阅读说明：本技术 一种水溶性荧光硅量子点的制备方法及其在选择性检测对硝基酚中的应用 (A kind of preparation method of water soluble fluorescence silicon quantum dot and its application in selective enumeration method paranitrophenol ) 是由 叶存玲 王远飞 武莹 王全坤 王治科 范顺利 于 2019-08-26 设计创作，主要内容包括：本发明属于荧光功能材料领域,具体涉及一种水溶性硅量子点及其制备方法,以及在对硝基酚的高灵敏度高选择性检测中的应用。本发明的技术方案要点为：3-氨丙基三乙氧基硅烷在85℃且剧烈搅拌条件下,加到超纯水中反应10min,再加入对乙酰氨基酚溶液,持续搅拌反应5h。本发明的硅量子点合成方法简便,反应条件温和,量子产率高,水溶性好,而且长时间保存,甚至在不同的pH、不同的离子强度条件下仍能保持优异的荧光性能。该硅量子点在398nm的荧光激发下发射495nm荧光,并且对硝基酚能特异性猝灭硅量子点的荧光。本发明硅量子点在快速高效、高选择性、高灵敏度检测对硝基酚方面显示了良好的应用前景。(The invention belongs to fluorescent functional Material Fields, and in particular to a kind of water-soluble silicon quantum dot and preparation method thereof, and the application in the highly selective detection of high sensitivity of paranitrophenol.Technical solution of the present invention main points are as follows: 3- aminopropyl triethoxysilane is added in ultrapure water under 85 DEG C and intense agitation and reacts 10min, adds acetaminophen solution, is persistently stirred to react 5h.Silicon quantum dot simple synthetic method of the invention, reaction condition is mild, and quantum yield is high, good water solubility, and saves for a long time, or even be still able to maintain excellent fluorescence property under different pH, different ionic strength conditions.The silicon quantum dot emits 495nm fluorescence under the fluorescence excitation of 398nm, and paranitrophenol can the specific fluorescence for quenching silicon quantum dot.Silicon quantum dot of the present invention shows good application prospect rapidly and efficiently, in terms of highly selective, highly sensitive detection paranitrophenol.)

1. a kind of preparation method of water soluble fluorescence silicon quantum dot, it is characterised in that specific steps are as follows: be added in collet beaker 1mL 3- aminopropyl triethoxysilane is added in 5mL ultrapure water under 85 DEG C of intense agitations, in 10min after be added 2mL, The acetaminophen solution of 50mM, is persistently stirred to react 5h, final that water-soluble hanced cyan fluorescent silicon quantum dot is made.

2. water soluble fluorescence silicon quantum dot is in highly selective, Sensitive Determination pair made from the method according to claim 11 Application in nitrophenols concentration, it is characterised in that detailed process are as follows: sequentially add in the reaction vessel 0.5mL silicon quantum dot and The PBS buffer solution of 0.2mL, pH=11, add paranitrophenol to be measured, and constant volume 4.00mL is being excited in 25 DEG C of reaction 40min Wavelength 398nm, launch wavelength 495nm measure mixed system fluorescence intensity, further according to the fluorescence intensity measured and combine linear side Paranitrophenol concentration to be measured is calculated in journey；Paranitrophenol concentration is within the scope of 1-80 μM, with fluorescent quenching efficiency (F₀- F)/F₀ Between there are preferable linear relationship, R²=0.9944, linear equation is (F₀- F)/F₀=0.007C+0.036, wherein F_0、F difference It is the fluorescence intensity that paranitrophenol fore-and-aft architecture is added, C is the concentration of paranitrophenol, unit μM, to 40 μM of paranitrophenol weight Multiple 11 measurements, relative standard deviation 0.9%, detection are limited to 0.87 μM.

Technical field

The invention belongs to fluorescent functional field of material technology, and in particular to a kind of preparation side of water soluble fluorescence silicon quantum dot Method and its application in selective enumeration method paranitrophenol.

