WO2019242221A1 - 一种pH平板光极荧光传感膜、制备方法及应用 - Google Patents

一种pH平板光极荧光传感膜、制备方法及应用 Download PDF

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WO2019242221A1
WO2019242221A1 PCT/CN2018/116081 CN2018116081W WO2019242221A1 WO 2019242221 A1 WO2019242221 A1 WO 2019242221A1 CN 2018116081 W CN2018116081 W CN 2018116081W WO 2019242221 A1 WO2019242221 A1 WO 2019242221A1
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hpts
sensing film
lipo
fluorescent dye
fluorescent
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French (fr)
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罗军
胡璇
梁潮根
方文
刘兆东
尹带霞
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南京大学
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/001—Pyrene dyes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G01N31/221—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating pH value
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6434—Optrodes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/7769—Measurement method of reaction-produced change in sensor
    • G01N2021/7786—Fluorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/80—Indicating pH value

Definitions

  • the invention belongs to the technical field of flat-plate photoelectrodes for monitoring two-dimensional pH values, and more particularly, relates to a pH flat-plate photoelectron fluorescence sensing film, a preparation method and applications.
  • pH is an important indicator that affects the geochemical cycle of various heavy metals and metalloid elements.
  • plant roots can affect the pH of the surrounding environment by secreting root exudates and other behaviors, causing rhizosphere acidification or alkalization. Therefore, the rhizosphere effect is important for studying the geochemical cycle of heavy metals and metalloids Important.
  • the traditional method for pH measurement is mainly based on electrode sensing.
  • it is more expensive and it is a single point measurement. If it is arranged in a large area in the rhizosphere, the cost is higher. And cause disturbances affecting rhizosphere activities. Needless to say, the ability to achieve in situ, real-time, non-invasive detection of the rhizosphere microenvironment or other microregions has become an urgent need in environmental research.
  • the prepared fluorescence sensor has high sensitivity, good stability, and can adapt to the heterogeneity of the environment, which is very suitable for the detection of the concentration of related substances to be tested and the study of environmental micro-interfaces.
  • optical sensors have received more and more attention, especially the development of flat-plate photoelectrode technology for two-dimensional imaging.
  • in-situ, real-time, non-invasive detection it has become an urgent need in environmental research.
  • the related art research on the fluorescence sensing film has published related applications, such as Chinese patent application number CN201410643390.4, and the application dated 2015.02.18 disclosed a pH fluorescence sensing film. It includes a thin film substrate, which uniformly mixes the fluorescent dye CPIPA and fluorescent yellow 10-GN, and fixes the two fluorescent dyes on the surface of the thin film substrate by a chemical embedding method. Based on the pH fluorescence sensing film, the invention also discloses a method for detecting the pH two-dimensional dynamic distribution of alkaline sediments. The pH fluorescence sensing film is placed in the sediment and obtained by an imaging device under the excitation light irradiation.
  • Spectral information of the two dyes was obtained by quantifying the fluorescence ratio of the R and B channels to the pH distribution characteristics of the sediment.
  • the sensing film of this application mixes CPIPA with fluorescent yellow 10-GN with a reference effect and a brightening effect as a fluorescent indicator, has high detection sensitivity, high spatial resolution, and is sensitive to changes in pH.
  • the method uses a flat electrode technology to quantitatively reduce optical interference through fluorescence ratios, and achieves real-time, in-situ acquisition of two-dimensional, dynamic distribution information of pH of alkaline sediments.
  • the fluorescent dye CPIPA in this application is only suitable for alkaline working range, which limits its application in the field of pH detection.
  • Chinese patent application number CN201110407804.X discloses an optical ion sensing film for detecting pH, which includes the following components by weight percentage: ETH5418 0.38% -0.42%; four [ 3,5-Di- (trifluoromethyl) benzene] sodium borate 0.44% -0.49%; Up-conversion nanorods 2.09% -2.14%; Polyvinyl chloride 33.13% -33.16%; Sebacic acid di (2-ethyl Hexyl) ester or o-nitrophenyloctyl ether or dioctyl phthalate make up to 100%.
  • the invention also discloses a preparation method of the optical ion sensing film and an application of the sensing film in pH detection.
  • the optical ion sensing film used in this application to detect pH is excited by light with a wavelength of 980 nm and the emission is also in the near-infrared region, and the sensor is not affected by background absorption and background fluorescence. Compared with the traditional organic system, this system It has higher quantum yield and can produce high intensity fluorescence. Various chemical reagents are consumed in the preparation process of the optical ion sensing film in this application, the cost is high, and it is not conducive to promotion.
  • HPTS is 8-hydroxy-1,3,6-trisulfonate fluorene, and it is also a fluorescent dye for preparing two-dimensional fluorescence sensing film. It is a type of fluorescent material that is spectrally selective for pH changes and has both green and blue fluorescence emission characteristics. It is widely used as a fluorescent dye for pH changes. Not only that, HPTS is a very low-toxicity water-soluble fluorescent substance. It exists in the form of protonated state and deprotonated state according to the pH environment in the aqueous solution. HPTS has a high optical quantum yield and a large Stokes shift, and its pKa value determines that HPTS is a fluorescent material that is very suitable for studying pH changes in the natural environment and in vivo. But at the same time, because of its strong water solubility, its application in the natural environment is limited.
