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CN112191284A - Laboratory analysis platform on microfluidic ultrasonic electrochemical chip - Google Patents

Laboratory analysis platform on microfluidic ultrasonic electrochemical chip Download PDF

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CN112191284A
CN112191284A CN202010556972.4A CN202010556972A CN112191284A CN 112191284 A CN112191284 A CN 112191284A CN 202010556972 A CN202010556972 A CN 202010556972A CN 112191284 A CN112191284 A CN 112191284A
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牛鹏飞
佘祥
庞慰
王小荷
郑宗威
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Tianjin University
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    • B01L3/5027Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
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Abstract

The invention discloses a laboratory analysis platform on a microfluidic ultrasonic electrochemical chip, which comprises: the micro-flow channel assembly is arranged on the micro-flow channel assembly, a cavity with an open top end and an open bottom end is formed by the wall of the through hole, the cavity is communicated with the outside of a laboratory analysis platform on the micro-flow ultrasonic electrochemical chip, so that liquid to be detected can be discharged into and out of the cavity, and the liquid to be detected in the cavity can be contacted with three electrodes of the electrochemical sensor chip and a vibration area of the micro-ultrasonic device. The invention realizes the combined use of the micro ultrasonic device and the electrochemical sensor chip, effectively improves the electrochemical sensing sensitivity, and the liquid inlet and the liquid outlet are opened in the vertical direction of the micro flow channel component, thereby being applicable to the design of a laboratory on the micro flow channel with small thickness.

Description

微流控超声电化学片上实验室分析平台Microfluidic Ultrasonic Electrochemical Lab-on-a-Chip Analysis Platform

技术领域technical field

本发明属于微流控电化学分析技术领域,具体来说涉及一种微流控超声电化学片上实验室分析平台。The invention belongs to the technical field of microfluidic electrochemical analysis, and in particular relates to a microfluidic ultrasonic electrochemical on-chip laboratory analysis platform.

背景技术Background technique

微流控片上实验室(microfluidic lab on a chip)将微量样品的制备、反应、分离、检测、废液回收等基本操作单元全部集成到一块芯片上,实现自动分析,避免潜在的交叉污染和人为操作错误的影响,广泛应用于化学、生物、医学分析领域。在微流控片上实验室中,液体在微流道内流动,垂直于液体流动方向的微流道尺寸通常需要小于1mm。Microfluidic lab on a chip integrates basic operation units such as micro sample preparation, reaction, separation, detection, waste liquid recovery, etc. into one chip to realize automatic analysis and avoid potential cross-contamination and artificial The influence of operating errors is widely used in the fields of chemical, biological, and medical analysis. In the microfluidic lab-on-a-chip, the liquid flows in the microfluidic channel, and the size of the microfluidic channel perpendicular to the liquid flow direction usually needs to be less than 1 mm.

电化学传感器芯片(工作、对比、参比电极在同一衬底上)具有尺寸小、能耗底、价格便宜、分析速度快、选择性好、测量范围广、易于集成等优势,集成有电化学传感器芯片的微流控片上实验室(微流控电化学片上实验室,如图1所示),广泛应用于原位快速检测水质和食品安全以及诊断人体疾病等领域。Electrochemical sensor chips (working, contrast, and reference electrodes on the same substrate) have the advantages of small size, low energy consumption, low price, fast analysis speed, good selectivity, wide measurement range, and easy integration. The microfluidic on-chip laboratory of the sensor chip (microfluidic electrochemical on-chip laboratory, as shown in Figure 1) is widely used in the fields of in situ rapid detection of water quality and food safety, and diagnosis of human diseases.

然而,微流控片上实验室的样品容量极小(通常是微升甚至纳升量级)以及传质受限(微腔室内液体对流困难)等因素限制了电化学传感器芯片的检测灵敏度。However, factors such as the extremely small sample volume (usually on the order of microliters or even nanoliters) and limited mass transfer (difficult liquid convection within the microchamber) in microfluidic lab-on-a-chip limit the detection sensitivity of electrochemical sensor chips.

将超声引入电化学分析过程,能够产生诸多优点,包括超声辐射大大加快电极表面附近电活性物质和产物的质量传递、减弱溶液中固有组分及电化学反应中涉及的组分在电极表面的吸附、活化电极表面等(张成孝.超声电化学及其研究进展[J].陕西师范大学学报(自然科学版),2001,29(2):103-109)。The introduction of ultrasound into the electrochemical analysis process can yield many advantages, including that ultrasonic radiation greatly accelerates the mass transfer of electroactive species and products near the electrode surface, and reduces the adsorption of intrinsic components in solution and components involved in electrochemical reactions on the electrode surface. , Activated electrode surface, etc. (Zhang Chengxiao. Ultrasonic electrochemistry and its research progress [J]. Journal of Shaanxi Normal University (Natural Science Edition), 2001, 29(2): 103-109).

然而目前超声电化学装置中普遍采用的超声浴及超声振幅杆等超声波发射装置尺寸庞大,不适于微流控电化学片上实验室检测平台(Timothy J.Mason,Verónica SáezBernal,An Introduction to Sono-electrochemistry,in book Power Ultrasound inElectrochemistry[M],Editor:Bruno G.Pollet,2012,Wiley)。However, ultrasonic emission devices such as ultrasonic baths and ultrasonic amplitude rods commonly used in ultrasonic electrochemical devices are large in size and are not suitable for microfluidic electrochemical on-chip laboratory detection platforms (Timothy J. Mason, Verónica Sáez Bernal, An Introduction to Sono-electrochemistry , in book Power Ultrasound in Electrochemistry [M], Editor: Bruno G. Pollet, 2012, Wiley).

