CN108424419A - A kind of double 1,2,3- triazoles rhodamine 6G class fluorescence probes of chain and its preparation and application - Google Patents

A kind of double 1,2,3- triazoles rhodamine 6G class fluorescence probes of chain and its preparation and application Download PDF

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CN108424419A
CN108424419A CN201810279079.4A CN201810279079A CN108424419A CN 108424419 A CN108424419 A CN 108424419A CN 201810279079 A CN201810279079 A CN 201810279079A CN 108424419 A CN108424419 A CN 108424419A
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王宇光
朱冰春
叶秋娟
王捍东
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Zhejiang University of Technology ZJUT
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Abstract

The invention discloses a kind of double 1,2, the 3 triazole rhodamine 6G class fluorescence probes of chain and its preparation and application, and the probe that the present invention synthesizes is to Fe3+With efficiently single-minded selectivity, Fe can be identified by color change and change in fluorescence3+, can be applied to the Fe in environmental water sample3+Detection.Detecting probe method of the present invention, which measures ferric ion concentration, has the characteristics that small error, high sensitivity, accuracy are high, especially in the ferric ion of low concentration, more shows superior sensitivity and accuracy.The characteristic place that the present invention designs the probe of synthesis is that receptor synthetic route is short, simple to operation, and to Fe3+Recognition effect it is ideal, its qualitative is applied to preliminary Fe in environmental water sample3+Detection, can also quantify to measure the Fe in water sample3+.It can be further applied in environment and biosystem to Fe in the future3+Detection.

Description

A kind of double 1,2,3- triazoles rhodamine 6G class fluorescence probes of chain and its preparation and application
(1) technical field
The present invention relates to a kind of double 1,2,3- triazoles rhodamine 6G class fluorescence probes of chain and its preparation and application.
(2) background technology
Rhodamine (Rhodamine) is a kind of catechol fluorochrome, and there are one oxa-s for its tool from a structural point Anthracene nucleus, molecule have rigid plane, stability is good, and with it is multiple can decorating site, it is small by sample interference；Its fluorescence is most Big transmitting is located at 500-700nm i.e. red visible region, and molar absorption coefficient is big, and quantum yield is high.Just because of sieve Red bright superior optical physics and photostability, it is in laser dye, fluorescence scale, coloring agent；It repaiies on the surface of nanometer polymer Decorations, the structure of particle and dynamic studies, single molecular imaging and bio-imaging etc. application are quite extensive.
Essential trace element of the iron as body burden, is present in multiple proteins and enzyme, is hemoglobin, blood red The important composition ingredient of plain, many enzymes and immune system compound etc.；The transport and storage of oxygen are participated in, and directly participates in energy Release；Promote human development；Increase the resistance to disease；Tissue respiration is adjusted, fatigue is prevented.Iron ion itself is in fact not With toxicity, but if taking in or may also lead to iron poisoning when wrongly taking excessive iron compound.And with social industrial progress Aggravation, iron ion content present in environment increases therewith, and enters human body by all means, endangers human health.Cause This, the probe of design synthesis detection ferric ion has important application value.
(3) invention content
It is an object of the present invention to provide the double 1,2,3- triazoles rhodamine 6G class fluorescence probe of chain shown in a kind of formula (IV) and its Nitrine alkane and rhodamine 6G are carried out cyclic coupling by preparation and application by click reactions, and alkane chain is linker by Luo Dan Bright 6G is connected to both ends, has synthesized the double 1,2,3-triazoles rhodamine 6G class fluorescence probes of chain, and unique using this probe molecule " on-off " mechanism, identifies and detects Fe3+.This method synthetic route is short, simple to operation, and to Fe3+Recognition effect it is good, It can effectively detect Fe in environmental water sample3+Content.
The technical solution adopted by the present invention is：
The double 1,2,3-triazoles rhodamine 6G class fluorescence probes of chain shown in a kind of formula (IV) of present invention offer,
In formula (IV), R is one of following：CH2、CH2CH2、CH2CH2CH2CH2、CH2CH2CH2CH2CH2、 CH2CH2CH2CH2CH2CH2、CH2CH2OCH2CH2。
The present invention provides a kind of preparation method of the double 1,2,3-triazoles rhodamine 6G class fluorescence probes of the chain, the method For：Using compound is raw material shown in compound shown in formula (II) and formula (III), with Cu+As catalyst, in tetrahydrofuran, 40-60 DEG C after the reaction was complete, reaction solution is isolated and purified, and obtains the double 1,2,3-triazoles rhodamine 6G class fluorescence of chain shown in formula (IV) Probe；
In formula (III), R is one of following：CH2、CH2CH2、CH2CH2CH2CH2、CH2CH2CH2CH2CH2、 CH2CH2CH2CH2CH2CH2、CH2CH2OCH2CH2。
Further, the ratio between the amount of substance that feeds intake of compound shown in compound shown in the formula (II) and formula (III) is 2.2: 1, for the catalyst amount with the gauge of Cu substances, the ratio between the Cu and the amount of combinations of materials shown in formula (III) are 1.2：1； The tetrahydrofuran volumetric usage is calculated as 44mL/mmol with the amount of combinations of materials shown in formula (III).
Further, the method that reaction solution isolates and purifies：After the reaction was complete, reaction solution is concentrated to dryness, is then added water-soluble Solution, dichloromethane are extracted (3 × 50mL), merge organic phase, then wash (2 × 100mL), nothing with saturated sodium-chloride water solution Water magnesium sulfate is dried, filtering, and thin-layer chromatography (CH is carried out after filtrate decompression solvent evaporated3OH:CH2Cl2=1:20, v/v be expansion Agent), the component of Rf values 0.4-0.5 is collected, the double 1,2,3-triazoles rhodamine 6G class fluorescence probes of chain shown in formula (IV) are obtained.
Further, compound shown in the formula (II) is prepared as follows：With formula (I) compound represented and propargylamine For raw material, in methyl alcohol, back flow reaction is complete, and reaction solution post-processing obtains compound shown in formula (II)；Chemical combination shown in formula (I) Feed intake the ratio between the amount of substance of object and propargylamine is 1:5；Methanol volumetric usage is calculated as with the amount of combinations of materials shown in formula (I) 20mL/mmol；
Further, reaction solution post-processing approach is：After the reaction was complete, reaction solution is concentrated to dryness, water dissolution is then added, Dichloromethane is extracted (3 × 50mL), merges organic phase, then washed (2 × 100mL) with saturated sodium-chloride water solution, anhydrous Magnesium sulfate is dried, filtering, and thin-layer chromatography (CH is carried out after filtrate decompression solvent evaporated3OH:CH2Cl2=1:20, v/v be expansion Agent), the component of Rf values 0.4-0.5 is collected, compound shown in formula (II) is obtained.