  • Single-point dual-parameter fluorescent optical fiber sensor probe comprising an optical fiber probe, a polyurethane hydrogel layer fixed on the optical fiber probe, and pH-sensitive particles and oxygen-sensitive particles dispersed and embedded in the polyurethane hydrogel layer
  • said pH-sensitive particles HPTS is prepared by covalently fixing HPTS to amino-modified p-HEMA
  • the oxygen-sensitive particles are prepared by embedding Ru (dpp) 3 2+ in an organic modified silicate by using a solvent chloroform.
  • the present invention provides a new fluorescent dye and a pH plate photoelectrode. Fluorescence sensing film, preparation method and application.
  • the invention provides a pH flat-plate photopolar fluorescence sensing film, the fluorescent sensing film is prepared by a fluorescent dye HPTS-lipo, and the fluorescent dye HPTS-lipo is a di-n-butylamine introduced into a sulfonic acid group of HPTS. Or dimethylamine. After the introduction of alkylamine groups, HPTS has successfully changed from water-soluble to fat-soluble. For details, see the LogD curve of the substance.
  • the preparation method of the fluorescent dye HPTS-lipo includes the following steps:
  • the preparation method of the pH flat-plate photopolar fluorescence sensing film includes the following steps:
  • the mass ratio of the hydrogel D4 to the fluorescent dye in the mixed solution is 100: 1.
  • the volume ratio of absolute ethanol to water in the aqueous solution containing absolute ethanol is 9: 1.
  • the present invention provides a flat-plate photoelectrode for monitoring a two-dimensional pH value, and the flat-plate photoelectrode is prepared by using a pH flat-plate photoelectron fluorescence sensing film.
  • the application method of a flat-plate photoelectrode for monitoring two-dimensional pH is characterized in that the fluorescent sensing film is fixed on the interface to be measured, and an image is used under an ultraviolet excitation light source.
  • the capture system dynamically obtains the spatiotemporal distribution of the pH of the interface to be measured.
  • the application method of the flat-plate photoelectrode for monitoring two-dimensional pH is characterized in that the wavelength of the ultraviolet excitation light source is 405 nm.
  • the application method of a flat-plate photoelectrode for monitoring two-dimensional pH is characterized in that the image capture system includes a CCD device and a storage terminal device.
  • the method for applying a flat-plate photoelectrode for monitoring a two-dimensional pH value includes the following steps:
  • the pH flat-plate photopolar fluorescence sensing film of the present invention is prepared by using a fluorescent dye HPTS-lipo, and the fluorescent dye HPTS-lipo is connected to an aromatic sulfonate structure in which the fluorescent dye HPTS is extremely soluble in water.
  • Derivatives derived from alkylamines can greatly enhance the hydrophobicity of fluorescent dyes, and therefore can exist in the environment for a longer period of time, thereby enabling the fluorescent sensing film to meet the needs of long-term experiments.
  • the pH flat-plate photopolar fluorescence sensing film of the present invention is prepared by using the fluorescent dye HPTS-lipo. Compared with the fluorescent dye HPTS, it has the characteristics of small polarity and strong hydrophobicity.
  • the preparation of the fluorescent sensing film in the gel D4 greatly reduces the possibility of dye leakage of the fluorescent sensing film and expands the application range of the fluorescent sensing film in the field of pH monitoring. Because the fluorescent dye HPTS is extremely water-soluble, if it is also embedded with hydrogel D4, it dissolves immediately after contact with water. The resulting fluorescent sensing film cannot be applied in the natural environment.
  • the special embedding agent or embedding method is used for processing, and the input cost is high.
  • the fluorescence sensing film for monitoring the two-dimensional pH value of the present invention is prepared from the fluorescent dye HPTS-lipo, and the pKa value of the modified fluorescent dye HPTS-lipo is significantly changed compared with the fluorescent dye HPTS. Therefore, the prepared fluorescent sensing film is suitable for monitoring different pH values and meets different experimental requirements.
  • the fluorescence sensing film for monitoring the two-dimensional pH value of the present invention the pH range of the fluorescent sensing film made by using dimethylamine-HPTS is 5-9, and the fluorescence produced by di-n-butylamine-HPTS is The applicable pH range of the sensing membrane is 3-11, and the derivative of the di-n-butylamine-modified fluorescent dye HPTS can be applied to a wider pH range and a wider application range.
  • the fluorescence sensing film for monitoring the two-dimensional pH value of the present invention the pH flat-plate photoelectrode prepared from the fluorescence sensing film can respond to the signal instantaneously in the actual application process, which is in line with the pH in the prior art. Compared with the flat photopole, the response time is greatly shortened, which is conducive to popularization.
  • the fluorescent sensing film for monitoring the two-dimensional pH value of the present invention the fluorescent dye HPTS-lipo is embedded with hydrogel D4 during the preparation process, the operation is simple and convenient, and the cost is low. Embedding reduces the difficulty of film formation.
  • the prepared fluorescent sensing film has a wide range of applications and is conducive to popularization.
