CN103217504B - Preparation method of Cr<3+> color indicator based on rhodamine B-diethylene triamine derivative - Google Patents
Preparation method of Cr<3+> color indicator based on rhodamine B-diethylene triamine derivative Download PDFInfo
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- CN103217504B CN103217504B CN201310033935.5A CN201310033935A CN103217504B CN 103217504 B CN103217504 B CN 103217504B CN 201310033935 A CN201310033935 A CN 201310033935A CN 103217504 B CN103217504 B CN 103217504B
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- rhodamine
- diethylenetriamine
- color indicator
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- HBFIHLWPBUKQGC-UHFFFAOYSA-N CCN(CC)C(C1)=CC=C2C1(C)Oc1cc(N(CC)CC)ccc1C2c1ccccc1C(O)=O Chemical compound CCN(CC)C(C1)=CC=C2C1(C)Oc1cc(N(CC)CC)ccc1C2c1ccccc1C(O)=O HBFIHLWPBUKQGC-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N NCCNCCN Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
Abstract
The invention relates to a chromium ion detection agent, and specifically relates to a preparation method of a Cr<3+> color indicator based on a rhodamine B-diethylene triamine derivative. According to the invention, a rhodamine B-diethylene triamine derivative is synthesized by using rhodamine B and diethylene triamine. A water-ethanol mixed solution based on the rhodamine B-diethylene triamine derivative can be used as a Cr<3+> color indicator. The high-efficiency color indicator used for rapidly analyzing specific Cr<3+> content in water sample has high anti-interference capacity against other metal ions (Cu<2+>, Zn<2+>, Fe<3+>, Cd<2+>, Pb<2+>, Hg<2+>, Mn<2+>, Fe<2+>, Ba<2+>, and Ag<+>). An applicable pH range is from weakly acidic to neutral. The color indicator is an ideal Cr<3+> color indicator. A response time of the Cr<3+> color indicator upon Cr<3+> is 5min, and a lower detection limit is 5.2*10<-7>mol/L. The color indicator provided by the invention has the advantages such as simple synthesis process, low cost, simple operation, good selectivity, high sensitivity, high response speed, low detection limit, wide application prospect, and the like. The color indicator can be used in complicated sample real-time and rapid detection, and can be used in semi-quantitative detections of micro/trace Cr<3+> in environment samples of different sources.
Description
Technical field
The present invention relates to a kind of chromium ion (Cr
3+) detection agent, be specifically related to a kind of Cr based on rhodamine B-diethylenetriamine derivant
3+the preparation method of colored indicator.
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 environment 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 pollution 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 fish culture in net pen, 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 that heavy metal cadmium content exceeds standard, and makes bank and downstream DRINKING WATER suffer serious threat safely.The illegal blowdown of cause Shi Liangge producer of this event causes cadmium leakage rate to reach about 20 tons.
Current China also has nearly 2,000 ten thousand mu by the cultivated area of the heavy metal pollutions such as cadmium, chromium, lead, accounts for 20% of total area under cultivation; Wherein Industrial " three Waste " pollutes 1,000 ten thousand mu, arable land, and the farmland area of sewage irrigation has reached more than 330 ten thousand mu.Sewage irrigation and discarded object etc. have caused large-area soil pollution to farmland.Within 2009, Environmental Protection Department discloses 12 heavy metal pollution events, causes 4035 human blood lead doping altogether, and 182 people's cadmiums exceed standard.There are 32 Mass disturbances caused by heavy metal pollution then.The ground such as Fengxiang, China Shaanxi, Jiangsu great Feng, Huaining, Anhui, Chenzhou, Hunan Province, Yunnan Heqing, Jiyuan, Henan, Longchang, Sichuan, Jiahe, Hunan, Gansu Guazhou County, Chongyang, Hubei occur that blood lead exceeds standard event [Zhang Jianjiang in succession, Jia Jimin, Ma Yonghong. the toxic heavy metal contamination situation of Chinese important water system. Occupational health, 2011,27:89-91].In August, 2011, Qujing of Yunnan has externally circulated a notice of the event of illegal dumping severe toxicity industrial waste chromium slag together, and local few hundred thousand tonnes of chromium slag muck in addition, high risks is created to the health of the livestock in local village and villager.