The present invention also provides a kind of double 1,2,3- triazoles rhodamine 6G class fluorescence probes of chain in detection Fe3+In answer With such fluorescence probe can be with Fe in Visual retrieval environmental water sample3+。
On the one hand, probe of the present invention can be with qualitative detection Fe3+, the application is：Sample to be tested is added and contains body In the PBS buffer solution of pH=6.5,10mM of product 50% acetonitrile of concentration, the double 1,2,3-triazoles rhodamines of 5 μm of ol/mL chains are added 6G class fluorescence probe acetonitrile solutions, it is to be measured if there is color to generate (color change can be generated in usually at room temperature 5-50min) Sample contains Fe3+。
On the other hand, probe of the present invention can quantify detection Fe3+, the application is：Sample to be tested addition is contained In the PBS buffer solution of pH=6.5,10mM of 50% acetonitrile of volumetric concentration, the double 1,2,3-triazoles Luo Dan of 5 μm of ol/mL chains are added After bright 6G classes fluorescence probe acetonitrile solution, fluorescent value is measured at 555nm, according to Fe3+Standard curve obtains in sample to be tested Fe3+Concentration；The sample to be tested is 1 with PBS buffer solution volume ratio:1, the sample to be tested is with probe acetonitrile solution volume ratio 10:1；The Fe3+Standard curve is under the same conditions with Fe3+Concentration of aqueous solution is abscissa, using fluorescent value as ordinate system At.
Further, the Fe3+Standard curve is prepared as follows：It is 0,0.01,0.05,0.5,1 by concentration gradient, The Fe of 1.5,2,2.5,3,3.5,4.5,5,5.5,6,6.5,7,7.5 μm of ol/mL3+Aqueous solution is separately added into containing volumetric concentration 50% In the PBS buffer solution of pH=6.5,10mM of acetonitrile, adds the double 1,2,3-triazoles rhodamine 6G class fluorescence of 5 μm of ol/mL chains and visit After needle acetonitrile solution, fluorescent value is measured at 555nm, with Fe3+A concentration of abscissa obtains Fe using fluorescent value as ordinate3+ Standard curve；The Fe3+Aqueous solution is 1 with PBS buffer solution volume ratio:1, the Fe3+Aqueous solution and probe acetonitrile solution volume Than being 10:1.
Compared with prior art, the beneficial effects are mainly as follows：(1) present invention successfully designs and synthesizes A kind of double 1,2,3- triazole rhodamine 6G class probes of chain shown in novel formula (IV)；(2) probe that the present invention synthesizes is to Fe3+Tool There is efficiently single-minded selectivity, can identify Fe by color change and change in fluorescence3+.(3) present invention passes through the double 1,2,3- of chain Triazole rhodamine 6G analog derivative probe identifies probe the recognition capability of metal ion and such probe different chain length Fe3+Ability whether have an impact etc. and to have carried out experiment and compare, analyze its structure-activity relationship, it is found that the alkane chain of five carbochains can be with The best spatial location of ferric ion and probe complexing is provided, and if can impact effect with the presence of oxonium ion in alkane chain.(4) The probe that the present invention synthesizes can be applied to the Fe in environmental water sample3+Detection.(5) detecting probe method of the present invention measure ferric iron from Sub- concentration has the characteristics that small error, high sensitivity, accuracy are high, more aobvious especially in the ferric ion of detection low concentration Superior sensitivity and accuracy are shown.The characteristic place that the present invention designs the probe of synthesis is that synthetic route is short, simple easy Operation, and to Fe3+Recognition effect it is ideal, its qualitative is applied to preliminary Fe in environmental water sample3+Detection, can also determine It measures to measure the Fe in water sample3+.It can be further applied in environment and biosystem to Fe in the future3+Detection.
(4) it illustrates
Fig. 1 is fluorescent probe compounds IV -4 and Fe in the embodiment of the present invention 93+The front and back solution colour of effect changes (A： Under fluorescence；B：For naked eyes as it can be seen that wherein left side is the variation of IV -4 solution colour of fluorescent probe compounds, right side is compound IV -4 and Fe3+Solution colour changes after effect).
Fig. 2 is the UV absorption spectrogram of IV -4 pair of each metal ion of fluorescent probe compounds in the embodiment of the present invention 9, a For uv-visible absorption spectra, abscissa is wavelength (nm), and ordinate is ultraviolet absorption value OD values.B is each metal ion Ultraviolet absorption value column diagram at 555nm.
Fig. 3 is the fluorescence intensity spectrogram of IV -4 pair of each metal ion of fluorescent probe compounds in the embodiment of the present invention 9.a For fluorescence intensity spectrogram, abscissa is wavelength (nm), and ordinate is fluorescence intensity.B is each metal-ion fluorescent strength bars.
Fig. 4 is the fluorescence intensity and IV -4+Fe of the fluorescent probe compounds IV -4 of the present invention3+The fluorescence of ionic complex The fluorescent emission figure (555nm) that intensity changes with pH respectively.Abscissa is pH, and ordinate is fluorescence intensity.
Fig. 5 is IV 1-6 of fluorescent probe compounds in the embodiment of the present invention 8 to Fe3+The fluorescence intensity change of recognition capability Fluorescent emission figure.Abscissa is wavelength (nm), and ordinate is fluorescence intensity.
Fig. 6 is the IV -4+Fe of fluorescent probe compounds in the embodiment of the present invention 113+The fluorescence intensity of ionic complex is distinguished The fluorescent emission figure (555nm) changed over time.Abscissa is Time (min), and ordinate is fluorescence intensity.
Fig. 7 is the IV -4+ metal ion complexes (IV -4+ of fluorescent probe compounds in the embodiment of the present invention 12 Metalions) with IV -4+Fe3++ metal ion complex (IV -4+metalions+Fe3+) fluorescence intensity compare block diagram (555nm).Abscissa is metal ion, and ordinate is fluorescence intensity.
Fig. 8 is fluorescent probe compounds IV -4 and various concentration Fe in the embodiment of the present invention 133+(0-30 times is measured) it is glimmering Intensity variation figure (a) abscissa is wavelength (nm), and ordinate is fluorescence intensity and Fe3+Concentration and fluorescence intensity variation line Property figure (b).
Fig. 9 is the IV -4+Fe of fluorescent probe compounds in the embodiment of the present invention 133+Job ' the s plot of ionic complex are bent Line chart, abscissa are [Fe3+]/[Fe3+]+[IV -4], ordinate is ultraviolet absorption value OD values.
Figure 10 is fluorescent probe compounds IV -4 and Fe in the embodiment of the present invention 153+The reversible experiment fluorescence intensity Variation diagram.Abscissa is wavelength (nm), and ordinate is fluorescence intensity.