Background technique

Paranitrophenol property is stable and can be dissolved in water, thus it can long-term existence in the natural environment, and because it is used extensively In the preparation of the chemical articles such as pesticide, medicine, rubber, explosive and dyestuff, often through water body and soil pollution and then serious shadow Ring the physical and mental health of people.Currently, the method for detecting paranitrophenol mainly has electrochemical method, capillary electrophoresis, color Spectrometry etc..However, more or less there are some defects in these methods.Fluorescence analysis method is low cost, efficient, Sensitive Detection pair Nitrophenols provides new approaches.

Summary of the invention

The technical problem to be solved by the present invention is to provide a kind of simple synthetic method, mild condition and fluorescence property are excellent The preparation method of water soluble fluorescence silicon quantum dot, this method are used using 3- aminopropyl triethoxysilane as silicon precursor, to acetyl Amino phenols is reducing agent, has prepared the bright cyan water soluble fluorescence silicon quantum dot of generation.The quantum yield of the silicon quantum dot is 12.8%, and possess water-soluble and good photoluminescent property well.And under strong acid, highly basic or high ionic strength, still It is able to maintain stable fluorescence property.This fluorescence chemical sensor has good selectivity and sensitivity, is used successfully to practical water The detection of paranitrophenol in sample.

A kind of technical solution of the present invention main points are as follows: preparation method of water soluble fluorescence silicon quantum dot, it is characterised in that tool Body step are as follows: 5mL ultrapure water is added in collet beaker, three ethoxy of 1mL 3- aminopropyl is added under 85 DEG C of intense agitations Base silane, in 10min after the acetaminophen solution of 2mL, 50mM is added, be persistently stirred to react 5h, it is final that water solubility is made Hanced cyan fluorescent silicon quantum dot.

Water soluble fluorescence silicon quantum dot of the present invention is in highly selective, answering in Sensitive Determination paranitrophenol concentration With, it is characterised in that detailed process are as follows: the PBS for sequentially adding 0.5mL silicon quantum dot and 0.2mL, pH=11 in the reaction vessel is slow Solution is rushed, paranitrophenol to be measured, constant volume 4.00mL, in 25 DEG C of reaction 40min, in excitation wavelength 398nm, launch wavelength are added 495nm measures mixed system fluorescence intensity, obtains further according to the fluorescence intensity measured and in conjunction with linear equation calculation to be measured to nitre Base phenol concentration；Paranitrophenol concentration is within the scope of 1-80 μM, with fluorescent quenching efficiency (F₀- F)/F₀Between exist it is preferable linear Relationship, R²=0.9944, linear equation is (F₀- F)/F₀=0.007C+0.036, wherein F_0、F is added before and after paranitrophenol respectively The fluorescence intensity of system, C are the concentration of paranitrophenol, and unit μM is repeated 11 times measurement, relative standard to 40 μM of paranitrophenols Deviation is 0.9%, and detection is limited to 0.87 μM.

Water-soluble silicon quantum dot produced by the present invention emits 495nm fluorescence under the fluorescence excitation of 398nm, and to nitro Phenol can the specific fluorescence for quenching silicon quantum dot.Water-soluble silicon quantum dot produced by the present invention rapidly and efficiently, it is highly selective, high Good application prospect is shown in terms of sensitivity technique paranitrophenol.

Detailed description of the invention

Fig. 1 is the stability of silicon quantum dot.

Fig. 2 is influence of the pH to silicon quantum dot fluorescence property.

Fig. 3 is influence of the ionic strength to silicon quantum dot fluorescence property.

Fig. 4 is the excitation and emission spectra figure of silicon quantum dot.

Fig. 5 is 3- aminopropyl triethoxysilane (APTS), paracetamol (APAP), silicon quantum dot (SiQDs) are red External spectrum.

Fig. 6 is the selectivity and interference free performance of measuring method.

Specific embodiment

Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair Bright range.