CN103113380B - Rhodamine derivative and preparation method and application thereof - Google Patents
Rhodamine derivative and preparation method and application thereof Download PDFInfo
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- CN103113380B CN103113380B CN201310074332.XA CN201310074332A CN103113380B CN 103113380 B CN103113380 B CN 103113380B CN 201310074332 A CN201310074332 A CN 201310074332A CN 103113380 B CN103113380 B CN 103113380B
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Abstract
The invention discloses a rhodamine derivative and a preparation method and application thereof. The rhodamine derivative is prepared by reacting rhodamine hydrazide and 4-chloro-7-nitro-2,1,3-benzoxaoxadiazole in the presence of an acid binding agent. The Cu<2+> and Fe<3+> can be respectively detected at high selectivity and high sensitivity. The designed and synthesized structure is short in synthetic route and mild in reaction conditions, the obtained derivative can be used for an aqueous phase system, and the ultraviolet-visible absorption spectrum and fluorescence spectrum are insensitive to the acid-base property of the system.
Description
Technical field
The present invention relates to a kind of Rhodamine Derivatives, and this Rhodamine Derivatives is as the application of spectral probe.
Background technology
In Rhodamine Derivatives structure, contain can Open loop and closed loop part, the opening and closing of ring can cause the considerable change of Rhodamine Derivatives ultraviolet-visible absorption spectroscopy and fluorescence spectrum, during closed loop, generally colourless, without fluorescence, or light, hypofluorescence, during open loop, coloured, fluorescence is strong, and Rhodamine Derivatives fluorescence quantum yield is high, photoluminescent property can regulate and control, low to the sensitivity of acid-basicity, excite with emission wavelength in visible region, these features become one of most widely used reporter group in spectral probe and sensor.A large amount of rhodamine spectral probes and sensor are in the news, but the rhodamine spectral probe of the different heavy metals of energy while multi-channel detection and transition metal ion and sensor are seldom.
Therefore, need to seek new Rhodamine Derivatives, to realize the highly selective multi-channel detection to different metal ion.
Summary of the invention
Goal of the invention of the present invention is to provide a kind of new Rhodamine Derivatives (RNBD), and the purposes of this Rhodamine Derivatives.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of Rhodamine Derivatives, and structural formula is shown below:
。
The preparation method of above-mentioned Rhodamine Derivatives, under acid binding agent exists, by rhodamine hydrazides and the chloro-7-of 4-nitro-2, the reaction of 1,3-benzo oxa-oxadiazoles prepares.
Reaction is at lucifuge and N
2under protective condition, take acetonitrile, tetrahydrofuran (THF) or methylene dichloride carries out as solvent.
Concrete preparation method is, first rhodamine hydrazides is dissolved in solvent, stir 10 minutes, again by acid binding agent and the chloro-7-of 4-nitro-2, after 1,3-benzo oxa-oxadiazoles is distributed in homogeneous solvent, slowly join in rhodamine hydrazides solution, stir 10 minutes again, then at 25～81 ℃, react 12～72 hours, cooling rear centrifuging or extraction obtain crude product; Crude product is separated by silicagel column, then obtains required Rhodamine Derivatives with sherwood oil or hexanaphthene washing purifying.
In technique scheme, the separatory eluent of silicagel column is ethanol/methylene, volume ratio 1:5, ethyl acetate/petroleum ether, volume ratio 1:5 or ethyl acetate/normal hexane, volume ratio 1:6.With obtaining orange red solid powder RNBD after sherwood oil or hexanaphthene washing purifying, productive rate is 12.5%～37.4%.
In technique scheme, described acid binding agent is selected from anhydrous K
2cO
3, triethylamine or DIPEA.
Preferably, the chloro-7-of rhodamine hydrazides, acid binding agent and 4-nitro-2, the mol ratio of 1,3-benzo oxa-oxadiazoles is 1.0: 1.0: (1.0 ~ 1.5).
The present invention provides above-mentioned Rhodamine Derivatives as Cu simultaneously
2+the application of probe.
