CN105136759B - 5 aromatic hydrocarbons of column is copolymerized in CHCl3The application of colorimetric detection cetylpyridinium chloride in system - Google Patents
5 aromatic hydrocarbons of column is copolymerized in CHCl3The application of colorimetric detection cetylpyridinium chloride in system Download PDFInfo
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- CN105136759B CN105136759B CN201510558417.4A CN201510558417A CN105136759B CN 105136759 B CN105136759 B CN 105136759B CN 201510558417 A CN201510558417 A CN 201510558417A CN 105136759 B CN105136759 B CN 105136759B
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Abstract
This hair discloses the 5 aromatic hydrocarbons inspection of copolymerization column in CHCl3The application of colorimetric detection cetylpyridinium chloride in system, belongs to compound test technical field.To specifically 5 aromatic hydrocarbons CHCl of column be copolymerized3It is made into bulk solution；The CHCl of surfactant cetylpyridinium chloride, brocide, cetrimonium bronmide, trimethylamine ethanol solution, triethanolamine, neopelex is respectively configured3Solution is as object solution；Object solution is added in aforementioned body solution, if the fluorescent quenching of bulk solution, illustrates that it is cetylpyridinium chloride to add object solution；If the fluorescence of bulk solution does not change, it is not cetylpyridinium chloride to illustrate object solution.This method monitoring cetylpyridinium chloride have the characteristics that it is quick, sensitive high, for single selective detection surfactant open new direction.
Description
Technical field
The present invention relates to a kind of detection method of surfactant cetylpyridinium chloride, more particularly to one kind is using altogether
The method of poly- 5 aromatic hydrocarbons of column detection cetylpyridinium chloride, belongs to compound test technical field.
Background technology
Surfactant due to wetting or it is anti-stick, emulsification or demulsification, blistering or defoaming and it is solubilized, scattered, washing,
The a series of physical such as anti-corrosion, antistatic chemical action and corresponding practical application, become a kind of versatile and flexible, widely used essence
Refine chemical product.For surfactant except being used as detergent in daily life, other application can almost cover all essences
Thin chemical field.Cetylpyridinium chloride is a kind of cationic quaternary ammonium compound, is also a kind of very important in life
Surface-active and fungicide.Under equal use condition, which is reluctant that bacterium killing rate is equal to heterotroph, iron bacteria and sulfate
Better than dodecyl benzyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide and other common quaternary ammonium salt bactericides
Agent.Add material to feed intake using impact type, general concentration is 20 ~ 80mL/L.But the content of cetylpyridinium chloride
It is larger then poisonous.Therefore, the detection for cetylpyridinium chloride is a highly important job.At present, for chlorination
The detection of cetyl pyridinium, measures usually using colorimetric determination, or with a matter of the same colour combination method.These detection methods need
Detection time is longer, detects unobvious or to be detected by more complicated instrument.
Column aromatic hydrocarbons has shown very outstanding effect as a new class of macrocycle molecule in terms of host-guest chemistry.It is logical
The modification to column aromatic hydrocarbons structure is crossed, many host-guest chemistry systems are developed well.It is well known that copolymerization 5 aromatic hydrocarbons of column carries
For a good cavity structure, so the guest molecule with suitable construction size, which can be penetrated into its cavity, reaches main
The result of object inclusion.Pyridine derivate and traditional macrocycle molecule such as crown ether, cyclodextrin, calixarenes construction host-guest inclusion
Thing.Therefore, using this property of column aromatic hydrocarbons, the identification of pyridine can be used for as new identification system.
The content of the invention
The purpose of the present invention is the property according to column aromatic hydrocarbons, there is provided copolymerization 5 aromatic hydrocarbons of column is in CHCl3Colorimetric detection chlorine in system
Change the application of cetyl pyridinium.
