CN104861960A - Fast-response Hg<2+> chromogenic-fluorescent probe preparation method based on rhodamine B-diethylenetriamine-cinnamic acid derivative - Google Patents
Fast-response Hg<2+> chromogenic-fluorescent probe preparation method based on rhodamine B-diethylenetriamine-cinnamic acid derivative Download PDFInfo
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Abstract
The invention relates to a fast-response Hg<2+> chromogenic-fluorescent probe preparation method based on a rhodamine B-diethylenetriamine-cinnamic acid derivative. According to the invention, rhodamine B and diethylenetriamine are subjected to a condensation acylation reaction, such that a rhodamine B-diethylenetriamine derivative is obtained; the rhodamine B-diethylenetriamine derivative is subjected to an acylchloriration reaction with cinnamic acid, such that the rhodamine B-diethylenetriamine-cinnamic acid derivative is obtained. A water-ethanol mixed solution based on the rhodamine B-diethylenetriamine-cinnamic acid derivative can be used as the fast-response Hg<2+> chromogenic-fluorescent probe. The fast-response chromogenic-fluorescent probe can be used for rapidly analyzing the Hg<2+> content in a water sample. The probe has high anti-interference capacity against other metal ions, and is an ideal Hg<2+> chromogenic-fluorescent probe. The response time of the Hg<2+> chromogenic indicator upon Hg<2+> is less than 3min, and a minimum detection limit is 1.0*10<-6>mol/L. The fast-response Hg<2+> chromogenic-fluorescent probe provided by the invention has the advantages of simple process, low cost, simple operation, high sensitivity, fast response, low detection limit, and the like.
Description
Technical field
The present invention relates to a kind of mercury ion (Hg
2+) detection agent, be specifically related to a kind of fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative
2+the preparation method of chromogenic-fluorogenic probe.
Background technology
In the middle of global industry process, human activity causes the heavy metal ion content in environment day by day to increase, and pollution range is expanding day also.China's heavy metal pollution of water body problem is very outstanding, the pollution rate of river,lake and reservior substrate up to 80.1% [Zhou Huaidong, Peng Wenqi etc. water surrounding and aquatic ecological restoration. Beijing: Chemical Industry Press, 2005].Just find in the investigation at the beginning of the eighties, in Jinsha jiang River, Xiang River, Ji canal, many water bodys such as Communities of The Jinzhou Bay all have heavy metal contamination in various degree, wherein the aqueous phase heavy metal concentration in serious location is up to hundreds of ppb, Heavy Metal In Sediments concentration reaches thousands of ppm [Ho K C, Hui K C C. Chemical contamination of the East River (Dongjiang) and its implication on sustainable development in the Pearl River Delta. Environment International, 2001, 26 (5, 6): 303-308].The pollution level of the basin sheet heavy metals exceeding standard section of ten large watersheds such as the Yellow River, Huaihe River, Song Hua River, the Liaohe River in 2003 be surpass V class [Hu Bibin. China ten large watershed sheet Water Pollution Problem and principal character. environmental science, 2003,25:15-17].On January 15th, 2012, there is a small amount of dead fish phenomenon in Long Jianghe La Lang power station, Guangxi cage culture, further investigation reveals that, the front 200 meters of water quality heavy metals exceeding standards 80 times of unrestrained harbour are drawn in Yizhou, river, Longjiang.In the Spring Festival in lunar calendar Year of the Dragon, section, Longjiang detects heavy metal Hg content overproof, makes bank and downstream DRINKING WATER suffer serious threat safely.The illegal blowdown of cause Shi Liangge producer of this event causes mercury spillage to reach about 20 tons.
Mercury is a kind of very harmful environmental pollutant, and China's " heavy metal contamination integrated control planning " and " planning of " 12 " key area topsoil groupcontrol " in recent years all lists major fields in the pollution of mercury and integrated control thereof.Explicitly point out in planning: " 12 " period, the computation model of typical coal unit emission inventories be set up, carry out the pilot work of coal-burning power plant's Mercury In The Air discharge on-line monitoring; Develop pilot project early as far as possible, while flue gas ash removal, desulphurization and denitration, control mercury pollution, realize jointly controlling of multi-pollutant, and net assessment is carried out to the economy of project, technology and environmental benefit.Environmental Protection Department it is also proposed the instruction advancing topsoil groupcontrol; strengthen clean energy to utilize; the discharge of strict control coal burning pollution, the multi-pollutant Collaborative Control technology such as development fired power generating unit flue gas ash removal, desulphurization and denitration and the removal of mercury, strengthen priority pollutant and prevent and treat dynamics.