Detection solution is CH
3cN/H
2o, volume ratio is that 1: 1, concentration are 1 μ M.
And above-mentioned Rhodamine Derivatives is as Fe
3+the application of probe.
Detection solution is CH
3cN/H
2o, volume ratio is that 1: 99, concentration are 5 μ M.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. the invention provides a kind of new Rhodamine Derivatives, can distinguish highly selective and high-sensitivity detection Cu
2+and Fe
3+.
2. it is short that the present invention designs synthetic structure synthetic route, and reaction conditions is gentle.
3. the derivative that the present invention obtains can be for aqueous phase system, and its ultraviolet-visible absorption spectroscopy and fluorescence spectrum are insensitive to system acid-basicity.
Accompanying drawing explanation
Fig. 1 is the ultraviolet-visible absorption spectroscopy in embodiment 11.
Fig. 2 is the fluorescence spectrum in embodiment 11.
Fig. 3 is the ultraviolet-visible absorption spectroscopy in embodiment 12.
Fig. 4 is the fluorescence spectrum in embodiment 12.
Fig. 5 is Cu in embodiment 13
2+concentration to RBND (1 μ M) acetonitrile/water (1/1, the v/v) impact of solution ultraviolet-visible absorption spectroscopy.
Fig. 6 is Cu in embodiment 13
2+concentration to RBND (1 μ M) acetonitrile/water (1/1, the v/v) impact of solution fluorescence spectrum.
Fig. 7 is Fe in embodiment 14
3+concentration to RBND (5 μ M) acetonitrile/water (1/99, the v/v) impact of solution fluorescence spectrum.
Fig. 8 be in embodiment 15 coexisting ion to RNBD (1 μ M)+Cu
2+near the impact of absorbancy (10 μ M) solution 560 nm.
Fig. 9 be in embodiment 15 coexisting ion to RNBD (1 μ M)+Cu
2+the impact of (10 μ M) solution maximum fluorescence intensity.
Figure 10 be in embodiment 16 coexisting ion to RNBD (5 μ M)+Fe
3+the impact of (50 μ M) solution maximum fluorescence intensity.
Figure 11 be in embodiment 17 pH value to RNBD (1 μ M) and RNB (1 μ M)+Cu
2+(10 μ M) CH
3cN/H
2o (1/1, near the v/v) impact of maximum absorbance solution 560.
Figure 12. pH value is to RNBD (1 μ M) and RNB (1 μ M)+Cu
2+(10 μ M) CH
3cN/H
2o (1/1, the v/v) impact of solution maximum fluorescence intensity.
Figure 13. pH value is to RNBD (5 μ M) and RNBD (5 μ M)+Fe
3+(50 μ M) CH
3cN/H
2o (1/99, the v/v) impact of solution maximum fluorescence intensity.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described:
Embodiment mono-: the preparation of intermediate rhodamine hydrazides (RBH)
Intermediate rhodamine hydrazides (RBH) reference literature is synthetic.
Dujols?V,?Ford?F,?Czarnik?AW.?A?long-wavelength?fluorescent?chemodosimeter?selective?for?Cu(II)?ion?in?water.?Am?Chem?Soc?1997;119:7386-7.
Yang?X-F,?Guo?X-Q,?Zhao?Y-B.?Development?of?a?novel?rhodamine-type?fluorescent?probe?to?determine?peroxynitrite.?Talanta?2002;57:883-90.
Wu?C-M,?Chen?Y-H,?Dayananda?K,?Shiue?T-W,?Hung?C-H,?Liaw?W-F,?Chen?P-Y,Wang?Y-M.?Sensitivity?evaluation?of?rhodamine?B?hydrazide?towards?nitric?oxide?and?its?application?for?macrophage?cells?imaging.?Anal?Chim?Acta?2011;708:141-8.