First, the preparation of molecule copolymerization 5 aromatic hydrocarbons of column
The preparation method of supermolecule copolymerization 5 aromatic hydrocarbons of column of the present invention, comprises the following steps that：
（1）The synthesis of intermediate：Using ethanol as solvent, sodium hydroxide and potassium iodide are catalyst, under nitrogen protection, to benzene
Diphenol is with bromohexadecane with 1:1~1:1.2 molar ratio 20 ~ 24h of back flow reaction, cooling, leaches out inorganic salts, vacuum rotary steam
Dry solvent, chloroform dissolving, distilled water extraction, is then dried, organic phase pillar layer separation, obtains centre with anhydrous sodium sulfate
Body；The dosage of sodium hydroxide is 3 ~ 4 times of hydroquinone mole；The dosage of potassium iodide is 0.5 ~ 1 times to bromododecane；
（2）It is copolymerized the synthesis of 5 aromatic hydrocarbons of column：With 1,2- dichloroethanes for solvent, boron trifluoride ether is catalyst, poly first
Aldehyde, intermediate and terephthaldehyde's ether are raw material, in 6 ~ 8h of room temperature reaction；Then methanol extraction, chloroform dissolving, distilled water extraction are used
Take, organic phase pillar layer separation, 5 aromatic hydrocarbons of column must be copolymerized.The dosage of terephthaldehyde's ether is the 0.8 ~ 1 of paraformaldehyde mole
Times；The dosage of intermediate is 4 ~ 6 times of the mole of terephthaldehyde's ether；The dosage of catalyst boron trifluoride ether is paraformaldehyde
0.5 ~ 1 times of mole.
Copolymerization 5 aromatic hydrocarbons of column is labeled as DCP5-16, its structural formula is as follows：
。
2nd, it is copolymerized the application of 5 aromatic hydrocarbons color of column detection cetylpyridinium chloride
1st, it is copolymerized 5 aromatic hydrocarbons of column（DCP5-16）To cetylpyridinium chloride（G）Unicity fluorescence identifying
By DCP5-16 CHCl3It is made into 2 × 10-3The bulk solution of mol/L, the solution are in light blue under 365nm ultraviolet lamps
Color fluorescence；The bulk solution of 0.5mL is taken to be separately added into the different surfaces activating agent of 0.5mL in 7 colorimetric cylinders respectively（Chlorination
Cetyl pyridinium, brocide, cetrimonium bronmide, trimethylamine ethanol solution, triethanolamine, 12
Sodium alkyl benzene sulfonate）Chloroformic solution（Concentration is 0.01mol/L）, with DMSO constant volumes to 5mL, stand after mixing.At this time
The concentration of DCP5-16 is 2 × 10-4mol/L.It turns out that：The addition of only cetylpyridinium chloride solution makes bulk solution
Bright blue fluorescence quenching, and the addition of other surfactants, the fluorescence of bulk solution, which does not change, not to be quenched
（See Fig. 1）.Illustrate to be copolymerized 5 aromatic hydrocarbons of column in CHCl3Energy colorimetric detection surfactant cetylpyridinium chloride in system, therefore
DCP5-16 can be as the sensor molecule of monitoring surfactant cetylpyridinium chloride.
2nd, cetylpyridinium chloride（G）To sensor molecule fluorescence titration
In order to further test in copolymerization 5 aromatic hydrocarbons of column the fluorescence intensity change after adding guest molecule, we have done fluorescence
Titration experiments.It is 2 × 10 in body concentration-4Guest molecule is added in the chloroformic solution of mol/L, there is very strong fluorescence when not adding
Emission peak, with the increase of guest molecule concentration, fluorescence intensity gradually weakens, when the hexadecyl pyrrole for adding 2 times of equivalents
Reach fluorescent quenching during pyridine（As shown in Figure 2）.This decrease is due to that the guest molecule of short of electricity subsystem penetrates into electron rich body
In the cavity of copolymerization 5 aromatic hydrocarbons of column of system so that electronics transfer causes host molecule fluorescent quenching, explanation can use " on-off " this
Kind pattern carrys out the detection that realization body molecule implements guest molecule cetylpyridinium chloride spectroscopy.
3rd, it is copolymerized measure of 5 aromatic hydrocarbons of column to cetylpyridinium chloride minimum detection limit
25 DEG C, using fluorescence emission spectrum, in copolymerization 5 aromatic hydrocarbons of column（2×10-3mol/L）Surfactant chlorination 16
Alkyl pyridine（0.01 mol/L）Titration experiments in, our volumes and titration according to the cetylpyridinium chloride added
Design sketch, you can obtain this receptor to the minimum detection limit of cetylpyridinium chloride ion up to 1.72 × 10-8 mol /L
（Fig. 3）, illustrate that being copolymerized identification of 5 aromatic hydrocarbons of column for cetylpyridinium chloride has very high sensitivity level.