  • Figure 1 is a reaction flow chart of the preparation of the fluorescent dye HPTS-lipo
  • Figure 2 is a schematic diagram of the chemical structure of dimethylamine-HPTS
  • Figure 3 is a schematic diagram of the chemical structure of di-n-butylamine-HPTS
  • Example 4 is a fitting spectrum obtained when the fluorescent sensing film of Example 1 is applied;
  • Figure 6 is a UV excitation spectrum of dimethylamine-HPTS
  • FIG. 8 is an ultraviolet excitation spectrum of di-n-butylamine-HPTS
  • FIG. 9 is an emission spectrum chart of di-n-butylamine-HPTS under 405 nm excitation
  • FIG. 10 is a schematic diagram of a device of a flat-plate photoelectrode experimental system
  • Figure 11 is the LogD curve of HPTS
  • Fig. 12 is a LogD curve of HPTS-dimethylamine.
  • HPTS-SO 2 Cl is dissolved in dichloromethane, and it is added dropwise at 1: 3.1 times the equivalent of dimethylamine under ice bath conditions. After the reaction is completed, the product is spin-evaporated and deprotected with 1 mol / L NaOH to obtain the final product. Pure product HPTS-lipo, dimethylamine-HPTS, was separated through the column.
  • Figure 2 is a schematic diagram of the chemical structure of dimethylamine-HPTS.
  • Figure 1 is a reaction flow chart of the preparation of the fluorescent dye HPTS-lipo.
  • the above-mentioned fluorescent dye HPTS-lipo is prepared into a two-dimensional pH fluorescent sensing film, and the operation steps are as follows:
  • the above fluorescent sensing film is used to make a flat photoelectrode for monitoring two-dimensional pH value.
  • This embodiment also provides an application method of flat photoelectrode for monitoring two-dimensional pH value, and the experimental equipment shown in FIG. 10 is set up.
  • the device diagram consists of two parts: a fluorescence sensing system and a signal capture system.
  • the fluorescence sensing system is composed of a flat-plate polar film and an excitation light source.
  • the excitation light source uses a special band of LED lights to provide excitation energy for fluorescent dyes.
  • the signal capture system consists of a computer and a signal capture device.
  • the computer is responsible for the connection between the hardware, software services, and subsequent data processing. These software are generally available through commercial channels.
  • the signal capture device usually uses a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor).
  • the single intensity quantification of the flat-plate photoelectron fluorescence sensing film in this embodiment includes the following steps:
  • FIG. 4 is a fitting spectrum obtained when the fluorescent sensing film of Example 1 is applied, and the results prove that the fluorescence intensity has a good fitting relationship under the condition of pH range 5-9.
  • FIG. 6 is a UV excitation spectrum of dimethylamine-HPTS. It can be seen from the spectrum that there are double excitation peaks at 425 nm and 500 nm in the spectrum.
  • the modified dimethylamine-HPTS has a large Stokes shift, which avoids the interference of the excitation light on the emitted light.
  • a 405nm UV LED is selected as the excitation light source.
  • Fluorescence emission spectrum set an excitation wavelength of 405 nm and a slit width of 1.0 nm.
  • the test solution was mixed with 0.01 mg / mL dimethylamine-HPTS methanol solution and different gradient pH buffers according to 4: 1.
  • FIG. 7 is an emission spectrum chart of dimethylamine-HPTS under 405 nm excitation; it can be known from the spectrum that dimethylamine-HPTS has a maximum emission wavelength at 550 nm. Therefore, a 550nm high-pass filter is set in front of the camera to shield the interference from other light sources.
  • the present invention is used for quantitative signal capture system and LED excitation light source system, and there is no special limitation on the source. It can be purchased in the market, obtained open source software or self-made.
  • single-intensity quantification has been described in the foregoing using a 405nm LED lamp as the excitation light source. Just fine.
  • the specific operation method for quantifying the fluorescence ratio is to use 425nm and 500nm LED lamps as the excitation light, respectively, and obtain the green channel fluorescence intensity values under the two excitation light and record them as I 425 and I 500 .
  • I 425 / I 500 can be scaled to eliminate interference caused by influencing factors such as uneven dye distribution and uneven excitation light source intensity distribution.
  • This type of quantification method is applicable to all flat-plate photoelectron fluorescence sensing films made of HPTS-lipo with dual excitation and single emission characteristics.
  • HPTS-dimethylamine is the HPTS-lipo derivative with the smallest octanol-water partition coefficient calculated by simulation. From the experimental results of potentiometric titration, the experimental requirements have been met. To achieve the purpose of fat-soluble modification.
  • FIG. 5 is a fitting spectrum obtained when the fluorescent sensing film of Example 2 is applied, and the result proves that the fluorescence intensity has a good fitting relationship under the condition of a pH range of 3-11.
  • the derivative using the di-n-butylamine-modified fluorescent dye HPTS can be applied to a wider pH range and a wider application range than the dimethylamine-HPTS derivative.
  • characterization and analysis of ultraviolet emission spectrum and fluorescent emission spectrum are respectively performed:
  • FIG. 8 is an ultraviolet excitation spectrum of di-n-butylamine-HPTS. It can be seen from the spectrum that there are double excitation peaks at 425 nm and 500 nm in the di-n-butylamine-HPTS spectrum.
  • the modified dimethylamine-HPTS has a large Stokes shift, which avoids the interference of the excitation light on the emitted light, and a 405 nm UV LED is selected as the excitation light source.