Concrete operations are: in 100 mL there-necked flasks, 2 g rhodamine Bs (RB) are dissolved in to 25 mL ethanol, stir 10 min, with dropping funnel, slowly add 6 mL hydrazine hydrates, stir 10 min again, be then heated to back flow reaction 6 h, reaction finishes, reaction solution cool to room temperature, rotary evaporation is removed ethanol and is obtained crude product.Crude product is dispersed in 50 mL deionized waters, filters, filter cake washes with water, and 50 ℃ of vacuum-dryings obtain yellowish pink pressed powder 1.27 g, and productive rate is: 66.9%.
Embodiment bis-: the preparation of spectral probe RNBD
At lucifuge and N
2under protective condition, take acetonitrile as solvent, with anhydrous K
2cO
3for acid binding agent, rhodamine hydrazides (RBH), acid binding agent and the chloro-7-of 4-nitro-2, the mol ratio n (RBH) of 1,3-benzo oxa-oxadiazoles (NBD-Cl): n (acid binding agent): n (NBD-Cl)=1:1:1.First RBH is dissolved in acetonitrile in 100 mL there-necked flasks, stirs 10 min, then by anhydrous K
2cO
3after being distributed in acetonitrile with NBD-Cl, slowly join in RBH solution, stirring reaction 36 h at 25 ℃, reaction solution rotary evaporation is removed to acetonitrile, residuum is first dispersed in deionized water, then use dichloromethane extraction, get organic phase, with anhydrous sodium sulfate drying, remove by filter sodium sulfate, filtrate rotary evaporation removes desolventizing and obtains crude product.Crude product is by silica gel column chromatography (eluent is ethyl acetate/petroleum ether, volume ratio 1:5), and hexanaphthene washs to obtain orange red pressed powder RNBD, and productive rate is 37.4%.
IR?(KBr)?cm
-1:?3453?(NH),?2971,?2927?(CH3,?CH2),?1710?(C=O),?1632?(C=N),?1613,?1515?(ArH),?1550?(NO2),?1119?(C-O-C).
?1H?NMR?(CDCl
3,?400?MHz):?
δ?ppm?8.12?(d,?
J=8.4?Hz,?1H,?ArH),?8.04?(d,?
J=7.6?Hz,?1H,?ArH),?7.69?(t,?
J=7.4?Hz,?1H,?ArH),?7.63?(t,?
J=7.4?Hz,?1H,?ArH),?7.33?(d,
?J=7.6?Hz,?1H,?ArH),?7.04?(s,?1H,?ArH),?6.54?(d,
?J=8.4?Hz,?2H,?ArH),?6.34?(d,
?J=8.4?Hz,?2H,?ArH),?6.21?(s,?2H,?ArH),?6.03?(d,
?J=8.8?Hz,?1H,?NH),?3.30?(d,?
J=6.8?Hz,?8H,?CH
2),?1.13?(t,
?J=6.6?Hz,?12H,?CH
3).?
13C?NMR?(CDCl
3,?300?MHz)?δ:?165.37,?154.36,?148.78,?143.43,?142.69,?134.74,?134.12,?129.50,?129.16,?128.30,?126.64,?124.73,?123.87,?108.13,?104.01,?102.67,?97.75,?67.49,?44.45,?12.43;?LC-MS?
m/z?calcd.?For?C
34H
33N
7O
5:620.26?[M+H]
+,?found:?620.26;?Anal.Calcd.?For?C
34H
33N
7O
5?(619.26):?C,?65.90;?H,?5.37;?N,?15.82;?found:?C,?65.48;?H,5.28;?N,?15.68.
Embodiment tri-: the preparation of spectral probe RNBD
At lucifuge and N
2under protective condition, take acetonitrile as solvent, with anhydrous K
2cO
3for acid binding agent, rhodamine hydrazides (RBH), acid binding agent and the chloro-7-of 4-nitro-2, the mol ratio n (RBH) of 1,3-benzo oxa-oxadiazoles (NBD-Cl): n (acid binding agent): n (NBD-Cl)=1.0:1.0:1.5.First RBH is dissolved in acetonitrile in 100 mL there-necked flasks, stirs 10 min, then by anhydrous K
2cO
3after being distributed in acetonitrile with NBD-Cl, slowly join in RBH solution, stirring reaction 36 h at 25 ℃, reaction solution rotary evaporation is removed to acetonitrile, residuum is first dispersed in deionized water, then use dichloromethane extraction, get organic phase, with anhydrous sodium sulfate drying, remove by filter sodium sulfate, filtrate rotary evaporation removes desolventizing and obtains crude product.Crude product is by silica gel column chromatography (eluent is ethyl acetate/petroleum ether, volume ratio 1:5), and hexanaphthene washs to obtain orange red pressed powder RNBD, and productive rate is 32.7%.
