CN117470806A - Polymer glucose sensor based on Mach-Zehnder structure - Google Patents

Polymer glucose sensor based on Mach-Zehnder structure Download PDF

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CN117470806A
CN117470806A CN202311767738.6A CN202311767738A CN117470806A CN 117470806 A CN117470806 A CN 117470806A CN 202311767738 A CN202311767738 A CN 202311767738A CN 117470806 A CN117470806 A CN 117470806A
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glucose sensor
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polymer
arm
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CN117470806B (en
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李鸿强
谢芳琳
马帅
韩明
张立震
赵瑞娜
孟文涛
曹梦威
任峰
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Wellcore Intelligent Technology Tianjin Co ltd
Tianjin Polytechnic University
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/41Refractivity; Phase-affecting properties, e.g. optical path length
    • G01N21/45Refractivity; Phase-affecting properties, e.g. optical path length using interferometric methods; using Schlieren methods
    • GPHYSICS
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    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/24Coupling light guides
    • G02B6/26Optical coupling means
    • G02B6/28Optical coupling means having data bus means, i.e. plural waveguides interconnected and providing an inherently bidirectional system by mixing and splitting signals
    • G02B6/2804Optical coupling means having data bus means, i.e. plural waveguides interconnected and providing an inherently bidirectional system by mixing and splitting signals forming multipart couplers without wavelength selective elements, e.g. "T" couplers, star couplers
    • G02B6/2808Optical coupling means having data bus means, i.e. plural waveguides interconnected and providing an inherently bidirectional system by mixing and splitting signals forming multipart couplers without wavelength selective elements, e.g. "T" couplers, star couplers using a mixing element which evenly distributes an input signal over a number of outputs
    • G02B6/2813Optical coupling means having data bus means, i.e. plural waveguides interconnected and providing an inherently bidirectional system by mixing and splitting signals forming multipart couplers without wavelength selective elements, e.g. "T" couplers, star couplers using a mixing element which evenly distributes an input signal over a number of outputs based on multimode interference effect, i.e. self-imaging
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/41Refractivity; Phase-affecting properties, e.g. optical path length
    • G01N21/45Refractivity; Phase-affecting properties, e.g. optical path length using interferometric methods; using Schlieren methods
    • G01N2021/458Refractivity; Phase-affecting properties, e.g. optical path length using interferometric methods; using Schlieren methods using interferential sensor, e.g. sensor fibre, possibly on optical waveguide

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Abstract

本发明公开了一种基于马赫曾德尔结构的聚合物葡萄糖传感器,包括PDMS下包层以及设置于所述PDMS下包层上的PMMA芯层,所述PMMA芯层为马赫曾德尔结构图案,将GOD通过酸性偶联剂固定在PMMA芯层的传感臂上形成三维矩形接触。本发明所提出的聚合物葡萄糖传感器无需借助电光、热光等外部调制手段,仅通过测量输出光功率的变化即可对大浓度范围的葡萄糖进行传感,且无需较长传感臂和复杂微流控芯片,具有器件结构简单、紧凑、灵敏度高等特点。

The invention discloses a polymer glucose sensor based on a Mach-Zehnder structure, which includes a PDMS lower cladding layer and a PMMA core layer arranged on the PDMS lower cladding layer. The PMMA core layer is a Mach-Zehnder structure pattern. GOD is fixed on the sensing arm of the PMMA core layer through an acidic coupling agent to form a three-dimensional rectangular contact. The polymer glucose sensor proposed by the present invention does not require external modulation means such as electro-optical light or thermal light. It can sense glucose in a wide concentration range only by measuring changes in output light power, and does not require long sensing arms and complex micro-electronics. Fluid control chip has the characteristics of simple device structure, compactness and high sensitivity.

Description

一种基于马赫曾德尔结构的聚合物葡萄糖传感器A polymer glucose sensor based on Mach-Zehnder structure

技术领域Technical field

本发明涉及葡萄糖光传感器件,特别是涉及一种基于马赫曾德尔结构的聚合物葡萄糖传感器,能用于大范围葡萄糖浓度测量。The present invention relates to a glucose light sensing device, and in particular to a polymer glucose sensor based on a Mach-Zehnder structure, which can be used for glucose concentration measurement in a wide range.

背景技术Background technique

葡萄糖传感器是一种用于测量环境中葡萄糖浓度的仪器,可以帮助人们了解环境中的葡萄糖浓度,从而更好地控制饮食和生活方式。与传统的测量方法相比,葡萄糖传感器具有响应速度快、灵敏度高、稳定性好等优点,因此被广泛应用于食品安全、生物技术和医学检测等领域。例如,在食品加工和制造中,葡萄糖传感器可以用于检测食品中的葡萄糖含量,以确保食品的质量和安全性;在农业领域中,葡萄糖传感器可以用于检测土壤中的葡萄糖含量,以评估土壤的肥力和作物生长情况;此外,在环境监测中,葡萄糖传感器还可以用于检测水体中的葡萄糖含量,以评估水体的污染程度和生态环境的健康状况。A glucose sensor is an instrument used to measure glucose concentration in the environment. It can help people understand the glucose concentration in the environment and better control their diet and lifestyle. Compared with traditional measurement methods, glucose sensors have the advantages of fast response, high sensitivity, and good stability, so they are widely used in fields such as food safety, biotechnology, and medical testing. For example, in food processing and manufacturing, glucose sensors can be used to detect the glucose content in food to ensure the quality and safety of food; in the agricultural field, glucose sensors can be used to detect the glucose content in soil to evaluate soil fertility and crop growth; in addition, in environmental monitoring, glucose sensors can also be used to detect glucose content in water bodies to assess the degree of pollution of water bodies and the health of the ecological environment.

葡萄糖监测仪器按照传感测量方法可分为波长测量法和光强测量法。波长测量法是基于葡萄糖溶液在特定波长下的吸收或反射光谱特性来确定其浓度,这种方法不仅需要使用复杂的光学元件,如滤光片、光栅或干涉仪,还需要结合精确的波长测量设备来实现精确的测量,这大大增加了系统的复杂性和成本。波长测量法在某些浓度下的波长偏移可能较小,因此其灵敏度容易受到光谱仪测量精度的影响。光强测量法是测量输出光功率强度变化的方法,这种测量方案不需要光谱仪,也大大降低了测量的成本。目前已报道的一些基于光强探测法传感器表现出灵敏度受限、结构复杂且结构不够紧凑、或者对光源要求高等缺点,对于快速响应待测物质与传感器的相互作用和较宽的动态范围都有一定的不足。Glucose monitoring instruments can be divided into wavelength measurement method and light intensity measurement method according to the sensing measurement method. The wavelength measurement method is based on the absorption or reflection spectral characteristics of a glucose solution at a specific wavelength to determine its concentration. This method not only requires the use of complex optical components, such as filters, gratings, or interferometers, but also requires precise wavelength measurement. equipment to achieve accurate measurements, which greatly increases the complexity and cost of the system. The wavelength shift of wavelength measurement methods may be small at certain concentrations, so their sensitivity is susceptible to the measurement accuracy of the spectrometer. The light intensity measurement method is a method of measuring changes in output light power intensity. This measurement solution does not require a spectrometer and greatly reduces the cost of measurement. Some sensors based on light intensity detection methods that have been reported so far have shortcomings such as limited sensitivity, complex and not compact structures, or high requirements for light sources. They have shortcomings such as fast response to the interaction between the substance to be measured and the sensor and a wide dynamic range. Certain shortcomings.