Figure 11 is fluorescent probe compounds IV -4 and Fe in the embodiment of the present invention 153+Recognition mechanism figure.
Figure 12 is various concentration Fe in IV -4 environment-identification water sample of fluorescent probe compounds in the embodiment of the present invention 163+'s The visual variation diagram of solution colour, from left to right Fe in figure3+Solution concentration is followed successively by 0,0.05,5.0,10.0mM.
(5) specific implementation mode
Ultra-pure water of the present invention refers to the distilled water that deionized water passes through that single flash obtains, and the room temperature is 25-30 ℃.With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited to that：
Embodiment 1：The synthesis of compound (II)
Rhodamine 6g (compound I) (1.25mmol, 1.0eq, 0.6g) is dissolved in the methanol reagent (analysis level) of 25mL, complete Bronzing is presented in solution after fully dissolved, then propargylamine (6.25mmol, 5.0eq, 0.34g) is added dropwise, and after completion of dropwise addition, is heated to reflux It reacts for 24 hours, reaction process TLC trace detections.Rotary Evaporators solvent evaporated is used after the reaction was complete, and 30mL water is then added, Dichloromethane is extracted (3 × 50mL), merges organic phase, then washed (2 × 100mL) with saturated sodium-chloride water solution, anhydrous Magnesium sulfate is dried, filtering, and filtrate decompression solvent evaporated carries out thin-layer chromatography (CH afterwards3OH:CH2Cl2=1:20, v/v be expansion Agent), the component that Rf is 0.4-0.5 is collected, it is dry, obtain compound II.
Compound II (pink solid, yield 65%) MS (ESI):M/z=452.2 [M+H]+DEG C .mp=259-261 .1H NMR(600MHz,CDCl3)δ8.02–7.88(m,1H),7.48–7.37(m,2H),7.11–7.02(m,1H),6.36(s, 2H), 6.28 (s, 2H), 3.93 (d, J=2.5Hz, 2H), 3.53 (dd, J=45.2,5.3Hz, 2H), 3.29-3.14 (m, 4H), 1.90 (s, 6H), 1.81-1.73 (m, 1H), 1.32 (t, J=7.2Hz, 6H)13C NMR(150MHz,CDCl3)δ167.63, 154.02,151.86,147.50,132.71,130.25,128.81,128.01,123.76,123.08,117.73,105.46, 96.60,78.37,77.28,77.03,76.78,70.05,64.99,38.40,28.65,16.66,14.76.IRνmax(cm-1): 3442.53,3278.00,2964.43,2929.15,2870.13,1704.041621.33,1517.19,1446.13, 1383.59,1158.70,938.78,811.98,664.70.
Embodiment 2：The synthesis of compound (IV -1)
Compound II (0.1mmol, 2.2eq, 0.04g) is dissolved in the anhydrous tetrahydro furan of 20mL, and compound III-1 is added (1.0eq), with Cu+As catalyst (cupric sulfate pentahydrate (1.2eq) is added and VC (1.2eq) generates Cu+(1.2eq).Reaction exists 55 DEG C or so progress 8-12h, reaction process TLC trace detections.After the reaction was complete, reaction solution is concentrated to dryness, and is then added 30mL water, dichloromethane extract (3 × 50mL), merge organic phase, then wash (2 × 100mL), nothing with saturated sodium-chloride water solution Water magnesium sulfate is dried, filtering, filtrate decompression solvent evaporated, thin-layer chromatography (CH3OH:CH2Cl2=1:20, v/v be solvent), it receives Integrate Rf as the component of 0.4-0.5, drying obtains target product IV -1.
Compound IV -1 (white solid, yield 35%) MS (ESI):M/z=1001.5 [M+H]+.mp=259-261 ℃.1H NMR(600MHz,CDCl3)δ8.07–7.94(m,2H),7.55–7.33(m,4H),7.17(s,1H),7.14–6.98 (m, 2H), 6.94-6.86 (m, 1H), 6.32 (s, 1H), 6.28 (d, J=6.0Hz, 1H), 6.18-6.06 (m, 2H), 5.86 (s, 1H), 5.79 (d, J=11.4Hz, 1H), 5.32 (d, J=17.7Hz, 2H), 4.56 (s, 1H), 4.47 (s, 1H), 3.28-3.12 (m, 6H), 2.97 (t, J=16.0Hz, 2H), 1.88-1.80 (m, 6H), 1.61 (s, 12H), 1.31 (t, J=7.1,4.8Hz, 6H), 1.23 (dd, J=13.7,6.5Hz, 6H)13C NMR(150MHz,CDCl3)δ168.10,153.82,152.70, 151.73,147.28,144.10,132.65,130.62,128.43,128.03,123.80,123.62,122.92,117.60, 115.85,105.58,96.60,77.24,77.03,76.82,66.95,65.15,49.14,38.35,35.14,29.70, 16.64,16.56,14.75.IRνmax(cm-1):3440.66,2968.25,1621.43,1517.46,1421.56,1269.83, 1216.44,1093.80,877.48,700.58,655.77.
Embodiment 3：The synthesis of compound (IV -2)
Compound II (0.1mmol, 2.2eq, 0.04g) is dissolved in the anhydrous tetrahydro furan of 20mL, and compound III-2 is added (1.0eq), with Cu+As catalyst (cupric sulfate pentahydrate (1.2eq) is added and VC (1.2eq) generates Cu+).Other same embodiments 2, obtain target product IV -2.
Compound IV -2 (white solid, yield 40%) MS (ESI):M/z=1015.5 [M+H]+.1H NMR (600MHz,CDCl3) δ 7.94 (dd, J=9.6,3.7Hz, 2H), 7.52-7.41 (m, 4H), 7.27 (d, J=6.4Hz, 1H), 7.04 (t, J=5.7Hz, 2H), 6.70 (d, J=6.2Hz, 2H), 6.30 (d, J=6.0Hz, 4H), 6.08 (d, J=5.6Hz, 4H), 4.42 (d, J=5.9Hz, 2H), 4.32 (d, J=6.1Hz, 2H), 3.22-3.12 (m, 8H), 1.83 (d, J=5.7Hz, 12H), 1.28 (dd, J=13.4,6.9Hz, 15H)13C NMR(150MHz,CDCl3)δ167.63,154.01,151.83, 147.49,132.73,130.22,128.79,128.01,123.75,123.07,117.73,105.40,96.58,78.35, 77.26,77.05,76.84,70.06,64.98,38.39,29.71,28.64,16.68,14.76.IRνmax(cm-1): 3397.93,2967.70,1689.81,1620.99,1518.51,1384.09,1270.71,1217.46,1141.17, 1092.13,1014.56,875.81,738.93,689.08,540.26.