Embodiment tetra-: the preparation of spectral probe RNBD
At lucifuge and N
2under protective condition, take methylene dichloride as solvent, with anhydrous K
2cO
3for acid binding agent, rhodamine hydrazides (RBH), acid binding agent and the chloro-7-of 4-nitro-2, the mol ratio n (RBH) of 1,3-benzo oxa-oxadiazoles (NBD-Cl): n (acid binding agent): n (NBD-Cl)=1:1:1.First RBH is dissolved in methylene dichloride in 100 mL there-necked flasks, stirs 10 min, then by anhydrous K
2cO
3after being distributed in methylene dichloride with NBD-Cl, slowly join in RBH solution, stirring reaction 36 h at 25 ℃, reaction solution rotary evaporation is removed to methylene dichloride, residuum is first dispersed in deionized water, then use dichloromethane extraction, get organic phase, with anhydrous sodium sulfate drying, remove by filter sodium sulfate, filtrate rotary evaporation removes desolventizing and obtains crude product.Crude product is by silica gel column chromatography (eluent is ethyl acetate/petroleum ether, volume ratio 1:5), and hexanaphthene washs to obtain orange red pressed powder RNBD, and productive rate is 12.5%.
Embodiment five: the preparation of spectral probe RNBD
At lucifuge and N
2under protective condition; take acetonitrile as solvent; take and heavily steam triethylamine as acid binding agent; rhodamine hydrazides (RBH), acid binding agent and the chloro-7-of 4-nitro-2; the mol ratio n (RBH) of 1,3-benzo oxa-oxadiazoles (NBD-Cl): n (acid binding agent): n (NBD-Cl)=1:1:1.First RBH is dissolved in acetonitrile in 100 mL there-necked flasks, stir 10 min, after again triethylamine and NBD-Cl being distributed in acetonitrile, slowly join in RBH solution, at 25 ℃, stirring reaction 36 h, remove acetonitrile by reaction solution rotary evaporation, residuum is first dispersed in deionized water, then use dichloromethane extraction, get organic phase, with anhydrous sodium sulfate drying, remove by filter sodium sulfate, filtrate rotary evaporation removes desolventizing and obtains crude product.Crude product is by silica gel column chromatography (eluent is ethyl acetate/petroleum ether, volume ratio 1:5), and hexanaphthene washs to obtain orange red pressed powder RNBD, and productive rate is 17.8%.
Embodiment six: the preparation of spectral probe RNBD
At lucifuge and N
2under protective condition, take acetonitrile as solvent, with anhydrous K
2cO
3for acid binding agent, rhodamine hydrazides (RBH), acid binding agent and the chloro-7-of 4-nitro-2, the mol ratio n (RBH) of 1,3-benzo oxa-oxadiazoles (NBD-Cl): n (acid binding agent): n (NBD-Cl)=1:1:1.First RBH is dissolved in acetonitrile in 100 mL there-necked flasks, stirs 10 min, then by anhydrous K
2cO
3after being distributed in acetonitrile with NBD-Cl, slowly join in RBH solution, at 25 ℃, stir 10 min, then be heated to 81 ℃ of reaction 36 h, reaction solution rotary evaporation is removed to acetonitrile, and residuum is first dispersed in deionized water, then uses dichloromethane extraction, get organic phase, with anhydrous sodium sulfate drying, remove by filter sodium sulfate, filtrate rotary evaporation removes desolventizing and obtains crude product.Crude product is by silica gel column chromatography (eluent is ethyl acetate/petroleum ether, volume ratio 1:5), and hexanaphthene washs to obtain orange red pressed powder RNBD, and productive rate is 28.9%.