Just because of heavy metal also exist to physical environment pollute continuation and chronicity, also adverse consequences can be produced when extremely micro-, how scientifically to evaluate the pollution level of environment metallic ion, how to prevent and remedy pollution etc. all be unable to do without the content analysis to metallic ion, and the analysis therefore carrying out metallic ion has great importance.Detection of heavy metal ion is all very important in environment, Food Monitoring etc.
At present, the detection method that metallic ion is commonly used can be divided into chemical method according to the difference of Cleaning Principle, Physical and bioassay method etc., the detection of heavy metal ion analytical approach of more employing has: atomic absorption spectrography (AAS) (AAS), atomic fluorescence method (AFS), UV-spectrophotometry (UV-Vis), inductively coupled plasma method (ICP), x ray fluorescence spectrometry (XRF), Inductively coupled plasma-mass spectrometry (ICP-MS), ICP-AES (ICP-AES), immunoassay, electrochemical process, biochemical sensor method etc.In environmental sample heavy metal ion the most reliably, the most effective determination method or the instrument detection method of above-mentioned routine, comprise atomic absorption spectrography (AAS), inductively coupled plasma detection etc.But these methods need costly large-scale instrument and equipment, 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 [Yu Ruozhen during solution of emergent event can not be met, Wang Hongmei, Fang Zheng etc. heavy metal ion Fast Detection Technique advances and application. environment project journal, 2011,1:438-442].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, metallic ion of a great variety, content is low, sample composition is complicated, have mobility and instability, the feature of metallic ion environmentally, the analytical technology and the method that determine heavy metal need sensitive, accurate, real-time, fast analysis.In order to cut down the number of intermediate links, record heavy metal content in the environment and pollution level, quantitatively detect pollutant 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, selectivity good, can be used for the measurement of complex sample, can supply large batch of detection, can be used for the environmental sample of separate sources.
In recent years, the color produced based on ion induction and change in fluorescence mechanism detect the colored indicator of metallic ion and fluorescent probe technique due to easy and simple to handle, detectability is low and [the Mao J that receives much concern, 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 colored indicator and fluorescent probe technique.Rhodamine (Rhodamine) is due to its outstanding spectral quality, as long wave effect weakening, larger fluorescent quantum conversion ratio and molar extinction coefficient [Haugland R P. A guide to fluorescent probes and labeling technologies. Invitrogen Corporation, Karlsbad, CA, 2005], a kind of colored indicator of being widely used and fluorescence probe is therefore become.In recent years, the carboxyl in rhodamine structure is utilized to generate unique five-membered 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 a lot.
Owing to having Response Mechanism uniqueness, detect the features such as sensitive, interference is few, be widely applied in the detection of heavy metal and transition metal ion based on the fluorescence probe of rhodamine molecule and colored indicator, detectable heavy metal ion comprises Cu
2+, Hg
2+, Pb
2+, Zn
2+deng.
Following formula gives the signal route of rhodamine B and heavy metal and transition metal ion effect.Be shown below, the rhodamine molecule molar absorptivity of closed loop configuration 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 Selective recognition to this ion.