近年来,声表面波以及薄膜体声波谐振器等经微纳机电系统技术(Micro-Electronics-Mechanical System,MEMS)开发,作为滤波器常用于手机等无线通讯设备的微型超声波发射器件,在超声电化学分析领域有了新的应用。声表面波及薄膜体声波谐振器发射的超声波能够在液体中产生强声流效应,显著促进液体中电化学活性物质向电极表面的质量传递,提高检测灵敏度([1].Kaplan E,Surface Acoustic Wave EnhancedElectroanalytical Sensors[D],University of Glasgow,2015;[2].Sakamoto Hiroakiet al,Development of a High Sensitive Electrochemical Detector with Micro-stirrer Driven by Surface Acoustic Waves[J],Sensors and Actuators B:Chemical,2018,26,705-709;[3].Zheng Tengfei et al,Focusing Surface Acoustic WavesAssisted Electrochemical Detector in Microfluidics[J],Electrophoresis,2020,doi:10.1002/elps.201900315;[4].Zheng Zongwei et al,Miniature GigahertzAcoustic Resonator and On-Chip Electrochemical Sensor:An Emerging Combinationfor Electroanalytical Microsystems[J],Analytical Chemistry,2019,91(24):15959-15966;[5].Wang Xiaohe et al,Miniature Acoustic Resonator for Enhanced Lab-on-a-Chip Electroanalysis[C],2019IEEE SENSORS,doi:10.1109/SENSORS43011.2019.8956499])。In recent years, surface acoustic wave and thin-film bulk acoustic wave resonators have been developed by Micro-Electronics-Mechanical System (MEMS) technology. There are new applications in the field of chemical analysis. The ultrasonic waves emitted by surface acoustic waves and thin-film bulk acoustic wave resonators can generate strong acoustic flow effects in the liquid, which can significantly promote the mass transfer of electrochemically active substances in the liquid to the electrode surface, and improve the detection sensitivity ([1]. Kaplan E, Surface Acoustic Wave Enhanced Electroanalytical Sensors[D],University of Glasgow,2015;[2].Sakamoto Hiroaki et al,Development of a High Sensitive Electrochemical Detector with Micro-stirrer Driven by Surface Acoustic Waves[J],Sensors and Actuators B:Chemical,2018,26,705 -709;[3].Zheng Tengfei et al,Focusing Surface Acoustic WavesAssisted Electrochemical Detector in Microfluidics[J],Electrophoresis,2020,doi:10.1002/elps.201900315;[4].Zheng Zongwei et al,Miniature GigahertzAcoustic Resonator and On -Chip Electrochemical Sensor: An Emerging Combination for Electroanalytical Microsystems[J],Analytical Chemistry,2019,91(24):15959-15966;[5].Wang Xiaohe et al,Miniature Acoustic Resonator for Enhanced Lab-on-a-Chip Electroanalysis [C], 2019 IEEE SENSORS, doi:10.1109/SENSORS43011.2019.8956499]).

然而,目前基于声表面波(图2)和固态装配型声波(图3)谐振器等微型超声波发射器件和电化学传感器芯片不适于集成到微流控片上实验室系统。However, current micro-ultrasonic emission devices and electrochemical sensor chips based on surface acoustic wave (Fig. 2) and solid-state assembled acoustic wave (Fig. 3) resonators are not suitable for integration into microfluidic lab-on-a-chip systems.

具体来说,如图2所示,微型声表面波器件的声表面波是通过对沉积在压电衬底表面的叉指电极施加交流电产生的,其与电化学传感器芯片集成的方式主要通过两种方案:1.将电化学传感器电极沉积到微型声表面波器件(图2(A)和(C)),这极大的限制了电化学传感器电极的材料、结构设计、加工成型等选择范围,同时压电衬底(通常是铌酸锂LiNbO3)价格非常昂贵,增加了成本;2.将电化学传感器芯片粘接到声表面波器件表面(图2(B)和(D)),这大大增加了电化学传感器芯片的选择范围,然而声波面波器件发射的声波是在固体(基底)表面传播,这对声波传播通道上的固体表面要求较高,电化学传感器芯片与声表面波器件之间的简单粘接很难达到声波传播的条件(Kaplan E,Surface Acoustic WaveEnhanced Electroanalytical Sensors[D],University of Glasgow,2015)。另外,适用于电化学传感领域的声表面波器件尺寸较大,其增强电化学分析性能的机理是声波在弹性材料表面传播,遇到液体后部分进入液体,引起促进液体流动(声流),这使得超声能量利用率偏低,能耗较高;再者,针对PI、PET等柔性薄膜衬底基电化学传感器芯片,其与声表面波器件的集成及能量利用等将更加困难。因此,微型声表面波器件与电化学传感器芯片的集成能力及使用性受限。Specifically, as shown in Figure 2, the surface acoustic wave of the miniature surface acoustic wave device is generated by applying alternating current to the interdigitated electrodes deposited on the surface of the piezoelectric substrate, and the way of integrating it with the electrochemical sensor chip is mainly through two Various schemes: 1. Deposition of electrochemical sensor electrodes on micro surface acoustic wave devices (Figure 2(A) and (C)), which greatly limits the selection of materials, structural design, processing and molding of electrochemical sensor electrodes. , while the piezoelectric substrate (usually lithium niobate LiNbO 3 ) is very expensive, increasing the cost; 2. Bonding the electrochemical sensor chip to the surface of the SAW device (Figure 2(B) and (D)), This greatly increases the selection range of electrochemical sensor chips. However, the acoustic wave emitted by the surface acoustic wave device propagates on the surface of the solid (substrate), which has higher requirements for the solid surface on the acoustic wave propagation channel. Simple bonding between devices is difficult to achieve the conditions of acoustic wave propagation (Kaplan E, Surface Acoustic WaveEnhanced Electroanalytical Sensors [D], University of Glasgow, 2015). In addition, the size of the surface acoustic wave device suitable for electrochemical sensing is relatively large, and the mechanism for enhancing the electrochemical analysis performance is that the sound wave propagates on the surface of the elastic material, and after encountering the liquid, part of it enters the liquid, causing the promotion of liquid flow (acoustic flow). , which makes the ultrasonic energy utilization rate low and energy consumption high. Furthermore, for electrochemical sensor chips based on flexible film substrates such as PI and PET, the integration with surface acoustic wave devices and energy utilization will be more difficult. Therefore, the integration capability and usability of the miniature surface acoustic wave device and the electrochemical sensor chip are limited.

