CN112143487A - Mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics - Google Patents
Mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics Download PDFInfo
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- CN112143487A CN112143487A CN202011022216.XA CN202011022216A CN112143487A CN 112143487 A CN112143487 A CN 112143487A CN 202011022216 A CN202011022216 A CN 202011022216A CN 112143487 A CN112143487 A CN 112143487A
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- mesoporous silicon
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- cosmetics
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 45
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 44
- 239000010703 silicon Substances 0.000 title claims abstract description 44
- 239000002537 cosmetic Substances 0.000 title claims abstract description 36
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 32
- 150000002500 ions Chemical class 0.000 title claims abstract description 27
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 14
- WPYJKGWLDJECQD-UHFFFAOYSA-N quinoline-2-carbaldehyde Chemical compound C1=CC=CC2=NC(C=O)=CC=C21 WPYJKGWLDJECQD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 9
- FZESPVBONPPRAW-UHFFFAOYSA-N 2-methyl-1h-imidazo[4,5-b]pyridine Chemical class C1=CC=C2NC(C)=NC2=N1 FZESPVBONPPRAW-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 2-methyl-4-azabenzimidazole salt ions Chemical class 0.000 claims abstract description 7
- FPOSCXQHGOVVPD-UHFFFAOYSA-N chloromethyl(trimethoxy)silane Chemical compound CO[Si](CCl)(OC)OC FPOSCXQHGOVVPD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 7
- 239000002210 silicon-based material Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 8
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 150000007530 organic bases Chemical class 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 238000005119 centrifugation Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003480 eluent Substances 0.000 abstract description 2
- 229910052785 arsenic Inorganic materials 0.000 description 6
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 208000009507 Nervous System Mercury Poisoning Diseases 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
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- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 208000024891 symptom Diseases 0.000 description 2
- 206010001497 Agitation Diseases 0.000 description 1
- 208000008316 Arsenic Poisoning Diseases 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 206010013954 Dysphoria Diseases 0.000 description 1
- 206010019280 Heart failures Diseases 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000003394 haemopoietic effect Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000036737 immune function Effects 0.000 description 1
- 206010022437 insomnia Diseases 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 208000013433 lightheadedness Diseases 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 210000004789 organ system Anatomy 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 231100000915 pathological change Toxicity 0.000 description 1
- 230000036285 pathological change Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 210000003934 vacuole Anatomy 0.000 description 1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C07—ORGANIC CHEMISTRY
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- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
A mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics is prepared by loading 2-methyl-4-azabenzimidazole salt ions and quinoline-2-formaldehyde on a mesoporous silicon material; the structure is shown in formula I:
the preparation method comprises the following steps: 1) preparing an intermediate A from substituted quinoline-2-carbaldehyde and 2-methyl-4-azabenzimidazole; 2) preparing an intermediate B from the intermediate A and chloromethyl trimethoxy silane; 3) dispersing SBA-15 with the template removed in an organic solvent under nitrogen atmosphere, adding the intermediate B, and suspending the suspensionRefluxing for 6-48 h under nitrogen atmosphere; obtaining the dry mesoporous silicon fluorescent probe. The fluorescent probe with the mesoporous silicon as the carrier can be conveniently separated from a water system through filtration or centrifugation, and the separated material can also remove and recycle adsorbed ions through an eluent.
Description
Technical Field
The invention belongs to the field of heavy metal detection, and particularly relates to a mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics.
Background
The cosmetics as daily necessities of many women occupy huge sales shares in the market, and stimulate more enterprises to be added into the cosmetic production industry. However, in the prior art, many manufacturers want to reduce the production cost while maintaining good product effects, so that the management requirements in the cosmetic production stage are reduced, and the products are extremely harmful due to the addition of various heavy metals including lead, mercury, arsenic and the like.