Embodiment seven: the preparation of spectral probe RNBD
At lucifuge and N
2under protective condition, take acetonitrile as solvent, with anhydrous K
2cO
3for acid binding agent, rhodamine hydrazides (RBH), acid binding agent and the chloro-7-of 4-nitro-2, the mol ratio n (RBH) of 1,3-benzo oxa-oxadiazoles (NBD-Cl): n (acid binding agent): n (NBD-Cl)=1:1:1.First RBH is dissolved in acetonitrile in 100 mL there-necked flasks, stirs 10 min, then by anhydrous K
2cO
3after being distributed in acetonitrile with NBD-Cl, slowly join in RBH solution, stirring reaction 72 h at 25 ℃, reaction solution rotary evaporation is removed to acetonitrile, residuum is first dispersed in deionized water, then use dichloromethane extraction, get organic phase, with anhydrous sodium sulfate drying, remove by filter sodium sulfate, filtrate rotary evaporation removes desolventizing and obtains crude product.Crude product is by silica gel column chromatography (eluent is ethyl acetate/petroleum ether, volume ratio 1:5), and hexanaphthene washs to obtain orange red pressed powder RNBD, and productive rate is 32.4%.
Embodiment eight: the preparation of spectral probe RNBD
At lucifuge and N
2under protective condition, take acetonitrile as solvent, with anhydrous K
2cO
3for acid binding agent, rhodamine hydrazides (RBH), acid binding agent and the chloro-7-of 4-nitro-2, the mol ratio n (RBH) of 1,3-benzo oxa-oxadiazoles (NBD-Cl): n (acid binding agent): n (NBD-Cl)=1:1:1.First RBH is dissolved in acetonitrile in 100 mL there-necked flasks, stirs 10 min, then by anhydrous K
2cO
3after being distributed in acetonitrile with NBD-Cl, slowly join in RBH solution, stirring reaction 36 h at 25 ℃, by reaction solution centrifuging disgorging, filtrate rotary evaporation is removed acetonitrile solvent and is obtained crude product.Crude product is by silica gel column chromatography (eluent is ethyl acetate/petroleum ether, volume ratio 1:5), and hexanaphthene washs to obtain orange red pressed powder RNBD, and productive rate is 31.5%.
Embodiment nine: the preparation of spectral probe RNBD
At lucifuge and N
2under protective condition, take acetonitrile as solvent, with anhydrous K
2cO
3for acid binding agent, rhodamine hydrazides (RBH), acid binding agent and the chloro-7-of 4-nitro-2, the mol ratio n (RBH) of 1,3-benzo oxa-oxadiazoles (NBD-Cl): n (acid binding agent): n (NBD-Cl)=1:1:1.First RBH is dissolved in acetonitrile in 100 mL there-necked flasks, stirs 10 min, then by anhydrous K
2cO
3after being distributed in acetonitrile with NBD-Cl, slowly join in RBH solution, stirring reaction 36 h at 25 ℃, reaction solution rotary evaporation is removed to acetonitrile, residuum is first dispersed in deionized water, then use dichloromethane extraction, get organic phase, with anhydrous sodium sulfate drying, remove by filter sodium sulfate, filtrate rotary evaporation removes desolventizing and obtains crude product.Crude product is by silica gel column chromatography (eluent is ethyl acetate/petroleum ether, volume ratio 1:5), and petroleum ether obtains orange red pressed powder RNBD, and productive rate is 29.3%.