因此,如何能在高精度测量葡萄糖浓度的前提下,探索一种光学葡萄糖测量方法,并获得高灵敏度、高线性度、高稳定性、低检测极限检测的葡萄糖传感器是本领域亟待解决的技术问题。Therefore, how to explore an optical glucose measurement method and obtain a glucose sensor with high sensitivity, high linearity, high stability, and low detection limit on the premise of measuring glucose concentration with high precision is an urgent technical problem to be solved in this field. .

术语解释:PDMS:聚二甲基硅氧烷;PMMA:聚甲基丙烯酸甲酯;GOD:葡萄糖氧化酶;MMI:多模干涉耦合器;PBS:磷酸盐。Explanation of terms: PDMS: polydimethylsiloxane; PMMA: polymethylmethacrylate; GOD: glucose oxidase; MMI: multimode interference coupler; PBS: phosphate.

发明内容Contents of the invention

本发明的目的是,提出一种基于马赫曾德尔结构的聚合物葡萄糖传感器,该葡萄糖传感器灵敏度高、线性度好、稳定性强且易于集成,能有效测量大范围葡萄糖浓度。The purpose of the present invention is to propose a polymer glucose sensor based on a Mach-Zehnder structure, which has high sensitivity, good linearity, strong stability and easy integration, and can effectively measure a wide range of glucose concentrations.

为实现上述目的,本发明的技术方案是:In order to achieve the above objects, the technical solution of the present invention is:

本发明提供一种基于马赫曾德尔结构的聚合物葡萄糖传感器,包括由下至上的PDMS下包层、PMMA芯层和PDMS上包层;所述PMMA芯层包括输入波导、输出波导、1×2 MMI耦合器、2×1 MMI耦合器、弯曲波导、传感臂和参考臂;传感臂和参考臂等长且平行,二者以中心线为轴对称设置;在40℃的温度下通过酸性偶联剂将GOD固定在PMMA芯层的传感臂上形成三维矩形接触结构,三维矩形接触结构的上表面低于PDMS上包层的上表面,且高于传感臂的上表面;The invention provides a polymer glucose sensor based on a Mach-Zehnder structure, which includes a PDMS lower cladding layer, a PMMA core layer and a PDMS upper cladding layer from bottom to top; the PMMA core layer includes an input waveguide, an output waveguide, a 1×2 MMI coupler, 2×1 MMI coupler, curved waveguide, sensing arm and reference arm; the sensing arm and the reference arm are equal in length and parallel, and they are arranged symmetrically with the center line as the axis; through acidic water at a temperature of 40°C The coupling agent fixes GOD on the sensing arm of the PMMA core layer to form a three-dimensional rectangular contact structure. The upper surface of the three-dimensional rectangular contact structure is lower than the upper surface of the PDMS upper cladding layer and higher than the upper surface of the sensing arm;

所述GOD的折射率变化范围为1.3352-1.3400,所述传感臂的臂长为1740µm,传感臂和参考臂之间的臂间距为130µm;所述弯曲波导的弯曲半径为800µm,弯曲波导的横向长度为430µm,弯曲波导的偏转角度为0.28rad;The refractive index variation range of the GOD is 1.3352-1.3400, the arm length of the sensing arm is 1740µm, and the arm spacing between the sensing arm and the reference arm is 130µm; the bending radius of the curved waveguide is 800µm, and the curved waveguide The lateral length of the curved waveguide is 430µm, and the deflection angle of the curved waveguide is 0.28rad;

所述基于马赫曾德尔结构的聚合物葡萄糖传感器的损耗控制在1.6dB以内,灵敏度为2.67 mW/(mg/mL)。The loss of the polymer glucose sensor based on the Mach-Zehnder structure is controlled within 1.6dB, and the sensitivity is 2.67 mW/(mg/mL).

优选地,所述基于马赫曾德尔结构的聚合物葡萄糖传感器的损耗为1.58dB,消光比为41.43dB。Preferably, the polymer glucose sensor based on Mach-Zehnder structure has a loss of 1.58dB and an extinction ratio of 41.43dB.

当输入光功率为10mW,葡萄糖溶液浓度为0mg/mL时,最大输出光功率为6.95mW,并且当葡萄糖溶液浓度为2.6mg/mL时,最小输出光功率为0.0005mW,传感器实现葡萄糖浓度在0-2.6mg/mL范围内的线性响应,葡萄糖浓度传感范围为0-2.6mg/mL。When the input light power is 10mW and the glucose solution concentration is 0mg/mL, the maximum output light power is 6.95mW, and when the glucose solution concentration is 2.6mg/mL, the minimum output light power is 0.0005mW, and the sensor achieves a glucose concentration of 0 -Linear response within the range of -2.6mg/mL, glucose concentration sensing range is 0-2.6mg/mL.

所述基于马赫曾德尔结构的聚合物葡萄糖传感器的相对标准偏差为(1.5-2.5)×10-3,最低检测极限为0.1mg/mL。The relative standard deviation of the polymer glucose sensor based on the Mach-Zehnder structure is (1.5-2.5)×10 -3 , and the lowest detection limit is 0.1 mg/mL.

所述PDMS下包层和PDMS上包层的厚度均为10µm,折射率为1.4040;PMMA芯层的厚度为1µm,折射率为1.4880;传感臂上表面到三维矩形接触结构上表面的距离为2-3µm。The thickness of the PDMS lower cladding layer and the PDMS upper cladding layer are both 10µm and the refractive index is 1.4040; the thickness of the PMMA core layer is 1µm and the refractive index is 1.4880; the distance from the upper surface of the sensing arm to the upper surface of the three-dimensional rectangular contact structure is 2-3µm.

优选地,所述弯曲波导的波导宽度为1.5µm,高度为1µm。Preferably, the waveguide width of the curved waveguide is 1.5µm and the height is 1µm.

GOD溶液的获得方式为:将GOD粉末溶于pH为5.5的PBS缓冲液中,形成质量浓度为30mg/mL的GOD溶液;The GOD solution is obtained by: dissolving GOD powder in PBS buffer with a pH of 5.5 to form a GOD solution with a mass concentration of 30 mg/mL;

在PMMA芯层的传感臂上滴加GOD溶液并固化,在传感臂上形成三维矩形接触结构。The GOD solution is dropped on the sensing arm of the PMMA core layer and solidified to form a three-dimensional rectangular contact structure on the sensing arm.