固态装配型声波谐振器的尺寸非常小(可达100μm以下),与微流道的尺寸相当,其在液体中的传播耗散能够引起剧烈的液体运动(声流),显著提高电化学传感器的分析能力(Zheng Zongwei et al,Miniature Gigahertz Acoustic Resonator and On-ChipElectrochemical Sensor:An Emerging Combination for ElectroanalyticalMicrosystems[J],Analytical Chemistry,2019,91(24):15959-15966)。如图3a所示为目前所开发的基于固态装配型谐振器smr的超声电化学平台。它包括储液平台(图3c)、固态装配型谐振器smr(图3f)、上下盖板(图3e)、电化学传感器芯片(图3d),各组件通过螺栓紧固成如图3b所示结构。然而,由于一些原因,目前所开发的基于固态装配型谐振器smr的微型超声电化学检测平台的检测腔室较大(直径6mm厚度5mm),远大于常用微流控片上实验室中微流道的尺寸要求范围(垂直于液体流动方向的微流道尺寸通常需要小于1mm)。检测腔室较大的原因如图3c所示,现有平台的液体出入口是通过在PMMA基储液平台厚度方向的中间位置切割通孔实现的,受加工难度的限制,孔的直径通常不能小于1mm,并且目前市场存在的导液管外直径大于1mm,因此基于此种液体出入方案的储液平台厚度很难达到2mm以下,不能与微流控片上实验室兼容。此外,该微型超声电化学平台是采用螺栓紧固方式(如图3b所示),这种紧固方式使各组件间紧密贴合的能力有限,组件间仍然会漏液,通常需要在储液平台的检测腔室上下开口处放置橡胶垫圈以达到密封作用。橡胶垫圈的厚度通常有约1mm,橡胶垫圈会因挤压变形,厚度会发生不可控制的改变(设一个橡胶圈引起的误差是0.25mm,两个就0.5mm,当检测腔室高度设置为1mm,那么相对误差就可能达到50%),这种不可计算的误差给微流控片上实验室腔室厚度方向带来较大的相对误差。所以,上述超声电化学平台不适合集成到微流控电化学片上实验室。The size of the solid-state assembled acoustic resonator is very small (up to 100 μm or less), which is comparable to the size of the microfluidic channel, and its propagation and dissipation in the liquid can cause violent liquid motion (acoustic flow), which significantly improves the electrochemical sensor. Analytical capability (Zheng Zongwei et al, Miniature Gigahertz Acoustic Resonator and On-Chip Electrochemical Sensor: An Emerging Combination for Electroanalytical Microsystems [J], Analytical Chemistry, 2019, 91(24): 15959-15966). Figure 3a shows the currently developed sonoelectrochemical platform based on the solid-state assembled resonator smr. It includes a liquid storage platform (Fig. 3c), a solid-state assembled resonator smr (Fig. 3f), upper and lower cover plates (Fig. 3e), an electrochemical sensor chip (Fig. 3d), and each component is fastened by bolts as shown in Fig. 3b structure. However, due to some reasons, the detection chamber of the currently developed miniature ultrasonic electrochemical detection platform based on solid-state assembled resonator smr is larger (diameter 6mm and thickness 5mm), which is much larger than the microfluidic channel in the commonly used microfluidic-on-a-chip laboratory. The size requirement range (the size of the microchannel perpendicular to the liquid flow direction usually needs to be less than 1mm). The reason why the detection chamber is large is shown in Figure 3c. The liquid inlet and outlet of the existing platform are realized by cutting through holes in the middle of the thickness direction of the PMMA-based liquid storage platform. Due to the limitation of processing difficulty, the diameter of the hole usually cannot be smaller than 1mm, and the outer diameter of the catheter currently existing in the market is greater than 1mm, so the thickness of the liquid storage platform based on this liquid entry and exit scheme is difficult to reach below 2mm, which is not compatible with the microfluidic on-chip laboratory. In addition, the micro ultrasonic electrochemical platform is fastened by bolts (as shown in Figure 3b). This fastening method has limited ability to closely fit the components, and there will still be liquid leakage between the components. Usually, it is necessary to store the liquid. Rubber gaskets are placed at the upper and lower openings of the detection chamber of the platform to achieve sealing. The thickness of the rubber gasket is usually about 1mm, the rubber gasket will be deformed by extrusion, and the thickness will change uncontrollably (the error caused by one rubber ring is 0.25mm, and the two are 0.5mm. When the height of the detection chamber is set to 1mm , then the relative error may reach 50%), this incalculable error brings a large relative error to the thickness direction of the laboratory chamber on the microfluidic chip. Therefore, the above-mentioned sonoelectrochemical platforms are not suitable for integration into microfluidic electrochemical on-chip laboratories.

综上所述,目前还不存在集成了超声发射器件的微流控电化学片上实验室分析平台,需要相关解决方案。To sum up, there is currently no microfluidic electrochemical on-chip laboratory analysis platform integrated with ultrasonic emission devices, and relevant solutions are needed.