  • FIG. 9 is an emission spectrum chart of di-n-butylamine-HPTS under 405 nm excitation. It can be seen from the spectrum that di-n-butylamine-HPTS has a maximum emission wavelength at 550 nm, so a 550 nm high-pass filter is set in front of the camera to shield interference from other light sources.
  • Step 2) After the reaction is completed, the product is spin-dried and deprotected with 1 mol / L NaOH, and the final product is separated through a column to obtain pure product HPTS-lipo.

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Abstract

一种监测二维pH值的荧光染料HPTS-lipo、荧光传感膜及应用，属于监测二维pH值领域。监测二维pH的荧光传感膜由荧光染料HPTS-lipo制备，制备过程中将HPTS-lipo采用水凝胶包埋。荧光染料HPTS-lipo通过在荧光染料HPTS的磺酸基团接入烷基胺制备。基于改性后的荧光染料HPTS-lipo与荧光染料HPTS相比其pKa值得到显著的变化，因此荧光传感膜适用于不同的pH值监测，满足不同实验需求，且荧光染料HPTS-lipo具有更好的疏水性，能在环境中保存更久时间，采用水凝胶包埋后进一步克服了染料泄露的问题。

Description

一种pH平板光极荧光传感膜、制备方法及应用 技术领域
本发明属于监测二维pH值的平板光极技术领域，更具体地说，涉及一种pH平板光极荧光传感膜、制备方法及应用。
背景技术
在环境领域，pH值是影响各类重金属、类金属元素地球化学循环的重要指标。以根际微区为例植物根系可通过分泌根系分泌物等行为影响到周边环境的pH值，引起根际酸化或碱化，因此根际效应对于研究重金属、类金属的地球化学循环来说至关重要。
目前传统方法对于pH的测量主要基于电极传感，一方面由于价格较为昂贵，且为单点测量，若在根际大面积布置成本较高，另一方面由于侵入性可能会破坏根际微界面并引起扰动影响根际活动。毋庸置疑，能对根际微环境或其它微区实现原位、实时、非侵入性检测，已经成为环境研究中的迫切需求。
自上世界90年代起，学者们对于二维荧光传感的研究进入了一个高速发展的时期，通过将荧光染料与包埋剂固定于一个平面内可实现对于待测物质的测量，目前已成功研发并施用于环境研究中的类似传感器包括：O 2、pH、CO 2及NH 3等。所制作成的荧光传感器灵敏度高、稳定性好且能适应环境的非均执性，十分适合用于相关待测物质的浓度检测及环境微界面的研究中。
近年来，光学传感器受到了越来越多的关注，尤其是对二维成像的平板光极技术的开发。由于具有原位、实时、非侵入性检测，已经成为环境研究中的迫切需求。
经检索，现有技术中对荧光传感膜的研究已公布了相关的申请案，如中国专利申请号CN201410643390.4，公开日期为2015.02.18的申请案公开了一种pH荧光传感膜，包括薄膜基材，其将荧光染料CPIPA和荧光黄10-GN均匀混合，通过化学包埋法将两种荧光染料固定在薄膜基材表面。基于所述的pH荧光传感膜，本发明还公开了一种碱性沉积物pH二维动态分布检测方法，将pH荧光传感膜置于沉积物中，在激发光照射下通过成像装置获得两种染料光谱信息，通过R和B通道荧光比率定量方式获得到沉积物pH的分布特征。该申请案的传感膜将CPIPA与具有参比效应和增亮效应的荧光黄10-GN混合作为荧光指示剂，检测灵敏度、空间分辨率高，对pH变化响应灵敏。所述的方法采用平板电极技术，通过荧光比率定量减少光学干扰，实现对碱性沉积物pH二维、动态分布信息的实时、原位获取。然而该申请案中的荧光染料CPIPA仅仅适用于偏碱性的工作范围，限制了其在pH检测领域的应用。
中国专利申请号CN201110407804.X，公开日期为2013.04.03的申请案公开了一种用于检测pH的光学离子传感膜，它包括如下重量百分比的组分：ETH5418 0.38％-0.42％；四[3，5-二-(三氟甲基)苯]硼酸钠0.44％-0.49％；上转换纳米棒2.09％-2.14％；聚氯乙烯33.13％-33.16％；癸二酸二(2-乙基己基)酯或邻硝基苯辛醚或邻苯二甲酸二辛酯补足至100％。本发明还公开了上述光学离子传感膜的制备方法及该传感膜在pH检测中的应用。该申请案的用于检测pH的光学离子传感膜，用980nm波长的光激发，且发射也在近红外区，传感器不会受到背景吸收和背景荧光的干扰；且相对于传统有机体系本体系有更高的量子产率，可以产生高强度荧光。该申请案中的光学离子传感膜制备过程中需要耗费各种化学试剂，成本较高，不利于推广。