与现有技术相比,本发明的有益效果是:Compared with the prior art, the beneficial effects of the present invention are:

1.本发明基于马赫曾德尔结构的聚合物葡萄糖传感器的输入光功率为10mW,在葡萄糖溶液浓度为0-2.6mg/mL时的输出光功率在0.0005-6.9500mW之间变化。本发明传感臂臂长为1740µm,极大地缩小了器件的尺寸,结构简单且紧凑,不需要长的传感臂和复杂的微流控芯片即可实现对大范围葡萄糖溶液浓度的测量。1. The input optical power of the polymer glucose sensor based on the Mach-Zehnder structure of the present invention is 10 mW, and the output optical power varies between 0.0005-6.9500 mW when the glucose solution concentration is 0-2.6 mg/mL. The length of the sensing arm of the present invention is 1740 µm, which greatly reduces the size of the device. The structure is simple and compact, and the measurement of a wide range of glucose solution concentrations can be achieved without the need for a long sensing arm and a complex microfluidic chip.

2.本发明葡萄糖传感器制备中通过控制GOD温度为40℃和pH为5.5,能保持GOD处于最佳活性,使马赫曾德尔结构的聚合物葡萄糖传感器输出光功率达到最大值,灵敏度为2.67 mW/(mg/mL),且损耗控制在1.6dB以内,具有高稳定性(相对标准偏差约(1.5-2.5)×10-3)、低检测极限(0.1mg/mL)的特点。2. During the preparation of the glucose sensor of the present invention, by controlling the GOD temperature to 40°C and the pH to 5.5, GOD can be kept at optimal activity, so that the output optical power of the polymer glucose sensor with a Mach-Zehnder structure reaches the maximum value, and the sensitivity is 2.67 mW/ (mg/mL), and the loss is controlled within 1.6dB. It has the characteristics of high stability (relative standard deviation about (1.5-2.5)×10 -3 ) and low detection limit (0.1mg/mL).

附图说明Description of the drawings

图1是本发明基于马赫曾德尔结构的聚合物葡萄糖传感器的结构示意图;Figure 1 is a schematic structural diagram of the polymer glucose sensor based on the Mach-Zehnder structure of the present invention;

图2是本发明基于马赫曾德尔结构的聚合物葡萄糖传感器的弯曲波导结构及参数示意图;其中(a)为不同偏转角度下横向长度对输出光功率变化量的影响图;(b)为在偏转角度为0.28rad下弯曲半径对输出光功率变化量的影响图;Figure 2 is a schematic diagram of the curved waveguide structure and parameters of the polymer glucose sensor based on the Mach-Zehnder structure of the present invention; (a) is a diagram of the influence of lateral length on the change in output optical power under different deflection angles; (b) is a diagram of the change in output light power under deflection The influence of bending radius on the change of output optical power at an angle of 0.28rad;

图3是本发明基于马赫曾德尔结构的聚合物葡萄糖传感器的不同臂间距输出光功率对比图;其中(a)为参考臂和传感臂发生耦合效应时的臂间距(左图)和对应的输出光功率情况(右图);(b)为参考臂和传感臂不发生耦合效应时的臂间距(左图)和对应的输出光功率情况(右图);(c)为不同臂间距下输出光功率随折射率变化情况的对比图;Figure 3 is a comparison diagram of the output optical power of different arm spacings of the polymer glucose sensor based on the Mach-Zehnder structure of the present invention; (a) is the arm spacing when the coupling effect occurs between the reference arm and the sensing arm (left picture) and the corresponding Output optical power (right picture); (b) is the arm spacing when no coupling effect occurs between the reference arm and the sensing arm (left picture) and the corresponding output optical power (right picture); (c) is different arm spacing Comparison chart of the change of output optical power with refractive index;

图4是本发明基于马赫曾德尔结构的聚合物葡萄糖传感器的不同传感臂臂长下的输出光功率响应对比图;Figure 4 is a comparison diagram of the output light power response under different sensing arm lengths of the polymer glucose sensor based on the Mach-Zehnder structure of the present invention;

图5是本发明基于马赫曾德尔结构的聚合物葡萄糖传感器的光场图;Figure 5 is a light field diagram of the polymer glucose sensor based on the Mach-Zehnder structure of the present invention;

图6是本发明基于马赫曾德尔结构的聚合物葡萄糖传感器的测量系统的示意图;Figure 6 is a schematic diagram of the measurement system of the polymer glucose sensor based on the Mach-Zehnder structure of the present invention;

图7是在不同温度和pH下获得的基于马赫曾德尔结构的聚合物葡萄糖传感器的输出光功率变化量的响应图;其中(a)为不同温度对输出光功率的影响图;(b)为不同pH对输出光功率的影响图;Figure 7 is a response diagram of the change in output light power of a polymer glucose sensor based on a Mach-Zehnder structure obtained at different temperatures and pH; (a) is a diagram of the influence of different temperatures on the output light power; (b) is Chart showing the influence of different pH on the output light power;

图8是本发明基于马赫曾德尔结构的聚合物葡萄糖传感器输出光功率随葡萄糖浓度变化的响应图;Figure 8 is a response diagram of the output optical power of the polymer glucose sensor based on the Mach-Zehnder structure of the present invention as the glucose concentration changes;

图9是本发明基于马赫曾德尔结构的聚合物葡萄糖传感器的特异性响应图;Figure 9 is a specific response diagram of the polymer glucose sensor based on the Mach-Zehnder structure of the present invention;

图10是本发明基于马赫曾德尔结构的聚合物葡萄糖传感器的稳定性响应图;Figure 10 is a stability response diagram of the polymer glucose sensor based on the Mach-Zehnder structure of the present invention;

图11是本发明基于马赫曾德尔结构的聚合物葡萄糖传感器的耐久性响应图;其中(a)为同一聚合物葡萄糖传感器在不同时间、不同葡萄糖浓度下的输出光功率对比图;(b)为同一聚合物葡萄糖传感器在不同时间、不同葡萄糖浓度下的灵敏度和损耗对比图;Figure 11 is a durability response diagram of the polymer glucose sensor based on the Mach-Zehnder structure of the present invention; (a) is a comparison diagram of the output light power of the same polymer glucose sensor at different times and under different glucose concentrations; (b) is Comparison of sensitivity and loss of the same polymer glucose sensor at different times and different glucose concentrations;

附图标记:Reference signs:

1、PDMS下包层,2、PMMA芯层,3、PDMS上包层,4、1×2 MMI耦合器,5、2×1 MMI耦合器,6、弯曲波导,7、传感臂,8、参考臂,9、输入波导,10、输出波导,11、中心线。1. PDMS lower cladding, 2. PMMA core layer, 3. PDMS upper cladding, 4. 1×2 MMI coupler, 5. 2×1 MMI coupler, 6. Curved waveguide, 7. Sensing arm, 8 , reference arm, 9. input waveguide, 10. output waveguide, 11. centerline.

具体实施方式Detailed ways

以下结合附图和具体实施例对本发明的技术方案进行详细说明。The technical solution of the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例,都属于本发明保护的范围,下面通过参考附图描述的实施例是示例性的,仅用于解释本发明的技术方案,而不应当理解为对本发明的限制。The described embodiments are only some of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention. The embodiments described below with reference to the drawings are exemplary. are only used to explain the technical solutions of the present invention and should not be understood as limitations of the present invention.