What mercury pollution produced has a strong impact on, and facilitates the continuous research and development of mercury ion detecting technology.Conventional has atomic absorption/emission spectrometry, atomic fluorescence method, inductively coupled plasma method, x ray fluorescence spectrometry, Inductively coupled plasma-mass spectrometry, inductively coupled plasma atomic emission spectrometry, immunoassay, electrochemical process, biochemical sensor method etc. to the method that mercury ion detects.Although each tool advantage of these methods, but still there is very large drawback in actual use, as low in sensitivity, expensive equipment and complicated operation etc., these methods need special laboratory, the operative technique personnel of specialty and the sample pretreatment process of complexity, expend consuming time, require too high, moreover it is insensitive to some heavy metal ion, the problem such as even cannot to detect, be not suitable for the detection to water sample, soil and food equal samples in daily life, needs during solution of emergent event can not be met.In the ecological risk investigation of burst mode tra nsmitter investigation and basin regional scale, because regional extent is wide, need the environmental sample quantity that gathers greatly, in the urgent need to high-throughout, real-time field screening technology.Therefore, a kind of simple, quick, sensitive heavy metal ion qualitative and quantitative detection technical meaning is sought great.
Secondly, the kind of mercury ion is many, content is low, sample composition is complicated, have mobility and unstable, the feature of mercury ion environmentally, and the analytical technology and the method that determine mercury ion need sensitive, accurate, real-time, fast analysis.In order to cut down the number of intermediate links, record mercury ion content in the environment and pollution level, carry out detection by quantitative to pollutent in real time.At present the developing direction of environment measuring is in the world: online, real-time, easy, portable, highly sensitive, and detection limit is low, susceptibility good, can be used for the measurement of complex sample, can supply large batch of detection, can be used for the environmental sample of different sources.
In addition, because mercury ion long-term existence chronic pollution physical environment, also adverse consequences can be produced when extremely micro-, how scientifically to evaluate the pollution level of Mercury In Environment ion, how to prevent and remedy pollution etc. all be unable to do without the content analysis to mercury ion, and the analysis therefore carrying out micro-/trace amount mercury ion has very important significance.
In recent years, the color produced based on ion induction and change in fluorescence mechanism detect the chromogenic-fluorogenic probe technique of metal ion owing to having the features such as highly sensitive, detectability is low, simple to operate, cost is low, become important means [the Mao J detecting mercury ion at present and pollute, He Q, Liu W S. An " off – on " fluorescence probe for chromium (III) ion determination in aqueous solution. Anal Bioanal Chemistry, 2010,396:1197-1203; Dong M, Wang Y W, Peng Y. Highly selective ratiometric fluorescent sensing for Hg
2+and Au
3+respectively in aqueous media. Organic Letters, 2010,12:5310-5313], people to achieve success greatly and are widely used in the fields such as chemistry, biology and environmental science utilizing Molecular Recognition Principle to design in each metal ion species chromogenic-fluorogenic probe technique.Rhodamine (Rhodamine) is due to its outstanding spectral quality, as long wave effect weakening, higher fluorescent quantum transformation efficiency and strong molar extinction coefficient [Haugland R P. A guide to fluorescent probes and labeling technologies. Invitrogen Corporation, Karlsbad, CA, 2005], a kind of chromogenic-fluorogenic probe be widely used therefore is become.In recent years, the carboxyl in rhodamine structure is utilized to generate unique five-ring lactam structure with uncle's ammonia react, by in conjunction with heavy metal ion, make originally not there is color, do not have the lactam structure molecule open loop of fluorescent effect to be converted into have very strong receptivity in visible-range and send the amide structure of very hyperfluorescenceZeng Yongminggaoyingguang, reach the report detecting certain heavy metal ion increasing.Owing to having Response Mechanism uniqueness, detect the features such as sensitive, interference is few, the chromogenic-fluorogenic probe based on rhodamine molecule is widely applied in the detection of heavy metal and transition metal ion, and detectable heavy metal ion comprises Cu
2+, Pb
2+, Zn
2+, Hg
2+deng.
