阅读说明：本技术 一种快速高效检测痕量对苯二胺的方法 (A method of rapidly and efficiently detecting trace p-phenylenediamine ) 是由 张胜利 刘伯芳 张思略 胡代燕 周祚万 裴彥博 于 2019-08-28 设计创作，主要内容包括：一种快速高效检测痕量对苯二胺的方法,具体地,将棉纤维素溶解制备再生纤维素膜,采用高碘酸钠将再生纤维素膜上的羟基选择性氧化为醛基,再通过两步席夫碱反应,制备得到发射黄色荧光的各体系固相荧光检测膜,用于对苯二胺的定性分析和定量检测,本发明具有简单快速、灵敏度高、选择性好的优点。(A method of rapidly and efficiently detecting trace p-phenylenediamine, specifically, gossypin dissolution is prepared into regenerated cellulose film, use sodium metaperiodate by the hydroxyl selective oxidation on regenerated cellulose film for aldehyde radical, pass through two step schiff base reactions again, each system solid phase fluorescent detection film of transmitting yellow fluorescence is prepared, for the qualitative analysis and quantitative detection of p-phenylenediamine, the present invention has the advantages that simple and quick, high sensitivity, selectivity are good.)

1. a kind of method for rapidly and efficiently detecting trace p-phenylenediamine, which comprises the following steps:

(1) gossypin is dissolved, prepares regenerated cellulose gel mould；

(2) the regenerated cellulose gel mould that (1) obtains is selectively oxidized using periodate as oxidant, preparation two Aldehyde cellulose gel film；

(3) dialdehyde fiber gel film is immersed in the p-phenylenediamine solution of different calibration concentration and is reacted, obtain the richness of different systems Collect the cellulose gel film of p-phenylenediamine；

(4) cellulose gel film of the enrichment p-phenylenediamine of different systems is immersed respectively in salicylide solution and is reacted, dried, obtain Each system solid phase fluorescent to transmitting yellow fluorescence detects film；

(5) under the ultraviolet light irradiation of 365nm, each system solid phase fluorescent detection film transmitting yellow fluorescence is for the qualitative of p-phenylenediamine Analysis；

(6) each system is tested in the fluorescence spectrum of 370nm excitation wavelength, using p-phenylenediamine concentration as abscissa, with launch wavelength The fluorescence intensity that different p-phenylenediamine concentration correspond to the detection film of solid phase fluorescent obtained by system under 545nm is ordinate, and building is linear Curve, the concentration of quantitative detection p-phenylenediamine to be measured.

2. a kind of method for rapidly and efficiently detecting trace p-phenylenediamine according to claim 1, which is characterized in that the step Suddenly the periodate in (2) is sodium metaperiodate；

In the step (3), it is 10-1000 μ g/L that p-phenylenediamine, which demarcates concentration, and reaction temperature is 0-45 DEG C, the reaction time 1- 120min, solution ph 4-9；

In the step (3), the solvent for preparing p-phenylenediamine solution is alcohol-water or dehydrated alcohol, wherein ethyl alcohol: water >=1:1.

Step (4) the salicylide solution concentration is 0.05%-1%, solution ph 4-9；Reaction temperature is 0-55 DEG C, reaction 1-60min of time.

In the step (4), the solvent for preparing salicylide solution is ethyl alcohol.

3. a kind of method for rapidly and efficiently detecting trace p-phenylenediamine according to claim 2, which is characterized in that the step Suddenly in (3), p-phenylenediamine solution is 0,10 ... ..., 1000 μ g/L；25 DEG C of reaction temperature, reaction time 1h, solution ph is 8；

In the step (4), salicylide solution concentration is 0.5%, uncomfortable pH value, and reaction temperature is 25 DEG C, and the reaction time is 10min。

Technical field

The present invention relates to the analyzing detecting methods of p-phenylenediamine, and in particular to detects trace using solid phase surface fluorescent spectrometry The method for measuring p-phenylenediamine.

Background technique

P-phenylenediamine is a kind of important Organic Chemicals, and it is anti-to be widely used in production dyestuff, pigment, hair dye, rubber Old agent etc..It can by suck, eat or skin penetrate into human body, liver, hematological system, nervous system etc. are caused seriously to damage Wound also has the effects that potential carcinogenic, mutagenesis, is a kind of important environmental contaminants.

Currently, the method for detection p-phenylenediamine mainly has UV-VIS spectrophotometry, gas chromatography (GC), Gao Xiang Liquid chromatography, Liquid Chromatography-Mass Spectrometry (GC-MS), electrophoresis etc..The sensitivity that these methods have is lower, some instrument Device is expensive, and some pretreatments are complicated, cumbersome.

Chinese patent literature has following disclosure.