HPTS为8-羟基-1，3，6-三磺酸基芘，也是一种制备二维荧光传感膜的荧光染料。其是一类光谱性对pH变化有选择性的荧光材料，且兼具绿蓝色荧光发射等特点，而被广泛选做荧光染料应用于pH变化的荧光染料。不仅如此，HPTS还是一种极低毒性的水溶性荧光物质，其在水溶液中根据所处pH环境分别以质子化状态及去质子化状态的形式存在，HPTS具有很高的光量子产率及较大的斯托克斯位移，并且其pKa值决定HPTS是一种非常适合使用于自然环境及生物体内研究pH变化的荧光材料。但同时因为其极强的水溶性，限制了其在自然环境中的应用。
对于HPTS应用于荧光光纤传感器的研究现有技术也也公开了相关的申请案，如中国专利申请号CN201510171727.0，公开日期为2017.11.24的申请案提供一种监测pH值和氧分压的单点双参数荧光光纤传感器探头，包括光纤探针、固定在光纤探针上的聚氨酯水凝胶层及分散嵌入在聚氨酯水凝胶层中的pH敏感微粒和氧敏感微粒，所述pH敏感微粒通过将HPTS共价固定于氨基改性的p-HEMA制备而成，所述氧敏感微粒通过溶剂三氯甲烷将Ru(dpp) 3 2+包埋于有机改性硅酸盐制备而成。然而该申请案的方法制备萤光膜的过程较为繁琐。
因此，基于HPTS水溶性强，在自然环境中应用受限、用于监测pH的荧光传感膜产生的荧光染料容易泄漏、应用范围较窄的问题，亟需对HPTS进行改进以在监测二维pH领域获得更广泛的应用价值。
发明内容
1.要解决的问题
针对HPTS水溶性强，在自然环境中应用受限、制备成的pH的荧光传感膜的荧光染料容易泄漏、应用范围较窄的问题，本发明提供一种新的荧光染料及pH平板光极荧光传感膜、制备方法及应用。
2.技术方案
为了解决上述问题，本发明所采用的技术方案如下：
本发明提供了一种pH平板光极荧光传感膜，所述荧光传感膜由荧光染料HPTS-lipo制备，所述的荧光染料HPTS-lipo是在HPTS的磺酸基团引入二正丁胺或二甲胺制备而成。在引入烷基胺基团后，HPTS已成功从水溶性变为脂溶性，详细情况可见物质LogD曲线。
作为本发明更进一步的改进，所述的荧光染料HPTS-lipo的制备方法包括以下步骤：
1)在NaOH溶液中，将HPTS与乙酸酐反应，无水乙醇提取产物并抽滤得羟基保护产品；
2)将羟基保护产品与氯化亚砜加热回流得到磺酰氯中间体；
3)以DCM为溶剂，将二正丁胺或二甲胺与磺酰氯中间体反应，反应结束后旋蒸、并用NaOH脱保护，得到HPTS-lipo。
作为本发明更进一步的改进，所述的pH平板光极荧光传感膜的制备方法，包括以下步骤：
a)取水凝胶D4溶于含有无水乙醇的水溶液中，制备成水凝胶D4储备液；
b)配制所述的荧光染料HPTS-lipo储备液；
c)取凝胶D4储备液和荧光染料HPTS-lipo储备液混合，取混合液制膜。
作为本发明更进一步的改进，所述的混合液中水凝胶D4与荧光染料的质量比为100：1。
作为本发明更进一步的改进，所述的含有无水乙醇的水溶液中无水乙醇与水的体积比为9：1。
作为本发明更进一步的改进，本发明提供了一种监测二维pH值的平板光极，所述平板光极采用pH平板光极荧光传感膜制备。
作为本发明更进一步的改进，所述的监测二维pH值的平板光极的应用方法，其特征在于：将所述的荧光传感膜固定在待测界面，在紫外激发光源下，利用图像捕捉系统动态获取待测界面pH的时空分布信息。
作为本发明更进一步的改进，所述的监测二维pH值的平板光极的应用方法，其特征在于：所述紫外激发光源的波长为405nm。
作为本发明更进一步的改进，所述的监测二维pH值的平板光极的应用方法，其特征在于：所述的图像捕捉系统包括CCD设备及存储终端设备。
作为本发明更进一步的改进，所述的监测二维pH值的平板光极的应用方法，包括以下步骤：
a)在10nm的Tris-HCl缓冲液中对所述的平板光极进行标定，分别用NaOH和HCl溶液调节pH；
b)在405nm LED灯的激发条件下逐点获取记录有荧光强度照片，并用ImageJ软件提取 绿色通道的荧光强度，在Origin中利用Boltzmann方程进行拟合；
c)得到标线作为定量依据，将本发明的荧光传感膜应用于环境时，注意将荧光传感膜紧贴物体表面，在405nm的LED灯激发下，用相机记录照片，并用ImageJ软件提取绿色通道的荧光强度值，代入先前所拟合的曲线进行后续的数据处理得到pH的二维分布信息。
3.有益效果
相比于现有技术，本发明的有益效果为：
(1)本发明的pH平板光极荧光传感膜，其采用荧光染料HPTS-lipo制备，所述的荧光染料HPTS-lipo是在荧光染料HPTS极易溶于水的芳香磺酸盐结构接上烷基胺从而得到的衍生物，使荧光染料的疏水性得到大大增强，因此能够在环境中存在时间更久，进而使荧光传感膜满足长期实验的需求。