Embodiment 4：The synthesis of compound (IV -3)
Compound II (0.1mmol, 2.2eq, 0.04g) is dissolved in the anhydrous tetrahydro furan of 20mL, and compound III-3 is added (1.0eq), with Cu+As catalyst (cupric sulfate pentahydrate (1.2eq) is added and VC (1.2eq) generates Cu+).Other same embodiments 2, obtain target product IV -3.
Compound IV -3 (faint yellow solid, yield 40%) MS (ESI):M/z=1043.3 [M+H]+.
1H NMR(600MHz,CDCl3)δ7.98–7.92(m,2H),7.49–7.42(m,4H),7.09–7.03(m,2H), 7.01 (d, J=21.3Hz, 2H), 6.34 (d, J=21.1Hz, 4H), 6.06 (d, J=31.8Hz, 4H), 4.44 (s, 4H), 4.15-4.07 (m, 4H), 3.29 (t, J=6.6Hz, 4H), 3.20 (dd, J=7.2,4.0Hz, 4H), 1.83 (s, 12H), 1.51 (dt, J=10.1,6.6Hz, 4H), 1.34-1.30 (m, 12H)13C NMR(150MHz,CDCl3)δ168.07,153.67, 151.84,147.32,144.33,132.64,130.76,128.46,128.07,123.85,122.93,122.17,117.56, 105.68,96.63,77.25,77.04,76.82,65.18,50.67,49.11,38.36,35.27,27.26,25.83, 16.61,14.75.IRνmax(cm-1):3427.73,2968.69,269.42,2097.17,1620.87,1518.23, 1421.34,1384.02,1269.56,1158.01,1091.99,1014.16,920.76,774.84.
Embodiment 5：The synthesis of compound (IV -4)
Compound II (0.1mmol, 2.2eq, 0.04g) is dissolved in the anhydrous tetrahydro furan of 20mL, and compound III-4 is added (1.0eq), with Cu+As catalyst (cupric sulfate pentahydrate (1.2eq) is added and VC (1.2eq) generates Cu+).Other same embodiments 2, obtain target product IV -4.
Compound IV -4 (whitewash solid, yield 45%) MS (ESI):M/z=1057.5 [M+H]+.1H NMR (600MHz,CDCl3) δ 7.95 (dd, J=6.2,2.0Hz, 2H), 7.50-7.40 (m, 4H), 7.10-6.97 (m, 4H), 6.32 (s, 4H), 6.09 (s, 4H), 4.44 (s, 4H), 4.15-3.97 (m, 4H), 3.96-3.80 (m, 4H), 3.75 (dd, J=11.2, 5.4Hz,4H),3.31–3.09(m,12H),1.86–1.78(m,16H),1.40–1.25(m,14H).13C NMR(150MHz, CDCl3)δ168.10,153.70,151.81,147.30,144.22,132.65,130.72,128.45,128.06,123.84, 122.92,122.18,117.54,105.65,104.09,96.62,77.24,77.03,76.82,67.11,66.04,65.18, 61.68,51.05,49.49,38.36,35.27,32.43,32.02,29.62,28.24,23.68,23.51,16.63, 14.75.IRνmax(cm-1):3428.86,2966.31,2095.48,1681.38,1620.92,1518.05,1420.44, 1384.36,1269.70,1201.42,1092.26,877.09,771.54.
Embodiment 6：The synthesis of compound (IV -5)
Compound II (0.1mmol, 2.2eq, 0.04g) is dissolved in the anhydrous tetrahydro furan of 20mL, and compound III-5 is added (1.0eq), with Cu+As catalyst (cupric sulfate pentahydrate (1.2eq) is added and VC (1.2eq) generates Cu+).Other same embodiments 2, obtain target product IV -5.
Compound IV -5 (pink solid, yield 40%) MS (ESI):M/z=1071.5 [M+H]+.mp=253-255 ℃.1H NMR(600MHz,CDCl3)δ8.00–7.92(m,2H),7.51–7.40(m,4H),7.09–6.95(m,4H),6.32 (s, 4H), 6.14-6.04 (m, 4H), 4.44 (s, 4H), 4.08 (dd, J=16.9,9.5Hz, 4H), 3.25 (t, J=6.8Hz, 4H),3.26–3.14(m,8H),1.88–1.79(m,12H),1.77–1.67(m,4H),1.59–1.52(m,4H),1.35– 1.28(m,12H).13C NMR(150MHz,CDCl3)δ168.09,153.71,151.80,147.30,144.16,132.64, 130.71,128.45,128.06,123.83,122.91,122.14,117.55,105.62,104.09,96.60,77.26, 77.05,76.84,67.10,66.00,65.18,61.62,51.23,49.61,38.35,35.26,32.42,32.03, 29.94,29.32,28.65,26.13,26.06,23.51,16.63,14.75.IRνmax(cm-1):3440.45,2931.24, 2094.83,1621.36,1517.74,1420.61,1269.67,1200.83,1092.00,1013.83,876.99, 812.60,743.93.
The synthesis of 7 compound of embodiment (IV -6)
Compound II (0.1mmol, 2.2eq, 0.04g) is dissolved in the anhydrous tetrahydro furan of 20mL, and compound III-6 is added (1.0eq), with Cu+As catalyst (cupric sulfate pentahydrate (1.2eq) is added and VC (1.2eq) generates Cu+).Other same embodiments 2, obtain target product IV -6.
Compound IV -6 (white solid, yield 35%) MS (ESI):M/z=1059.5 [M+H]+.mp=263-266 ℃.1H NMR(600MHz,CDCl3) δ 7.93 (dd, J=19.3,7.1Hz, 2H), 7.41-7.29 (m, 4H), 6.77 (d, J= 7.6Hz,2H),5.93(s,7H),4.27–4.17(m,4H),3.99–3.80(m,7H),3.79–3.52(m,8H),3.26– 3.04(m,8H),2.05–1.79(m,12H),1.39–1.26(m,12H).13C NMR(150MHz,CDCl3)δ166.58, 152.96,150.77,146.43,131.69,129.17,127.76,126.97,122.71,122.03,116.68,104.34, 95.51,77.30,76.20,75.99,75.78,69.02,63.91,37.35,28.68,27.60,15.65,13.72.IRνmax (cm-1):3397.93,2967.70,1689.81,1620.99,1518.51,1384.09,1270.71,1217.46, 1141.17,1092.13,1014.56,875.81,738.93,689.08,540.26.
The metalloform-selective of 8 probe IV -1~IV -6 of embodiment
(1) preparation of probe mother liquor
Accurate probe molecule powder (IV -1)~(IV -6) for weighing institute embodiment 2-7 preparations, are dissolved with chromatographic grade acetonitrile The probe acetonitrile solution of 5 μm of ol/mL is made.It is protected from light low-temperature storage.
