CN104090035A - Method for separating and detecting diphenylamine and rhodamine B by using gold nano channel - Google Patents

Method for separating and detecting diphenylamine and rhodamine B by using gold nano channel Download PDF

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Publication number
CN104090035A
CN104090035A CN201410329537.2A CN201410329537A CN104090035A CN 104090035 A CN104090035 A CN 104090035A CN 201410329537 A CN201410329537 A CN 201410329537A CN 104090035 A CN104090035 A CN 104090035A
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gold nano
gold
diphenylamine
rhodamine
pond
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钟桐生
黄杉生
王亚东
马腾飞
杨乐乐
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Hunan City University
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Hunan City University
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Abstract

The invention discloses a method for separating and detecting diphenylamine and rhodamine B by using a gold nano channel. A PC (polycarbonate) membrane is used as a template, and gold is deposited on hole walls of the PC membrane template with nano aperture by adopting a chemical deposition method to obtain a functional hydrophobic gold nano channel; diphenylamine serving as a hydrophobic molecule easily passes through the hydrophobic gold nano channel; the rhodamine B is a cationic compound, belongs to a hydrophilic molecule and can not migrate in the hydrophobic gold nano channel; separation of the diphenylamine and the rhodamine B is realized according to the difference of the hydrophobic property of the two; the transmission quantity of each of the diphenylamine and the rhodamine B passing through the gold nano channel is detected by using an ultraviolet detector. The method can be applied to the fields of contemporary medicinal chemistry, agricultural chemistry, food chemistry and biochemistry, and is particularly used for separating carcinogenic substances such as food dyes and protecting food safety and body health.

