CN107686668A - A kind of preparation and application of the sour cyanines probe in water solubility side of sulfonic group modification - Google Patents

A kind of preparation and application of the sour cyanines probe in water solubility side of sulfonic group modification Download PDF

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Publication number
CN107686668A
CN107686668A CN201710776692.2A CN201710776692A CN107686668A CN 107686668 A CN107686668 A CN 107686668A CN 201710776692 A CN201710776692 A CN 201710776692A CN 107686668 A CN107686668 A CN 107686668A
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China
Prior art keywords
water solubility
group modification
probe
sulfonic group
sour cyanines
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CN201710776692.2A
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刘晓骞
李娜
王建浩
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Changzhou University
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Changzhou University
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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
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/16—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing hetero atoms
    • C09B23/162—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing hetero atoms only nitrogen atoms
    • C09B23/164—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing hetero atoms only nitrogen atoms containing one nitrogen atom
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/3103—Atomic absorption analysis

Abstract

The invention belongs to chemical analysis test field, and in particular to a kind of preparation and application of the sour cyanines probe in water solubility side of sulfonic group modification.First by 2,3,3 trimethyl 3H indoles and 1 iodine valeric acid reaction generation compound A, then flowed back 4 hours with square diethyl phthalate and obtain compound B, acidification reaction product again, and with 1 ethyl 2,3, the sulphonic acid ester of 3 trimethyl 3H indoles 15 is heated to reflux, and by separating-purifying, obtains final products.The sour cyanine compound in side that the present invention obtains has excellent optical property and ion selectivity, is advantageous to the detection to mercury ion and iron ion.