Embodiment ten: the preparation of spectral probe RNBD
At lucifuge and N
2under protective condition, take acetonitrile as solvent, with anhydrous K
2cO
3for acid binding agent, rhodamine hydrazides (RBH), acid binding agent and the chloro-7-of 4-nitro-2, the mol ratio n (RBH) of 1,3-benzo oxa-oxadiazoles (NBD-Cl): n (acid binding agent): n (NBD-Cl)=1:1:1.First RBH is dissolved in acetonitrile in 100 mL there-necked flasks, stirs 10 min, then by anhydrous K
2cO
3after being distributed in acetonitrile with NBD-Cl, slowly join in RBH solution, stirring reaction 36 h at 25 ℃, reaction solution rotary evaporation is removed to acetonitrile, residuum is first dispersed in deionized water, then use dichloromethane extraction, get organic phase, with anhydrous sodium sulfate drying, remove by filter sodium sulfate, filtrate rotary evaporation removes desolventizing and obtains crude product.Crude product is by silica gel column chromatography (eluent is ethanol/methylene, volume ratio 1:20), and hexanaphthene washs to obtain orange red pressed powder RNBD, and productive rate is 28.9%.
Embodiment 11: RNBD is to Cu
2+selectivity and sensitivity
Fig. 1 and Fig. 2 be containing with RBND (the 1 μ M) acetonitrile/water of metal ion (10 μ M) not (1/1, v/v) ultraviolet-visible absorption spectroscopy of solution and fluorescence spectrum.As seen from Figure 1, in numerous ions, only has Cu
2+the absorption spectrum that makes RBND disappears at the absorption peak of 480 nm left and right, and occurs a new absorption peak in 560 nm left and right, and absorbancy strengthens greatly, so the absorption spectrum of RBND is to Cu
2+there are very high selectivity and sensitivity.As can be seen from Figure 2, in numerous ions, also only has Cu
2+the fluorescence of RBND is strengthened greatly, and the fluorescence spectrum of visible RBND is to Cu
2+also there are very high selectivity and sensitivity.Therefore RBND can be used as highly selective and highly sensitive Cu
2+colorimetric probe and fluorescent probe.
Embodiment 12: RNBD is to Fe
3+selectivity and sensitivity
Fig. 3 and Fig. 4 be containing with RBND (the 5 μ M) acetonitrile/water of metal ion (50 μ M) not (1/99, v/v) ultraviolet-visible absorption spectroscopy of solution and fluorescence spectrum.As seen from Figure 3, Cu
2+, Pb
2+, Mn
2+, Cr
3+can make the absorption spectrum of RBND in the absorption peak disappearance of 450 nm left and right, and occur a new absorption peak in 560 nm left and right, so the absorption spectrum of RBND is poor to the selectivity of ion.But, as seen from Figure 4, only have Fe
3+can make the fluorescence of RBND greatly strengthen, so the fluorescence spectrum of RBND is to Fe
3+have good selectivity and sensitivity, RBND can be used as highly selective and highly sensitive Fe
3+fluorescent probe.
Embodiment 13: RNBD uv-vis spectra and fluorescence spectrum are with Cu
2+the variation of concentration
From Fig. 5 and Fig. 6, can see, (1/1, v/v) absorbancy of solution and fluorescence intensity are with Cu for RNBD acetonitrile/water
2+concentration increases and strengthens, within the scope of 0 ~ 4 μ M, RNBD acetonitrile/water (1/1, near the v/v) absorbancy of solution 560 nm, and near the fluorescence intensity 570 nm and Cu
2+concentration is good linear relationship, according to these two linear relationships, can detect Cu by colorimetry and fluorescence spectroscopy
2+.
Embodiment 14: RNBD fluorescence spectrum is with Fe
3+the variation of concentration
As seen from Figure 7, (1/99, v/v) fluorescence intensity of solution is with Fe for RNBD acetonitrile/water
3+concentration increases and strengthens, within the scope of 10 ~ 90 μ M, RNBD acetonitrile/water (1/99, near v/v) fluorescence intensity and the Fe of solution 575 nm
3+concentration is good linear relationship, according to this linear relationship, can detect Fe by fluorescent spectrometry
3+.