Document one: " a kind of highly selective method for detecting p-phenylenediamine in aqueous solution " (application number 201510464161.0) Using aggregation fluorescence enhancement mechanism, the p-phenylenediamine in aqueous solution is detected using liquid phase fluorescent spectrometry,

Document one there are the shortcomings that: first, the prior art is to the detection of p-phenylenediamine still using traditional liquid phase fluorescence point Analysis method, detection limit are higher.From the point of view of the fluorescent emission map that the prior art is announced, the p-phenylenediamine fluorescent emission of 0.5mg/L is strong Degree only 800 or so；And fluorescence intensity reaches 5700 under the same concentration of the present invention, sensitivity greatly improves, and detection limit reaches 7.5 μ g/L.Second, the testing principle of the prior art is that double salicylaldehyde contracting p-phenylenediamine Schiff is synthesized with p-phenylenediamine using salicylide Alkali, the latter have aggregation Enhancement of Fluorescence.In our patent, an amido and the dialdehyde cellulose membrane of p-phenylenediamine Aldehyde radical occurs schiff base reaction and is enriched to film surface, another amido and salicylide, which react to be made, later occurs yellow fluorescence Transparency cellulose film.Meanwhile cellulose membrane plays restriction effect to the vibration and rotation of strand so that non-radiative channel by Resistance, it is easier to be released energy with radiation mode, so fluorescence intensity greatly increases.

Document two: (patent that seminar applies before this) patent 1 " a kind of PEI modified cellulose membrane adsorbent and its preparation Method " (application number 201711273187.2), a kind of " the preparation side of polyethyleneimine amido chloramines type antibacterial cellulose film of patent 2 Method and application " (application number 201810897797.8) and patent 3 " a kind of PEI modified cellulose membrane adsorbent and preparation method thereof " (application number 201811530631.9).

3 patents only disclose the preparation method of respective fiber element film and oxycellulose film in document two, without regard to The detection method of p-phenylenediamine.Using regenerated cellulose film as solid-phase matrix material, by selective oxidation, dialdehyde is made in this patent Tunica fibrosa.The film link of above-mentioned three kinds of patents is identical as this patent；Link is aoxidized, patent 1 (uses hydrogen peroxide as oxidant) Different from this patent, patent 2 and patent 3 (making oxidant using sodium metaperiodate) are identical as this patent.That present invention is in oxidation ring Should section select hydrogen peroxide or sodium metaperiodate to make oxidant actually in order to answer this problem, this patent is in oxidation link warp Crossing Principle Study adds series batch experiment is just final to determine that selection sodium metaperiodate makees oxidant.In fact, the link oxidant is really Determine to those skilled in the art, not making the creative labor can not obtain.Other than being film-made, aoxidizing link, on Three, face patent and this patent are entirely different in terms of subsequent grafting and application purpose.The former is to prepare heavy metal Adsorbent or antibacterial cellulose film, and the present invention is using cellulose membrane as solid-phase matrix material tests p-phenylenediamine.

Summary of the invention

A kind of good, high sensitivity the method for detecting trace p-phenylenediamine that the object of the present invention is to provide selectivity.

The present invention is implemented as follows: a kind of method for rapidly and efficiently detecting trace p-phenylenediamine, comprising the following steps:

(1) gossypin is dissolved, prepares regenerated cellulose gel mould；

(2) the regenerated cellulose gel mould that (1) obtains is selectively oxidized using periodate as oxidant, is made Standby dialdehyde cellulose gel film；

(3) dialdehyde fiber gel film is immersed in the p-phenylenediamine solution of different calibration concentration and is reacted, obtain different systems Enrichment p-phenylenediamine cellulose gel film；

(4) cellulose gel film of the enrichment p-phenylenediamine of different systems is immersed respectively in salicylide solution and is reacted, dried It is dry, obtain each system solid phase fluorescent detection film of transmitting yellow fluorescence；

(5) under the ultraviolet light irradiation of 365nm, each system solid phase fluorescent detection film transmitting yellow fluorescence is for p-phenylenediamine Qualitative analysis；

(6) each system is tested in the fluorescence spectrum of 370nm excitation wavelength, using p-phenylenediamine concentration as abscissa, with transmitting It is ordinate, building that different p-phenylenediamine concentration, which correspond to the fluorescence intensity of the detection film of solid phase fluorescent obtained by system, under wavelength 545nm Linearity curve, the concentration of quantitative detection p-phenylenediamine to be measured.

Periodate in the step (2) is sodium metaperiodate；

In the step (3), p-phenylenediamine concentration is 0-1000 μ g/L, and reaction temperature is 0-45 DEG C, reaction time 1- 120min, solution ph 4-9；

In the step (3), the solvent for preparing p-phenylenediamine solution is alcohol-water or dehydrated alcohol, wherein ethyl alcohol: water >= 1:1.

Step (4) the salicylide solution concentration is 0.05%-1%, and solution ph 4-9, reaction temperature is 0-55 DEG C, Reaction time 1-60min.