(2)本发明的pH平板光极荧光传感膜，其采用荧光染料HPTS-lipo制备，相比荧光染料HPTS具有小极性、疏水性强的特点，将荧光染料HPTS-lipo包埋于水凝胶D4中制备成荧光传感膜后，大大降低了荧光传感膜染料泄漏的可能性，拓展了荧光传感膜在pH监测领域的应用范围。而荧光染料HPTS由于具有极强的水溶性，如同样采用水凝胶D4进行包埋，在接触到水后即刻溶出，得到的荧光传感膜无法在自然环境中的应用，只能采用更为特殊的包埋剂或包埋方式进行处理，投入成本较高。
(3)本发明的监测二维pH值的荧光传感膜，由荧光染料HPTS-lipo制备而成，基于改性后的荧光染料HPTS-lipo与荧光染料HPTS相比其pKa值得到显著的变化，因此使制备而成的荧光传感膜适用于不同的pH值监测，满足不同实验需求。
(4)本发明的监测二维pH值的荧光传感膜，采用二甲胺-HPTS制得的荧光传感膜适用的pH范围为5～9，而二正丁胺-HPTS制得的荧光传感膜适用的pH范围为3～11，采用二正丁胺改性荧光染料HPTS的衍生物可适用于更广泛的pH范围，应用范围更广。
(5)本发明的监测二维pH值的荧光传感膜，由此荧光传感膜制备成的pH平板光极在实际应用过程中能够瞬间对信号做出响应，与现有技术中的pH平板光极相比响应时间大大缩短，利于推广。
(6)本发明的监测二维pH值的荧光传感膜，制备过程中将荧光染料HPTS-lipo采用水凝胶D4包埋，操作简单方便、成本低廉，相比采用复杂手段对染料分子进行包埋，降低了制膜难度，制备而成的荧光传感膜应用范围广，利于推广。
附图说明
图1是荧光染料HPTS-lipo制备的反应流程图；
图2是二甲胺-HPTS化学结构示意图；
图3是二正丁胺-HPTS化学结构示意图；
图4是实施例1的荧光传感膜应用时得到的拟合图谱；
图5是实施例2的荧光传感膜应用时得到的拟合图谱；
图6是二甲胺-HPTS紫外激发光谱图；
图7是二甲胺-HPTS在405nm激发下的发射光谱图；
图8是二正丁胺-HPTS紫外激发光谱图；
图9是二正丁胺-HPTS在405nm激发下的发射光谱图；
图10是平板光极实验系统的装置示意图；
图11是HPTS的LogD曲线；
图12是HPTS-二甲胺的LogD曲线。
具体实施方式
下面结合具体实施例对本发明进一步进行描述。
实施例1
本实施例的荧光染料HPTS-lipo制备过程包括以下步骤：
1)在2mol/L的NaOH溶液中，HPTS与乙酸酐按照1：3倍当量在室温条件下反应，无水乙醇提取产物并抽滤得羟基保护产品；
2)羟基保护的HPTS与氯化亚砜按照1：4倍当量于90℃条件下加热回流2h得到磺酰氯中间体，将氯化亚砜旋干后，得到HPTS-SO 2Cl；
3)将HPTS-SO 2Cl溶解于二氯甲烷中，在冰浴条件下按照1：3.1倍当量二甲胺逐滴加入，反应结束后旋蒸并用1mol/L的NaOH脱保护，得到终产物过柱分离得纯产品HPTS-lipo，即二甲胺-HPTS，图2是二甲胺-HPTS化学结构示意图。
图1是荧光染料HPTS-lipo制备的反应流程图。
将上述荧光染料HPTS-lipo制备成二维pH荧光传感膜，操作步骤如下：
1)取1g水凝胶D4溶于10mL 90％的无水乙醇：水溶液中(V/V＝90/10)，制备成水凝胶D4储备液；
2)配制浓度为1mg/mL的二甲胺-HPTS储备液；
3)取等体积凝胶D4储备液和二甲胺-HPTS储备液涡旋震荡至完全混合，所述的混合液中水凝胶D4与荧光染料的质量比为100：1。取适量混合液，利用100μm厚度的四面制备器及涂膜机均匀刮至PET基材的表面，待有机溶剂完全挥发后，获得厚度约10μm的荧光传感膜。
将上述荧光传感膜用于制作监测二维pH值的平板光极，本实施例还提供了一种监测二维 pH值的平板光极的应用方法，搭建了如图10所示的实验设备装置图，由荧光传感系统及信号捕集系统两部分组成。荧光传感系统由平板光极薄膜和激发光源组成，激发光源使用特殊波段的LED灯为荧光染料提供激发能量。信号捕集系统由电脑和信号捕集设备组成，电脑负责硬件之间的连接、软件服务、以及后续的数据处理，这些软件一般可通过商业渠道获得。信号捕集设备通常使用CCD(charge coupled device，电感耦合元件)或CMOS(complementary metal oxide semiconductor，互补金属氧化物半导体)捕捉。本实施例中平板光极荧光传感膜的单强度定量包括以下步骤：
a)在10nm的Tris-HCl缓冲液中进行pH平板光极的标定，分别用1mol/L的NaOH和HCl溶液调节pH；
b)在405nm LED灯的激发条件下逐点获取记录有荧光强度照片，并用ImageJ软件提取绿色通道的荧光强度，在Origin中利用Boltzmann方程进行拟合，