Embodiment 15: RNBD detects Cu
2+time immunity from interference
Fig. 8 is that coexisting ion is to RNBD (1 μ M)+Cu
2+near the impact of absorbancy (10 μ M) solution 560 nm.Solvent: CH
3cN/H
2o (1/1, v/v).Fig. 9 is that coexisting ion is to RNBD (1 μ M)+Cu
2+the impact of (10 μ M) solution maximum fluorescence intensity.Solvent: CH
3cN/H
2o (1/1, v/v); Mn
2+, Co
2+, Ca
2+, Na
+, Mg
2+, Zn
2+, Ni
2+, Fe
2+, Cd
2+, Hg
2+, K
+: 10 μ M, Fe
3+, Pb
2+: 5 μ M, Fe
2+: 3 μ M, Cr
3+: 2 μ M, excitation wavelength: 500 nm, slit width: 5 nm.
From Fig. 8 and Fig. 9, a certain amount of Na
+, K
+, Ca
2+, Mg
2+, Fe
3+, Zn
2+, Cr
3+, Pb
2+, Ni
2+, Fe
2+, Mn
2+, Co
2+, Cd
2+, Hg
2+multiple coexistent metallic ion is to RNBD+Cu
2+acetonitrile/water (1/1, v/v) near the impact of the fluorescence intensity of solution near the absorbancy 560 nm and 570 nm is little, and therefore, multiple coexistent metallic ion is to RNBD colorimetric and fluoroscopic examination Cu
2+significantly do not disturb.
Embodiment 16: RNBD detects Fe
3+time immunity from interference
Figure 10 is that coexisting ion is to RNBD (5 μ M)+Fe
3+the impact of (50 μ M) solution maximum fluorescence intensity.
Solvent: CH
3cN/H
2o (1/99, v/v); Cr
3+, Pb
2+, Ni
2+: 50 μ M, Ca
2+, Na
+, Mg
2+, K
+: 25 μ M, Mn
2+, Co
2+, Zn
2+, Fe
2+, Cd
2+: 10 μ M, Cu
2+: 5 μ M, Hg
2+: 2 μ M, excitation wavelength: 500 nm, slit width: 5 nm.
As can be seen from Figure 10, a certain amount of Na
+, K
+, Ca
2+, Mg
2+, 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 RNBD+Fe
3+acetonitrile/water (1/99, v/v) near the impact of the fluorescence intensity of solution 575 nm is little, therefore, multiple coexistent metallic ion to RNBD as Fe
3+the behavior of fluorescent probe is not significantly disturbed.
Embodiment 17: the pH susceptibility of RNBD
Figure 11 is that pH value is to RNBD (1 μ M) and RNB (1 μ M)+Cu
2+(10 μ M) CH
3cN/H
2o (1/1, near the v/v) impact of maximum absorbance solution 560.
Figure 12 is that pH value is to RNBD (1 μ M) and RNB (1 μ M)+Cu
2+(10 μ M) CH
3cN/H
2o (1/1, the v/v) impact of solution maximum fluorescence intensity.Excitation wavelength: 500 nm, slit width: 5 nm.
Figure 13 is that pH value is to RNBD (5 μ M) and RNBD (5 μ M)+Fe
3+(50 μ M) CH
3cN/H
2o (1/99, the v/v) impact of solution maximum fluorescence intensity.Excitation wavelength: 500 nm, slit width: 5 nm.
From Figure 11,12 and 13, along with the increase of pH value, RNBD (1 μ M) and RNBD (1 μ M)+Cu
2+the CH of (10 μ M)
3cN/H
2o (1/1, v/v) solution, RNBD (5 μ M) and RNBD (5 μ M)+Fe
3+the CH of (50 μ M)
3cN/H
2(1/99, v/v) maximum absorbance of solution and fluorescence intensity slightly reduce O.But, within the scope of very wide pH value, before adding maximum absorbance after ion and fluorescence intensity (curve b) and adding ion, (a) compare and all keep significantly distinguishing, so RNBD goes for Cu in multiple acid-basicity system by curve with fluorescence intensity for corresponding maximum absorbance
2+and Fe
3+detection.
Claims (10)
1. a Rhodamine Derivatives, is characterized in that, structural formula is shown below:
。
2. the preparation method of Rhodamine Derivatives described in claim 1, is characterized in that: under acid binding agent exists, by rhodamine hydrazides and the chloro-7-of 4-nitro-2, the reaction of 1,3-benzo oxa-oxadiazoles prepares.