Description

A kind of preparation and application of the sour cyanines probe in water solubility side of sulfonic group modification
Technical field
The invention belongs to chemical analysis test field, and in particular to a kind of sour cyanines probe in water solubility side of sulfonic group modification Prepare and apply.
Background technology
Mercury and mercuric compounds belong to extremely toxic substance, and mercury is deposited in nature in the form of mercury metal, organic mercury and inorganic mercury , inorganic mercury is smaller relative to the toxicity of organic mercury and mercury metal, but enter human body in inorganic mercury ion can be changed into poison Property bigger organic mercury, entered by food chain in human body, can in vivo put aside, cause systemic toxicity profiles.One of eight big public hazards of the world Minamata disease, precisely due to patient long-term consumption containing caused by the higher fish of mercury concentration, shellfish.Mercury and mercuric compounds can pass through Respiratory tract, alimentary canal or skin are absorbed by the body.Mercury generally has higher chemical stability, and various processing, cooking method are all It can not be got rid of, easily by enteron aisle, mucosal absorption.The content of Standard Drinking Water mercury ion should be less than 0.001mg/L。
Iron ion is also a kind of important metallic element, is the weight in human body hemoglobin, myosin and cytochromes Want composition.Research shows that iron deficiency can cause hypoferric anemia and alpastic anemia, and it is gentle easily to make one generation weakness of limbs Breathe heavily symptom.
Design and enjoyed in recent years with synthesizing the chemical sensor that there is Selective recognition function for mercury ion and iron ion Concern, have become the study hotspot in the fields such as chemical science, environmental science and life science.Common mercury ion and iron ion Detection method has atomic absorption spectrography (AAS), fluorescence spectrophotometric method, oscilloscopic polarography etc..But these detection methods are for instrument Equipment and operation have very high requirement, and cost is high, and time-consuming.Therefore, people there is an urgent need to one kind can quickly, it is accurate, The method of analysis detection mercury ion and iron ion at low cost, it is simple to prepare a kind of synthetic method, easy control of reaction conditions New function dyestuff, there is higher application prospect.
The content of the invention
The invention provides a kind of sour cyanines probe in water solubility side of sulfonic group modification, the structural formula of the probe is：
Present invention also offers a kind of preparation method of the sour cyanines probe in water solubility side of above-mentioned sulfonic group modification：
(1) 2,3,3- trimethyl -3H- indoles and 1- iodine valeric acids are dissolved in anhydrous acetonitrile and flowed back 18 hours, is removed under reduced pressure Solvent obtains crude product, and crude product is washed with the ether of abundance, obtains yellow solid A.
(2) in round-bottomed flask, yellow solid A that step (1) is obtained, square diethyl phthalate and triethylamine are dissolved in ethanol and obtained To reactant mixture, by reactant mixture at 65~80 DEG C, heat 0.5~2 hour, evaporation of solvent, obtain orange-yellow solid Body B.
(3) in round-bottomed flask, the orange/yellow solid B that step (2) obtains is dissolved in 10mL ethanol, it is water-soluble to add NaOH Liquid obtains reactant mixture, and reactant mixture is flowed back 30 minutes, cooling, then adds the stirring of 1N HCl solutions, obtains chemical combination Thing C.
(4) the compound C for obtaining step (3) and 1- ethyl -2,3,3- trimethyl -3H- indoles -1--5- sulphonic acid esters Volume ratio is dissolved in as 1:In 1 toluene and n-butanol solvent system, it is heated to reflux at 100~120 DEG C.Solvent is removed through decompression, Column chromatography for separation obtains final products.
Wherein, the mol ratio of 2,3,3- trimethyl -3H- indoles and 1- iodine valeric acids is 1~2 in step (1):1~3.
The mol ratio of yellow solid A and square diethyl phthalate is 1 in step (2)：1；, the heating temperature of mixture in step (2) Degree is preferably 70 DEG C, and the heat time is preferably 1 hour.
The mol ratio of compound C and 1- ethyls -2,3,3- trimethyls -3H- indoles -1--5- sulphonic acid esters is in step (4) 1:1, it is preferably 110 DEG C to be heated to reflux temperature.
The chemical reaction of method made above is：
Present invention also offers a kind of application of the sour cyanines probe in water solubility side of above-mentioned sulfonic group modification：The probe is used to select Selecting property identifies Hg2+And Fe3+, in certain dicyandiamide solution, by the way that under specific wavelength, the change of absorbance can be directly perceived , selectivity of the unaided eye discrimination probe for specific ion.
Carbonyl on probe four-membered ring can provide hydrogen bond action, the metal ion of electron deficient can by with probe molecule Between hydrogen bond action formed coordination.Probe is by the radius size of ion, coordination ability and not to the selectivity of different ions What the power for the hydrogen bond action that same solvent environment provides was determined.
Probe aligns to form aggregation easily by intermolecular pi-pi accumulation in aqueous, and in surfactant Under cetyl trimethylammonium bromide solution effect, the distribution of probe in the solution can be readjusted, prevents the self aggregation of probe. This change can also be embodied in the change for absorbance in ion M8003 line.
The inventive method is solved in different dicyandiamide solutions to Hg2+And Fe3+The problem of Selective recognition, from reaction Seen in phenomenon, add Fe3+Absorption of the probe at 620nm is caused to weaken after complexing, solution colour is by blue yellowing.Add Hg2+Cause the enhancing of probe absorbance at 620nm after complexing, color becomes navy blue by blueness.
The beneficial effects of the present invention are：The present invention has synthesized a kind of asymmetric with side chain carboxyl and sulfonic group modification The sour cyanines probe structure in side, the introducing of substituent can increase the water solubility of probe, prevent from absorbing by the self aggregation of probe and It is quenched.Meanwhile asymmetric structure can adjust the optical property of the probes such as the absorbing wavelength of probe, Stokes shift.