The Cheng Huanyu ring opening process of rhodamine B lactam structure
[the Zheng H such as Zheng, Qian Z, Xu L, et al. Switching the recognition preference of rhodamine B spirolactam by replacing one atom:Design of rhodamine B thiohydrazide for recognition of Hg (II) in aqueous solution. Organic Letters, 2006,8:859-861] synthesized a kind of rhodamine sulfonyl hydrazine molecule, can with Hg
2+combine with the stoichiometric proportion of 2:1, and ultraviolet and fluorescence analysis can be utilized to detect Hg in aqueous phase
2+.[Huang J, Xu Y, the Qian X. A Rhodamine-based Hg such as Huang
2+sensor with high selectivity and sensitivity in aqueous solution:a NS2-containing receptor. Journal of Organic Chemistry, 2009,74:2167-2170] a kind of reversible Hg of design and synthesis
2+fluorescence probe, detection agent molecule with Hg
2+in conjunction with after show aubergine, and carry out semi-quantitative analysis by further fluoroscopic examination.And after adding EDTA in the equilibrium system to colour developing, system can become colorless from aubergine again.In addition, the fluorescence response speed of this individual system is very fast, is applicable to the real-time analysis to environment or biological sample.[Song C, Zhang X, Jia C, the et al. Highly sensitive and selective fluorescence sensor based on functional SBA-15 for detection of Hg such as Song
2+in Aqueous Media. Talanta, 2010,81:643-649] obtain one to Hg with paranitrobenzaldehyde and rhodamine B
2+selectively molecule, and it is connected by hydrogen bond with hollow porous material SBA-15, obtaining one can to Hg in pure water environment
2+carry out the detection agent detected in real time, and detectability reaches 1 μ g/L.[the Ko S such as Ko, Yang Y, Tae J, et al. In vivo monitoring of mercury ions using a rhodamine-based molecular probe. Journal of the American Chemical Society, 2006,128:14150-14155] be then parent with rhodamine 6G, connect thiosemicarbazides synthesize a kind of can pure water mutually in the Hg of application
2+fluorescence probe.This probe has good water solubility, signal response rapidly (<1s), the features such as the pH scope of application large (7 ~ 14), and there is cell and biological tissue's permeability, in mammalian cell and zebra fish body, successfully achieve Hg
2+identification.[Yang Y, Yook K, the Tae J. A rhodamine-based fluorescent and colorimetric chemodosimeter for the rapid detection of Hg such as Yang
2+ions in aqueous media. Journal of the American Chemical Society, 2005,127:16760-16761] thiocarbamide structure is introduced rhodamine molecule, utilize thiocarbamide and Hg
2+response obtained a kind of mercury ion probe, after this probe molecule is combined with mercury ion, water sample presents obvious redness, and fluorescence intensity also promotes at once.The Li Fu friend seminar of Fudan University then utilizes the combination of ferrocene and mercury to obtain mercury ion probe [Yang H, Zhou Z, Huang K, et al. Multisignaling optical-electrochemical sensor for Hg
2+based on a rhodamine derivative with a ferrocene unit. Organic Letters, 2007,9:4729-4732], this probe also can utilize the fluorescent effect of rhodamine to detect mercury ion efficiently in biological cell.[the Huang W such as Bhalla, Song C, He C, et al. Recognition preference of rhodamine-thiospirolactams for mercury (II) in aqueous solution. Inorganic Chemistry, 2009,48:5061-5072] a kind of mercury ion detecting agent that can be recycled that utilized terphenyl and rhodamine B to obtain, after adding tetrabutylammonium iodide (TBAI) to titration in the detection agent sample after being combined with mercury ion, detection agent can be separated with mercury ion, thus again can be used as water sample detection.[the Shiraishi Y such as Shiraishi, Sumiya S, Kohno Y, et al. A rhodaminecyclen conjugate as a highly sensitive and selective fluorescent chemosensor for Hg (II). Journal of Organic Chemistry, 2008,73:8571-8574] on rhodamine B molecule, connect 1,4,7,10-tetraazacyclododecanand, due to 1,4,7,10-tetraazacyclododecanand and metallic ion have stronger combination, and therefore obtained molecule is to Hg
2+there is very strong fluorescence identifying effect, when adding the Hg of 10 times of concentration in the acetonitrile solution to detection agent concentration being 50 μm of ol/L
2+time, the fluorescence intensity of system enhances 1700 times, is the rhodamine Hg that the fluorescence response that obtains so far is the strongest
2+detection agent.
