K
2cO
3, then NBD-Cl is dissolved in homogeneous solvent and is added drop-wise in above-mentioned solution, at room temperature react 30 min, rotary evaporation is except desolventizing, and resistates is separated by silica gel column chromatography, developping agent: ethyl acetate/petroleum ether (volume ratio 2/1), obtain Orange red solid target product RPBD, productive rate 78.3 %.
Embodiment four: H
+the preparation of probe RPBD
N-aminoethyl piperazine (AEP), rhodamine B (RB), DIPEA, 4-chloro-7-nitro-2,1,3-Ben Yang Za oxadiazole (NBD-Cl), K
2cO
3mol ratio be: 7:1: 12: 1.5: 1.At N
2under protection, AEP and DIPEA is dissolved in acetonitrile in 100 mL there-necked flasks, RB is dissolved in acetonitrile and is added drop-wise in above-mentioned solution; at room temperature stir 30 min, then heating reflux reaction 12 h, then cools; rotary evaporation removing acetonitrile, residuum washes rear acetonitrile with water and dissolves, and adds K
2cO
3, then NBD-Cl is dissolved in homogeneous solvent and is added drop-wise in above-mentioned solution, at room temperature react 30 min, rotary evaporation is except desolventizing, and resistates is separated by silica gel column chromatography, developping agent: ethyl acetate/petroleum ether (volume ratio 2/1), obtain Orange red solid target product RPBD, productive rate 81.3 %.
Embodiment five: H
+the preparation of probe RPBD
N-aminoethyl piperazine (AEP), rhodamine B (RB), DIPEA, 4-chloro-7-nitro-2,1,3-Ben Yang Za oxadiazole (NBD-Cl), K
2cO
3mol ratio be: 7:1: 12: 1: 1.At N
2under protection, AEP and DIPEA is dissolved in acetonitrile in 100 mL there-necked flasks, RB is dissolved in acetonitrile and is added drop-wise in above-mentioned solution; at room temperature stir 30 min, then heating reflux reaction 24 h, then cools; rotary evaporation removing acetonitrile, residuum washes rear acetonitrile with water and dissolves, and adds K
2cO
3, then NBD-Cl is dissolved in homogeneous solvent and is added drop-wise in above-mentioned solution, at room temperature react 30 min, rotary evaporation is except desolventizing, and resistates is separated by silica gel column chromatography, developping agent: ethyl acetate/petroleum ether (volume ratio 2/1), obtain Orange red solid target product RPBD, productive rate 75.1 %.
Embodiment six: H
+the preparation of probe RPBD
N-aminoethyl piperazine (AEP), rhodamine B (RB), DIPEA, 4-chloro-7-nitro-2,1,3-Ben Yang Za oxadiazole (NBD-Cl), K
2cO
3mol ratio be: 7:1: 12: 1: 1.At N
2under protection, AEP and DIPEA is dissolved in acetonitrile in 100 mL there-necked flasks, RB is dissolved in acetonitrile and is added drop-wise in above-mentioned solution; at room temperature stir 30 min, then heating reflux reaction 12 h, then cools; rotary evaporation removing acetonitrile, residuum washes rear acetonitrile with water and dissolves, and adds K
2cO
3, then NBD-Cl is dissolved in homogeneous solvent and is added drop-wise in above-mentioned solution, at room temperature react 120 min, rotary evaporation is except desolventizing, and resistates is separated by silica gel column chromatography, developping agent: ethyl acetate/petroleum ether (volume ratio 2/1), obtain Orange red solid target product RPBD, productive rate 80.4 %.
Embodiment seven: H
+the preparation of probe RPBD
N-aminoethyl piperazine (AEP), rhodamine B (RB), DIPEA, 4-chloro-7-nitro-2,1,3-Ben Yang Za oxadiazole (NBD-Cl), K
2cO
3mol ratio be: 7:1: 12: 1: 1.At N
2under protection, AEP and DIPEA is dissolved in acetonitrile in 100 mL there-necked flasks, RB is dissolved in acetonitrile and is added drop-wise in above-mentioned solution; at room temperature stir 30 min, then heating reflux reaction 12 h, then cools; rotary evaporation removing acetonitrile, residuum washes rear dissolve with ethanol with water, adds K
2cO
3, then NBD-Cl is dissolved in homogeneous solvent and is added drop-wise in above-mentioned solution, at room temperature react 30 min, rotary evaporation is except desolventizing, and resistates is separated by silica gel column chromatography, developping agent: ethyl acetate/petroleum ether (volume ratio 2/1), obtain Orange red solid target product RPBD, productive rate 79.4 %.