发明内容SUMMARY OF THE INVENTION

针对现有技术的不足,本发明的目的在于提供一种微流控超声电化学片上实验室分析平台,该微流控超声电化学片上实验室分析平台在微流控片上实验室上集成微型超声发射器件和电化学传感器芯片。In view of the deficiencies of the prior art, the purpose of the present invention is to provide a microfluidic ultrasonic electrochemical on-chip laboratory analysis platform, which integrates micro-ultrasound on the microfluidic on-chip laboratory Emitting devices and electrochemical sensor chips.

本发明的目的是通过下述技术方案予以实现的。The purpose of the present invention is achieved through the following technical solutions.

一种微流控超声电化学片上实验室分析平台,包括:电化学传感器芯片以及平行设置的微流道组件和支撑衬底,所述电化学传感器芯片、微流道组件和支撑衬底从上至下依次设置,其中,所述支撑衬底的顶面设置有一微型超声器件,所述微流道组件上形成有通孔,所述通孔的孔壁围成一顶端和底端均敞口的腔体,所述腔体与微流控超声电化学片上实验室分析平台外相通,以使能够向该腔体排入和排出待测液体,所述腔体内的待测液体能够与电化学传感器芯片的三电极和所述微型超声器件的振动区域接触。A microfluidic ultrasonic electrochemical on-chip laboratory analysis platform, comprising: an electrochemical sensor chip, a microfluidic channel component and a supporting substrate arranged in parallel, the electrochemical sensor chip, the microfluidic channel component and the supporting substrate from above They are arranged in sequence from the bottom, wherein a micro ultrasonic device is arranged on the top surface of the support substrate, a through hole is formed on the micro flow channel component, and the hole wall of the through hole encloses a top end and a bottom end that are open. The cavity is in communication with the outside of the microfluidic ultrasonic electrochemical on-chip laboratory analysis platform, so that the liquid to be tested can be discharged into and discharged from the cavity, and the liquid to be tested in the cavity can interact with the electrochemical The three electrodes of the sensor chip are in contact with the vibration area of the micro ultrasonic device.

在上述技术方案中,所述微流道组件内形成有进液腔和出液腔,所述进液腔通过一第一通道与所述腔体连通,所述出液腔通过第二通道与所述腔体连通,所述腔体通过进液腔和出液腔与微流控超声电化学片上实验室分析平台外相通。In the above technical solution, a liquid inlet cavity and a liquid outlet cavity are formed in the microfluidic assembly, the liquid inlet cavity is communicated with the cavity through a first channel, and the liquid outlet cavity is connected to the cavity through a second channel. The cavity is communicated with the outside of the microfluidic ultrasonic electrochemical on-chip laboratory analysis platform through a liquid inlet cavity and a liquid outlet cavity.

在上述技术方案中,所述通孔的高度为10μm~10mm,所述通孔的宽度为1mm~10mm。In the above technical solution, the height of the through hole is 10 μm˜10 mm, and the width of the through hole is 1 mm˜10 mm.

在上述技术方案中,所述进液腔、出液腔、腔体、第一通道和第二通道共同形成微流道,所述第一通道和第二通道的宽度分别为10μm~1mm,第一通道和第二通道的长度分别为2mm-2cm,进液腔和出液腔位于腔体的两侧或同一侧。In the above technical solution, the liquid inlet cavity, the liquid outlet cavity, the cavity, the first channel and the second channel together form a micro-flow channel, and the width of the first channel and the second channel are respectively 10 μm to 1 mm. The lengths of the first channel and the second channel are respectively 2mm-2cm, and the liquid inlet cavity and the liquid outlet cavity are located on two sides or the same side of the cavity.

在上述技术方案中,进液腔和出液腔的结构一致,第一通道和第二通道的结构一致,进液腔和第一通道的长度和为2.5mm~2.5cm。In the above technical solution, the liquid inlet cavity and the liquid outlet cavity have the same structure, the first channel and the second channel have the same structure, and the sum of the lengths of the liquid inlet cavity and the first channel is 2.5mm-2.5cm.

在上述技术方案中,所述电化学传感器芯片的长度为1.5cm~5cm。In the above technical solution, the length of the electrochemical sensor chip is 1.5 cm-5 cm.

在上述技术方案中,所述微流道组件为聚二甲基硅氧烷PDMS、聚甲基丙烯酸甲酯PMMA或纸。In the above technical solution, the microfluidic component is polydimethylsiloxane PDMS, polymethylmethacrylate PMMA or paper.

在上述技术方案中,所述微型超声器件的长度为100um~10mm,所述微型超声器件的振动区域的长度为10μm~10mm。In the above technical solution, the length of the micro ultrasonic device is 100um~10mm, and the length of the vibration region of the micro ultrasonic device is 10μm~10mm.

在上述技术方案中,还包括:与所述微流道组件平行的电化学传感器区域限定组件,所述电化学传感器区域限定组件上形成有一第一开口,所述电化学传感器芯片与所述微型超声器件为平行设置或非平行设置,其中,当为平行设置时,所述待测液体能够穿过所述第一开口与所述三电极的传感区域接触;当为非平行设置时,所述电化学传感器芯片穿过所述第一开口与所述待测液体接触。In the above technical solution, it further includes: an electrochemical sensor area defining component parallel to the microfluidic component, a first opening is formed on the electrochemical sensor area defining component, the electrochemical sensor chip and the micro The ultrasonic device is arranged in parallel or in a non-parallel arrangement, wherein, when it is arranged in parallel, the liquid to be tested can pass through the first opening to contact the sensing area of the three electrodes; when it is arranged in a non-parallel arrangement, the The electrochemical sensor chip is in contact with the liquid to be measured through the first opening.