4th, the fluorescent quenching time measures
The response time of copolymerization 5 aromatic hydrocarbons Surfactant cetylpyridinium chloride of column sees Fig. 4.As shown in Figure 4, by table
After face activating agent cetylpyridinium chloride solution instills bulk solution, reach fluorescent quenching in the time of 5 seconds, illustrate copolymerization
5 aromatic hydrocarbons of column can be quickly identification surfactant cetylpyridinium chloride.
3rd, it is copolymerized the mechanism of 5 aromatic hydrocarbons of column identification surfactant cetylpyridinium chloride
It is well known that copolymerization 5 aromatic hydrocarbons of column contains cavity structure in itself, so the suitable guest molecule of scale topography can
Inclusion is into its cavity, and pyridine derivate is usually by inclusion to crown ether, cyclodextrin, in calixarenes.In order to illustrate 5 virtue of copolymerization column
Hydrocarbon identifies the mechanism of surfactant cetylpyridinium chloride, we illustrate this Subjective and Objective complexation process with one-dimensional nuclear-magnetism
（See Fig. 5）.When the guest molecule that one times of equivalent is added into bulk solution（G）When, H on guest molecule pyridine ringa–HeWith it is sub- from N
The nearer H of methylfSubstantially moved to High-Field, it was demonstrated that the completion of inclusion process.Equally, this inclusion process is also proved with mass spectrum
It is 1:1 complexing（Fig. 6）.
In order to prove the correlation of subject and object, we have been two-dimentional nuclear-magnetism NOSEY（See Fig. 7）.Work as same molar
Main body DCP5-16 and object G when testing, H on object Ga–HfWith H on main body DCP5-161–H4There is very strong correlation, say
Pyridine loop section is acted on by C-H π and cation π on bright object, with 1:1 formation host-guest inclusion is common so as to penetrate into
In the cavity of poly- 5 aromatic hydrocarbons of column, this and mass spectrum survey data and match.
Many experiments show, in the chloroformic solution of acceptor molecule, the concentration of acceptor molecule is 2 × 10-3Mol/L, copolymerization
5 aromatic hydrocarbons sensor molecule Surfactant cetylpyridinium chloride of column passes through 1:1 complexing complete host-guest chemistry process and
Cause the fluorescent quenching of main body, this decrease is due to that the guest molecule of short of electricity subsystem penetrates into the copolymerization column of electron rich system
In the cavity of 5 aromatic hydrocarbons so that electronics transfer causes host molecule fluorescent quenching（Such as Fig. 8）, reach specific recognition surface-active
Agent cetylpyridinium chloride.This method is opened up in terms of Novel pole aromatic hydrocarbons sensor molecule unicity detects surfactant
New direction.
Brief description of the drawings
Fig. 1 is the specificity fluorescence identifying of copolymerization 5 aromatic hydrocarbons sensor Surfactant cetylpyridinium chloride of column.
Fig. 2 is surfactant（Cetylpyridinium chloride）Fluorescence titration figure to being copolymerized 5 aromatic hydrocarbons sensor molecule of column
Spectrum.
Fig. 3 is measure collection of illustrative plates of copolymerization 5 aromatic hydrocarbons of column to cetylpyridinium chloride minimum detection limit.
Fig. 4 is the response time of copolymerization 5 aromatic hydrocarbons Surfactant cetylpyridinium chloride of column.
Fig. 5 assembles one-dimensional nuclear-magnetism for copolymerization 5 aromatic hydrocarbons of column and cetylpyridinium chloride.
Fig. 6 assembles mass spectrogram for copolymerization 5 aromatic hydrocarbons of column and cetylpyridinium chloride.
Fig. 7 is copolymerization 5 aromatic hydrocarbons of column and the two-dimentional nuclear-magnetism NOSEY of cetylpyridinium chloride assembling.
Fig. 8 is copolymerization 5 aromatic hydrocarbons of column and surfactant cetylpyridinium chloride recognition mechanism figure.
Embodiment
Below by preparation of the specific embodiment to present invention copolymerization 5 aromatic hydrocarbons of column and the side of detection cetylpyridinium chloride
Method is described further.