Embodiment eight: H
+the preparation of probe RPBD
N-aminoethyl piperazine (AEP), rhodamine B (RB), DIPEA, 4-chloro-7-nitro-2,1,3-Ben Yang Za oxadiazole (NBD-Cl), K
2cO
3mol ratio be: 7:1: 12: 1: 1.At N
2under protection; AEP and DIPEA is dissolved in acetonitrile in 100 mL there-necked flasks; RB is dissolved in acetonitrile and is added drop-wise in above-mentioned solution; at room temperature stir 30 min; then heating reflux reaction 12 h, then cools, rotary evaporation removing acetonitrile; residuum washes rear methylene dichloride with water and dissolves, and adds K
2cO
3, then NBD-Cl is dissolved in homogeneous solvent and is added drop-wise in above-mentioned solution, at room temperature react 30 min, rotary evaporation is except desolventizing, and resistates is separated by silica gel column chromatography, developping agent: ethyl acetate/petroleum ether (volume ratio 2/1), obtain Orange red solid target product RPBD, productive rate 74.6 %.
Embodiment nine: RPBD is to H
+selectivity and sensitivity
Acetonitrile/Bloomsbury smooth-Robison's buffered soln (1:1, v/v) in add RPBD, H respectively
+ion and metal ion Na
+, K
+, Ca
2+, Mg
2+, Fe
3+, Cu
2+, Zn
2+, Cr
3+, Pb
2+, Ni
2+, Fe
2+, Mn
2+, Co
2+, Cd
2+and Hg
2+, be configured to pure RPBD, RPBD/H
+with RPBD/ metal ion solution; Wherein the concentration of RPBD is 20 μMs, and the concentration of metal ion is 200 μMs, H
+the concentration of ion is 3.46 mM.
Accompanying drawing 1 and accompanying drawing 2 are ultraviolet-visible absorption spectroscopy and the fluorescence spectrum figure of above-mentioned solution.As seen from Figure 1, in numerous ion, H is only had
+make the absorption spectrum of RPBD at the absorption peak blue shift of about 480 nm and weaken, and occurring a significantly new absorption peak at about 560 nm, and having macroscopic colour-change, so the absorption spectrum of RBND is to H
+there are very high selectivity and sensitivity.As can be seen from Figure 2, in numerous ion, also H is only had
+the fluorescence of RPBD is strengthened greatly, and has the two emission peaks near 536 and 580 nm, excite with blue light and green glow under fluorescent microscope and can observe green and red fluorescence respectively.The fluorescence spectrum of visible RPBD is to H
+also very high selectivity and sensitivity is had.
Embodiment ten: RPBD detects H
+time immunity from interference
Acetonitrile/Bloomsbury smooth-Robison's buffered soln (1:1, v/v) in add RPBD, H respectively
+ion and metal ion Na
+, K
+, Ca
2+, Mg
2+, Fe
3+, Cu
2+, Zn
2+, Cr
3+, Pb
2+, Ni
2+, Fe
2+, Mn
2+, Co
2+, Cd
2+and Hg
2+, be configured to RPBD/H
+/ metal ion solution; Wherein the concentration of RPBD is 20 μMs, and the concentration of metal ion is 200 μMs, H
+the concentration of ion is 3.46 mM.
Accompanying drawing 3 is that coexisting ion is to RPBD/H
+the effect diagram of solution absorbance and fluorescence intensity, wherein a and b is the absorbancy adding 560 nm places before and after metal ion, c and d is the fluorescence intensity adding 536 nm places before and after metal ion, e and f is the fluorescence intensity adding 580 nm places before and after metal ion.As can be seen from Figure 3, Na
+, K
+, Ca
2+, Mg
2+, Fe
3+, Cu
2+, Zn
2+, Cr
3+, Pb
2+, Ni
2+, Fe
2+, Mn
2+, Co
2+, Cd
2+, Hg
2+multiple coexistent metallic ion is to RPBD/H
+the absorbancy of solution near 560 nm, and the fluorescence intensity near 536 and 580 nm affects little, visible, multiple coexistent metallic ion is to RPBD colorimetric and fluoroscopic examination H
+significantly do not disturb.Therefore RPBD can be used as highly selective and highly sensitive H
+colorimetric probe and fluorescent probe, and triple channel can detect H
+.
Claims (10)
1. one kind has the rhodamine-oxadiazole derivative of structure shown in formula I:
Formula I.