图4是实施例1的荧光传感膜应用时得到的拟合图谱，结果证明：荧光强度在pH范围5～9的条件下具有良好的拟合关系。
c)得到标线作为定量依据，将本发明的荧光传感膜应用于环境时，注意将荧光传感膜紧贴物体表面，在405nm的LED灯激发下，用相机记录照片，并用ImageJ软件提取绿色通道的荧光强度值，代入先前所拟合的曲线进行后续的数据处理得到pH的二维分布信息。
在《High-resolution Imaging of pH in Alkaline Sediments and Water Based on a New Rapid Response Fluorescent Planar Optode》的文献中，Han等人采用CPIPA做出的pH光极，响应时间在120s左右。而本发明的荧光传感膜制备的pH光极能够瞬间响应，大大缩短了现有技术中pH光极的响应时间。
分别进行紫外发射光谱及荧光发射光谱表征分析：
1)紫外发射光谱，狭缝宽度为1.0nm。待测液由0.01mg/mL二甲胺-HPTS甲醇溶液和不同梯度的pH缓冲液按照4：1混合。
图6是二甲胺-HPTS紫外激发光谱图，由图谱可知，光谱图中存在425nm及500nm双激发峰。改性后的二甲胺-HPTS具有极大的斯托克斯位移，避免了激发光对发射光的干扰，在应用中选择405nm的紫外LED作为激发光源。
2)荧光发射光谱：设置405nm的激发波长，狭缝宽度为1.0nm。待测液由0.01mg/mL二甲胺-HPTS甲醇溶液和不同梯度的pH缓冲液按照4：1混合。
图7是二甲胺-HPTS在405nm激发下的发射光谱图；由图谱可知，二甲胺-HPTS在550nm处存在最大发射波长。因此，在相机前设置550nm的高通滤光片来屏蔽其它光源的干扰。
进一步需要说明的是，本发明用于定量的信号捕捉系统及LED激发光源系统，对来源没 有特殊的限制，在市场上购买、获取开源软件或自制均可。
进一步说明的是，由于所制备染料所具有的双激发单发射的特点，定量方式可以采用单强度定量或荧光比例定量法两种，单强度定量在前文已做介绍使用405nm的LED灯作为激发光源即可。而荧光比例定量具体的操作手段为采用425nm和500nm的LED灯分别作为激发光，分别获取两个激发光下的绿色通道荧光强度值记为I 425和I 500。由于染料的发射荧光强度在两类激发光下随着pH变化趋势相反，故I 425/I 500可做比例来消除例如染料分布不均、激发光源强度分布不均等影响因素所带来的干扰。此类定量方法适用于具有双激发单发射特点的所有由的HPTS-lipo制作成的平板光极荧光传感膜。
进一步说明的是，为了验证HPTS-lipo相比于HPTS是否达到脂溶性改性的目的，采用Pulse TM仪器以电位滴定法分别测试了HPTS和HPTS-二甲胺的辛醇-水分配吸收随pH的变化(Log D)情况，图11即HPTS的Log D曲线，辛醇-水分配系数随着pH先升高再降低，但整体上均呈现为水溶性，图12为HPTS-二甲胺的Log D曲线，辛醇-水分配系数随着pH逐渐降低，酸性条件下呈现脂溶性，随着pH的升高，在pH9以上的环境中呈现水溶性。值得注意的是HPTS-二甲胺是模拟计算所得辛醇-水分配系数最小的HPTS-lipo衍生物。从电位滴定的实验结果来看已满足实验需求。达到脂溶性改性的目的。
实施例2
本实施例的荧光染料HPTS-lipo制备过程包括以下步骤：
1)在2mol/L的NaOH溶液中，HPTS及乙酸酐按照1：3倍当量在室温条件下反应，无水乙醇提取产物并抽滤得羟基保护产品；
2)羟基保护的HPTS与氯化亚砜按照1：4倍当量于90℃条件下加热回流2h得到磺酰氯中间体，将氯化亚砜旋干后，得到HPTS-SO 2Cl。
3)将HPTS-SO 2Cl溶解于二氯甲烷中，在冰浴条件下按照1：3.1倍当量将二正丁胺逐滴加入，反应结束后旋蒸并用1mol/L的NaOH脱保护，得到终产物过柱分离得纯产品HPTS-lipo，即二正丁胺-HPTS，图3是二正丁胺-HPTS化学结构示意图。
采用上述荧光染料HPTS-lipo制备二维pH荧光传感膜的步骤如下：
1)取1g水凝胶D4溶于10mL 90％的无水乙醇：水溶液中(V/V＝90/10)，制备成水凝胶D4储备液；
2)配制浓度为1mg/mL的二正丁胺-HPTS储备液；
3)取等体积凝胶D4储备液和二正丁胺-HPTS储备液涡旋震荡至完全混合，所述的混合液中水凝胶D4与荧光染料的质量比为100：1。取适量混合液，利用100μm厚度的四面制备器及涂膜机均匀刮至PET基材的表面，待有机溶剂完全挥发后，获得厚度为10μm左右的荧 光传感膜。
在10nM的Tris-HCl缓冲液中进行pH平板光极的标定，分别用1M的NaOH和HCl溶液调节pH，在405LED灯的激发条件下逐点获取记录有荧光强度的照片，并用ImageJ软件提取荧光强度，在Origin中利用Boltzmann方程进行拟合。