(2) preparation of metal ion mother liquor
Inorganic salts MgSO is weighed respectively4·7H2O、KCl、CuSO4·5H2O、FeCl3、FeSO4·7H2O、MnSO4·H2O、 Al(NO3)3·9H2O、CaCl2、NaCl、AgNO3、Pb(CH3COO)2·3H2O、Co(NO3)2·6H2O、BaCl2·2H2O、Zn (CH3COO)2·2H2O、NiSO4·6H2O、CrCl3·6H2O、LiCl2·H2O、HgCl2、RuCl3, it is transferred in 10mL centrifuge tubes and uses Ultra-pure water is settled to 8mL, obtains the metal ion mother liquor of a concentration of 1.25mmol/mL, and it is Mg to correspond to ion respectively2+、K+、Cu2+、 Fe3+、Fe2+、Mn2+、Al3+、Ca2+、Na+、Ag+、Pb2+、Co2+、Ba2+、Zn2+、Ni2+、Cr3+、Li2+、Hg2+、Ru2+.It is protected from light low temperature Storage.
(3) metalloform-selective of probe IV -1~IV -6
At room temperature, in pH=6.5,10mM PBS buffer solution of 50% acetonitrile containing volumetric concentration, each probe molecule IV-is measured 1~IV -6 couple of Fe3+Selectivity.
100 μ are taken after the metal ion mother liquor of 1.25mmol/mL in step (2) is diluted to 12.5 μm of ol/mL with ultra-pure water L, is added the 100 μ L of pH=6.5,10mM PBS buffer solution of 50% acetonitrile containing volumetric concentration, then 5 μ being separately added into step (1) After 10 μ L of mol/mL probes acetonitrile solution (IV -1~IV -6), its corresponding fluorescence spectrum is measured, as a result as shown in Figure 5.
As can be seen from Figure 5 in -6 plurality of probes of compounds Ⅳ -1~IV, -4 couples of Fe of compounds Ⅳ3+Recognition capability most By force, compounds Ⅳ -2 and IV -6 couple of Fe3+Recognition capability it is most weak, this may be because in different chain length, five carbochains Alkane chain can provide the best spatial location of ferric ion and probe complexing, and if can shadow with the presence of oxonium ion in alkane chain Ring recognition effect.
The metalloform-selective of 9 probe IV -4 of embodiment
At room temperature, in pH=6.5,10mM PBS buffer solution of 50% acetonitrile containing volumetric concentration, IV -4 probe molecule is measured To the selectivity of metal ion.
By 12.5 μm of ol/mL Fe3+PH=6.5,10mMPBS of 50% acetonitrile containing volumetric concentration is added in 100 μ L of aqueous solution 100 μ L of buffer solution after adding 5 μm of 10 μ L of ol/mL probes acetonitrile solution (IV -4), measure its corresponding fluorescence property variation.Together Under the conditions of sample, by Fe3+Al is replaced with respectively3+、Mg2+、K+、Cu2+、Fe3+、Fe2+、Mn2+、Ca2+、Na+、Ag+、Pb2+、Co2+、Ba2 +、Zn2+、Ni2+、Cr3+、Li2+、Hg2+、Ru2+, solution colour changes after reaction, and the variation of UV absorption and fluorescence intensity obtains Corresponding ultra-violet absorption spectrum and fluorescence emission spectrum, it is as shown in Figure 1, Figure 2, Figure 3 shows respectively.
As can be seen from Figure 1, compounds Ⅳ -4 is in Fe3+It is preceding there is no color, Fe is added3+After, -4 solution of compounds Ⅳ becomes red Color, solution colour displaing yellow under fluorescence, and experiments have shown that Fe is added3+Other outer metal ions do not have color.From Fig. 2 and Fig. 3 In it can be seen that -4 couples of Fe of compounds Ⅳ3+There is preferable selectivity, ultra-violet absorption spectrum is in 530nm or more almost without absorption The fluorescent emission of peak and compounds Ⅳ -4 is also very weak；There is strong absorption peak at 530nm in ultraviolet-visible spectrum, and absorbs Intensity increases about 4.5 times.Select 490nm for excitation wavelength, chemical combination when measuring fluorescence spectrum according to ultra-violet absorption spectrum Object IV -4 and Fe3+Have strong fluorescence emission wavelengths at 555nm, and fluorescence intensity is greatly enhanced, it was demonstrated that compound it is interior Amide ring has already turned on.Uniquely it is worth mentioning that as the Al that identical multiple is added3+Afterwards, certain UV absorption enhancing is caused And Fluorescence Increasing, but under the same conditions, Al3+The Fluorescence Increasing of induction will be far below Fe3+Caused UV absorption and fluorescence Enhancing, this illustrates -4 couples of Fe of compounds Ⅳ3+Selectivity it is weaker by the interference of other coexisting ions, show to Fe3+Height The selectivity of effect.
Influences of the embodiment 10pH to the recognition performance of probe IV -4
In order to apply probe IV -4 in more complicated system, pH has been investigated in experimentation to Fe3+Recognition performance Influence.At room temperature, using the PBS solution of 50% acetonitrile containing volumetric concentration within the scope of pH3.5-12.0 measure probe IV -4 and IV -4+Fe of probe3+Fluorescence intensity variation.
By 12.5 μm of ol/mL Fe3+100 μ L of aqueous solution, be separately added into different pH (3.5,4.0,4.5,5.0,5.5,6.0, 6.5,7.0,7.5,8.0,8.5,9.0,9.5,10.0,10.5,11.0,11.5,12.0) 50% acetonitrile containing volumetric concentration 100 μ L of PBS buffer solution after adding 5 μm of 10 μ L of ol/mL probes acetonitrile solution (IV -4), measure its corresponding fluorescence at 555nm Value variation.To be not added with Fe under similarity condition3+Aqueous solution is as a contrast.As a result as shown in Figure 4.
Such as Fig. 4 it is shown that in pH=6.5,10mM PBS buffer solution of 50% acetonitrile containing volumetric concentration, probe IV -4 There is no Fe in solution3+In the presence of and have a Fe3+In the presence of under condition of different pH, using 490nm as excitation wavelength, record launch wavelength The variation of fluorescence intensity at 555nm.It can be seen from the figure that without Fe3+In the presence of, do not have between being 3.5 to 11.5 in pH It observes apparent change in fluorescence, illustrates that probe IV -4 itself is insensitive to pH.As addition Fe3+Afterwards, within the scope of identical pH, Probe is to Fe3+It responds different, works as pH<Fluorescence intensity is stronger when 7.0, and when pH=5.5, fluorescence intensity is most strong.When solution is When alkaline, Fe3+Weaken with the binding ability of probe IV -4, there is no apparent fluorescence.Generally speaking, probe IV -4 can be at one (pH3.5-9) is realized to Fe within the scope of wider pH3+Effective identification.In view of the environment of other ions of experimentation, So in next performance test, select pH=6.5,10mM PBS buffer solution of 50% acetonitrile containing volumetric concentration as molten Agent system.