[the Dujols V such as Dujols, Ford F, Czarnik A W. A Long-wavelength fluorescent chemodosimeter selective for Cu (II) ion in water. Journal of the American Chemical Society, 1997, 119:7386-7387] and [the Tang L such as Tang, Li F, Liu M, et al. A new rhodamine B derivative as a colorimetric chemosensor for recognition of copper (II) Ion. Bull Korean Chemistry Society, 2010, 31:3212-3216] successively report copper ion colorimetric detection agent based on rhodamine B, both are higher to the detection sensitivity of copper ion, preparation method is also fairly simple.Mei etc. can identify Cu so that rhodamine B hydrazides and salicylaldhyde Reactive Synthesis are a kind of
2+fluorescence probe [Mei L, Xiang Y, Li N, et al. A new fluorescent probe of rhodamine B derivative for the detection of copper ion. Talanta, 2007,72:1717-1722], this probe is to Cu
2+demonstrate reversible fluorescence and UV response change, probe and Cu
2+during effect, uv absorption is maximum can strengthen 500 times, and in water/acetonitrile (1:1, φ) solution, this probe can realize being the Cu of 25 nmol/L to concentration
2+the mensuration of actual sample.[the Zhang X such as Zhang, Shiraishi Y, Hirai T. Cu (II)-selective green fluorescence of a rhodamine-diacetic acid conjugate. Organic Letters, 2007,9:5039-5042] a kind of rhodamine detection agent showing green fluorescence of reported first, this Rhodamine Derivatives containing ethylenediamine-N, N '-oxalic acid group with Cu
2+in conjunction with time produce very strong green fluorescence, and with other metallic ions in conjunction with time produce weak fluorescent orange, utilize the difference of this fluorescence emission wavelengths, can realize Cu
2+accurate detection.
Rhodamine B and methoxy amine hydrochlorate is utilized to react, [the Bae S such as Bae, Tae J. Rhodamine-hydroxamate-based fluorescent chemosensor for FeIII. Tetrahedron Letters, 2007,48:5389-5392] obtain a kind of Fe
3+detection agent, after detection agent molecule is dissolved in acetonitrile/water solution (1:1, φ), adds Fe
3+solution fluorescence intensity can be made obviously to strengthen.[Kwon J, Jang Y, Lee Y, the et al. A highly selective fluorescent chemosensor for Pb such as Kwon
2+. Journal of the American Chemical Society, 2005,127:10107-10111] on rhodamine B molecule, introduce two pyridine rings, obtained molecule is to Pb
2+there is very strong selectivity, with Pb
2+can produce fluorescence in conjunction with rear solution, be a kind of comparatively ideal lead ion detection agent.[the Tomat E such as Tomat, Lippard S. Ratiometric and Intensity-Based Zinc Sensors Built on Rhodol and Rhodamine Platforms. Inorganic Chemistry, 2010,49:9113-9115] detection agent reported is equally containing pyridine ring, and this detection agent is to Zn
2+there is good detection sensitivity, can quantitatively record Zn in water sample
2+content.[the Zhou Z such as Zhou, Yu M, Yang H, et al. FRET-based sensor for imaging chromium (III) in living cells. Chemical Communications, 2008,29:3387-3389] synthesize a kind of Cr based on rhodamine
3+detection agent, and its Detection results in Hela cell is explored.In addition, the Cd based on rhodamine-5N derivant is also had
2+the report [Soibinet M, Souchon V, Leray I, et al. Rhod-5N as a Fluorescent Molecular Sensor. Journal of Fluorescence. 2008,18:1077-1082] of ion fluorescence probe.
But the principle of colour developing heavy metal analysis agent many employings organic group complexation of metal ions that research is more at present, thus detection agent mostly is the molecule containing organic heterocyclic, and solubleness is not satisfactory in aqueous.In addition, except the characteristic reaction of the minority ions such as mercury ion is very sensitive, most heavy metal ion and detection agent still not ideal enough in conjunction with effect, therefore detection sensitivity and the scope of application are subject to many restrictions, for these heavy metal ion, finding more suitable, efficient detection agent is still the difficult problem of pendulum in face of us.