本实施例基于马赫曾德尔结构的聚合物葡萄糖传感器(简称聚合物葡萄糖传感器)的结构如图1所示。包括由下至上的PDMS下包层1、PMMA芯层2和PDMS上包层3。PMMA芯层2包括输入波导9、输出波导10、1×2 MMI耦合器4、2×1 MMI耦合器5、弯曲波导6、传感臂7和参考臂8,传感臂7和参考臂8以中心线11为轴对称设置,在传感臂7所在区域附近刻蚀PDMS上包层3,将传感臂7的上、左、右三个侧面全部裸露,GOD填充刻蚀区域并通过酸性偶联剂固定在PMMA芯层2的传感臂7上,形成三维矩形接触结构,三维矩形接触结构的上表面低于PDMS上包层3的上表面,且高于传感臂7的上表面。The structure of the polymer glucose sensor (polymer glucose sensor for short) based on the Mach-Zehnder structure in this embodiment is shown in Figure 1 . It includes PDMS lower cladding layer 1, PMMA core layer 2 and PDMS upper cladding layer 3 from bottom to top. PMMA core layer 2 includes input waveguide 9, output waveguide 10, 1×2 MMI coupler 4, 2×1 MMI coupler 5, curved waveguide 6, sensing arm 7 and reference arm 8, sensing arm 7 and reference arm 8 Set up axially symmetrically with the center line 11, etch the PDMS upper cladding 3 near the area where the sensing arm 7 is located, expose all the upper, left and right sides of the sensing arm 7, GOD fills the etched area and passes through the acidic The coupling agent is fixed on the sensing arm 7 of the PMMA core layer 2 to form a three-dimensional rectangular contact structure. The upper surface of the three-dimensional rectangular contact structure is lower than the upper surface of the PDMS upper cladding layer 3 and higher than the upper surface of the sensing arm 7 .

本实施例中PDMS下包层和PDMS上包层的厚度均为10µm,折射率为1.4040;PMMA芯层的厚度为1µm,折射率为1.4880;传感臂上表面到三维矩形接触结构上表面的距离为2-3µm。In this embodiment, the thickness of the PDMS lower cladding layer and the PDMS upper cladding layer are both 10µm, and the refractive index is 1.4040; the thickness of the PMMA core layer is 1µm, and the refractive index is 1.4880; the distance from the upper surface of the sensing arm to the upper surface of the three-dimensional rectangular contact structure The distance is 2-3µm.

本实施例基于马赫曾德尔结构的聚合物葡萄糖传感器的弯曲波导结构及参数如图2所示。在选择弯曲波导6时,选用波导宽度为1.5µm和高度1µm的矩形波导与前端的1×2MMI耦合器4进行耦合对接。弯曲波导6的弯曲半径、横向长度和偏转角度是对光学损耗影响较大的三个重要因素,图2中(a)图为不同偏转角度下横向长度对输出光功率变化量的影响,在偏转角度为0.28rad下,其输出光功率损耗较小,且较稳定。图2中(b)图为在偏转角度为0.28rad下弯曲半径对输出光功率变化量的影响,在偏转角度为0.28rad、横向长度为430µm下,弯曲半径为800µm时其输出光功率损耗最小且较稳定。本发明综合考虑后选取弯曲波导6的弯曲半径为800µm、横向长度为430µm和偏转角度为0.28rad,此时弯曲波导6的波导损耗达到极小值,其归一化输出光功率为0.96a.u.。The curved waveguide structure and parameters of the polymer glucose sensor based on the Mach-Zehnder structure in this embodiment are shown in Figure 2. When selecting the curved waveguide 6, a rectangular waveguide with a waveguide width of 1.5µm and a height of 1µm is selected for coupling and docking with the 1×2MMI coupler 4 at the front end. The bending radius, lateral length and deflection angle of the curved waveguide 6 are three important factors that have a greater impact on optical loss. (a) in Figure 2 shows the impact of the lateral length on the change in output optical power under different deflection angles. In deflection When the angle is 0.28rad, the output optical power loss is smaller and more stable. (b) in Figure 2 shows the effect of bending radius on the change in output optical power when the deflection angle is 0.28rad. When the deflection angle is 0.28rad and the lateral length is 430µm, the output optical power loss is the smallest when the bending radius is 800µm. And relatively stable. After comprehensive consideration, the present invention selects the bending radius of the curved waveguide 6 as 800µm, the lateral length as 430µm, and the deflection angle as 0.28rad. At this time, the waveguide loss of the curved waveguide 6 reaches a minimum value, and its normalized output optical power is 0.96a.u.

本实施例基于马赫曾德尔结构的聚合物葡萄糖传感器的不同臂间距输出光功率对比图如图3所示。传感臂7和参考臂8的臂间距太近会导致耦合效应的发生(左侧波导输入的能量随着传播距离的增加逐渐被耦合到右侧波导中),同时也会影响传感器的传感性能。当臂间距不大于4µm时,从图3中(a)图可以看出,此时臂间距太近,将严重影响传感器的传感性能;综合考虑弯曲波导6的弯曲半径、横向长度和偏转角度与臂间距的共同作用,确定当臂间距为130µm时,传感臂7和参考臂8之间不会产生波导之间的耦合效应,如图3中(b)图所示,其输出光功率可以达到最大值,此时器件损耗最小,如图3中(c)图所示。The comparison chart of the output optical power at different arm spacings of the polymer glucose sensor based on the Mach-Zehnder structure in this embodiment is shown in Figure 3. If the distance between the sensing arm 7 and the reference arm 8 is too close, the coupling effect will occur (the energy input by the left waveguide is gradually coupled to the right waveguide as the propagation distance increases), and it will also affect the sensing of the sensor. performance. When the arm spacing is not greater than 4µm, it can be seen from (a) in Figure 3 that the arm spacing is too close at this time, which will seriously affect the sensing performance of the sensor; comprehensively consider the bending radius, lateral length and deflection angle of the curved waveguide 6 Together with the arm spacing, it is determined that when the arm spacing is 130µm, there will be no coupling effect between the waveguides between the sensing arm 7 and the reference arm 8. As shown in (b) of Figure 3, the output optical power The maximum value can be reached, at which time the device loss is minimal, as shown in (c) of Figure 3.