在上述技术方案中,当所述电化学传感器芯片与所述微型超声器件为非平行设置时,所述电化学传感器芯片固定在所述电化学传感器区域限定组件上且该所述电化学传感器芯片的三电极的传感区域穿过所述第一开口并能够与所述待测液体接触。In the above technical solution, when the electrochemical sensor chip and the micro ultrasonic device are arranged non-parallel, the electrochemical sensor chip is fixed on the electrochemical sensor area defining component and the electrochemical sensor chip is The sensing area of the three electrodes passes through the first opening and can be in contact with the liquid to be tested.

在上述技术方案中,当所述电化学传感器芯片与所述微型超声器件为非平行设置时,所述第一开口为一细缝;当所述电化学传感器芯片与所述微型超声器件为平行设置时,所述第一开口的尺寸大于等于所述三电极的传感区域的尺寸且小于等于所述通孔的横截面的尺寸。In the above technical solution, when the electrochemical sensor chip and the micro ultrasonic device are arranged non-parallel, the first opening is a slit; when the electrochemical sensor chip and the micro ultrasonic device are parallel When set, the size of the first opening is greater than or equal to the size of the sensing area of the three electrodes and less than or equal to the size of the cross section of the through hole.

在上述技术方案中,还包括:位于所述电化学传感器芯片上方的顶盖,所述顶盖上形成有用于向所述进液腔内输入待测液体的第一通孔和排出出液腔内待测液体的第二通孔,当所述电化学传感器芯片与所述微型超声器件为非平行设置时,所述顶盖上还形成有一第三开口,用于穿过所述电化学传感器芯片。In the above technical solution, it further includes: a top cover located above the electrochemical sensor chip, the top cover is formed with a first through hole for inputting the liquid to be tested into the liquid inlet chamber and a discharge liquid chamber The second through hole of the liquid to be measured inside, when the electrochemical sensor chip and the micro ultrasonic device are arranged non-parallel, a third opening is also formed on the top cover for passing through the electrochemical sensor chip.

在上述技术方案中,当所述电化学传感器芯片与所述微型超声器件为平行设置时,所述电化学传感器芯片和/或电化学传感器区域限定组件与所述第一通孔和第二通孔相对的位置形成有孔;当所述电化学传感器芯片与所述微型超声器件为非平行设置时,所述电化学传感器区域限定组件与所述第一通孔和第二通孔相对的位置形成有孔,以使所述第一通孔能够通入所述进液腔且所述第二通孔能够通入所述出液腔。In the above technical solution, when the electrochemical sensor chip and the micro ultrasonic device are arranged in parallel, the electrochemical sensor chip and/or the electrochemical sensor area defining component and the first through hole and the second through hole A hole is formed at the opposite position of the hole; when the electrochemical sensor chip and the micro ultrasonic device are not arranged in parallel, the position of the electrochemical sensor area defining component is opposite to the first through hole and the second through hole A hole is formed so that the first through hole can pass into the liquid inlet cavity and the second through hole can pass into the liquid outlet cavity.

在上述技术方案中,还包括:设置在所述微流道组件和支撑衬底之间的微流道下底板,所述微流道下底板上形成有一第二开口,所述待测液体能够通过所述第二开口与微型超声器件的振动区域接触,所述进液腔、第一通道、出液腔和第二通道的底面为敞口并被所述微流道下底板的顶面密封。In the above technical solution, it further includes: a micro-channel lower bottom plate disposed between the micro-channel component and the supporting substrate, a second opening is formed on the micro-channel lower bottom plate, and the liquid to be tested can be The second opening is in contact with the vibration area of the micro ultrasonic device, and the bottom surfaces of the liquid inlet cavity, the first channel, the liquid outlet cavity and the second channel are open and sealed by the top surface of the lower bottom plate of the micro flow channel .

在上述技术方案中,还包括:位于所述支撑衬底下方的底盖。In the above technical solution, it further includes: a bottom cover located under the supporting substrate.

在上述技术方案中,所述进液腔和出液腔位于所述腔体的两侧或同一侧。In the above technical solution, the liquid inlet cavity and the liquid outlet cavity are located on two sides or the same side of the cavity.

在上述技术方案中,所述支撑衬底的厚度为0.1mm~2mm。In the above technical solution, the thickness of the supporting substrate is 0.1 mm˜2 mm.

在上述技术方案中,所述微流道下底板的厚度为0.0125mm~1mm。In the above technical solution, the thickness of the lower bottom plate of the micro-channel is 0.0125 mm to 1 mm.

在上述技术方案中,所述电化学传感器区域限定组件的厚度为0.0125mm~1mm。In the above technical solution, the thickness of the electrochemical sensor area defining component is 0.0125 mm˜1 mm.

在上述技术方案中,所述微流控超声电化学片上实验室分析平台通过螺栓方式实现紧固、胶粘合或通过磁力吸合。In the above technical solution, the microfluidic ultrasonic electrochemical on-chip laboratory analysis platform is fastened, glued or magnetically attracted by means of bolts.

在上述技术方案中,所述电化学传感器区域限定组件的下表面具有粘接性。In the above technical solution, the lower surface of the electrochemical sensor area defining component has adhesiveness.

在上述技术方案中,所述微流道下底板的上表面具有粘接性。In the above technical solution, the upper surface of the lower bottom plate of the microfluidic channel has adhesiveness.

在上述技术方案中,所述电化学传感器区域限定组件的上表面具有粘接性。In the above technical solution, the upper surface of the electrochemical sensor area defining component has adhesiveness.

在上述技术方案中,所述微流道下底板的下表面具有粘接性。In the above technical solution, the lower surface of the lower bottom plate of the microfluidic channel has adhesiveness.