In the step (4), the solvent for preparing salicylide solution is dehydrated alcohol

In the step (3), p-phenylenediamine solution concentration is 0,10 ... ..., 1000 μ g/L；25 DEG C of reaction temperature, reaction Time is 1h, solution ph 8；P-phenylenediamine solution ph is adjusted with the hydrochloric acid of 0.1mol/L or sodium hydroxide 's.

In the step (4), bigcatkin willow aldehyde concentration is 0.5%, uncomfortable pH value, and reaction temperature is 25 DEG C, and the reaction time is 10min。

Compared with prior art, the invention has the characteristics that and advantage:

(1) select regenerated cellulose film for the solid-phase matrix material of solid phase surface fluorescence analysis.Solid phase surface fluorescence spectrum The key of method is the suitable solid-phase matrix material of selection, currently used solid matrix materials have silica gel, aluminium oxide, nylon membrane, Filter paper and glycan gellike etc..But the fluorescence background that these materials have is high, some poor selectivities.It compares, regenerated cellulose film Have many advantages, such as that optical clarity height, fluorescence background interfere small, high mechanical strength, Yi Jinhang chemical modification.

(2) using dialdehyde cellulose membrane as solid-phase matrix, by two step schiff base reactions, establish a kind of collection solid phase enrichment with The new method for the detection p-phenylenediamine that solid phase fluorescent detection is integrated.Using dialdehyde cellulose membrane as host material, not only optics Transparency is high, fluorescence background interferes small, high mechanical strength, and has solid phase enrichment to target contaminant p-phenylenediamine.

New method of the invention integrates solid phase enrichment and detects with solid phase fluorescent.

(3) there are two ranges of linearity of 0.01-0.1mg/L and 0.1-1mg/L, sides when built new method detection p-phenylenediamine The detection of method is limited to 7.5 μ g/L.Concentration of aniline is lower than 10mg/L or isophthalic two lower than 100mg/L, o-phenylenediamine concentration in system Amine concentration does not interfere the measurement of p-phenylenediamine when being lower than 1mg/L.

(4) solid phase enrichment is with solid phase fluorescent detection mechanism: the first step, sodium metaperiodate is by C2 in cellulose molecular chain and C3 Secondary hydroxyl selective oxidation be dialdehyde-based, obtain dialdehyde cellulose membrane (DCM).Second step, the aldehyde radical of dialdehyde cellulose membrane with Schiff base reaction occurs for one amido of p-phenylenediamine, and p-phenylenediamine is enriched to film surface.Third step, the p-phenylenediamine of enrichment Another amido react with salicylide, must emit yellow fluorescence solid phase fluorescent detection film.

(5) using cellulose membrane as solid-phase matrix, vibration and rotational energy of the two-dimension plane structure to reaction product strand Restriction effect is played, non-radiative access denial is made, it is easier to be released energy with radiation mode, so fluorescence intensity greatly increases.

Method there are the preprocessing process of sample to be tested cumbersome, the complicated for operation or detecting instrument of detection p-phenylenediamine at present The disadvantages of being not easy to micromation, cannot quickly detecting in time.The present invention have it is simple and quick, sample consumption is few, high sensitivity, The features such as selectivity is good has potential advantages to the detection of the especially trace p-phenylenediamine of low concentration in environment.

Detailed description of the invention

Fig. 1 is that (bigcatkin willow aldehyde concentration is 0.5% to made solid phase fluorescent detection film, reaction under different p-phenylenediamine concentration conditions 25 DEG C of temperature, reaction time 10min；P-phenylenediamine concentration is 0,10 ... ..., 1000 μ g/L, and p-phenylenediamine solution solvent is nothing Water-ethanol, solution ph 8,25 DEG C of reaction temperature, reaction time 1h) fluorescence spectra.

Fig. 2 is that (there are 0.01-0.1mg/ when the present invention detects p-phenylenediamine for the relationship of fluorescence intensity and p-phenylenediamine concentration Two ranges of linearity of L and 0.1-1mg/L, the detection of method are limited to 7.5ug/L).

Fig. 3 dialdehyde cellulose membrane (DCM), dialdehyde cellulose membrane leaching salicylide (DCM+ salicylide), solid phase fluorescent detect film The fluorescence spectra of (DCM+ p-phenylenediamine+salicylide).

Fig. 4 dialdehyde cellulose membrane is first acted on aniline, o-phenylenediamine, m-phenylene diamine (MPD) and the p-phenylenediamine of 1mg/L respectively, then With the fluorescence spectra of immobilon-p obtained by bigcatkin willow aldehyde reaction.

Specific embodiment

The present invention is further elaborated combined with specific embodiments below, but these embodiments are not constituted the present invention Any restrictions, the present invention can be implemented by formula either described in summary of the invention.

Hereinafter, the concentration being not specified is mass concentration.