Following formula gives the signal route of rhodamine B and heavy metal ion effect.Be shown below, the rhodamine molecule molar absorptivity of closed-loop structure and fluorescence quantum yield are all very low, almost do not have fluorescence.But after connecting recognition group R, can have an effect with certain heavy metal species or transition metal ion under the synergy of carbonyl and recognition group, thus cause the lactam bond of probe to rupture, form open loop structure, cause the fluorescence intensity of molecule significantly to strengthen, realize the susceptibility identification to this ion.
The Cheng Huanyu ring opening process of rhodamine B lactam structure
But the principle of chromogenic-fluorogenic probe many employings organic group complexation of metal ions of the mercury ion that research is more at present, thus chromogenic-fluorogenic probe mostly is the molecule containing organic heterocyclic, and solubleness is not satisfactory in aqueous.In addition, micro-/trace amount mercury ion and chromogenic-fluorogenic probe still not ideal enough in conjunction with effect, therefore detection sensitivity and the scope of application are subject to many restrictions, and for mercury ion, finding sensitiveer, efficient detection agent is still the difficult problem of pendulum in face of us.
Summary of the invention
The object of the invention is to the deficiency overcoming prior art existence, propose a kind of fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative
2+chromogenic-fluorogenic probe preparation method.
A kind of fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative that the present invention proposes
2+chromogenic-fluorogenic probe, is characterized in that: first carry out condensation acylation reaction by rhodamine B and diethylenetriamine, obtains rhodamine B diethylenetriamine derivative; This rhodamine B diethylenetriamine derivative again with styracin generation acyl chloride reaction, obtain a kind of rhodamine B-diethylenetriamine-cinnamic acid derivative; The water-ethanol mixing solutions of this rhodamine B-diethylenetriamine-cinnamic acid derivative can be used as Hg
2+color fluorescent probe, at the Hg of this rhodamine B-diethylenetriamine-cinnamic acid derivative
2+hg is added in the water-ethanol mixing solutions of chromogenic-fluorogenic probe
2+after, the color of mixing solutions becomes pink from colourless, and in corresponding uv-visible absorption spectroscopy, the absorption peak at 565nm place is along with Hg
2+the rising of concentration and strengthening; The fast-response Hg of this rhodamine B-diethylenetriamine-cinnamic acid derivative
2+chromogenic-fluorogenic probe is to Hg
2+time of response be less than 3 minutes, lowest detection is limited to 1.0 × 10
-6mol/L, and can be used for micro-in water surrounding/trace Hg
2+half-quantitative detection.
A kind of fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative that the present invention proposes
2+the preparation method of chromogenic-fluorogenic probe, the synthetic route of this rhodamine B-diethylenetriamine-cinnamic acid derivative is as follows:
Concrete steps are as follows:
(1) 1 ~ 10 g rhodamine B is taken and 20 ~ 200 mL organic solvents join in 250 mL reaction flasks, abundant stirring makes rhodamine B dissolve completely, 1 ~ 10 mL diethylenetriamine is dropwise added when keeping stirring, under nitrogen protection in 75 ~ 85 DEG C of reaction 4 ~ 40 h, after reaction terminates, reaction flask is cooled to room temperature, suction filtration also revolves steaming except desolventizing, gained Light brown solid 40 ~ 400 mL dichloromethane extraction 2 ~ 4 times, merge organic phase, wash 3 ~ 5 times with water, with anhydrous sodium sulfate drying 2 ~ 20 hours, filter, collect filtrate, revolve and steam to obtain safran solid, after column chromatography for separation, (developping agent is methyl alcohol: methylene dichloride=1:5, v/v), obtain rhodamine B-diethylenetriamine derivative, productive rate is 85%-95%.
(2) 0.5 ~ 5 g styracin is taken and 5 ~ 50 mL sulfur oxychlorides join in 100 mL reaction flasks; abundant stirring makes styracin dissolve completely; drip 0.1 ~ 1 mL dimethyl formamide; under nitrogen protection in 75 ~ 85 DEG C of reflux 1 ~ 10 h; underpressure distillation removing sulfur oxychloride; obtain light yellow solid powder, be styracin acyl chlorides, productive rate is 90% ~ 95%.