所述基于马赫曾德尔结构的聚合物葡萄糖传感器的灵敏度S可表示为:The sensitivity S of the polymer glucose sensor based on the Mach-Zehnder structure can be expressed as:

,

式中λ为波长,L为传感臂的臂长,n c 为待测液体的折射率,N eff 为传感臂的有效折射率,为传感臂的有效折射率随葡萄糖浓度的变化关系。通过公式分析可知,不仅传感臂的有效折射率N eff 会影响葡萄糖传感器的灵敏度,而且传感臂的臂长L也会影响其灵敏度,同时结合折射率与马赫曾德尔结构的聚合物葡萄糖传感器传输功率分析,增大光场与待测物接触的倏逝场范围也可提高其传感灵敏度。对于光强型马赫曾德尔结构的聚合物葡萄糖传感器,其光强在一个变化周期内会重复出现两次,因此只考虑1/2个周期的光强响应变化。In the formula, λ is the wavelength, L is the arm length of the sensing arm, n c is the refractive index of the liquid to be measured, N eff is the effective refractive index of the sensing arm, is the relationship between the effective refractive index of the sensing arm and the change of glucose concentration. Through formula analysis, it can be seen that not only the effective refractive index N eff of the sensing arm will affect the sensitivity of the glucose sensor, but also the arm length L of the sensing arm will also affect its sensitivity. At the same time, the polymer glucose sensor that combines the refractive index and Mach-Zehnder structure Transmission power analysis, increasing the evanescent field range in which the light field contacts the object to be measured can also improve its sensing sensitivity. For the light-intensity Mach-Zehnder structure polymer glucose sensor, the light intensity will repeat twice in a change period, so only the light intensity response change of 1/2 period is considered.

在特异性催化葡萄糖反应后,GOD的折射率是减小的,不同浓度的葡萄糖溶液在与酶发生催化反应后,溶液的折射率也是减小的。此外,马赫曾德尔结构的聚合物葡萄糖传感器的灵敏度与传感范围是一对相互制约的量。本实施例设置GOD的折射率变化范围为1.3352-1.3400,传感臂7的臂长为1740µm,如果臂长继续增长会导致检测的葡萄糖浓度范围减小,且在GOD的折射率变化范围为1.3352-1.3400的区间内,其输出光功率不单调;同样,如果臂长再继续增长会导致检测的葡萄糖灵敏度减小,且当传感臂7为三个面均接触待测物的矩形波导结构,臂间距为130µm,弯曲波导6的弯曲半径为800µm,横向长度为430µm和偏转角度为0.28 rad时,其在此折射率区间上有较高的灵敏度和线性度,并且在保证最大传感范围的同时实现器件的最小化。After specifically catalyzing the glucose reaction, the refractive index of GOD decreases. After the catalytic reaction of glucose solutions with enzymes of different concentrations, the refractive index of the solution also decreases. In addition, the sensitivity and sensing range of the Mach-Zehnder structure polymer glucose sensor are a pair of mutually restrictive quantities. In this embodiment, the refractive index change range of GOD is set to 1.3352-1.3400, and the arm length of the sensing arm 7 is 1740µm. If the arm length continues to increase, the detected glucose concentration range will be reduced, and the refractive index change range of GOD is 1.3352. Within the range of -1.3400, its output optical power is not monotonous; similarly, if the arm length continues to increase, the sensitivity of detected glucose will decrease, and when the sensing arm 7 is a rectangular waveguide structure with three surfaces in contact with the object to be measured, When the arm spacing is 130µm, the bending radius of the curved waveguide 6 is 800µm, the lateral length is 430µm and the deflection angle is 0.28 rad, it has high sensitivity and linearity in this refractive index range, and ensures the maximum sensing range. At the same time, minimization of devices is achieved.

本实施例基于马赫曾德尔结构的聚合物葡萄糖传感器的不同传感臂臂长下的输出光功率响应对比图如图4所示。当GOD的折射率变化范围在1.3352-1.3400区间上,区间端点输出光功率差值最大且在此区间上单调时,灵敏度达到最大。只有当传感臂7的臂长为1740µm时,GOD折射率变化范围才在1.3352-1.3400区间上且输出光功率在此区间上单调;当传感臂臂长小于1740µm时,GOD折射率变化范围在1.3352-1.3400区间上的灵敏度将会减小,无法满足葡萄糖检测要求。The comparison chart of the output light power response of the polymer glucose sensor based on the Mach-Zehnder structure under different sensing arm arm lengths in this embodiment is shown in Figure 4. When the refractive index change range of GOD is in the 1.3352-1.3400 interval, the output optical power difference at the end point of the interval is the largest and is monotonic in this interval, the sensitivity reaches the maximum. Only when the arm length of the sensing arm 7 is 1740µm, the GOD refractive index change range is in the interval 1.3352-1.3400 and the output optical power is monotonic in this interval; when the sensing arm length is less than 1740µm, the GOD refractive index change range The sensitivity in the 1.3352-1.3400 range will decrease and cannot meet the glucose detection requirements.

本实施例基于马赫曾德尔结构的聚合物葡萄糖传感器的光场图如图5所示。当传感臂7的臂长为1740µm且传感臂7为三个面均接触待测物的矩形波导结构,在臂间距为130µm,弯曲波导6的弯曲半径为800µm,横向长度为430µm和偏转角度为0.28rad的情况下,光场被有效地限制在PMMA芯层2区域内,此时葡萄糖传感器的消光比为41.43dB。The light field diagram of the polymer glucose sensor based on the Mach-Zehnder structure in this embodiment is shown in Figure 5. When the arm length of the sensing arm 7 is 1740µm and the sensing arm 7 is a rectangular waveguide structure with three sides in contact with the object to be measured, the arm spacing is 130µm, the bending radius of the curved waveguide 6 is 800µm, the lateral length is 430µm and the deflection When the angle is 0.28rad, the light field is effectively limited to the PMMA core layer 2 area. At this time, the extinction ratio of the glucose sensor is 41.43dB.

本实施例基于马赫曾德尔结构的聚合物葡萄糖传感器的测量系统如图6所示。对硅烷化偶联修饰GOD后的基于马赫曾德尔结构的聚合物葡萄糖传感器滴加葡萄糖溶液进行传感测量,可调谐激光器发出波长为1550nm的光通过偏振控制器后,再通过锥形光纤耦合输入到基于马赫曾德尔结构的聚合物葡萄糖传感器的输入波导9,输入光经由传感臂7和参考臂8发生干涉现象,由输出波导10经过锥形光纤耦合输出到光功率计中,从而得到基于马赫曾德尔结构的聚合物葡萄糖传感器的浓度与输出光功率的关系。The measurement system of the polymer glucose sensor based on the Mach-Zehnder structure in this embodiment is shown in Figure 6 . The polymer glucose sensor based on the Mach-Zehnder structure after silanization coupling modification of GOD is dripped with glucose solution for sensing measurement. The tunable laser emits light with a wavelength of 1550 nm through the polarization controller and then coupled into the tapered optical fiber. To the input waveguide 9 of the polymer glucose sensor based on the Mach-Zehnder structure, the input light interferes with the sensing arm 7 and the reference arm 8, and is coupled and output to the optical power meter by the output waveguide 10 through the tapered optical fiber, thereby obtaining the result based on The relationship between concentration and output light power of polymer glucose sensor with Mach-Zehnder structure.

本实施例中在固定GOD时,需要控制GOD所处的温度和pH,在保持GOD最佳活性的同时,使基于马赫曾德尔结构的聚合物葡萄糖传感器性能达到最优。In this embodiment, when fixing GOD, it is necessary to control the temperature and pH of the GOD, so as to optimize the performance of the polymer glucose sensor based on the Mach-Zehnder structure while maintaining the optimal activity of GOD.