在上述技术方案中,所述电化学传感器区域限定组件的材质为聚二甲基硅氧烷PDMS、聚甲基丙烯酸甲酯PMMA或聚对苯二甲酸乙二醇酯PET。In the above technical solution, the material of the electrochemical sensor area defining component is polydimethylsiloxane PDMS, polymethyl methacrylate PMMA or polyethylene terephthalate PET.

在上述技术方案中,所述电化学传感器区域限定组件的长度为1cm~10cm。In the above technical solution, the length of the electrochemical sensor area defining component is 1 cm˜10 cm.

在上述技术方案中,所述第二开口的尺寸大于等于所述微型超声器件的振动区域的尺寸且小于等于所述通孔的横截面的尺寸。In the above technical solution, the size of the second opening is greater than or equal to the size of the vibration region of the micro ultrasonic device and less than or equal to the size of the cross section of the through hole.

本发明的有益效果如下:The beneficial effects of the present invention are as follows:

1.本发明实现了微型超声器件与电化学传感器芯片组合使用,有效提高了电化学传感灵敏度。1. The present invention realizes the combined use of a micro ultrasonic device and an electrochemical sensor chip, and effectively improves the sensitivity of electrochemical sensing.

2.本发明的液体出入口是在微流道组件的竖直方向开口,不会影响厚度大小的设计,可用于厚度小的微流控片上实验室的设计。2. The liquid inlet and outlet of the present invention are opened in the vertical direction of the microfluidic component, which will not affect the thickness design, and can be used for the design of the microfluidic on-chip laboratory with small thickness.

3.本发明不但可以采用螺栓紧固、橡胶垫圈密封,而且还可以使电化学传感器区域限定组件和微流道下底板具有粘接性,使组件间紧固性更好,密封性更好,厚度控制更精确,适合应用于微流控片上实验室分析。3. The present invention can not only use bolts to fasten and seal with rubber gaskets, but also can make the electrochemical sensor area limiting component and the bottom plate of the micro-channel have adhesiveness, so that the tightness and sealing between components are better. Thickness control is more precise and suitable for laboratory analysis on microfluidic chips.

4.本发明由多个独立组件共同组成,可根据检测需求,灵活改变每个组件的特性,包括组件形状,器件类型,材料属性等。4. The present invention is composed of multiple independent components, and the characteristics of each component, including component shape, device type, material properties, etc., can be flexibly changed according to detection requirements.

附图说明Description of drawings

图1为典型微流控电化学片上实验室平台的结构示意图;Figure 1 is a schematic structural diagram of a typical microfluidic electrochemical on-chip laboratory platform;

图2为声表面波器件与电化学传感器芯片集成结构示意图,其中,(A)为结构示意图,(B)为结构示意图,(C)为实物图,(D)为实物图;Figure 2 is a schematic diagram of the integrated structure of a surface acoustic wave device and an electrochemical sensor chip, wherein (A) is a schematic diagram of the structure, (B) is a schematic diagram of the structure, (C) is a physical diagram, and (D) is a physical diagram;

图3为固态装配型声波谐振器型超声器件与电化学传感器芯片的集成结构示意图;3 is a schematic diagram of the integrated structure of a solid-state assembled acoustic resonator-type ultrasonic device and an electrochemical sensor chip;

图4为本发明微流控超声电化学片上实验室分析平台的结构示意图(电化学传感器芯片与微型超声器件为平行设置);4 is a schematic structural diagram of the microfluidic ultrasonic electrochemical on-chip laboratory analysis platform of the present invention (the electrochemical sensor chip and the micro ultrasonic device are arranged in parallel);

图5为本发明微流道的结构示意图;Fig. 5 is the structural schematic diagram of the microfluidic channel of the present invention;

图6为微型超声器件的结构示意图,其中,a为微型超声器件的断面结构示意图,b为微型超声器件的振动区域形状,c为微型超声器件的俯视图;6 is a schematic structural diagram of a micro ultrasonic device, wherein a is a schematic cross-sectional structure of the micro ultrasonic device, b is the shape of the vibration region of the micro ultrasonic device, and c is a top view of the micro ultrasonic device;

图7为电化学传感器芯片的结构示意图,其中,a为电化学传感器芯片的传感区域构型,b为电化学传感器芯片的传感区域构型,c为电化学传感器芯片的传感区域构型,d为电化学传感器芯片的整体结构;7 is a schematic structural diagram of an electrochemical sensor chip, wherein a is the sensing area configuration of the electrochemical sensor chip, b is the sensing area configuration of the electrochemical sensor chip, and c is the sensing area configuration of the electrochemical sensor chip type, d is the overall structure of the electrochemical sensor chip;

图8为电化学传感器区域限定组件的结构示意图,其中,a为电化学传感器区域限定组件的俯视图,b为第一开口的形状,c为第一开口投影到电化学传感器芯片的示意图;8 is a schematic structural diagram of the electrochemical sensor area defining assembly, wherein a is a top view of the electrochemical sensor area defining assembly, b is the shape of the first opening, and c is a schematic diagram of the projection of the first opening onto the electrochemical sensor chip;

图9为本发明微流道及腔体的结构示意图,其中,a为微流道,b为微流道,c为微流道,d为微流道,e为腔体的横截面形状;9 is a schematic structural diagram of a micro-channel and a cavity of the present invention, wherein a is a micro-channel, b is a micro-channel, c is a micro-channel, d is a micro-channel, and e is the cross-sectional shape of the cavity;

图10为采用本发明的循环伏安曲线;10 is a cyclic voltammetry curve using the present invention;

图11为循环伏安曲线;Figure 11 is a cyclic voltammetry curve;

图12为循环伏安曲线;Figure 12 is a cyclic voltammetry curve;

图13为方波阳极溶出伏安曲线;Figure 13 is a square wave anode stripping voltammetry curve;

图14为本发明微流控超声电化学片上实验室分析平台的结构示意图(电化学传感器芯片与微型超声器件为非平行设置)。FIG. 14 is a schematic structural diagram of the microfluidic ultrasonic electrochemical on-chip laboratory analysis platform of the present invention (the electrochemical sensor chip and the micro ultrasonic device are arranged non-parallel).