This probe is synthesized by multistep and obtained, and different types of electron donor is synthesized step by step first, finally in the bar of backflow Connect under part with the sour ring in side, obtain final product.The reaction being related in building-up process, it is not necessary to anhydrous, anaerobic severe Quarter condition, easy control of reaction conditions, reaction by simply handling can just obtain pure product after terminating.As Fe3+With Hg2+The chemical sensor of detection, party's acid cyanines probe high sensitivity, selectivity are good, can be in different solvents optionally Identify Fe3+And Hg2+, such as in surfactant：Fe can be identified in cetyl trimethylammonium bromide dicyandiamide solution3+From Son；, can be with Selective recognition Hg in pure water solvent2+Ion, there is high application.
Brief description of the drawings
Fig. 1 is the sour cyanines probe in water solubility side of sulfonic group modification prepared by embodiment 1 with 1 × 10-6Mol/L concentration is ten Abosrption spectrogram after being acted in six alkyl trimethyl ammonium bromide solution with different ions.
Fig. 2 is the sour cyanines probe in water solubility side of sulfonic group modification prepared by embodiment 1 with 1 × 10-6Mol/L concentration is pure In water with 4mol/L cetyl trimethylammonium bromide solutions for Fe3+Absorption spectrum curve compare.
Fig. 3 is the sour cyanines probe in water solubility side of sulfonic group modification prepared by embodiment 1 with 1 × 10-6Mol/L concentration is pure Abosrption spectrogram after being acted in water with different ions.
Note：In Fig. 1 and Fig. 3, due to Hg2+Ion or Fe3+The solution concentration very little that ion is made into, in this case, Comprise only Hg2+Ion or Fe3+The solution of ion is all colourless transparent solution.
Embodiment
The present invention is described in further detail with reference to embodiment：
Embodiment 1：
(1) 3.17g (20mmol) 2,3,3- trimethyl -3H- indoles and 6.81g (30mmol) 1- iodine valeric acids are dissolved in In 100mL anhydrous acetonitriles, reactant mixture is flowed back 18 hours, after the completion of reaction, pressurization removes solvent, and crude product is washed with ether Wash, obtain yellow solid A5.7g.
(2) in round-bottomed flask, the yellow solid 3g (11mmol) that will be obtained in step (1), and 1.86g (11mmol) sides Diethyl phthalate and 0.8mL triethylamines are dissolved in 10mL ethanol, and reactant mixture is heated 1 hour at 70 DEG C, obtained orange-yellow molten Liquid, removal of solvent under reduced pressure, obtain product B 2g.
(3) in round-bottomed flask, step (2) product B 2g (5mmol) are dissolved in 10mL ethanol, then add NaOH water Solution.Reactant mixture is flowed back 30 minutes, then cooled down, the stirring of 1N HCl solutions is then added, obtains compound C.
(4) by the compound C 1.8g (4.5mmol) obtained in step (3) and 1- ethyl -2,3,3- trimethyl -3H- Yin Diindyl -1--5- sulphonic acid esters 1.21g (4.5mmol) is 1 in volume ratio:Flow back, depressurize at 110 DEG C in 1 toluene n-butanol system Except solvent, final product blue solid is obtained through column chromatography for separation.
The sour cyanines probe in water solubility side of sulfonic group modification prepared by embodiment 1 is with 1 × 10-6Mol/L concentration is in 4mol/L Show in abosrption spectrogram such as Fig. 1, Fig. 1 after being acted in cetyl trimethylammonium bromide solution with different ions and add dropwise Enter 1 × 10-6After mol/L different ions solution, the absorbance change situation of probe.When being added dropwise 1 × 10-6Mol/L Fe3 +During solution, there occurs significant reduction, (curve l), solution become yellow to probe absorption value by blueness.And the probe is 16 Alkyl trimethyl ammonium bromide solution is as in solvent, and for change of other ions without particularly apparent absorbance, (curve a is extremely L), so as to showing in the system middle probe for Fe3+Selective recognition effect.
Fig. 2 is the sour cyanines probe in water solubility side of sulfonic group modification prepared by embodiment 1 with 1 × 10-6Mol/L concentration is pure In water with 4mol/L cetyl trimethylammonium bromide solutions for Fe3+Absorption spectrum curve compare.Containing iron ion Pure water in add the front and rear of surfactant cetyl trimethylammonium bromide, the absorbance of solution becomes there occurs obvious Change, it is shown that the influence that surfactant detects for iron ion.
Fig. 3 is the sour cyanines probe in water solubility side of sulfonic group modification prepared by embodiment 1 with 1 × 10-6Mol/L concentration is pure Abosrption spectrogram after being acted in water with different ions, show in Fig. 3 and be added dropwise 1 × 10-6Mol/L different ions solution Afterwards, the absorbance change situation of probe, when being added dropwise 1 × 10-6Mol/L Hg2+During solution, the enhancing of probe absorption intensity is (bent Line a), solution become navy blue by blueness；And the probe is in pure water, for other ions without particularly apparent absorbance Change (curve a to k), so as to show in the system middle probe for Hg2+Selective recognition effect.
Embodiment 2
(1) 4.76g (30mmol) 2,3,3- trimethyl -3H- indoles and 10.22g (30mmol) 1- iodine valeric acids are dissolved in In 100mL anhydrous acetonitriles, reactant mixture is flowed back 18 hours.After the completion of reaction, pressurization removes solvent, and crude product is washed with ether Wash, obtain yellow powder A 8.6g.
(2) in round-bottomed flask, the yellow solid A6g (22mmol) that will be obtained in step (1), and 3.72g (22mmol) Square diethyl phthalate and 1mL triethylamine is dissolved in 15mL ethanol.Reactant mixture is heated 1 hour at 70 DEG C, obtained orange-yellow molten Liquid, removal of solvent under reduced pressure, obtain product B 3.5g.
(3) in round-bottomed flask, step (2) product B 3g (7.5mmol) is dissolved in 10mL ethanol, then add NaOH The aqueous solution.Reactant mixture is flowed back 30 minutes, then cooled down, the stirring of 1N HCl solutions is then added, obtains compound C.
(4) by the compound C 2.16g (5.4mmol) obtained in step (3) and 1- ethyl -2,3,3- trimethyl -3H- Yin Diindyl -1--5- sulphonic acid esters 1.45g (5.4mmol) is 1 in volume ratio:Flow back, depressurize at 110 DEG C in 1 toluene n-butanol system Except solvent, final product blue solid is obtained through column chromatography for separation.