There is no both at home and abroad about the Cr based on rhodamine B-diethylenetriamine derivant at present
3+the document of the preparation method of colored indicator and patent report.
Summary of the invention
The object of the invention is to the deficiency overcoming prior art existence, propose a kind of Cr based on rhodamine B-diethylenetriamine derivant
3+the preparation method of colored indicator.
A kind of Cr based on rhodamine B-diethylenetriamine derivant that the present invention proposes
3+colored indicator, synthesizes a kind of rhodamine B-diethylenetriamine derivant by rhodamine B and diethylenetriamine; This rhodamine B-diethylenetriamine derivant can be used as Cr
3+colored indicator, adds Cr in the water-ethanol mixed solution of this rhodamine B-diethylenetriamine derivant
3+after, the color of mixed solution becomes redness from colourless, and in corresponding uv-visible absorption spectroscopy, the absorption peak at 561 nm places is along with Cr
3+the rising of concentration and strengthening; Should based on the Cr of rhodamine B-diethylenetriamine derivant
3+colored indicator is to Cr
3+response time at about 5 min, lowest detection is limited to 5.2 × 10
-7mol/L, and can be used for micro-in water environment/trace Cr
3+half-quantitative detection.
A kind of Cr based on rhodamine B-diethylenetriamine derivant that the present invention proposes
3+the preparation method of colored indicator, concrete steps are as follows:
(1) 1-10 g rhodamine B is taken and 5 ~ 50 mL organic solvents add in 100 mL reaction bulbs; abundant stirring makes rhodamine B dissolve completely; 1 ~ 10 g diethylenetriamine is dropwise added when keeping stirring; under nitrogen protection in 75-85 DEG C of reaction 6-24 h; after reaction terminates, reaction bulb is cooled to room temperature; filtration obtains pale solid powder; finally that this light-colored powder absolute ethyl alcohol cyclic washing is extremely colourless; use anhydrous sodium sulfate drying 6-48 h again; obtain a kind of based on rhodamine B-diethylenetriamine derivant, productive rate is 70%-95%.
(2) take 1 ~ 3 g should based on rhodamine B-diethylenetriamine derivant be dissolved in 10 ~ 30 g water and organic solvent composition mixed solution in obtain a kind of Cr based on rhodamine B-diethylenetriamine derivant
3+colored indicator.
In the present invention, organic solvent described in step (1) adopts any one in ethanol, methyl alcohol or isopropyl alcohol.
In the present invention, organic solvent described in step (2) adopts any one in ethanol, methyl alcohol or isopropyl alcohol, the volume ratio of water and organic solvent is 1:1 ~ 10:1, good solubleness should be had based on rhodamine B-diethylenetriamine derivant, reach 0.01 ~ 1 mmol/L, can be used as a kind of Cr based on rhodamine B-diethylenetriamine derivant
3+colored indicator.
Should be as follows based on the synthetic route of rhodamine B-diethylenetriamine derivant:
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 mixed solvent based on rhodamine B-diethylenetriamine derivant can be the mixed solution (water: ethanol=1:1 ~ 10:1, volume ratio) of water and ethanol, also can be the mixed solution of water and methyl alcohol or water and isopropyl alcohol.In the mixed solvent (water: ethanol=1:1 ~ 10:1, volume ratio) of water and ethanol, should can reach 0.01 ~ 1 mmol/L based on solubleness of rhodamine B-diethylenetriamine derivant, can be used as a kind of Cr based on rhodamine B-diethylenetriamine derivant
3+colored indicator.
Advantage of the present invention is: 1. the present invention is a kind of Cr based on rhodamine B-diethylenetriamine derivant
3+the preparation method of colored indicator, can be used for Cr in express-analysis water sample
3+the efficient colored indicator of content, it is to other coexistent metallic ions (Cu in water sample
2+, Zn
2+, Fe
3+, Cd
2+, Pb
2+, Hg
2+, Mn
2+, Fe
2+, Ba
2+, Ag
+) antijamming capability strong, applicable pH range wide (faintly acid is to neutral) is a kind of efficient chromium ion colored indicator; 2. this Cr
3+colored indicator is to Cr
3+response time within 5 minutes, lowest detection is limited to 5.2 × 10
-7mol/L; 3. the present invention has the advantages such as synthesis technique is simple, with low cost, easy and simple to handle, selectivity is good, 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 environment, also can be used for the half-quantitative detection of micro-/Determination of Trace Chromium ion concentration.