Description

A kind of method of utilizing gold nano channel separation to detect diphenylamine and rhodamine B
Technical field
The invention belongs to technical field of nano material, specifically, is a kind of method of utilizing gold nano channel separation to detect diphenylamine and rhodamine B.
Background technology
Nanochannel finger-hole footpath is at hole or the pipeline configuration of 0.1 ~ 100 nm.Special nano effect makes nanometer technology in the evolution of nearly more than 50 years, receive increasing concern.Nanochannel is because of its unique small size, physicochemical property, and the application table at aspects such as Material Physics, chemistry, biomedicines reveals the superiority of height.
In recent years, nanochannel technology is as the field important branch of nanometer biotechnology research, because of its unique structure and physicochemical property, obtain in the world in recent years extensive concern, in the researchs such as gene sequencing, single molecule analysis, the design of bionical ion channel and medicine loading, embodied unique superiority.Nanochannel detects still rarely seen report to the separation of chiral material.With nanochannel technical modelling biological membrane, developing highly sensitive, high selectivity separation means, the research of developing the aspects such as nanochannel of various base materials, researchers are being faced with great opportunities and challenges.
Diphenylamine (Diphenylamine; N-Phenylaniline, is called for short DPA) be a kind of important industrial chemicals, DPA is mainly used in the synthetic of dyestuff, antioxidant, medicine, explosive and agricultural chemicals, and its toxic action is similar to aniline, can damage nervous system, cardiovascular system and hematological system.After Long Term Contact, skin and mucosa occurs stimulating phenomenon, also can cause carcinoma of urinary bladder, occurs the symptoms such as frequent micturition or blood urine.Rhodamine (RhB) is a kind of oxa-a species of orchid fluorochrome, has been widely used in the fields such as food, environmental protection, mining industry as fluorescent reagent.According to IARC (IARC) chemicals carcinogenic risk evaluation, show: this material of picked-up, suction and skin contact all can cause acute and chronic middle toxicity damage.Have zoopery to show, this material has carcinogenesis while sucking, and may cause that mutagenesis becomes teratogenesis .
Therefore, quick and precisely and effectively separation, analysis DPA and RhB component have very important significance in the research in the fields such as contemporary pharmaceutical chemistry, agriculture chemistry, Food Chemistry and biological chemistry.
Summary of the invention
Technical matters to be solved by this invention is: solve the problem that above-mentioned prior art exists; and a kind of method of utilizing gold nano channel separation to detect diphenylamine and rhodamine B is provided; be widely used in contemporary pharmaceutical chemistry, agriculture chemistry, Food Chemistry and biochemical field; particularly can separated food dye etc. carcinogen, protection food security and people's health.
The technical solution used in the present invention is:
Utilize gold nano channel separation to detect a method for diphenylamine and rhodamine B, take PC film as template, adopt chemical deposition deposited gold in the hole wall of nano aperture PC film template, make the gold nano passage of nano aperture; Utilize gold-sulfide linkage covalent bonding that Stearyl mercaptan is modified in gold nano passage, obtain the hydrophobicity gold nano passage of functionalization; Diphenylamine is as hydrophobic molecule, easily by this hydrophobic gold nano passage; And rhodamine B is cationic compound, belong to hydrophilic molecule, can not in hydrophobicity gold nano passage, move; According to the difference of diphenylamine and rhodamine B hydrophilic and hydrophobic, utilize the selectivity of functionalization gold nano passage, realize the separation of the two; With UV-detector detection diphenylamine and rhodamine B, see through the transit dose of gold nano passage.
In technique scheme, concrete steps are as follows:
1) preparation of gold nano channel membrane:
Adopt chemical deposition in aperture, be Φ 50 nm polycarbonate leaching films (being PCTE) thus in the hole wall of template, deposited gold nano particle makes gold nano passage; Specific as follows: PCTE to be immersed to hplc grade methanol 20 min and activate cleaning; PCTE filter membrane after cleaning immerses and contains 0.025 mol/L SnCl 2with 0.007 mol/L CF 3in the methanol-water solution (V/V=1:1) of COOH, put constant-temperature table medium speed 150 r/min and shake 45 min, make Sn 2+be adsorbed on equably the inwall in hole; With methyl alcohol purge 3 times; Again PCTE filter membrane is immersed to 0.029 mol/L Ag (NH 3) 2 +in, pass into N simultaneously 2, purge 15 min; PCTE filter membrane is taken out, use respectively each purge of methyl alcohol and ultrapure water 3-4 time, each 2 ~ 3 min, then immerse PCTE filter membrane to contain 7.9 * 10 -4in the catalyst solution of mol/L gold sodium sulfide and 0.5 mol/L formaldehyde (pH=10.00), temperature is 4 ℃ of deposited gold 4 h, gold is reduced the surface that is deposited on PCTE filter membrane and fenestra wall, and the gold nano channel membrane of deposited gold is taken out with ultrapure washing 3 times, uses 25% HNO 3soak 12 h, to remove the upper Ag in surface etc., ultrapure water is used N after cleaning 2dry up and can obtain Au nanochannel arrays film, standby;
2) modification of gold nano channel membrane:
Gold nano channel membrane is immersed to 24 h in the 1mmol/L Stearyl mercaptan solution dissolving with ethanol, alkyl sulfhydryl passes through the self assembly of Au-S key on gold nano passage, then with ethanol, clean and remove the not Stearyl mercaptan of absorption, after modification, gold nano channel membrane is taken out and uses washed with methanol three times, N 2dry up standby;
3) DPA is separated in gold nano passage with RhB, and measures separating effect:
Adopt U-shaped pond as diphenylamine (being DPA) and the separated device of rhodamine B (being RhB), U-shaped pond is divided sample inlet pool and is seen through pond two parts, the gold nano channel membrane of above-mentioned functionalization is placed in to sample inlet pool and sees through in the middle of pond, and sample inlet pool with see through pond and be communicated with by gold nano channel membrane, in the sample inlet pool in U shape pond, add containing 2.09 * 10 -5mol/L DPA and 2.09 * 10 -5mixed solution 3 mL of mol/L RhB, see through in pond and add 3 mL water, the liquid level maintaining in two ponds is parallel, until DPA and RhB mixed liquor, penetrate after gold nano passage, in seeing through pond, get appropriate solution and with ultraviolet-visible pectrophotometer, at wavelength 281nm and 554nm place, measure respectively the content of DPA and RhB.
The inventive method science, reasonable, process, implements easily, DPA is separated with RhB quick and precisely effective, and apparatus structure is simple, easy to operate, be easy to amplify, can be widely used in the fields such as contemporary pharmaceutical chemistry, agriculture chemistry, Food Chemistry and biological chemistry, application prospect is good.Particularly the inventive method provides a kind of new approaches new technology for carcinogens such as separated food dyes, has protected food security and people healthy, significant.
Accompanying drawing explanation
Fig. 1 is the experimental provision schematic diagram of the separated DPA of the present invention and RhB;
Fig. 2 is the FESEM figure of the gold nano channel membrane that obtains after chemogenic deposit of the present invention gold 4h;
Fig. 3 is the TEM figure after the gold nano channel membrane in Fig. 2 dissolves with methylene chloride;
Fig. 4 is not for adopting gold nano passage filtration of the present invention, the amount concentration changes with time graph of a relation of DPA and RhB potpourri;
Fig. 5 is that DPA of the present invention and RhB potpourri are crossed amount of substance concentration changes with time graph of a relation in Au-Mem-C18 osmotic cell.
In figure, 1-U shape pond, 2-sample inlet pool, 3-sees through pond, 4-gold nano channel membrane, 5-magnetic stirring apparatus, a-DPA, b-RhB.
Embodiment
Referring to accompanying drawing, the method for utilizing gold nano channel separation to detect diphenylamine and rhodamine B of the present invention, take PC film as template, adopts chemical deposition deposited gold in the hole wall of nano aperture PC film template, makes the gold nano passage of nano aperture; Utilize gold-sulfide linkage covalent bonding that Stearyl mercaptan is modified in gold nano passage, obtain the hydrophobicity gold nano passage of functionalization; Diphenylamine is as hydrophobic molecule, easily by this hydrophobic gold nano passage; And rhodamine B is cationic compound, belong to hydrophilic molecule, can not in hydrophobicity gold nano passage, move; According to the difference of diphenylamine and rhodamine B hydrophilic and hydrophobic, utilize the selectivity of functionalization gold nano passage, realize the separation of the two; With UV-detector detection diphenylamine and rhodamine B, see through the transit dose of gold nano passage.
In technique scheme, concrete steps are as follows:
1) preparation of gold nano channel membrane:
Adopt chemical deposition in aperture, be Φ 50 nm polycarbonate leaching films (being PCTE) thus in the hole wall of template, deposited gold nano particle makes gold nano passage; Specific as follows: PCTE to be immersed to hplc grade methanol 20 min and activate cleaning; PCTE filter membrane after cleaning immerses 0.025 mol/L SnCl 2and 0.007 mol/L CF 3cOOH methanol-water solution (V/V=1:1) SnCl 2in solution, put constant-temperature table medium speed 150 r/min and shake 45 min, make Sn 2+be adsorbed on equably the inwall in hole; With methyl alcohol purge 3 times; Again PCTE filter membrane is immersed to 0.029 mol/L Ag (NH 3) 2 +in, pass into N simultaneously 2, purge 15 min; PCTE filter membrane is taken out, use respectively each purge of methyl alcohol and ultrapure water 3-4 time, each 2 ~ 3 min, then PCTE filter membrane being immersed to concentration is 7.9 * 10 -4in mol/L gold sodium sulfide and the 0.5 mol/L formaldehyde solution as the solution (pH=10.00) of catalyzer, temperature is 4 ℃ of deposited gold 4 h, gold is reduced the surface that is deposited on PCTE filter membrane and fenestra wall, and the gold nano channel membrane of deposited gold is taken out with ultrapure washing 3 times, uses 25% HNO 3soak 12 h, to remove the upper Ag in surface etc., ultrapure water is used N after cleaning 2dry up and can obtain Au nanochannel arrays film, standby;
2) modification of gold nano channel membrane:
Gold nano channel membrane is immersed to 24 h in the 1mmol/L Stearyl mercaptan solution dissolving with ethanol, alkyl sulfhydryl passes through the self assembly of Au-S key on gold nano passage, then with ethanol, clean and remove the not Stearyl mercaptan of absorption, after modification, gold nano channel membrane is taken out and uses washed with methanol three times, N 2dry up standby;
3) DPA is separated in gold nano passage with RhB, and measures separating effect:
Adopt U-shaped pond as diphenylamine (being DPA) and the separated device of rhodamine B (being RhB), U-shaped pond is divided sample inlet pool and is seen through pond two parts, the gold nano channel membrane of above-mentioned functionalization is placed in to sample inlet pool and sees through in the middle of pond, and sample inlet pool with see through pond and be communicated with by gold nano channel membrane, in the sample inlet pool in U shape pond, add containing 2.09 * 10 -5mol/L DPA and 2.09 * 10 -5mixed solution 3 mL of mol/L RhB, see through in pond and add 3 mL water, the liquid level maintaining in two ponds is parallel, until DPA and RhB mixed liquor, penetrate after gold nano passage, in seeing through pond, get appropriate solution and with ultraviolet-visible pectrophotometer, at wavelength 281nm and 554nm place, measure respectively the content of DPA and RhB.
Embodiment:
DPA and RhB's is separated:
Adopt U-shaped pond, U-shaped pond is divided sample inlet pool, is seen through pond two parts, adds the mixed solution of DPA and RhB in sample inlet pool, adds water in osmotic cell, and detectable concentration relation.
The hydrophobicity gold nano channel membrane of above-mentioned functionalization is placed in to sample inlet pool and sees through in the middle of pond, effective transmission area of film is 0.196 cm 2.
Respectively by 2.09 * 10 -5mol/L DPA and 2.09 * 10 -5mixed solution 3 mL of mol/L RhB are placed in sample inlet pool, see through pond and place 3 mL water, every two hours, with ultraviolet spectrophotometer DPA (measuring at 281 nm wavelength places with ultraviolet-visible pectrophotometer) and RhB(use ultraviolet-visible pectrophotometer in detecting osmotic cell, at 554 nm wavelength places, measure) transit dose, the relation that obtains DPA and RhB time of penetration and infiltration capacity in osmotic cell, the ratio of gained straight slope is defined as the degree of separation of two kinds of determinands.
Fig. 4, Fig. 5 be the concentration of material with the variation relation figure that spends the film time, the degree of separation S of DPA and RhB is defined as:
S?=? KDPA?/? KRhB
Wherein kdPA and kfilm speed, the i.e. slope of figure cathetus excessively of RhB; kdPA is film speed, the i.e. slope of red line in figure excessively of DPA.Hence one can see that, the degree of separation of DPA and RhB sbe tending towards infinitely great, DPA obtains complete separated with RhB.
In above-mentioned specific embodiment mode, the experimental technique of unreceipted actual conditions, is all undertaken by common normal condition, as operation manual, or the condition of advising according to manufacturer.
Should be noted that, these embodiments only do not limit the scope of the invention for the present invention is described.In addition, after having read the content of the present invention's description, those skilled in the art may make various changes or modifications the present invention, and the change of these equivalent form of values or modification fall within the scope that the application's claim limits equally.