Embodiment one, copolymerization 5 aromatic hydrocarbons of column（Compound DCP5-16）Synthesis
1st, the synthesis of intermediate：By hydroquinone（4.4g, 40mmol）, sodium hydroxide (10g, 4mmol), potassium iodide
(4g, 24mmol), bromohexadecane (26.8g, 88mmol) and ethanol (300.0mL) are added in 500mL round-bottomed flasks, are stirred
Mix reaction 3 days（72h）, solid precipitation, obtains intermediate.1H NMR (400MHz, CDCl3, 298 K) δ (ppm): 6.82
(d, 4H), 3.96 (t, 4H), 1.75 (t, 4H), 1.43 (t, 4H), 1.26 (t, 48H), 0.86 (s,
6H)..Yield is 80%.
2nd, it is copolymerized the synthesis of 5 aromatic hydrocarbons of column：Intermediate (2.79g, 5mmol), terephthaldehyde's ether (2.76g, 20mmol) are added
Enter into 1,2-dichloroethanes of 80mL and dissolve；Again by paraformaldehyde (0.75g, 25mmol), boron trifluoride ether (3.2mL,
25mmol) it is added in solution, reaction 8h is stirred at room temperature.After reaction solution is poured into separate out in methanol and precipitated, mistake
Filter, precipitation are dissolved with chloroform, the extraction of distilled water 30ml × 3 time, dry, organic phase pillar layer separation（Petrol ether/ethyl acetate
=50:1 v/v）, obtain white solid DCP5-12 (0.95 g), yield 18%.
Product DCP5-16：m.p. 126℃.1H NMR (600 MHz, chloroform–d 3 , 293K) δ (ppm):
6.81–6.78 (d, 10H), 3.83 (t, 4H), 3.77 (s, 10H), 3.67 (s, 24H), 1.78 (t, 4H),
1.33– 1.15(m, 52H), 0.87-0.83 (3, 6H). The 13C NMR (150 MHz, chloroform–d,
293K) δ (ppm): 150.74, 150.69, 150.01, 128.41, 128.27, 128.22, 128.13,
128.09, 68.49, 55.62, 31.88, 29.81, 29.76, 29.72, 29.70, 29.59, 29.49, 29.40,
26.23, 22.63, 14.08. ESI-MS m/z: [M+NH4]+ Calcd for 1188; Found 1188.8, [M+Na
]+ 1193.8, [M+K]+ 1209.7。
The synthesis type of DCP5-12 is as follows：
Embodiment two, copolymerization 5 aromatic hydrocarbons of column（DCP5-16）Identify surfactant cetylpyridinium chloride
By DCP5-16 CHCl3It is made into 2 × 10-3The bulk solution of mol/L；The bulk solution of 0.5mL is taken respectively in 7
In colorimetric cylinder.The different surfaces activating agent of 0.5mL is respectively configured（Cetylpyridinium chloride, brocide, bromination
Hexadecyl trimethylamine, trimethylamine ethanol solution, triethanolamine, neopelex）Chloroformic solution（Concentration is
0.01mol/L）As object solution.Above-mentioned object solution is separately added into 7 colorimetric cylinders, if the fluorescent quenching of bulk solution,
It is cetylpyridinium chloride that then explanation, which adds object solution,；If the fluorescence of bulk solution does not change, illustrate object
Solution is not cetylpyridinium chloride.
Claims (9)
1. 5 aromatic hydrocarbons of column is copolymerized in CHCl3The application of colorimetric detection cetylpyridinium chloride in system, it is characterised in that：Will copolymerization
5 aromatic hydrocarbons CHCl of column3It is made into bulk solution；Surfactant cetylpyridinium chloride, hexadecyl pyrrole is respectively configured
Pyridine, cetrimonium bronmide, trimethylamine ethanol solution, triethanolamine, the CHCl of neopelex3Solution conduct
Object solution；Object solution is added in aforementioned body solution, if the fluorescent quenching of bulk solution, illustrates that addition object is molten
Liquid is cetylpyridinium chloride；If the fluorescence of bulk solution does not change, it is not chlorination 16 to illustrate object solution
Alkyl pyridine.