Accompanying drawing explanation
Fig. 1 is the chemical structural formula based on rhodamine B-diethylenetriamine derivant.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram based on rhodamine B-diethylenetriamine derivant.
Fig. 3 is the Cr based on rhodamine B-diethylenetriamine derivant
3+the color situation of change of colored indicator after adding different heavy metal ion (from left to right: Cu
2+, Zn
2+, Fe
3+, Cd
2+, Pb
2+, Hg
2+, Mn
2+, Fe
2+, Ba
2+, Ag
+, Cr
3+).
Fig. 4 is the Cr based on rhodamine B-diethylenetriamine derivant
3+colored indicator is adding different metal ion (Na
+, K
+, Ni
2+, Hg
2+, Fe
3+, Mn
2+, Co
2+, Cd
2+, Cu
2+, Pb
2+, Zn
2+, Mg
2+, Ba
2+, Ag
+, Fe
2+, Ce
3+) after uv-visible absorption spectrum figure.
Fig. 5 is the Cr based on rhodamine B-diethylenetriamine derivant
3+variable concentrations Cr is added in colored indicator
3+after uv-visible absorption spectrum figure.
Fig. 6 is the Cr based on rhodamine B-diethylenetriamine derivant
3+after colored indicator mixes with chromium ion solution, UV-Visible absorption intensity over time.
Fig. 7 is low concentration Cr
3+with the Cr based on rhodamine B-diethylenetriamine derivant
3+the UV-Visible absorption intensity fitting a straight line (wavelength 561 nm) of colored indicator.
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 5 g rhodamine Bs and 15 mL absolute ethyl alcohols add in 100 mL reaction bulbs; abundant stirring makes rhodamine B dissolve completely; 3 mL diethylenetriamines are dropwise added when keeping stirring; under nitrogen protection in 80 DEG C of reaction 12 h; after reaction terminates, reaction bulb is cooled to room temperature; filtration obtains pale solid powder; by this pale solid powder absolute ethyl alcohol cyclic washing to colourless; with anhydrous sodium sulfate drying 24 h; obtain a kind of based on rhodamine B-diethylenetriamine derivant, productive rate is 75%.Take 2 g based on rhodamine B-diethylenetriamine derivant, to be dissolved in the mixed solvent (water: ethanol=4:1, volume ratio) of 20 g water and ethanol, to obtain a kind of Cr based on rhodamine B-diethylenetriamine derivant
3+colored indicator.
Should based on rhodamine B-diethylenetriamine derivant chemical structural formula and
1h-NMR nuclear magnetic spectrogram respectively as depicted in figs. 1 and 2.Fig. 3 is this Cr based on rhodamine B-diethylenetriamine derivant
3+the color situation of change of colored indicator after adding different heavy metal ion (from left to right: Cu
2+, Zn
2+, Fe
3+, Cd
2+, Pb
2+, Hg
2+, Mn
2+, Fe
2+, Ba
2+, Ag
+, Cr
3+).Fig. 4 is the Cr based on rhodamine B-diethylenetriamine derivant
3+different metal ion (Na is added in colored indicator
+, K
+, Ni
2+, Hg
2+, Fe
3+, Mn
2+, Co
2+, Cd
2+, Cu
2+, Pb
2+, Zn
2+, Mg
2+, Ba
2+, Ag
+, Fe
2+, Ce
3+) after uv-visible absorption spectrum figure.Fig. 5 is the Cr based on rhodamine B-diethylenetriamine derivant
3+variable concentrations Cr is added in colored indicator
3+after uv-visible absorption spectrum figure.Fig. 6 is the Cr based on rhodamine B-diethylenetriamine derivant
3+after colored indicator mixes with chromium ion solution, UV-Visible absorption intensity over time.Fig. 7 is low concentration Cr
3+with this Cr based on rhodamine B-diethylenetriamine derivant
3+the UV-Visible absorption intensity fitting a straight line (wavelength 561 nm) of colored indicator.