11 probe compound of embodiment, IV -4 couple of Fe3+Time response
At room temperature, in pH=6.5,10mM PBS buffer solution of 50% acetonitrile containing volumetric concentration, probe molecule IV -4 is measured To Fe3+Recognition performance.
By 12.5 μm of ol/mLFe3+PH=6.5,10mM PBS of 50% acetonitrile containing volumetric concentration is added in 100 μ L of aqueous solution 100 μ L of buffer solution respectively in 120min, exist after adding 5 μm of 10 μ L of ol/mL probes acetonitrile solution (IV -4) every 5min Its corresponding fluorescent value variation is measured at 555nm, to determine the length of action time.As a result as shown in Figure 6.
It is found from Fig. 6, compounds Ⅳ -4 and Fe in 5min3+Reaction can generate fluorescence, and it is good to illustrate that probe itself has Good sensitivity also enhances as the time increases generated fluorescence intensity, it is strong that maximum fluorescence is reached after 45min therewith Degree, and enhance at any time, fluorescence intensity is stablized, and apparent decline is had no.This shows IV -4 couple of Fe of probe3+Identification have it is fast Response and for a long time stability of identification.This real-time monitoring is of great significance in practical applications.Therefore, it is surveyed later Trial work in making each sample be added metal ion place carry out after 30-40min it is spectrometric.
12 probe compound of embodiment, IV -4 couple of Fe3+Anti-interference experiment
At room temperature, in pH=6.5,10mM PBS buffer solution second of 50% acetonitrile containing volumetric concentration, IV -4 pair of probe molecule Fe3+Recognition performance.
Respectively by the metal ion mother liquor (Mg of 1.25mmol/mL in 8 step of embodiment (2)2+、Na+、Cu2+、K+、Al3+、 Fe2+、Ca2+、Ag+、Ba2+、Co2+、Pb2+、Zn2+、Mn2+、Ni2+、Cr3+、Fe3+、Li+、Ru2+、Hg2+) with ultra-pure water it is diluted to 12.5 100 μ L are taken after μm ol/mL, and the 100 μ L of pH=6.5,10mM PBS buffer solution of 50% acetonitrile containing volumetric concentration are added, add 5 μ After 10 μ L of mol/mL probes acetonitrile solution (IV -4), using not metal ion as blank control, fluorescence is measured at 555nm Value, is shown in grey column in Fig. 7.
12.5 μm of ol/m L Fe are added in above-mentioned each metal ion solution3+100 μ L of aqueous solution are measured at 555nm Fluorescent value is shown in black column in Fig. 7, and the comparison by measuring fluorescence intensity twice obtains the presence of its ion to Fe3+Influence.
As shown in fig. 7, the block diagram explanation of grey is in addition to iron ions, other ions will not cause strong fluorescent emission Variation, and on the basis of above-mentioned solution, add the Fe of same equivalent3+After solution, it can be seen that fluorescence intensity sharply increases (black Color column).The result shows that -4 couples of Fe of compounds Ⅳ3+Recognition reaction it is smaller by the interference of other coexisting ions, therefore, it was demonstrated that IV -4 couple of Fe3+The selectivity having had.
13 probe of embodiment, IV -4 couple of Fe3+Fluorescence titration and be complexed ratio measurement
1), IV -4 couple of Fe of probe3+Titration and fitting
At room temperature, into pH=6.5,10mM PBS buffer solution of 50% acetonitrile containing volumetric concentration, 5 μm of ol/mL is added and visit 10 μ L of needle acetonitrile solution (IV -4) carry out Fe3+Titration experiments, i.e., thereto titrate 5 μm of ol/mL Fe3+Aqueous solution is often added dropwise Complete 10 μ L measure solution first order fluorescence emission spectrum, titrate the beam titration that finishes to the 30th 10 μ L, survey 31 times altogether (i.e. to probe (IV -4) Fe is carried out3+The 0-30.0 times of titration experiments measured).As a result as shown in Figure 8.
As can be seen from Figure 8, with Fe3+The increase of concentration, fluorescent emission intensity gradually increases at 555nm, when adding Enter the Fe to 15.0 times of amount left and right3+Afterwards, reaction basically reaches saturation, and the fluorescence intensity of solution enhances unobvious.It is strong by fluorescence Degree is with Fe3+The changing rule of concentration can calculate the binding constant of complex compound, it is assumed that Fe3+And the combination ratio of compounds Ⅳ -4 1:1, following equation is pressed to the fluorescence intensity of compounds Ⅳ -4 with Fe by Origin softwares3+Concentration variation diagram carry out it is non-thread Property least square method fitting, a smoothed curve (b in Fig. 8) can be obtained, linearly dependent coefficient R values are more than 0.99, effectively Demonstrate hypothesis be set up, Fe3+And the combination ratio of compounds Ⅳ -4 is 1:1, while it is 2.25 to calculate binding constant value ×105M-1, binding constant so illustrate greatly this complex compound have preferable stability.
In formula (1), Y represents the fluorescence intensity after ion is added；Y0Represent the fluorescence intensity of organic compound；YlimGeneration The limiting value of the fluorescence intensity change after ion is added in table；CMRepresent the concentration of added metal ion；CLRepresent organic compound Concentration；Ks is binding constant.
2) probe IV -4 and Fe3+In conjunction with than measurement
In order to further illustrate IV -4 and Fe3+It is 1:1 combination, according to Fe3+Molar fraction increase and UV absorption Job ' s plot curve graphs (Fig. 9) are made in the variation of value.It can be seen that IV -4 and Fe3+Total concentration be 100 μM, work as Fe3+ Molar fraction be 0.5 when, fluorescent emission intensity reaches maximum value, this illustrates 4d and Fe3+Combination ratio be 1:1, and it is above-mentioned non- Linear fit is consistent.
Embodiment 14Fe3+The determination of concentration and the regression equation of IV -4 fluorescence intensity change relationship of probe
In order to develop the actual application value of the probe, Fe has been carried out3+Concentration and IV -4 fluorescence intensity change relationship of probe The experiment of regression equation determine that specific experiment method is：By the Fe of 1.25mmol/mL in embodiment 83+Ion mother liquor is with ultrapure Its concentration is set to be respectively 0,0.01,0.05,0.5,1,1.5,2,2.5,3,3.5,4.5,5,5.5,6,6.5,7,7.5 after water dilution μm ol/mL respectively takes 100 μ L, and the 100 μ L of pH=6.5,10mM PBS buffer solution of 50% acetonitrile containing volumetric concentration are added, add 5 After μm 10 μ L of ol/mL probes acetonitrile solution (IV -4), fluorescence intensity is measured in 555nm.According to surveyed Fe3+Ion is dense corresponding The relationship of fluorescence intensity data, obtains with Fe3+Concentration (μm ol/mL) is independent variable x, the recurrence side that fluorescence intensity is dependent variable y Journey y=251.625+2526.47x.