本实施例采用共价偶联法实现GOD简单、高效、稳定的固定。首先使用硅烷溶液对传感臂7的表面进行表面功能化修饰,通过硅烷在酶和聚合物材料的界面之间架起“分子桥”;然后利用 1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐和N-羟基琥珀酰亚胺构成的交联剂对传感臂7表面做进一步偶联处理;This embodiment uses covalent coupling method to achieve simple, efficient and stable fixation of GOD. First, use a silane solution to functionalize the surface of the sensing arm 7, and use silane to build a "molecular bridge" between the interface of the enzyme and the polymer material; then use 1-(3-dimethylaminopropyl)-3 -The cross-linking agent composed of ethylcarbodiimide hydrochloride and N-hydroxysuccinimide further couples the surface of the sensing arm 7;

将GOD粉末溶于pH为5.5的PBS缓冲液中,形成30mg/mL的GOD溶液,将刻蚀完PDMS上包层3后的器件放置于高低温试验箱中,并控制温度为40℃,滴加GOD溶液并固化,在传感臂上形成三维矩形接触结构,并用PBS缓冲液冲洗传感臂7表面未固定的GOD,即完成了GOD的固定。Dissolve GOD powder in PBS buffer with a pH of 5.5 to form a 30 mg/mL GOD solution. Place the device after etching the PDMS upper cladding layer 3 in a high and low temperature test chamber, and control the temperature to 40°C. Add GOD solution and solidify to form a three-dimensional rectangular contact structure on the sensing arm, and rinse the unfixed GOD on the surface of sensing arm 7 with PBS buffer to complete the fixation of GOD.

本实施例在不同温度和pH下获得的基于马赫曾德尔结构的聚合物葡萄糖传感器的输出光功率变化量的响应图如图7所示。本发明通过高低温试验箱控制温度在35-45℃之间变化,采用相同浓度、相同体积、不同温度的葡萄糖溶液进行实验,分析基于马赫曾德尔结构的聚合物葡萄糖传感器对应的光学传输特性曲线随温度的变化情况。温度对光学传输特性的影响如图7中(a)图所示,当将GOD所处的温度提高到40℃时,传感臂7表面发生特异性催化反应最强烈,传感臂7有效折射率变化最大,因此输出光功率变化量达到最大;进一步提高PBS缓冲液的温度值,传感臂7有效折射率变化将会减小,进而导致基于马赫曾德尔结构的聚合物葡萄糖传感器的输出光功率变化量降低。The response diagram of the change in output light power of the polymer glucose sensor based on the Mach-Zehnder structure obtained at different temperatures and pH in this example is shown in Figure 7 . The present invention controls the temperature to change between 35-45°C through a high and low temperature test chamber, uses glucose solutions of the same concentration, the same volume, and different temperatures to conduct experiments, and analyzes the optical transmission characteristic curve corresponding to the polymer glucose sensor based on the Mach-Zehnder structure. changes with temperature. The effect of temperature on optical transmission characteristics is shown in Figure 7 (a). When the temperature of GOD is increased to 40°C, the most intense specific catalytic reaction occurs on the surface of sensing arm 7, and the sensing arm 7 effectively refracts The rate change is the largest, so the output light power change reaches the maximum; further increasing the temperature value of the PBS buffer, the effective refractive index change of the sensing arm 7 will decrease, which will lead to the output light of the polymer glucose sensor based on the Mach-Zehnder structure. The amount of power variation is reduced.

本发明通过选择pH=4.0和pH=8.0的PBS缓冲液与HCl和NaOH混合,将其pH值控制在一定范围内,并通过pH计进行测量,然后再以0.5 pH间隔缩小pH范围寻找最适pH。采用相同浓度、相同体积、不同pH的葡萄糖溶液进行滴加测量。溶液pH值对光学传输特性的影响如图7中(b)图所示,当增加PBS缓冲液的pH值到5.5时,GOD分子上活性基团处于解离状态,在传感臂7表面发生特异性催化反应后,传感臂7有效折射率将会变化最大,因此输出光功率达到最大变化量。进一步提高PBS缓冲液的pH值,GOD分子上活性基团的解离状态受到抑制,不利于酶和葡萄糖结合,传感臂7有效折射率变化将会减小,进而导致基于马赫曾德尔结构的聚合物葡萄糖传感器的输出光功率变化量降低。In the present invention, the pH value of the PBS buffer solution with pH=4.0 and pH=8.0 is mixed with HCl and NaOH, controlled within a certain range, and measured by a pH meter, and then narrows the pH range at 0.5 pH intervals to find the optimum pH. Use glucose solutions of the same concentration, same volume, and different pH for drop measurement. The influence of the pH value of the solution on the optical transmission characteristics is shown in (b) of Figure 7. When the pH value of the PBS buffer is increased to 5.5, the active groups on the GOD molecules are in a dissociated state and occur on the surface of the sensing arm 7. After the specific catalytic reaction, the effective refractive index of the sensing arm 7 will change the most, so the output light power reaches the maximum change. Further increasing the pH value of the PBS buffer, the dissociation state of the active groups on the GOD molecule is inhibited, which is not conducive to the binding of enzyme and glucose. The effective refractive index change of the sensing arm 7 will be reduced, which will lead to the Mach-Zehnder structure-based The change in output light power of the polymer glucose sensor is reduced.

为了检测基于马赫曾德尔结构的聚合物葡萄糖传感器的传感范围和灵敏度,配置了0-3mg/mL不同浓度的葡萄糖溶液,并以浓度间隔0.1mg/mL的浓度变化分别配置不同浓度梯度的葡萄糖溶液,例如配置1mg/mL浓度的葡萄糖溶液,将10mg的葡萄糖粉末加入在10mLpH为5.5的PBS缓冲液中并使用磁力搅拌器搅拌均匀。In order to test the sensing range and sensitivity of the polymer glucose sensor based on the Mach-Zehnder structure, glucose solutions with different concentrations of 0-3mg/mL were configured, and glucose solutions with different concentration gradients were configured at a concentration interval of 0.1mg/mL. Solution, for example, prepare a glucose solution with a concentration of 1 mg/mL. Add 10 mg of glucose powder to 10 mL of PBS buffer with a pH of 5.5 and stir evenly using a magnetic stirrer.