图5是实施例2的荧光传感膜应用时得到的拟合图谱，结果证明荧光强度在pH范围3～11的条件下具有良好的拟合关系。
因此可得，采用二正丁胺改性荧光染料HPTS的衍生物与二甲胺-HPTS衍生物相比，可适用于更广泛的pH范围，应用范围更广。
针对于本实施例分别进行紫外发射光谱及荧光发射光谱表征分析：
1)紫外发射光谱，狭缝宽度为1.0nm。待测液由0.01mg/mL二正丁胺-HPTS甲醇溶液和不同梯度的pH缓冲液按照4：1混合。图8是二正丁胺-HPTS紫外激发光谱图，由图谱可知，二正丁胺-HPTS光谱图中存在425nm及500nm双激发峰。改性后的二甲胺-HPTS具有极大的斯托克斯位移，避免了激发光对发射光的干扰，选择405nm的紫外LED作为激发光源。
2)荧光发射光谱，设置405nm的激发波长，狭缝宽度为1.0nm。待测液由0.01mg/mL二正丁胺-HPTS甲醇溶液和不同梯度的pH缓冲液按照4：1混合。图9是二正丁胺-HPTS在405nm激发下的发射光谱图。由图谱可知，二正丁胺-HPTS于550nm处存在最大发射波长，因此在相机前设置550nm的高通滤光片来屏蔽其它光源的干扰。
实施例3
本实施例的荧光染料HPTS-lipo制备过程包括以下步骤：
1)在2mol/L的NaOH溶液中，HPTS及乙酸酐按照1：3倍当量在室温条件下反应，无水乙醇提取产物并抽滤得羟基保护产品；
2)羟基保护的HPTS与氯化亚砜于90℃条件下加热回流2h得到磺酰氯中间体；在冰浴条件下以DCM做溶剂并将二正丁胺逐滴加入；
3)步骤2)反应结束后旋蒸干燥并用1mol/L的NaOH脱保护，得到终产物过柱分离得纯产品HPTS-lipo。
采用上述荧光染料HPTS-lipo制备二维pH荧光传感膜的步骤如下：
1)取1g水凝胶D4溶于10mL 90％的无水乙醇：水溶液中(V/V＝90/10)，制备成水凝胶D4储备液；
2)配制浓度为1mg/mL的二正丁胺-HPTS储备液；
3)取等体积凝胶D4储备液和二正丁胺-HPTS储备液涡旋震荡至完全混合，所述的混合 液中水凝胶D4与荧光染料的质量比为100：1。取适量混合液，利用100μm厚度的四面制备器及涂膜机均匀刮至PET基材的表面，待有机溶剂完全挥发后，获得厚度约10μm的荧光传感膜。
以上对本发明所提供的二维pH荧光传感膜的制作方法进行了详细的介绍。本文中采用具体实施例对本发明的原理及实施方式进行了阐述，以上实施例的说明仅用于帮助理解本发明的方法及其中心思想。应当指出，对于本领域的普通技术人员来说，在不脱离本方法原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围。

Claims (9)

  1. 一种pH平板光极荧光传感膜，其特征在于：所述荧光传感膜由荧光染料HPTS-lipo制备，所述的荧光染料HPTS-lipo是在HPTS的磺酸基团引入二正丁胺或二甲胺制备而成，在引入烷基胺基团后，HPTS从水溶性变为脂溶性。
  2. 根据权利要求1所述的pH平板光极荧光传感膜，其特征在于：所述的荧光染料HPTS-lipo的制备方法包括以下步骤：
    1)在NaOH溶液中，将HPTS与乙酸酐反应，无水乙醇提取产物并抽滤得羟基保护产品；
    2)将羟基保护产品与氯化亚砜加热回流得到磺酰氯中间体；
    3)以DCM为溶剂，将二正丁胺或二甲胺与磺酰氯中间体反应，反应结束后旋蒸、并用NaOH脱保护，得到HPTS-lipo。
  3. 权利要求1或2所述的pH平板光极荧光传感膜的制备方法，其特征在于：包括以下步骤：
    a)取水凝胶D4溶于含有无水乙醇的水溶液中，制备成水凝胶D4储备液；
    b)配制所述的荧光染料HPTS-lipo储备液；
    c)取凝胶D4储备液和荧光染料HPTS-lipo储备液混合，取混合液制膜。
  4. 根据权利要求3所述的pH平板光极荧光传感膜的制备方法，其特征在于：所述的混合液中水凝胶D4与荧光染料的质量比为100：1。
  5. 根据权利要求3或4所述的pH平板光极荧光传感膜的制备方法，其特征在于：所述的含有无水乙醇的水溶液中无水乙醇与水的体积比为9：1。
  6. 一种监测二维pH值的平板光极，其特征在于：所述平板光极采用权利要求1或2所述的pH平板光极荧光传感膜制备。
  7. 权利要求6所述的监测二维pH值的平板光极的应用方法，其特征在于：将所述的荧光传感膜固定在待测界面，在紫外激发光源下，利用图像捕捉系统动态获取待测界面pH的时空分布信息。
  8. 根据权利要求7所述的监测二维pH值的平板光极的应用方法，其特征在于：所述紫外激发光源的波长为405nm。
  9. 根据权利要求7或8所述的监测二维pH值的平板光极的应用方法，其特征在于：所述的图像捕捉系统包括CCD设备及存储终端设备。
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