15 probe of embodiment, IV -4 couple of Fe3+The reversible measurement of identification
At room temperature, pH=6.5,10mM PBS buffer solution 100 the μ L, 12.5 μm of ol/mL of 50% acetonitrile containing volumetric concentration Fe3+100 μ L of aqueous solution, after 5 μm of IV -4 acetonitrile solution of ol/mL probes, 10 μ L are added, the situation of change of observing response fluorescence measures Fluorescence spectrum, curve a in the result is shown in Figure 10.Excessive ETDA complexing agents are added, the situation of change of observing response fluorescence is surveyed again Determine fluorescence spectrum, curve b in the result is shown in Figure 10.The Fe of 12.5 μm of ol/mL is finally added thereto again3+100 μ L of aqueous solution, observation The situation of change of fluorescence is reacted, fluorescence spectrum is measured, curve c in the result is shown in Figure 10.
After compounds Ⅳ -4 and ferric ion solution reaction, solution becomes pink from colourless, measures at this time glimmering Light intensity value, after excess EDTA is added in this solution, solution colour shoals, and measures fluorescence intensity level at this time again.It adds The Fe of identical equivalent3+Solution colour is restored afterwards, but weaker than most starting, this may be that there are excessive because of solution EDTA, also can be with Fe as complex compound3+Complexing, to influence Fe3+With the complexing of probe IV -4, and fluorescent value is measured again. IV -4 and Fe of this explanation3+Between there is coordination, and Fe3+Bigger with IV -4 complexation constant, coordination is stronger, is added Fe3+Lactam nucleus is opened in making IV -4, and the EDTA of addition can be by Fe3+It is eliminated from probe system, tests and probe IV -4 can be explained For Fe3+Identification process be reversible.
According to IV -4 and Fe3+Between combination ratio be 1:1 and the reversible experiment, judge such probe to Fe3+Knowledge Other mechanism is as shown in figure 11.
16 probe of embodiment, IV -4d Fe in qualitative detection water sample3+Application
Probe IV -4 is after spectral detection is tested, by metal cations Fe of its Preliminary Applications in environmental water sample3+Detection In, take various concentration gradient Fe3+Aqueous solution, for the Fe of various concentration in water sample3+Visualization can be generated after being acted on probe Different color changes, carry out qualitative detection water sample in Fe3+'s.Implementation is as follows：
4 parts of 0.2mL various concentration gradients Fe are taken respectively3+Aqueous solution (0,0.05,5.0,10.0 μM) sample is added and contains volume 5 μm of IV -4 acetonitrile solution 0.02mL of ol/mL probes are added in the 200 μ L of pH=6.5,10mM PBS buffer solution of 50% acetonitrile of concentration, Specific color change is shown in Figure 12.
Figure 12:It is respectively from left to right the Fe of 0,0.05,5.0,10.0 μM of concentration gradient3+Solution, color is gradually by colourless Become red.
17 probe IV -4 of embodiment Fe in quantitative detection water sample3+The application of concentration
In order to verify the Fe in detecting water sample of probe IV -43+Application performance, prepared 7.5 with ultra-pure water respectively, 6.0, 4.0, the Fe of 2.0,1.0,0.5,0.1,0.05,0.01,0.005,0.001 μm of ol/mL3+Aqueous solution, as sample to be tested.Using Detecting probe method and phenanthroline method of the present invention measures to measure above-mentioned Fe3+The concentration of solution, concrete operations are as follows：
(1) detecting probe method of the present invention measures Fe3+The concentration of solution takes the pH=of 100 μ L 50% acetonitriles containing volumetric concentration respectively 6.5,10mM PBS buffer solution is added separately to the Fe of the above-mentioned prepared various concentrations of 100 μ L3+In aqueous solution, then add respectively After entering 5 μm of 10 μ L of ol/mL probes acetonitrile solution (IV -4), fluorescence intensity is measured at 555nm.The fluorescent value measured is updated to In the regression equation y=251.625+2526.47x that embodiment 14 obtains, Fe is obtained3+Concentration is shown in Table 1.
(2) phenanthroline method measures Fe3+The concentration of solution
A, the preparation of acetic acid-sodium acetate buffer solution (pH=4.5)：164g sodium acetates are weighed, 500mL ultra-pure waters are dissolved in In, 84mL glacial acetic acids are added, 1000mL is diluted to ultra-pure water.
B, the preparation of 20g/L ascorbic acid solutions：10.0g ascorbic acid is dissolved in 200mL ultra-pure waters, and 0.2g second is added Edetate disodium (EDTA) and 8.0mL formic acid, then it is diluted to 500mL with ultra-pure water, it shakes up, is stored in brown bottle.
C, the preparation of 2.0g/L phenanthrolines solution：2.0g phenanthrolines are weighed, are dissolved in 800mL ultra-pure waters, then with super Pure water is diluted to 1000mL.
D, the preparation of 40.0g/L potassium persulfate solutions：4.0g potassium peroxydisulfates are weighed, with ultrapure water dissolution and determine molten arrive 100mL。
E, the preparation of 0.1mg/mL ammonium ferric sulfates standard solution I：0.863g ammonium ferric sulfates are weighed, are placed in 200mL beakers, 100mL ultra-pure waters are added, the 10mL concentrated sulfuric acids are fixed molten to 1000mL after dissolving.
F, the preparation of 0.01mg/mL ammonium ferric sulfates standard solution II：1mL 0.1mg/mL ammonium ferric sulfate standard solution I are taken, 10 times of dilution, only good the day use.
G, the drafting of working curve：Take respectively 0mL (blank), 1.00mL, 2.00mL, 4.00mL, 6.00mL, 8.00mL, The ammonium ferric sulfate standard solution II that 10.00mL steps f is prepared adds ultra-pure water to about 40mL, adds in 7 100mL volumetric flasks (water is 1 with 98% concentrated sulfuric acid volume ratio of mass concentration to 0.50mL sulfuric acid solutions：35 prepare), pH value is transferred to 2, adds 3.0mL steps b The 20g/L ascorbic acid solutions of middle preparation, the acetic acid-sodium acetate buffer solution prepared in 10mL steps a are prepared in 5mL steps c Phenanthroline solution.It is diluted to scale with ultra-pure water, is shaken up.It places 15 minutes at room temperature, with spectrophotometer in 510nm Place is returned to zero with reagent blank and surveys absorbance.Using the absorbance measured as ordinate, corresponding Fe3+It is abscissa to measure (μm ol) Draw to obtain working curve y=0.00064+0.37936x.