本实施例基于马赫曾德尔结构的聚合物葡萄糖传感器输出光功率随葡萄糖浓度变化的响应图如图8所示。实验测量中使用10mW的输入光功率,测量基于马赫曾德尔结构的聚合物葡萄糖传感器的葡萄糖浓度传感范围C L 及其对不同浓度葡萄糖的响应能力。为了消除每次不同浓度的葡萄糖溶液带来的干扰,需在每次独立测量前用去离子水冲洗传感臂7。图8显示了基于马赫曾德尔结构的聚合物葡萄糖传感器在不同葡萄糖浓度下的光学输出特性,随着葡萄糖溶液浓度的增加,输出光功率向功率减小的方向变化。实验结果表明当葡萄糖溶液浓度为0mg/mL时,最大输出光功率为6.95mW,并且当葡萄糖溶液浓度为2.6mg/mL时,最小输出光功率为0.0005mW,器件实现了在葡萄糖浓度范围在0-2.6mg/mL内的线性响应。基于马赫曾德尔结构的聚合物葡萄糖传感器的消光比为41.43dB,C L 为0-2.6mg/mL,灵敏度为2.67 mW/(mg/mL)。The response diagram of the output optical power of the polymer glucose sensor based on the Mach-Zehnder structure in this embodiment changes with the glucose concentration is shown in Figure 8. In the experimental measurement, an input optical power of 10 mW was used to measure the glucose concentration sensing range C L of the polymer glucose sensor based on the Mach-Zehnder structure and its response ability to different concentrations of glucose. In order to eliminate the interference caused by glucose solutions of different concentrations each time, the sensing arm 7 needs to be rinsed with deionized water before each independent measurement. Figure 8 shows the optical output characteristics of the polymer glucose sensor based on the Mach-Zehnder structure under different glucose concentrations. As the concentration of the glucose solution increases, the output optical power changes in the direction of power reduction. Experimental results show that when the glucose solution concentration is 0mg/mL, the maximum output light power is 6.95mW, and when the glucose solution concentration is 2.6mg/mL, the minimum output light power is 0.0005mW. The device achieves a glucose concentration range of 0 Linear response within -2.6mg/mL. The polymer glucose sensor based on the Mach-Zehnder structure has an extinction ratio of 41.43dB, a C L of 0-2.6mg/mL, and a sensitivity of 2.67 mW/(mg/mL).

本实施例基于马赫曾德尔结构的聚合物葡萄糖传感器的特异性响应图如图9所示。对比了传感器对三种不同溶液(PBS、NaCl和葡萄糖)的强度响应,其中基于马赫曾德尔结构的聚合物葡萄糖传感器对葡萄糖的最大输出光功率响应变化量为6.95mW,对PBS和NaCl的最大输出光功率响应变化量分别为0.16mW和0.11mW,结果表明传感臂7上的GOD可以特异性识别葡萄糖,因此,基于马赫曾德尔结构的聚合物葡萄糖传感器对葡萄糖具有良好的选择性。The specific response diagram of the polymer glucose sensor based on the Mach-Zehnder structure in this embodiment is shown in Figure 9. The intensity response of the sensor to three different solutions (PBS, NaCl and glucose) was compared. The maximum output light power response change of the polymer glucose sensor based on the Mach-Zehnder structure to glucose was 6.95mW, and the maximum output light power response to PBS and NaCl was 6.95mW. The output light power response changes were 0.16mW and 0.11mW respectively. The results show that the GOD on sensing arm 7 can specifically recognize glucose. Therefore, the polymer glucose sensor based on the Mach-Zehnder structure has good selectivity for glucose.

本实施例基于马赫曾德尔结构的聚合物葡萄糖传感器的稳定性响应图如图10所示。稳定性是聚合物葡萄糖传感器的另一个重要性能指标,也是测量结果准确性的重要表征。聚合物葡萄糖传感器的稳定性可以表示为:在相同的实验环境下(相同浓度、温度、pH、体积的葡萄糖溶液)对输出光功率的重复多次测量,表征其测量输出光功率的波动情况,因此可以用相对标准偏差来衡量基于马赫曾德尔结构的聚合物葡萄糖传感器的稳定性。对浓度为1mg/mL和2mg/mL的葡萄糖溶液分别进行重复10次的测量,每隔5分钟记录一次测量结果,测量输出光功率随时间波动曲线如图10所示,实验结果表明虽然传感器测量的输出光功率随时间变化有不同程度的波动,但也是在极小范围内波动,浓度单点测量的相对标准偏差约为2×10-3,因此本发明基于马赫曾德尔结构的聚合物葡萄糖传感器对葡萄糖溶液浓度测量有较好的稳定性。The stability response diagram of the polymer glucose sensor based on the Mach-Zehnder structure in this embodiment is shown in Figure 10. Stability is another important performance indicator of polymer glucose sensors and an important indicator of the accuracy of measurement results. The stability of the polymer glucose sensor can be expressed as: repeated measurements of the output light power under the same experimental environment (same concentration, temperature, pH, and volume of glucose solution) to characterize the fluctuation of the measured output light power. Therefore, the relative standard deviation can be used to measure the stability of the polymer glucose sensor based on the Mach-Zehnder structure. The measurements of glucose solutions with concentrations of 1 mg/mL and 2 mg/mL were repeated 10 times, and the measurement results were recorded every 5 minutes. The measured output light power fluctuation curve with time is shown in Figure 10. The experimental results show that although the sensor measurement The output optical power fluctuates to varying degrees with time, but it also fluctuates within a very small range. The relative standard deviation of the single-point concentration measurement is about 2×10 -3 . Therefore, the polymer glucose based on the Mach-Zehnder structure of the present invention The sensor has good stability in measuring the concentration of glucose solution.

本实施例基于马赫曾德尔结构的聚合物葡萄糖传感器的耐久性响应图如图11所示。耐久性是指对不同浓度葡萄糖溶液的光强响应可以维持良好的一致性和准确度,优异的耐久性是传感器实现长期使用的必要前提。对在室温环境下储存不同时间后的聚合物葡萄糖传感器进行响应测试,具体实验操作如下:将同一聚合物葡萄糖传感器分别在室温环境中存放15天和40天后,使用不同浓度的葡萄糖溶液对其进行测量,不同时间不同葡萄糖浓度下的光学输出特性曲线如图11中(a)图所示,15天和40天后与最初测量结果显示出一致的变化趋势,随着浓度不断增加输出光功率明显地向减小的方向移动,15天和40天后变化率分别为2.2%和3.2%。同时还考察了灵敏度和损耗这两个主要的性能参数,可以看出经过15天和40天后,测量结果如图11中(b)图所示,基于马赫曾德尔结构的聚合物葡萄糖传感器的损耗和灵敏度并没有明显变化,损耗变化范围为2.36-2.50dB,灵敏度变化范围为2.67-2.53mW/(mg/mL)。虽然放置一段时间的器件响应强度、损耗和灵敏度相对于加工后立即测试时的性能略有下降,但是基于马赫曾德尔结构的聚合物葡萄糖传感器对葡萄糖的传感区间并没有明显变化,说明在室温下存放不同时间后的聚合物葡萄糖传感器仍然对葡萄糖的响应维持高度的一致性。The durability response diagram of the polymer glucose sensor based on the Mach-Zehnder structure in this embodiment is shown in Figure 11. Durability means that the light intensity response to glucose solutions of different concentrations can maintain good consistency and accuracy. Excellent durability is a necessary prerequisite for long-term use of the sensor. The response test of the polymer glucose sensor after being stored at room temperature for different times was carried out. The specific experimental operations were as follows: After the same polymer glucose sensor was stored at room temperature for 15 days and 40 days respectively, it was tested using glucose solutions of different concentrations. Measurement, the optical output characteristic curves under different glucose concentrations at different times are shown in (a) in Figure 11. After 15 days and 40 days, they show a consistent change trend with the initial measurement results. As the concentration continues to increase, the output optical power obviously increases. Moving in the decreasing direction, the change rates after 15 days and 40 days are 2.2% and 3.2% respectively. At the same time, the two main performance parameters of sensitivity and loss were also examined. It can be seen that after 15 days and 40 days, the measurement results are shown in (b) in Figure 11. The loss of the polymer glucose sensor based on the Mach-Zehnder structure There is no significant change in the sensitivity, the loss range is 2.36-2.50dB, and the sensitivity range is 2.67-2.53mW/(mg/mL). Although the response intensity, loss and sensitivity of the device after being left for a period of time are slightly reduced compared to the performance when tested immediately after processing, the glucose sensing range of the polymer glucose sensor based on the Mach-Zehnder structure does not change significantly, indicating that at room temperature The polymer glucose sensor still maintains a high degree of consistency in its response to glucose after being stored for different times.