(3) the obtained rhodamine B-diethylenetriamine derivative of 0.5 ~ 5 g step (1) is taken and 10 ~ 100 mL methylene dichloride join in 250 mL reaction flasks, abundant stirring makes to dissolve completely, add 1 ~ 10 mL triethylamine, 0.2 ~ 2 g sodium bicarbonate, the styracin acid chloride dissolves 0.5 ~ 5 g step (2) obtained again is in 2 ~ 20 mL methylene dichloride, constant pressure funnel is used dropwise to add in 250 mL reaction vessels, under nitrogen protection in room temperature reaction 3 ~ 30 h, revolve after reaction terminates and steam methylene dichloride, with 20 ~ 200 ml dichloromethane extraction 1 ~ 3 time, merge organic phase, wash 3 ~ 5 times again with water, obtain organic phase, with anhydrous sodium sulfate drying 1 ~ 10 hour, revolve and steam methylene dichloride, after column chromatography for separation, (developping agent is methyl alcohol: methylene dichloride=1:15, v/v) yellow-brown solid is obtained, be rhodamine B-diethylenetriamine-cinnamic acid derivative, productive rate 80%-90%.
(4) take rhodamine B-diethylenetriamine-cinnamic acid derivative prepared by 0.01 ~ 0.1 g step (3) to be dissolved in the mixing solutions of 100 ~ 1000 g water and organic solvent composition and to obtain a kind of fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative
2+chromogenic-fluorogenic probe.
In the present invention, organic solution described in step (1) and (4) adopts any one in ethanol, methyl alcohol or Virahol, described in step (4), the volume ratio of water and organic solvent is 1:10 ~ 10:1, this rhodamine B-diethylenetriamine-cinnamic acid derivative has good solubleness, reach 0.01 ~ 1 mmol/L, can be used as a kind of fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative
2+chromogenic-fluorogenic probe.
In the present invention, the chemical structural formula of rhodamine B is as follows:
。
In the present invention, the chemical structural formula of diethylenetriamine is as follows:
。
In the present invention, the chemical structural formula of styracin is as follows:
。
In the present invention, the chemical structural formula of sulfur oxychloride is as follows:
。
In the present invention, the chemical structural formula of dimethyl formamide is as follows:
。
In the present invention, the mixing solutions based on rhodamine B-diethylenetriamine-cinnamic acid derivative can be the mixing solutions (water: ethanol=1:10 ~ 10:1, volume ratio) of water and ethanol, also can be the mixing solutions of water and methyl alcohol or water and Virahol.At the mixed solvent (water: ethanol=1:10 ~ 10:1 of water and ethanol, volume ratio) in, the solubleness of this rhodamine B-diethylenetriamine-cinnamic acid derivative can reach 0.01 ~ 1 mmol/L, can be used as a kind of fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative
2+chromogenic-fluorogenic probe.
Advantage of the present invention is: 1. the present invention is a kind of fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative
2+the preparation method of chromogenic-fluorogenic probe, can be used for Hg in real-time analysis water sample
2+the fast-response chromogenic-fluorogenic probe of content, it is to other coexistent metallic ions (Na in water sample
+, Fe
3+, Pb
2+, Zn
2+, Mg
2+, Fe
2+, Cr
3+) immunity from interference strong, applicable pH range wide (acid to neutral) is a kind of mercury ion color fluorescent probe efficiently; 2. should based on the fast-response Hg of rhodamine B-diethylenetriamine-cinnamic acid derivative
2+chromogenic-fluorogenic probe is to Hg
2+time of response be less than 3 minutes, lowest detection is limited to 1.0 × 10
-6mol/L; 3. the present invention has the advantages such as synthesis technique is simple, with low cost, easy and simple to handle, highly sensitive, fast response time, detectability are low, application prospect is extensive, can be used for the real-time and Quick Measurement of complex sample in water surrounding, also can be used for the half-quantitative detection of micro-/trace amount mercury ion concentration.