Lead is a common heavy metal element in cosmetics, and although finely processed in the production stage, it still causes harm to human health if used for a long time. Especially, lead is dissolved into food or air, and once the lead enters a human body, the lead can be quickly absorbed, and particularly, the lead cannot be timely discharged after entering blood, so that the hematopoietic function of the human body is influenced, and symptoms such as light-headedness and the like can appear in a short time. If the lead content of the human body is too high, heart failure can be caused, and the life safety can be threatened in a serious condition.
Many cosmetics contain heavy metal mercury, and compounds of mercury permeate into skin for a long time, so that the central nervous system of a human can be damaged, and the kidney filtering function can be weakened. Inorganic mercury poisoning can cause mild hyperexcitability, neurasthenia and serious liver and kidney damage to people; after organic mercury poisoning, symptoms such as hypodynamia, dizziness, dreaminess, insomnia, hypomnesis, dysphoria and movement disorder will appear.
Arsenic has high toxicity, if only a small amount of arsenic is absorbed, the arsenic can be discharged in time in a corresponding mode, but if the absorption amount is too large, arsenic poisoning can be caused, body organs can be gradually exhausted, and the running speed of a human body is influenced. Excessive arsenic content in cosmetics can cause skin pigmentation (loss), hyperkeratosis and cell canceration, and can also affect kidney morphology and function. Chronic arsenic contact can cause renal pathological changes such as vacuole degeneration of tubular cells, deep lithocyte and the like, inhibit the immunologic function of a human body, and cause brain injury, cardiovascular and cerebrovascular diseases and the like.
The heavy metal components in the cosmetics directly define the use feeling of the quality of the cosmetics to users, if the heavy metal components in the cosmetics are too high, the heavy metal components can threaten the health of human bodies and damage more or less human organs and nervous systems. Therefore, it is necessary to detect heavy metals in cosmetics.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics.
In order to achieve the purpose, the invention adopts the following technical scheme:
a mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics is prepared by loading 2-methyl-4-azabenzimidazole salt ions and quinoline-2-formaldehyde on a mesoporous silicon material; the structure is as follows:
wherein R in the formula is selected from one of hydrogen atom, alkyl of C1-C4, halogen and nitro.
A mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics comprises the following steps:
1) dissolving substituted quinoline-2-formaldehyde and 2-methyl-4-azabenzimidazole in n-butanol according to the molar ratio of 1:1.1, adding organic base serving as a condensation catalyst, reacting at 120 ℃ for 2-6 hours, and recrystallizing after the reaction is finished to obtain an intermediate A;
2) dissolving the intermediate A and chloromethyl trimethoxy silane in n-butanol according to the molar ratio of 1:1.2, stirring for 24-48 hours at 60 ℃, separating out a precipitate, filtering, washing with diethyl ether and drying to obtain an intermediate B;
3) in a nitrogen atmosphere, dispersing the SBA-15 without the template in an organic solvent, adding an intermediate B, and refluxing the suspension for 6-48 h in a nitrogen atmosphere; and centrifuging to collect the product, fully washing with methanol and drying in vacuum at room temperature to obtain the dry mesoporous silicon fluorescent probe.
Preferably, the organic base in step 1) is one of triethylamine, dimethylamine, aniline and pyridine; a more preferred organic base is triethylamine.
Preferably, in the step 3), the ratio of SBA-15: intermediate B is 1-2:1.
Preferably, in the step 3), the organic solvent is one or a mixture of more of ethanol, methanol, acetone, tetrahydrofuran and acetonitrile in any proportion.
The invention has the following beneficial effects:
1. the organic small molecular fluorescent compound in the mesoporous silicon fluorescent probe provided by the invention emits weak fluorescence under a fluorescence instrument, and the mesoporous silicon fluorescent probe is dispersed into a cosmetic solution containing heavy metal ions, so that the fluorescence of a fluorescence spectrum is obviously enhanced. Therefore, the mesoporous silicon fluorescent probe provided by the invention has the characteristics of obvious phenomenon and high sensitivity when being used for detecting heavy metal ions in cosmetics. The method is easy to operate, easy to carry and good in anti-interference performance, can achieve the purposes of naked eye identification and field inspection implementation, and has a good application prospect.