本发明未述及之处适用于现有技术。The parts not described in the present invention are applicable to the existing technology.

Claims (7)

1.一种基于马赫曾德尔结构的聚合物葡萄糖传感器,包括由下至上的PDMS下包层、PMMA芯层和PDMS上包层;其特征在于,所述PMMA芯层包括输入波导、输出波导、1×2 MMI耦合器、2×1 MMI耦合器、弯曲波导、传感臂和参考臂;传感臂和参考臂等长且平行,二者以中心线为轴对称设置;在40℃的温度下通过酸性偶联剂将GOD固定在PMMA芯层的传感臂上形成三维矩形接触结构,三维矩形接触结构的上表面低于PDMS上包层的上表面,且高于传感臂的上表面;1. A polymer glucose sensor based on Mach-Zehnder structure, including a PDMS lower cladding layer, a PMMA core layer and a PDMS upper cladding layer from bottom to top; characterized in that the PMMA core layer includes an input waveguide, an output waveguide, 1×2 MMI coupler, 2×1 MMI coupler, curved waveguide, sensing arm and reference arm; the sensing arm and the reference arm are equal in length and parallel, and they are set symmetrically with the center line as the axis; at a temperature of 40°C GOD is fixed on the sensing arm of the PMMA core layer through an acidic coupling agent to form a three-dimensional rectangular contact structure. The upper surface of the three-dimensional rectangular contact structure is lower than the upper surface of the PDMS upper cladding layer and higher than the upper surface of the sensing arm. ; 所述GOD的折射率变化范围为1.3352-1.3400,所述传感臂的臂长为1740µm,传感臂和参考臂之间的臂间距为130µm;所述弯曲波导的弯曲半径为800µm,弯曲波导的横向长度为430µm,弯曲波导的偏转角度为0.28rad;The refractive index variation range of the GOD is 1.3352-1.3400, the arm length of the sensing arm is 1740µm, and the arm spacing between the sensing arm and the reference arm is 130µm; the bending radius of the curved waveguide is 800µm, and the curved waveguide The lateral length of the curved waveguide is 430µm, and the deflection angle of the curved waveguide is 0.28rad; 所述基于马赫曾德尔结构的聚合物葡萄糖传感器的损耗控制在1.6dB以内,灵敏度为2.67 mW/(mg/mL)。The loss of the polymer glucose sensor based on the Mach-Zehnder structure is controlled within 1.6dB, and the sensitivity is 2.67 mW/(mg/mL). 2.如权利要求1所述的基于马赫曾德尔结构的聚合物葡萄糖传感器,其特征在于,所述基于马赫曾德尔结构的聚合物葡萄糖传感器的损耗为1.58dB,消光比为41.43dB。2. The polymer glucose sensor based on Mach-Zehnder structure as claimed in claim 1, characterized in that the polymer glucose sensor based on Mach-Zehnder structure has a loss of 1.58dB and an extinction ratio of 41.43dB. 3.如权利要求1所述的基于马赫曾德尔结构的聚合物葡萄糖传感器,其特征在于,当输入光功率为10mW,葡萄糖溶液浓度为0mg/mL时,最大输出光功率为6.95mW,并且当葡萄糖溶液浓度为2.6mg/mL时,最小输出光功率为0.0005mW,传感器实现了葡萄糖浓度在0-2.6mg/mL范围内的线性响应,葡萄糖浓度传感范围为0-2.6mg/mL。3. The polymer glucose sensor based on Mach-Zehnder structure as claimed in claim 1, characterized in that when the input optical power is 10mW and the glucose solution concentration is 0mg/mL, the maximum output optical power is 6.95mW, and when When the glucose solution concentration is 2.6mg/mL, the minimum output light power is 0.0005mW. The sensor achieves a linear response to the glucose concentration in the range of 0-2.6mg/mL, and the glucose concentration sensing range is 0-2.6mg/mL. 4.如权利要求1所述的基于马赫曾德尔结构的聚合物葡萄糖传感器,其特征在于,所述基于马赫曾德尔结构的聚合物葡萄糖传感器的相对标准偏差为(1.5-2.5)×10-3,最低检测极限为0.1mg/mL。4. The polymer glucose sensor based on Mach-Zehnder structure as claimed in claim 1, wherein the relative standard deviation of the polymer glucose sensor based on Mach-Zehnder structure is (1.5-2.5)×10 -3 , the lowest detection limit is 0.1mg/mL. 5.如权利要求1所述的基于马赫曾德尔结构的聚合物葡萄糖传感器,其特征在于,所述PDMS下包层和PDMS上包层的厚度均为10µm,折射率为1.4040;PMMA芯层的厚度为1µm,折射率为1.4880;传感臂上表面到三维矩形接触结构上表面的距离为2-3µm。5. The polymer glucose sensor based on Mach-Zehnder structure as claimed in claim 1, characterized in that the thickness of the PDMS lower cladding layer and the PDMS upper cladding layer are both 10 μm, and the refractive index is 1.4040; the PMMA core layer The thickness is 1µm and the refractive index is 1.4880; the distance from the upper surface of the sensing arm to the upper surface of the three-dimensional rectangular contact structure is 2-3µm. 6.如权利要求1所述的基于马赫曾德尔结构的聚合物葡萄糖传感器,其特征在于,所述弯曲波导的波导宽度为1.5µm,高度为1µm。6. The polymer glucose sensor based on Mach-Zehnder structure according to claim 1, wherein the waveguide width of the curved waveguide is 1.5 μm and the height is 1 μm. 7.如权利要求1所述的基于马赫曾德尔结构的聚合物葡萄糖传感器,其特征在于,GOD溶液的获得方式为:将GOD粉末溶于pH为5.5的PBS缓冲液中,形成质量浓度为30mg/mL的GOD溶液;7. The polymer glucose sensor based on the Mach-Zehnder structure as claimed in claim 1, wherein the GOD solution is obtained by dissolving GOD powder in a PBS buffer with a pH of 5.5 to form a mass concentration of 30 mg. /mL GOD solution; 在PMMA芯层的传感臂上滴加GOD溶液并固化,在传感臂上形成三维矩形接触结构。The GOD solution is dropped on the sensing arm of the PMMA core layer and solidified to form a three-dimensional rectangular contact structure on the sensing arm.
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