Accompanying drawing explanation
Fig. 1 is the chemical structural formula of rhodamine B-diethylenetriamine-cinnamic acid derivative.
Fig. 2 is the nuclear-magnetism hydrogen collection of illustrative plates of rhodamine B-diethylenetriamine-cinnamic acid derivative.
Fig. 3 is the infrared spectrogram of rhodamine B-diethylenetriamine-cinnamic acid derivative.
Fig. 4 is the fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative
2+the colour-change situation of chromogenic-fluorogenic probe after adding different heavy metal ion (from left to right: Mg
2+, Na
+, K
+, Cr
3+, Zn
2+, Pb
2+, Fe
3+, Hg
2+).
Fig. 5 is the fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative
2+chromogenic-fluorogenic probe is adding Hg
2+the uv-visible absorption spectrum figure (solvent: water-ethanol, 5:1, v/v) of rear different time.
Fig. 6 is the fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative
2+different concns Hg is added in chromogenic-fluorogenic probe
2+after uv-visible absorption spectrum figure (solvent: water-ethanol, 5:1, v/v).
Fig. 7 is the fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative
2+chromogenic-fluorogenic probe is adding different metal ion (Hg
2+, Na
+, Fe
3+, Pb
2+, Zn
2+, Mg
2+, Fe
2+, Cr
3+deng) after fluorescence spectrum spectrogram.
Embodiment
Below in conjunction with specific embodiment, such scheme is described further.Should be understood that these embodiments are not limited to for illustration of the present invention limit the scope of the invention.The implementation condition adopted in embodiment can do further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in normal experiment.
Describe the present invention in detail below in conjunction with embodiment, should be appreciated that citing described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
Take 3 g rhodamine Bs and 60 mL ethanol join in 250 mL there-necked flasks, abundant stirring makes rhodamine B dissolve completely, dropwise drip 3.00 mL diethylenetriamines, dropwise 80 DEG C of back flow reaction 10 hours, reaction process leads to nitrogen, after reaction terminates, reaction flask is cooled to room temperature, suction filtration, revolve and steam removing ethanol, gained Light brown solid 100 mL dichloromethane extraction 3 times, merge organic phase, wash 4 times with water, with anhydrous sodium sulfate drying 2 hours, filter, collect filtrate, revolve and steam to obtain safran solid, after column chromatography for separation, (developping agent is methyl alcohol: methylene dichloride=1:5, v/v), obtain rhodamine B-diethylenetriamine derivative, productive rate is 93.2%.
Take 1 g styracin and 10 mL sulfur oxychlorides join in 100 mL reaction flasks; abundant stirring makes styracin dissolve completely; drip 0.2 mL dimethyl formamide; under nitrogen protection in 78 DEG C of reflux 3 h; underpressure distillation removing sulfur oxychloride; obtain light yellow solid powder, be styracin acyl chlorides, productive rate is 94.5%.
Take the obtained rhodamine B diethylenetriamine of 1.5 g steps (1) and 40 mL methylene dichloride join in 250 mL reaction flasks, abundant stirring makes to dissolve completely, add 2 mL triethylamines, 0.5 g sodium bicarbonate, the styracin acid chloride dissolves 1.9 g steps (2) obtained again is in 2 ~ 20 mL methylene dichloride, constant pressure funnel is used dropwise to add in 250 mL reaction vessels, under nitrogen protection in room temperature reaction 24 h, revolve after reaction terminates and steam methylene dichloride, with 100 ml dichloromethane extraction 2 times, merge organic phase, wash 4 times again with water, obtain organic phase, with anhydrous sodium sulfate drying 2 hours, revolve and steam methylene dichloride, after column chromatography for separation, (developping agent is methyl alcohol: methylene dichloride=1:15, v/v) yellow-brown solid is obtained, be rhodamine B-diethylenetriamine-cinnamic acid derivative, productive rate 89.6%.
Take rhodamine B-diethylenetriamine-cinnamic acid derivative prepared by 0.01 g step (3), be dissolved in the mixing solutions (water: ethanol=5:1 of 500 g water and ethanol, volume ratio) in, obtain a kind of fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative
2+chromogenic-fluorogenic probe.