H, the measurement of ferric ion concentration：It takes in 8mL samples to be tested to 100mL volumetric flasks, adds ultra-pure water to about 40mL, With sulfuric acid solution, (water is 1 with 98% concentrated sulfuric acid volume ratio of mass concentration：35 prepare) pH value is transferred to 2 (ammonium water can be used when necessary Adjust), add the 20g/L ascorbic acid solutions prepared in 3.0mL steps b, the acetic acid-acetate buffer prepared in 10mL steps a Solution, the phenanthroline solution prepared in 5mL steps c.It is diluted to scale with ultra-pure water, is shaken up.It places 15 minutes, uses at room temperature Spectrophotometer is returned to zero with reagent blank at 510nm and surveys absorbance, the results are shown in Table 1.
It is calculated as follows by the concentration C of unit iron ion of μm ol/mL：
C=m/ (55.8434*V)
m:With the amount of the μ g iron ions indicated；
V：The volume of sample indicated with mL.
1 probe IV -4 of table Fe in detecting water sample3+Application
From upper table 1, ferric ion used in the present invention detection method error is small, high sensitivity, accuracy height etc. Feature, the especially ferric ion in detection low concentration, more show superior sensitivity and accuracy.

Claims (10)

1. a kind of double 1,2,3-triazoles rhodamine 6G class fluorescence probes of chain shown in formula (IV),
In formula (IV), R is one of following：CH2、CH2CH2、CH2CH2CH2CH2、CH2CH2CH2CH2CH2、 CH2CH2CH2CH2CH2CH2、CH2CH2OCH2CH2。
2. a kind of preparation method of the double 1,2,3-triazoles rhodamine 6G class fluorescence probes of chain described in claim 1, it is characterised in that The method is：Using compound is raw material shown in compound shown in formula (II) and formula (III), with Cu+As catalyst, in tetrahydrochysene In furans, 40-60 DEG C after the reaction was complete, reaction solution is isolated and purified, and obtains the double 1,2,3-triazoles rhodamines of chain shown in formula (IV) 6G class fluorescence probes；
In formula (III), R is one of following：CH2、CH2CH2、CH2CH2CH2CH2、CH2CH2CH2CH2CH2、 CH2CH2CH2CH2CH2CH2、CH2CH2OCH2CH2。
3. method as claimed in claim 2, it is characterised in that compound shown in the formula (II) and compound shown in formula (III) The ratio between the amount of substance of feeding intake is 2.2:1, the catalyst amount is with the gauge of Cu substances, the Cu and chemical combination shown in formula (III) The ratio between amount of object substance is 1.2：1；The tetrahydrofuran volumetric usage is calculated as with the amount of combinations of materials shown in formula (III) 44ml/mmol。
4. method as claimed in claim 2, it is characterised in that the method that reaction solution isolates and purifies is：It, will be anti-after the reaction was complete It answers liquid to be concentrated to dryness, water dissolution is then added, dichloromethane is extracted, and takes organic phase, then washed with saturated sodium-chloride water solution It washs, anhydrous magnesium sulfate drying, filtering, thin-layer chromatography is carried out after filtrate decompression solvent evaporated, with volume ratio 1:20 CH3OH: CH2Cl2For solvent, the component of Rf values 0.4-0.5 is collected, it is glimmering to obtain the double 1,2,3-triazoles rhodamine 6G classes of chain shown in formula (IV) Light probe.
5. method as claimed in claim 2, it is characterised in that compound is prepared as follows shown in the formula (II)：With formula (I) compound represented and propargylamine are raw material, and in methyl alcohol, back flow reaction is complete, and reaction solution post-processing obtains formula (II) institute Show compound；Feed intake the ratio between the amount of substance of compound shown in formula (I) and propargylamine is 1:5；Methanol volumetric usage is with shown in formula (I) The amount of combinations of materials is calculated as 20ml/mmol；
6. method as claimed in claim 5, it is characterised in that reaction solution post-processing method be：After the reaction was complete, it will react Liquid is concentrated to dryness, and water dissolution is then added, and dichloromethane is extracted, and takes organic phase, then washed with saturated sodium-chloride water solution, Anhydrous magnesium sulfate is dried, filtering, thin-layer chromatography is carried out after filtrate decompression solvent evaporated, with volume ratio 1:20 CH3OH:CH2Cl2 For solvent, the component of Rf values 0.4-0.5 is collected, obtains compound shown in formula (II).
7. a kind of double 1,2,3- triazoles rhodamine 6G class fluorescence probes of chain described in claim 1 are in detection Fe3+In application.
8. the use as claimed in claim 7, it is characterised in that the application is：Sample to be tested is added and contains volumetric concentration In the PBS buffer solution of pH=6.5,10mM of 50% acetonitrile, it is glimmering to add the double 1,2,3-triazoles rhodamine 6G classes of 5 μm of ol/mL chains Light probe acetonitrile solution, if there is color generation, sample to be tested contains Fe3+。
9. the use as claimed in claim 7, it is characterised in that the application is：Sample to be tested is added and contains volumetric concentration In the PBS buffer solution of pH=6.5,10mM of 50% acetonitrile, it is glimmering to add the double 1,2,3-triazoles rhodamine 6G classes of 5 μm of ol/mL chains After light probe acetonitrile solution, fluorescent value is measured at 555nm, according to Fe3+Standard curve obtains Fe in sample to be tested3+Concentration； The sample to be tested is 1 with PBS buffer solution volume ratio:1, the sample to be tested is 10 with probe acetonitrile solution volume ratio:1；Institute State Fe3+Standard curve is with Fe3+Concentration of aqueous solution is abscissa, is made using fluorescent value of ordinate.
10. application as claimed in claim 9, it is characterised in that the Fe3+Standard curve is prepared as follows：It will be a concentration of The Fe of 0,0.01,0.05,0.5,1,1.5,2,2.5,3,3.5,4.5,5,5.5,6,6.5,7,7.5 μm of ol/mL3+Aqueous solution is distinguished It is added in the PBS buffer solution of pH=6.5,10mM of 50% acetonitrile containing volumetric concentration, adds 5 μm of ol/mL chains double 1,2,3- tri- After azoles rhodamine 6G class fluorescence probe acetonitrile solution, fluorescent value is measured at 555nm, with Fe3+A concentration of abscissa, with fluorescent value For ordinate, Fe is obtained3+Standard curve；The Fe3+Aqueous solution is 1 with PBS buffer solution volume ratio:1, the Fe3+Aqueous solution with Probe acetonitrile solution volume ratio is 10:1.
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