3. the preparation method of Rhodamine Derivatives according to claim 2, is characterized in that: reaction is at lucifuge and N
2under protective condition, take acetonitrile, tetrahydrofuran (THF) or methylene dichloride carries out as solvent.
4. the preparation method of Rhodamine Derivatives according to claim 3, it is characterized in that: first rhodamine hydrazides is dissolved in solvent, stir 10 minutes, again by acid binding agent and the chloro-7-of 4-nitro-2, after 1,3-benzo oxa-oxadiazoles is distributed in homogeneous solvent, slowly join in rhodamine hydrazides solution, stir 10 minutes again, then at 25～81 ℃, react 12～72 hours, cooling rear centrifuging or extraction obtain crude product; Crude product is separated by silicagel column, then obtains required Rhodamine Derivatives with sherwood oil or hexanaphthene washing purifying.
5. the preparation method of Rhodamine Derivatives according to claim 2, is characterized in that: described acid binding agent is selected from anhydrous K
2cO
3, triethylamine or DIPEA.
6. the preparation method of Rhodamine Derivatives according to claim 2, is characterized in that: the chloro-7-of rhodamine hydrazides, acid binding agent and 4-nitro-2, the mol ratio of 1,3-benzo oxa-oxadiazoles is 1.0: 1.0: (1.0 ~ 1.5).
Described in claim 1 Rhodamine Derivatives as Cu
2+the application of probe.
8. application according to claim 7, is characterized in that: detection solution is CH
3cN/H
2o, volume ratio is that 1: 1, concentration are 1 μ M.
Described in claim 1 Rhodamine Derivatives as Fe
3+the application of probe.
10. application according to claim 9, is characterized in that: detection solution is CH
3cN/H
2o, volume ratio is that 1: 99, concentration are 5 μ M.
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| CN103421015B (en) * | 2013-07-16 | 2015-08-12 | 安徽大学 | Switch type ferric ion fluorescent probe and preparation method thereof |
| CN103570736B (en) * | 2013-11-05 | 2015-06-10 | 苏州大学 | Rhodamine-oxadiazole derivative and preparation method and application thereof |
| CN104262378B (en) * | 2014-08-28 | 2017-05-03 | 中国人民解放军第二军医大学 | Silicon-based rhodamine derivative, preparation method and applications thereof |
| 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 |
| CN104949949B (en) * | 2015-06-26 | 2017-12-12 | 华南师范大学 | Compound and preparation method and application containing rhodamine group and benzofuraxan group |
| CN105784655A (en) * | 2016-03-14 | 2016-07-20 | 上海电力学院 | Method for detecting concentration of iron ions in bioleaching system |
| CN106011217B (en) * | 2016-05-19 | 2019-07-16 | 苏州大学 | Application of the compound based on rhodamine B and aminoethyl thioether in living cells imaging |
| CN108636387B (en) * | 2018-07-13 | 2021-01-05 | 武汉工程大学 | Iron ion adsorption sponge and preparation method and application thereof |
| CN111848544B (en) * | 2020-08-03 | 2022-03-04 | 首都医科大学 | Amino acid derivative capable of being traced by fluorescence and preparation method and application thereof |
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| EP0098151A2 (en) * | 1982-06-29 | 1984-01-11 | Mita Industrial Co. Ltd. | Heat-sensitive black recording element |
| EP1972327A1 (en) * | 2007-03-20 | 2008-09-24 | L'Oreal | Use of a composition for dyeing keratinous fibres comprising a halochromic compound and/or the dye corresponding to this compound |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0098151A2 (en) * | 1982-06-29 | 1984-01-11 | Mita Industrial Co. Ltd. | Heat-sensitive black recording element |
| EP1972327A1 (en) * | 2007-03-20 | 2008-09-24 | L'Oreal | Use of a composition for dyeing keratinous fibres comprising a halochromic compound and/or the dye corresponding to this compound |
| 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 |
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