Claims (2)

1. utilize gold nano channel separation to detect a method for diphenylamine and rhodamine B, it is characterized in that, take PC film as template, adopt chemical deposition deposited gold in the hole wall of nano aperture PC film template, make the gold nano passage of nano aperture; Utilize gold-sulfide linkage covalent bonding that Stearyl mercaptan is modified in gold nano passage, obtain the hydrophobicity gold nano passage of functionalization; Diphenylamine is as hydrophobic molecule, easily by this hydrophobic gold nano passage; And rhodamine B is cationic compound, belong to hydrophilic molecule, can not in hydrophobicity gold nano passage, move; According to the difference of diphenylamine and rhodamine B hydrophilic and hydrophobic, utilize the selectivity of functionalization gold nano passage, realize the separation of the two; With UV-detector detection diphenylamine and rhodamine B, see through the transit dose of gold nano passage.
2. the method for utilizing gold nano channel separation to detect diphenylamine and rhodamine B according to claim 1, is characterized in that, concrete steps are as follows:
1) preparation of gold nano channel membrane:
Adopt chemical deposition in aperture, be Φ 50 nm polycarbonate leaching films (being PCTE) thus in the hole wall of template, deposited gold nano particle makes gold nano passage; Specific as follows: PCTE to be immersed to hplc grade methanol 20 min and activate cleaning; PCTE filter membrane after cleaning immerses and contains 0.025 mol/L SnCl 2with 0.007 mol/L CF 3in the methanol-water solution (V/V=1:1) of COOH, put constant-temperature table medium speed 150 r/min and shake 45 min, make Sn 2+be adsorbed on equably the inwall in hole; With methyl alcohol purge 3 times; Again PCTE filter membrane is immersed to 0.029 mol/L Ag (NH 3) 2 +in, pass into N simultaneously 2, purge 15 min; PCTE filter membrane is taken out, use respectively each purge of methyl alcohol and ultrapure water 3-4 time, each 2 ~ 3 min, then immerse PCTE filter membrane to contain 7.9 * 10 -4in the catalyst solution of mol/L gold sodium sulfide and 0.5 mol/L formaldehyde, temperature is 4 ℃ of deposited gold 4 h, and gold is reduced the surface that is deposited on PCTE filter membrane and fenestra wall, and the gold nano channel membrane of deposited gold is taken out with ultrapure washing 3 times, uses 25% HNO 3soak 12 h, to remove the upper Ag in surface etc., ultrapure water is used N after cleaning 2dry up and can obtain Au nanochannel arrays film, standby;
2) modification of gold nano channel membrane:
Gold nano channel membrane is immersed to 24 h in the 1mmol/L Stearyl mercaptan solution dissolving with ethanol, alkyl sulfhydryl passes through the self assembly of Au-S key on gold nano passage, then with ethanol, clean and remove the not Stearyl mercaptan of absorption, after modification, gold nano channel membrane is taken out and uses washed with methanol three times, N 2dry up standby;
3) DPA is separated in gold nano passage with RhB, and measures separating effect:
Adopt U-shaped pond as diphenylamine (being DPA) and the separated device of rhodamine B (being RhB), U-shaped pond is divided sample inlet pool and is seen through pond two parts, the gold nano channel membrane of above-mentioned functionalization is placed in to sample inlet pool and sees through in the middle of pond, and sample inlet pool with see through pond and be communicated with by gold nano channel membrane, in the sample inlet pool in U shape pond, add containing 2.09 * 10 -5mol/L DPA and 2.09 * 10 -5mixed solution 3 mL of mol/L RhB, see through in pond and add 3 mL water, the liquid level maintaining in two ponds is parallel, until DPA and RhB mixed liquor, penetrate after gold nano passage, in seeing through pond, get appropriate solution and with ultraviolet-visible pectrophotometer, at wavelength 281nm and 554nm place, measure respectively the content of DPA and RhB.
CN201410329537.2A 2014-07-11 2014-07-11 Method for separating and detecting diphenylamine and rhodamine B by using gold nano channel Pending CN104090035A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107421899A (en) * 2017-06-28 2017-12-01 重庆市宇驰检测技术有限公司 Determine the detection method of water quality aniline, formaldehyde simultaneously based on ultraviolet-visible absorption spectroscopy

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107421899A (en) * 2017-06-28 2017-12-01 重庆市宇驰检测技术有限公司 Determine the detection method of water quality aniline, formaldehyde simultaneously based on ultraviolet-visible absorption spectroscopy

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