其中,in,

1:底盖,2:支撑衬底,2-1:微型超声器件,3:微流道下底板,3-1:第二开口,4:微流道组件,4-1:进液腔,4-2:出液腔,4-3:腔体,4-4:第一通道,4-5:第二通道,5:电化学传感器区域限定组件,5-1:第一开口,6:电化学传感器芯片,7:顶盖,7-1:第一通孔,7-2:第二通孔,7-3:第三开口。1: Bottom cover, 2: Support substrate, 2-1: Micro ultrasonic device, 3: Bottom bottom plate of microchannel, 3-1: Second opening, 4: Microchannel assembly, 4-1: Liquid inlet chamber, 4-2: Liquid outlet chamber, 4-3: Chamber, 4-4: First channel, 4-5: Second channel, 5: Electrochemical sensor area defining assembly, 5-1: First opening, 6: Electrochemical sensor chip, 7: top cover, 7-1: first through hole, 7-2: second through hole, 7-3: third opening.

具体实施方式Detailed ways

下面结合具体实施例进一步说明本发明的微流控超声电化学片上实验室分析平台。The microfluidic ultrasonic electrochemical on-chip laboratory analysis platform of the present invention is further described below with reference to specific embodiments.

微型超声器件2-1的超声声流搅拌作用与电化学传感器芯片6结合能有效提高电化学检测灵敏度,传统的超声电化学分析平台难以做到微型化。本发明的微流控超声电化学片上实验室平台实现了超声电化学与小型的微流控检测平台结合起来,可广泛用于微量试剂的高灵敏度检测。The combination of the ultrasonic acoustic flow stirring effect of the micro ultrasonic device 2-1 and the electrochemical sensor chip 6 can effectively improve the electrochemical detection sensitivity, and it is difficult to miniaturize the traditional ultrasonic electrochemical analysis platform. The microfluidic ultrasonic electrochemical on-chip laboratory platform of the invention realizes the combination of ultrasonic electrochemistry and a small microfluidic detection platform, and can be widely used for high-sensitivity detection of trace reagents.

实施例1Example 1

如图4和14所示,一种微流控超声电化学片上实验室分析平台,包括:电化学传感器芯片6以及平行设置的微流道组件4和支撑衬底2,电化学传感器芯片6、微流道组件4和支撑衬底2从上至下依次设置,其中,支撑衬底2的顶面设置有一微型超声器件2-1,微流道组件4上形成有通孔,通孔的高度为10μm~10mm,通孔的宽度为1mm~10mm。通孔的孔壁围成一顶端和底端均敞口的腔体4-3(即上下通透),腔体4-3用于超声电化学检测,腔体4-3与微流控超声电化学片上实验室分析平台外相通,以使能够向该腔体4-3排入和排出待测液体,腔体4-3内的待测液体能够与电化学传感器芯片6的三电极和微型超声器件2-1的振动区域接触。微型超声器件2-1产生的超声波在腔体4-3内的待测液体中传播和衰减,引起待测液体剧烈对流运动,增强物质向电化学传感器芯片6的三电极表面的质量传递效率,提高电化学传感器的检测灵敏度。As shown in Figures 4 and 14, a microfluidic ultrasonic electrochemical on-chip laboratory analysis platform includes: an electrochemical sensor chip 6, a parallel microfluidic channel assembly 4 and a supporting substrate 2, an electrochemical sensor chip 6, The microchannel assembly 4 and the support substrate 2 are arranged in sequence from top to bottom, wherein a micro ultrasonic device 2-1 is arranged on the top surface of the support substrate 2, and a through hole is formed on the microchannel assembly 4, and the height of the through hole is is 10 μm to 10 mm, and the width of the through hole is 1 mm to 10 mm. The hole wall of the through hole surrounds a cavity 4-3 with open top and bottom ends (that is, the upper and lower ends are transparent), the cavity 4-3 is used for ultrasonic electrochemical detection, and the cavity 4-3 is connected to the microfluidic ultrasonic The electrochemical laboratory-on-a-chip analysis platform communicates with the outside, so that the liquid to be tested can be discharged into and discharged from the cavity 4-3, and the liquid to be tested in the cavity 4-3 can be connected with the three electrodes and the micro-electrode of the electrochemical sensor chip 6. The vibration area of the ultrasonic device 2-1 is in contact. The ultrasonic wave generated by the micro ultrasonic device 2-1 propagates and attenuates in the liquid to be measured in the cavity 4-3, causing violent convective movement of the liquid to be measured, enhancing the mass transfer efficiency of the substance to the surface of the three electrodes of the electrochemical sensor chip 6, Improve the detection sensitivity of electrochemical sensors.

微流道组件4为聚二甲基硅氧烷PDMS、聚甲基丙烯酸甲酯PMMA或纸等。The microfluidic channel component 4 is polydimethylsiloxane PDMS, polymethyl methacrylate PMMA or paper or the like.