2. The silanol on the surface of the mesoporous channel has high density, so that various active reaction groups can be fixed on the surface of the inner wall of the pore channel after the siloxane coupling agent is treated.
The 3.2-methyl-4-azabenzimidazole is connected to the surface of the inner wall of the pore channel through a quaternary ammonium group, the quaternary ammonium group has high hydrophilicity, the synthesized mesoporous silicon fluorescent probe has good dispersibility in aqueous solution, is not easy to precipitate from a water system, can keep the dispersion state of the aqueous solution for a long time in the detection process, and is favorable for accurately determining the ion concentration.
4. The fluorescent probe with mesoporous silicon as a carrier can be conveniently separated from a water system through filtration or centrifugation, and the separated material can also remove and recycle adsorbed ions through an eluent.
Drawings
FIG. 1 is an infrared spectrum of a mesoporous silicon fluorescent probe prepared in example 1;
FIG. 2 is a scanning electron micrograph of the mesoporous silicon fluorescent probe obtained in example 1;
FIG. 3 is a fluorescence spectrum of the mesoporous silica fluorescence probe obtained in example 1 for detecting heavy metal ions in a cosmetic solution.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics is prepared by loading 2-methyl-4-azabenzimidazole salt ions and quinoline-2-formaldehyde on a mesoporous silicon material; the structure is as follows:
a mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics comprises the following steps:
1) dissolving 15.7g of quinoline-2-formaldehyde and 14.6g of 2-methyl-4-azabenzimidazole in 50mL of n-butanol, adding 5.0g of triethylamine, reacting at 120 ℃ for 2 hours, and recrystallizing after the reaction is finished to obtain 19.0g of an intermediate A;
2) dissolving 13.6g of intermediate A and 10.2g of chloromethyl trimethoxy silane in 50mL of n-butanol, stirring for 24 hours at 60 ℃, separating out a precipitate, filtering, washing with diethyl ether and drying to obtain 21.7g of intermediate B;
3) in nitrogen atmosphere, dispersing 20g of SBA-15 with the template removed in ethanol, adding 20g of intermediate B, and refluxing the suspension in nitrogen atmosphere for 6 h; and centrifuging to collect the product, fully washing with methanol and drying in vacuum at room temperature to obtain 30g of the dried mesoporous silicon fluorescent probe.
Example 2
A mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics is prepared by loading 2-methyl-4-azabenzimidazole salt ions and quinoline-2-formaldehyde on a mesoporous silicon material; the structure is as follows:
a mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics comprises the following steps:
1) dissolving 15.7g of quinoline-2-formaldehyde and 14.6g of 2-methyl-4-azabenzimidazole in 50mL of n-butanol, adding 5.0g of triethylamine, reacting at 120 ℃ for 4 hours, and recrystallizing after the reaction is finished to obtain 19.2g of an intermediate A;
2) dissolving 13.6g of intermediate A and 10.2g of chloromethyl trimethoxy silane in 50mL of n-butanol, stirring for 30 hours at 60 ℃, separating out a precipitate, filtering, washing with diethyl ether and drying to obtain 22.3g of intermediate B;
3) dispersing 28g of SBA-15 with the template removed in ethanol in a nitrogen atmosphere, adding 20g of intermediate B, and refluxing the suspension for 12h in the nitrogen atmosphere; and centrifuging to collect a product, fully washing with methanol and drying in vacuum at room temperature to obtain 36g of the dried mesoporous silicon fluorescent probe.