The chemical structural formula of this rhodamine B-diethylenetriamine-cinnamic acid derivative as shown in Figure 1, Fig. 2 is the nuclear-magnetism hydrogen collection of illustrative plates of rhodamine B-diethylenetriamine-cinnamic acid derivative, Fig. 3 is the infrared spectrogram of rhodamine B-diethylenetriamine-cinnamic acid derivative, and Fig. 4 is the fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative
2+the colour-change situation of chromogenic-fluorogenic probe after adding different heavy metal ion (from left to right: Mg
2+, Na
+, K
+, Cr
3+, Zn
2+, Pb
2+, Fe
3+, Hg
2+), Fig. 5 is the fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative
2+chromogenic-fluorogenic probe is adding Hg
2+the uv-visible absorption spectrum figure (solvent: water-ethanol, 5:1, v/v) of rear different time, Fig. 6 is the fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative
2+different concns Hg is added in chromogenic-fluorogenic probe
2+after uv-visible absorption spectrum figure (solvent: water-ethanol, 5:1, v/v), Fig. 7 is the fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative
2+chromogenic-fluorogenic probe is adding different metal ion (Hg
2+, Na
+, Fe
3+, Pb
2+, Zn
2+, Mg
2+, Fe
2+, Cr
3+deng) after fluorescence spectrum spectrogram.
Embodiment 2: identical with embodiment 1, but in step (4), the volume ratio of water and ethanol becomes 4:1.
Embodiment 3: identical with embodiment 1, but in step (4), the volume ratio of water and ethanol becomes 6:1.
Embodiment 4: identical with embodiment 1, but in step (4), the volume ratio of water and ethanol becomes 3:1.
Embodiment 5: identical with embodiment 1, but in step (4), the volume ratio of water and ethanol becomes 2:1.
Embodiment 6: identical with embodiment 1, but step (1) and (4) middle ethanol become methyl alcohol, and in step (4), the volume ratio of water and methyl alcohol is 4:1.
Embodiment 7: identical with embodiment 1, but step (1) and (4) middle ethanol become methyl alcohol, and in step (4), the volume ratio of water and methyl alcohol is 6:1.
Embodiment 8: identical with embodiment 1, but step (1) and (4) middle ethanol become Virahol, and in step (4), the volume ratio of water and Virahol is 6:1.
Embodiment 9: identical with embodiment 1, but step (1) and (4) middle ethanol become Virahol, and in step (4), the volume ratio of water and Virahol is 4:1.
Rhodamine B-diethylenetriamine-the cinnamic acid derivative obtained in embodiment 2-9 and Hg
2+there is special keying action, and with other common metal ion (Na
+, Fe
3+, Pb
2+, Zn
2+, Mg
2+, Fe
2+, Cr
3+) then not there is this effect.Hg is added in the water-ethanol mixing solutions of this rhodamine B-diethylenetriamine-cinnamic acid derivative
2+after, solution colour becomes redness from colourless, occurs absorption peak in uv-visible absorption spectroscopy in 565 nm place correspondences, shows that it is a kind of Hg efficiently
2+chromogenic-fluorogenic probe.Should based on the Hg of rhodamine B-diethylenetriamine-cinnamic acid derivative
2+the lowest detection of chromogenic-fluorogenic probe to ion concentration of mercury is limited to 1.0 × 10
-6mol/L, applicable pH range is acid to neutral.Should based on the Hg of rhodamine B-diethylenetriamine-cinnamic acid derivative
2+the probe chromogenic-fluorogenic time of response is less than 3 minutes, and the intensity of UV-Visible absorption characteristic peak and fluorescence intensity are along with Hg
2+the rising of concentration and strengthening, still meets linear relationship at low concentrations, can be used for the half-quantitative detection of micro-/trace amount mercury ion concentration.
Above-mentioned example, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations of doing according to spirit of the present invention or modification, all should be encompassed within protection scope of the present invention.