Embodiment 2: identical with embodiment 1, but in step (2), the volume ratio of water and ethanol becomes 3:1.
Embodiment 3: identical with embodiment 1, but in step (2), the volume ratio of water and ethanol becomes 5:1.
Embodiment 4: identical with embodiment 1, but in step (2), ethanol becomes methyl alcohol, and the volume ratio of water and methyl alcohol is 3:1.
Embodiment 5: identical with embodiment 1, but in step (2), ethanol becomes isopropyl alcohol, and the volume ratio of water and isopropyl alcohol is 5:1.
The Cr based on rhodamine B-diethylenetriamine derivant obtained in embodiment 1-5
3+colored indicator and Cr
3+there is special combination, and with other common metal ion (Cu
2+, Zn
2+, Fe
3+, Cd
2+, Pb
2+, Hg
2+, Mn
2+, Fe
2+, Ba
2+, Ag
+) then not there is this effect.At this Cr based on rhodamine B-diethylenetriamine derivant
3+cr is added in colored indicator
3+after, solution colour becomes redness from colourless, occurs absorption peak in uv-visible absorption spectroscopy in 561 nm place correspondences, shows that it is a kind of Cr efficiently
3+colored indicator.Should based on the Cr of rhodamine B-diethylenetriamine derivant
3+the lowest detection of colored indicator to chromium ion concentration is limited to 5.2 × 10
-7mol/L, applicable pH range is that faintly acid is to neutrality.Should based on the Cr of rhodamine B-diethylenetriamine derivant
3+the response time of colored indicator is less than 5 min, and uv-visible absorption spectroscopy characteristic peak is along with Cr
3+the rising of concentration and strengthening, still meets linear relationship at low concentrations, can be used for the half-quantitative detection of micro-/Determination of Trace Chromium ion concentration.
Above-described embodiment, 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 Essence of the present invention or modification, all should be encompassed within protection scope of the present invention.
Claims (1)
1. the Cr based on rhodamine B-diethylenetriamine derivant
3+the preparation method of colored indicator, is characterized in that concrete steps are as follows:
(1) 1-10 g rhodamine B is taken and 5 ~ 50 mL organic solvents add in reaction bulb, abundant stirring makes rhodamine B dissolve completely, 1 ~ 10 g diethylenetriamine is dropwise added when keeping stirring, under nitrogen protection in 75-85 DEG C of reaction 6-24 h, after reaction terminates, reaction bulb is cooled to room temperature, filtration obtains pale solid powder, finally that this light-colored powder absolute ethyl alcohol cyclic washing is extremely colourless, use anhydrous sodium sulfate drying 6-48 h again, obtain a kind of based on rhodamine B-diethylenetriamine derivant, productive rate is 70%-95%; Described organic solvent is any one in ethanol, methyl alcohol or isopropyl alcohol;
(2) take 1 ~ 3 g should based on rhodamine B-diethylenetriamine derivant be dissolved in 10 ~ 30 g water and organic solvent composition mixed solvent in obtain a kind of Cr based on rhodamine B-diethylenetriamine derivant
3+colored indicator; Described organic solvent is any one in ethanol, methyl alcohol or isopropyl alcohol, and the volume ratio of water and organic solvent is 1:1 ~ 10:1.
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| CN104861960B (en) * | 2015-04-16 | 2017-01-18 | 同济大学 | Fast-response Hg＜2+＞ chromogenic-fluorescent probe preparation method based on rhodamine B-diethylenetriamine-cinnamic acid derivative |
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| CN107192693A (en) * | 2016-03-15 | 2017-09-22 | 南京工业大学 | A kind of preparation and application based on rhodamine base heavy metal ion solid phase fluorescent sensor |
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