Claims (9)

  1. A kind of 1. sour cyanines probe in water solubility side of sulfonic group modification, it is characterised in that：The structural formula of the probe is：
  2. 2. the preparation method of the sour cyanines probe in water solubility side of sulfonic group modification as claimed in claim 1, it is characterised in that：It is described Preparation method be：
    (1) 2,3,3- trimethyl -3H- indoles and 1- iodine valeric acids are dissolved in anhydrous acetonitrile and flowed back 18 hours, removal of solvent under reduced pressure Crude product is obtained, crude product is washed with ether, obtains yellow solid A；
    (2) the yellow solid A for obtaining step (1), square diethyl phthalate and triethylamine are dissolved in ethanol and obtain reactant mixture, will be anti- Answer mixture to heat, evaporation of solvent, obtain orange/yellow solid B；
    (3) the orange/yellow solid B that step (2) obtains is dissolved in ethanol, adds the NaOH aqueous solution and obtain reactant mixture, will react Mixture flows back 30 minutes, cooling, adds 1N HCl, obtains compound C；
    (4) the compound C for obtaining step (3) dissolves with 1- ethyl -2,3,3- trimethyl -3H- indoles -1--5- sulphonic acid esters In dicyandiamide solution, it is heated to reflux, removes solvent through decompression, obtain the sour cyanines probe in water solubility side of sulfonic group modification.
  3. 3. the preparation method of the sour cyanines probe in water solubility side of sulfonic group modification as claimed in claim 2, it is characterised in that：Step (1) mol ratio of 2,3,3- trimethyls -3H- indoles and 1- the iodine valeric acid is：1~2:1~3.
  4. 4. the preparation method of the sour cyanines probe in water solubility side of sulfonic group modification as claimed in claim 2, it is characterised in that：Step (2) mol ratio of the yellow solid A and square diethyl phthalate is：1：1；Reactant mixture heating-up temperature is：65~80 DEG C, heating Time is：0.5~2 hour.
  5. 5. the preparation method of the sour cyanines probe in water solubility side of sulfonic group modification as claimed in claim 2, it is characterised in that：Step (4) mol ratio of the compound C and 1- ethyls -2,3,3- trimethyls -3H- indoles -1--5- sulphonic acid esters is：1:1.
  6. 6. the preparation method of the sour cyanines probe in water solubility side of sulfonic group modification as claimed in claim 2, it is characterised in that：Step (4) dicyandiamide solution is:Volume ratio is 1:1 toluene and n-butanol, being heated to reflux temperature is:100~120 DEG C.
  7. 7. the preparation method of the sour cyanines probe in water solubility side of sulfonic group modification as claimed in claim 2, it is characterised in that：Step (2) the reactant mixture heating-up temperature is：70 DEG C, the heat time is：1 hour.
  8. 8. the preparation method of the sour cyanines probe in water solubility side of sulfonic group modification as claimed in claim 2, it is characterised in that：Step (4) being heated to reflux temperature described in is：110℃.
  9. 9. the application of the sour cyanines probe in water solubility side of sulfonic group modification as claimed in claim 1, it is characterised in that：Described sulphur The sour cyanines probe in water solubility side of acidic group modification is used for Selective recognition Hg2+And Fe3+。
CN201710776692.2A 2017-09-01 2017-09-01 A kind of preparation and application of the sour cyanines probe in water solubility side of sulfonic group modification Pending CN107686668A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115108966A (en) * 2022-06-23 2022-09-27 西南医科大学 Benzoindole squarylium cyanine metal ion probe and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040166515A1 (en) * 1998-04-08 2004-08-26 Terpetschnig Ewald A. Luminescent compounds

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040166515A1 (en) * 1998-04-08 2004-08-26 Terpetschnig Ewald A. Luminescent compounds

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ANATOLIY L. TATARETS ET AL.: "Synthesis of water-soluble, ring-substituted squaraine dyes and their evaluation as fluorescent probes and labels", 《ANALYTICA CHIMICA ACTA》 *
LARYSA I. MARKOVA ET AL.: "Comparison of a series of hydrophilic squaraine and cyanine dyes for use as biological labels", 《DYES AND PIGMENTS》 *
宋波 等: "新型水溶性荧光标示剂吲哚方酸菁染料的合成及光谱性能", 《高等学校化学学报》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115108966A (en) * 2022-06-23 2022-09-27 西南医科大学 Benzoindole squarylium cyanine metal ion probe and preparation method and application thereof
CN115108966B (en) * 2022-06-23 2023-06-09 西南医科大学 Benzoindole squaraine metal ion probe and preparation method and application thereof

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Application publication date: 20180213