Claims (5)
1. the fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative
2+the preparation method of chromogenic-fluorogenic probe, is characterized in that concrete steps are as follows:
(1) 1 ~ 10 g rhodamine B is taken and 20 ~ 200 mL organic solvents join in 250 mL reaction flasks, abundant stirring makes rhodamine B dissolve completely, 1 ~ 10 mL diethylenetriamine is dropwise added when keeping stirring, under nitrogen protection in 75 ~ 85 DEG C of reaction 4 ~ 40 h, after reaction terminates, reaction flask is cooled to room temperature, suction filtration also revolves steaming except desolventizing, gained Light brown solid 40 ~ 400 mL dichloromethane extraction 2 ~ 4 times, merge organic phase, wash 3 ~ 5 times with water, with anhydrous sodium sulfate drying 2 ~ 20 hours, filter, collect filtrate, revolve and steam to obtain safran solid, after column chromatography for separation, (developping agent is methyl alcohol: methylene dichloride=1:5, v/v), obtain rhodamine B-diethylenetriamine derivative, productive rate is 85%-95%,
(2) 0.5 ~ 5 g styracin is taken and 5 ~ 50 mL sulfur oxychlorides join in 100 mL reaction flasks, abundant stirring makes styracin dissolve completely, drip 0.1 ~ 1 mL dimethyl formamide, under nitrogen protection in 75 ~ 85 DEG C of reflux 1 ~ 10 h, underpressure distillation removing sulfur oxychloride, obtain light yellow solid powder, be styracin acyl chlorides, productive rate is 90% ~ 95%;
(3) the obtained rhodamine B-diethylenetriamine derivative of 0.5 ~ 5 g step (1) is taken and 10 ~ 100 mL methylene dichloride join in 250 mL reaction flasks, abundant stirring makes to dissolve completely, add 1 ~ 10 mL triethylamine, 0.2 ~ 2 g sodium bicarbonate, the styracin acid chloride dissolves 0.5 ~ 5 g step (2) obtained again is in 2 ~ 20 mL methylene dichloride, constant pressure funnel is used dropwise to add in 250 mL reaction vessels, under nitrogen protection in room temperature reaction 3 ~ 30 h, revolve after reaction terminates and steam methylene dichloride, with 20 ~ 200 ml dichloromethane extraction 1 ~ 3 time, merge organic phase, wash 3 ~ 5 times again with water, obtain organic phase, with anhydrous sodium sulfate drying 1 ~ 10 hour, revolve and steam methylene dichloride, after column chromatography for separation, (developping agent is methyl alcohol: methylene dichloride=1:15, v/v) yellow-brown solid is obtained, be rhodamine B-diethylenetriamine-cinnamic acid derivative, productive rate 80%-90%,
(4) take rhodamine B-diethylenetriamine-cinnamic acid derivative prepared by 0.01 ~ 0.1 g step (3) to be dissolved in the mixing solutions of 100 ~ 1000 g water and organic solvent composition and to obtain a kind of fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative
2+chromogenic-fluorogenic probe.
2. a kind of fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative according to claim 1
2+the preparation method of chromogenic-fluorogenic probe, it is characterized in that organic solvent described in step (1) and (4) is any one in ethanol, methyl alcohol or Virahol, described in step (4), the volume ratio of water and organic solvent is 1:10 ~ 10:1, and this rhodamine B-solubleness of diethylenetriamine-cinnamic acid derivative in mixed solvent is 0.01 ~ 1 mmol/L.
3. a kind of fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative according to claim 1
2+the preparation method of chromogenic-fluorogenic probe, is characterized in that the chemical structural formula of rhodamine B-diethylenetriamine-cinnamic acid derivative is as follows:
。
4. a kind of fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative according to claim 1
2+the preparation method of chromogenic-fluorogenic probe, is characterized in that the chemical structural formula of rhodamine B is as follows:
。
5. a kind of fast-response Hg based on rhodamine B-diethylenetriamine-cinnamic acid derivative according to claim 1
2+the preparation method of chromogenic-fluorogenic probe, is characterized in that the chemical structural formula of styracin is as follows:
。
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CN105486668A (en) * | 2015-12-25 | 2016-04-13 | 同济大学 | Preparation method of fast-respondability Hg2+developing fluorescence probe based on rhodamine B-thiophene derivative |
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CN109320520A (en) * | 2018-09-28 | 2019-02-12 | 南京林业大学 | A kind of rhodamine B Hg based on pyridine -3- sulfonic acid chloride2+The preparation and application of fluorescent optical sensor |
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