Example 3
A mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics is prepared by loading 2-methyl-4-azabenzimidazole salt ions and quinoline-2-formaldehyde on a mesoporous silicon material; the structure is as follows:
a mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics comprises the following steps:
1) dissolving 15.7g of quinoline-2-formaldehyde and 14.6g of 2-methyl-4-azabenzimidazole in 50mL of n-butanol, adding 5.0g of triethylamine, reacting at 120 ℃ for 5 hours, and recrystallizing after the reaction is finished to obtain 19.4g of an intermediate A;
2) dissolving 13.6g of intermediate A and 10.2g of chloromethyltrimethoxysilane in 50mL of n-butanol, stirring at 60 ℃ for 36 hours, separating out a precipitate, filtering, washing with diethyl ether, and drying to obtain 22.9g of intermediate B;
3) dispersing 35g of SBA-15 with the template removed in ethanol in a nitrogen atmosphere, adding 20g of intermediate B, and refluxing the suspension for 36h in the nitrogen atmosphere; and centrifuging to collect a product, fully washing with methanol and drying in vacuum at room temperature to obtain 40g of the dried mesoporous silicon fluorescent probe.
Example 4
A mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics is prepared by loading 2-methyl-4-azabenzimidazole salt ions and quinoline-2-formaldehyde on a mesoporous silicon material; the structure is as follows:
a mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics comprises the following steps:
1) dissolving 15.7g of quinoline-2-formaldehyde and 14.6g of 2-methyl-4-azabenzimidazole in 50mL of n-butanol, adding 5.0g of triethylamine, reacting at 120 ℃ for 6 hours, and recrystallizing after the reaction is finished to obtain 19.6g of an intermediate A;
2) dissolving 13.6g of intermediate A and 10.2g of chloromethyl trimethoxy silane in 50mL of n-butanol, stirring for 48 hours at 60 ℃, separating out a precipitate, filtering, washing with diethyl ether and drying to obtain 23.1g of intermediate B;
3) dispersing 40g of SBA-15 with the template removed in ethanol in a nitrogen atmosphere, adding 20g of intermediate B, and refluxing the suspension for 48h in the nitrogen atmosphere; the product was collected by centrifugation, washed thoroughly with methanol and dried under vacuum at room temperature to obtain 52g of dry mesoporous silicon fluorescent probe.
Specific detection
1. Comparing the mesoporous silicon fluorescent probe of example 1 with the original SBA-15 (shown in FIG. 1), peaks at 1468 and 1390 cm-1, which are both attributed to bending vibration of C-H bonds caused by silicon-oxygen bonds, were observed in the infrared spectrum of the mesoporous silicon fluorescent probe. In addition, new peaks appear near 1562 cm-1 and 2954 cm-1 in the infrared spectrum of the mesoporous silicon fluorescent probe, which are caused by the stretching vibration of benzene ring and pyridine on quinoline. At the same time, a new spike appeared at 3451 cm-1 due to the C ═ N characteristic oscillation of 2-methyl-4-azabenzimidazole, from which results it can be concluded that the intermediate B fluorescent molecule has grafted onto the surface of the material.
2. The morphology of the mesoporous silicon fluorescent probe obtained in example 1 is represented by a scanning electron microscope and a transmission electron microscope, as shown in fig. 2, the scanning electron microscope image shows that the material is rod-shaped, and the transmission electron microscope image shows that the material has a good ordered pore structure, which indicates that the material has good stability, and the ordered and complete morphology can still be maintained through multi-step chemical modification.
3. First, a cosmetic sample to be detected is completely dissolved at a temperature of 30 to 50 ℃, the mesoporous silicon fluorescent probe prepared in example 1 is added, and the change of the fluorescence intensity of the mesoporous silicon fluorescent probe before and after the addition of the cosmetic solution is measured, and the result is shown in fig. 3.
Claims (6)
1. A mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics is characterized in that the mesoporous silicon fluorescent probe is prepared by loading 2-methyl-4-azabenzimidazole salt ions and quinoline-2-formaldehyde on a mesoporous silicon material; the structure is shown in formula I:
wherein R in the formula is selected from one of hydrogen atom, alkyl of C1-C4, halogen and nitro.