2. copolymerization 5 aromatic hydrocarbons of column is in CHCl as claimed in claim 13The application of colorimetric detection cetylpyridinium chloride in system, its
It is characterized in that：The concentration of the bulk solution is higher than 2 × 10-4mol/L。
3. copolymerization 5 aromatic hydrocarbons of column is in CHCl as claimed in claim 13The application of colorimetric detection cetylpyridinium chloride in system, its
It is characterized in that：The concentration of the object solution is higher than 1.72 × 10-8 mol/L。
4. 5 aromatic hydrocarbons of column is copolymerized as described in claim 1 ~ 3 any type in CHCl3Colorimetric detection hexadecyl pyrrole in system
The application of pyridine, it is characterised in that：It is described copolymerization 5 aromatic hydrocarbons of column structure be：
。
5. copolymerization 5 aromatic hydrocarbons of column is in CHCl as claimed in claim 43The application of colorimetric detection cetylpyridinium chloride in system, its
It is characterized in that：Copolymerization 5 aromatic hydrocarbons of column has following methods to be prepared：
（1）The synthesis of intermediate：Using ethanol as solvent, sodium hydroxide and potassium iodide are catalyst, under nitrogen protection, hydroquinone
With bromohexadecane with 1:1~1:1.2 molar ratio 20 ~ 24h of back flow reaction, cooling, leaches out inorganic salts, vacuum rotary steam is done molten
Agent, chloroform dissolving, distilled water extraction, is then dried, organic phase pillar layer separation, obtains intermediate with anhydrous sodium sulfate；
（2）It is copolymerized the synthesis of 5 aromatic hydrocarbons of column：With 1,2- dichloroethanes for solvent, boron trifluoride ether is catalyst, paraformaldehyde,
Intermediate, terephthaldehyde's ether are raw material, in 3 ~ 4h of room temperature reaction；Then methanol extraction, chloroform dissolving are used, distilled water extracts, so
Dried afterwards with anhydrous sodium sulfate, organic phase pillar layer separation, 5 aromatic hydrocarbons of column must be copolymerized.
6. copolymerization 5 aromatic hydrocarbons of column is in CHCl as claimed in claim 53The application of colorimetric detection cetylpyridinium chloride in system, its
It is characterized in that：Step（1）In, the dosage of sodium hydroxide is 3 ~ 4 times of hydroquinone mole；The dosage of potassium iodide is to bromo
0.5 ~ 1 times of dodecane.
7. copolymerization 5 aromatic hydrocarbons of column is in CHCl as claimed in claim 53The application of colorimetric detection cetylpyridinium chloride in system, its
It is characterized in that：Step（2）In, the dosage of terephthaldehyde's ether is 0.8 ~ 1 times of paraformaldehyde mole.
8. copolymerization 5 aromatic hydrocarbons of column is in CHCl as claimed in claim 53The application of colorimetric detection cetylpyridinium chloride in system, its
It is characterized in that：Step（2）In, the dosage of intermediate is 4 ~ 6 times of the mole of terephthaldehyde's ether.
9. copolymerization 5 aromatic hydrocarbons of column is in CHCl as claimed in claim 53The application of colorimetric detection cetylpyridinium chloride in system, its
It is characterized in that：Step（2）In, the dosage of catalyst boron trifluoride ether is 0.5 ~ 1 times of paraformaldehyde mole.
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| CN105622406B (en) * | 2016-02-04 | 2018-06-15 | 广西大学 | Functionalization column [5] aromatic hydrocarbons trimer preparation method and application |
| CN109187472B (en) * | 2018-09-12 | 2020-11-24 | 西北师范大学 | Host-guest self-assembly-based supramolecular sensor and preparation and application thereof |
| CN109655436B (en) * | 2018-12-07 | 2021-03-30 | 武汉工程大学 | Column aromatic modified cyanide ion fluorescence detection test paper, and preparation method and detection method thereof |
| CN111220584A (en) * | 2020-01-15 | 2020-06-02 | 扬州大学 | Method for detecting quaternary ammonium salt cationic surfactant by using sulfonic acid group calix [ n ] arene |
| CN111320899B (en) * | 2020-03-13 | 2021-09-03 | 四川大学 | Kit and application thereof in preparation of visual organic solvent indicator and writing of confidential documents |
| CN115015348B (en) * | 2022-05-12 | 2022-12-20 | 昆明医科大学 | Pillared arene and pillared arene-graphyne composite material with MA (MA) specificity recognition, preparation method and application thereof |
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