2. a preparation method for rhodamine-oxadiazole derivative according to claim 1, is characterized in that, comprises the steps:
(1) at N
2under protective condition, N-aminoethyl piperazine, DIPEA are joined in acetonitrile and dissolve, after stirring, adds the acetonitrile solution of rhodamine B again; Stirred at ambient temperature 30 minutes, then back flow reaction 12 ~ 24h; Be cooled to room temperature, removing acetonitrile, resistates washing obtains salmon coloured solid;
(2) above-mentioned salmon coloured solid is dissolved in solvent, after stirring, adds K
2cO
3and 4-chloro-7-nitro-2,1,3-Ben Yang Za oxadiazole solution, room temperature reaction 30 ~ 120 minutes; Except desolventizing, resistates is separated by silicagel column, obtains Orange red solid, is described rhodamine-oxadiazole derivative; Wherein 4-chloro-7-nitro-2,1,3-Ben solvent in Yang Za oxadiazole solution is consistent with the solvent dissolving described salmon coloured solid;
Described N-aminoethyl piperazine, rhodamine B, DIPEA, 4-chloro-7-nitro-2,1,3-Ben Yang Za oxadiazole and K
2cO
3mol ratio be (1 ~ 10): 1: (1 ~ 20): (1 ~ 1.5): 1.
3. preparation method according to claim 2, is characterized in that, described N-aminoethyl piperazine, rhodamine B, DIPEA, 4-chloro-7-nitro-2,1,3-Ben Yang Za oxadiazole and K
2cO
3mol ratio be 7: 1: 12: 1: 1.
4. preparation method according to claim 2, is characterized in that, the described method except desolventizing is that rotary evaporation desolventizes method.
5. preparation method according to claim 2, is characterized in that, eluent when silicagel column is separated in described step (2) is ethyl acetate and sherwood oil mixed solution, and wherein the volume ratio of ethyl acetate and sherwood oil is 2: 1.
6. preparation method according to claim 2, is characterized in that, in described step (2), solvent is acetonitrile, ethanol or methylene dichloride.
7. rhodamine-oxadiazole derivative according to claim 1 is as H
+the application of fluorescent probe.
8. rhodamine-oxadiazole derivative according to claim 1 is as H
+the application of colorimetric probe.
9. the application according to claim 7 or 8, is characterized in that, the solvent system of employing is: acetonitrile and Bloomsbury smooth-Robison's buffered soln.
10. application according to claim 9, is characterized in that, described acetonitrile and Bloomsbury smooth-volume ratio of Robison's buffered soln is 1: 1.
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| CN104530064B (en) * | 2014-12-15 | 2017-02-22 | 湖南科技大学 | Preparation method of colorimetric mercury ion sensor based on rhodamine derivative and application |
| CN104892618B (en) * | 2015-05-21 | 2017-09-05 | 苏州大学 | A kind of pair of response type rhodamine fluorescence probe and its production and use |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011066804A1 (en) * | 2009-12-03 | 2011-06-09 | 大连理工大学 | Fluorescent probe compounds, preparation method and use thereof |
| CN102746313A (en) * | 2012-06-20 | 2012-10-24 | 山东大学 | Rhodamine-B hydrazide derivative containing 1,2,4-triazole structural unit, preparation method and application thereof |
| CN102827175A (en) * | 2012-09-04 | 2012-12-19 | 国家地质实验测试中心 | N-(2,4-dinitrophenyl)-rhodamine B hydrazide and preparation method and application thereof |
| CN103113380A (en) * | 2013-03-08 | 2013-05-22 | 苏州大学 | Rhodamine derivative and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011066804A1 (en) * | 2009-12-03 | 2011-06-09 | 大连理工大学 | Fluorescent probe compounds, preparation method and use thereof |
| CN102746313A (en) * | 2012-06-20 | 2012-10-24 | 山东大学 | Rhodamine-B hydrazide derivative containing 1,2,4-triazole structural unit, preparation method and application thereof |
| CN102827175A (en) * | 2012-09-04 | 2012-12-19 | 国家地质实验测试中心 | N-(2,4-dinitrophenyl)-rhodamine B hydrazide and preparation method and application thereof |
| CN103113380A (en) * | 2013-03-08 | 2013-05-22 | 苏州大学 | Rhodamine derivative and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| A highly sensitive and selective ratiometric and colorimetric sensor for Hg2+ based on a rhodamine–nitrobenzoxadiazole conjugate;Ke Liu,等;《Inorganic Chemistry Communications》;20110826;1798-1801 * |
| Hong-Shui Lva,等.Highly selective and sensitive pH-responsive fluorescent probe in living Hela and HUVEC cells.《Sensors and Actuators B: Chemical》.2012,第956-963页. * |
| Nazmiye B. Yapici,等.Determination of intracellular pH using sensitive, clickable fluorescent probes.《Bioorganic & Medicinal Chemistry Letters》.2012,第2440-2443页. * |
| Preferences of rhodamine coupled (aminoalkyl)-piperazine probes towards Hg(II) ion and their FRET mediated signaling;Biswonath Biswal，等;《Organic &Biomolecular Chemistry》;20130814;第11卷(第30期);第4975–4992页，Scheme1，Fig.1-Fig.9，Table 1 * |
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