2. The mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics as claimed in claim 1, wherein the preparation method of the mesoporous silicon fluorescent probe comprises the following steps:
1) dissolving substituted quinoline-2-formaldehyde and 2-methyl-4-azabenzimidazole in n-butanol according to the molar ratio of 1:1.1, adding organic base serving as a condensation catalyst, reacting at 120 ℃ for 2-6 hours, and recrystallizing after the reaction is finished to obtain an intermediate A;
2) dissolving the intermediate A and chloromethyl trimethoxy silane in n-butanol according to the molar ratio of 1:1.2, stirring for 24-48 hours at 60 ℃, separating out a precipitate, filtering, washing with diethyl ether and drying to obtain an intermediate B;
3) in a nitrogen atmosphere, dispersing the SBA-15 without the template in an organic solvent, adding an intermediate B, and refluxing the suspension for 6-48 h in a nitrogen atmosphere; and centrifuging to collect the product, fully washing with methanol and drying in vacuum at room temperature to obtain the dry mesoporous silicon fluorescent probe.
3. The mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics as claimed in claim 1, wherein the organic base in step 1) is one of triethylamine, dimethylamine, aniline and pyridine.
4. The mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics as claimed in claim 1, wherein the organic base in step 1) is triethylamine.
5. The mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics as claimed in claim 1, wherein in the step 3), the ratio of SBA-15: intermediate B is 1-2:1.
6. The mesoporous silicon fluorescent probe for detecting heavy metal ions in cosmetics as claimed in claim 1, wherein in step 3), the organic solvent is one or a mixture of ethanol, methanol, acetone, tetrahydrofuran and acetonitrile in any proportion.
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| JP3899736B2 (en) * | 1999-09-09 | 2007-03-28 | 三菱化学株式会社 | Coumarin compound and method for producing the same |
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| CN109722238A (en) * | 2017-10-27 | 2019-05-07 | 泰山医学院 | Pyrido [1,2-a] the benzimidazole SO of pyridine modification32-Ratio fluorescent probe and its application |
| CN110055056A (en) * | 2019-05-15 | 2019-07-26 | 三峡大学 | The quinolinones fluorescence probe and its preparation method and application that benzimidazolyl replaces |
| CN110698409A (en) * | 2019-10-23 | 2020-01-17 | 湖北理工学院 | Reactive benzimidazole fluorescent probe for specifically recognizing mercury ions as well as preparation method and application of reactive benzimidazole fluorescent probe |
| CN111285897A (en) * | 2020-03-03 | 2020-06-16 | 江苏海洋大学 | Mesoporous silicon fluorescent probe for copper ion detection and separation and preparation method thereof |
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2020
- 2020-09-25 CN CN202011022216.XA patent/CN112143487A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3899736B2 (en) * | 1999-09-09 | 2007-03-28 | 三菱化学株式会社 | Coumarin compound and method for producing the same |
| CN108219774A (en) * | 2017-10-19 | 2018-06-29 | 泰山医学院 | A kind of quinolines of pyrido [1,2-a] benzimidazole substitution detect hypochlorous fluorescence probe and its application |
| CN109722238A (en) * | 2017-10-27 | 2019-05-07 | 泰山医学院 | Pyrido [1,2-a] the benzimidazole SO of pyridine modification32-Ratio fluorescent probe and its application |
| CN110055056A (en) * | 2019-05-15 | 2019-07-26 | 三峡大学 | The quinolinones fluorescence probe and its preparation method and application that benzimidazolyl replaces |
| CN110698409A (en) * | 2019-10-23 | 2020-01-17 | 湖北理工学院 | Reactive benzimidazole fluorescent probe for specifically recognizing mercury ions as well as preparation method and application of reactive benzimidazole fluorescent probe |
| CN111285897A (en) * | 2020-03-03 | 2020-06-16 | 江苏海洋大学 | Mesoporous silicon fluorescent probe for copper ion detection and separation and preparation method thereof |
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