如图7d所示,电化学传感器芯片6是工作电极、对比电极和参比电极(即三电极)集成到一个衬底上,可以采用已商业化的电化学传感器芯片,也可以根据需要自行设计构建,三电极的形状和布局依据电化学传感器芯片的通用规则,可以但不限于图7所示结构,工作电极、对比电极的材料包括碳、金、铂金属等,参比电极可以与工作电极、对比电极同材质,也可以是银/氯化银Ag/AgCl等经典参比电极,电化学传感器芯片的衬底可以是PET、PI等柔性材料,也可以是玻璃等硬质材料。电化学传感器芯片6的长度为1.5cm~5cm,以横纵向计,电化学传感器芯片6的工作电极、对比电极、参比电极的三电极的总体工作区域单向长度介于10μm与10mm之间。As shown in Figure 7d, the electrochemical sensor chip 6 is a working electrode, a contrast electrode and a reference electrode (ie three electrodes) integrated on one substrate, which can be a commercialized electrochemical sensor chip, or can be designed according to needs. Construction, the shape and layout of the three electrodes are based on the general rules of electrochemical sensor chips, which can be but not limited to the structure shown in Figure 7. The materials of the working electrode and the reference electrode include carbon, gold, platinum metal, etc. The reference electrode can be combined with the working electrode. The material of the reference electrode is the same, and it can also be a classic reference electrode such as silver/silver chloride Ag/AgCl. The substrate of the electrochemical sensor chip can be a flexible material such as PET and PI, or a hard material such as glass. The length of the electrochemical sensor chip 6 is 1.5 cm to 5 cm. In terms of the horizontal and vertical directions, the overall working area of the three electrodes of the electrochemical sensor chip 6, the working electrode, the contrast electrode and the reference electrode, has a one-way length between 10 μm and 10 mm. .

微型超声器件2-1是通过MEMS工艺制造而成,可以是薄膜体声波谐振器FBAR、固态装配型谐振器smr、微机械压电超声换能器pMUT等。如图6a、c所示,主体呈电极/压电层/电极的三明治结构,微型超声器件2-1设置于支撑衬底上,支撑衬底2的厚度为0.1mm~2mm,支撑衬底可以是硬质或者柔性衬底,例如支撑衬底可以为硅衬底、聚酰亚胺薄膜衬底等。基于逆压电效应,当对微型超声器件施加交变信号时,压电层产生机械振动,发射出超声波。压电层的材料可以是氮化铝、氧化锌、压电陶瓷PZT、铌酸锂、石英晶体、有机柔性材料聚偏氟乙烯PVDF等。The micro ultrasonic device 2-1 is manufactured by a MEMS process, and may be a thin-film bulk acoustic resonator FBAR, a solid-state assembled resonator smr, a micromachined piezoelectric ultrasonic transducer pMUT, and the like. As shown in Figures 6a and 6a, the main body is in a sandwich structure of electrode/piezoelectric layer/electrode, and the micro ultrasonic device 2-1 is arranged on a supporting substrate. The thickness of the supporting substrate 2 is 0.1 mm to 2 mm. It is a rigid or flexible substrate, for example, the supporting substrate can be a silicon substrate, a polyimide film substrate, or the like. Based on the inverse piezoelectric effect, when an alternating signal is applied to the micro ultrasonic device, the piezoelectric layer generates mechanical vibration and emits ultrasonic waves. The material of the piezoelectric layer can be aluminum nitride, zinc oxide, piezoelectric ceramic PZT, lithium niobate, quartz crystal, organic flexible material polyvinylidene fluoride PVDF, and the like.

如图6b所示,微型超声器件2-1的振动区域可以呈圆形、椭圆形、四边形、五边形、六边形等多种形状,振动区域可以是一个振源,也可以是多个振源的阵列,含有多个振源的微型超声器件2-1的振动区域包含不同振源之间的间隔区域,微型超声器件2-1的振动区域的长度为10μm~10mm。微型超声器件通常呈长方形或正方形,包含信号连接线和支撑衬垫在内,微型超声器件2-1的长度为100um~10mm,信号连接线可以很长,将信号引出微流道以外,方便与外接电路相连。As shown in Fig. 6b, the vibration area of the micro ultrasonic device 2-1 can be in various shapes such as circle, ellipse, quadrilateral, pentagon, hexagon, etc. The vibration area can be one vibration source or multiple In the array of vibration sources, the vibration area of the micro ultrasonic device 2-1 containing multiple vibration sources includes spaced areas between different vibration sources, and the length of the vibration area of the micro ultrasonic device 2-1 is 10 μm˜10 mm. The micro ultrasonic device is usually rectangular or square, including the signal connection line and the support pad. The length of the micro ultrasonic device 2-1 is 100um ~ 10mm, and the signal connection line can be very long. connected to an external circuit.

实施例2Example 2

在实施例1的基础上,如图5所示,微流道组件4内形成有进液腔4-1和出液腔4-2,进液腔4-1通过一第一通道4-4与腔体4-3连通,出液腔4-2通过一第二通道4-5与腔体4-3连通,腔体4-3通过进液腔4-1和出液腔4-2与微流控超声电化学片上实验室分析平台外相通。On the basis of Example 1, as shown in FIG. 5 , a liquid inlet chamber 4-1 and a liquid outlet chamber 4-2 are formed in the microfluidic channel assembly 4, and the liquid inlet chamber 4-1 passes through a first channel 4-4 It communicates with the cavity 4-3, the liquid outlet cavity 4-2 communicates with the cavity 4-3 through a second channel 4-5, and the cavity 4-3 communicates with the cavity 4-3 through the liquid inlet cavity 4-1 and the liquid outlet cavity 4-2. The microfluidic ultrasonic electrochemical on-chip laboratory analysis platform communicates with the outside.

进液腔4-1、出液腔4-2、腔体4-3、第一通道4-4和第二通道4-5共同形成微流道,第一通道4-4和第二通道4-5的宽度分别为10μm~1mm,第一通道4-4和第二通道4-5的长度分别为2mm-2cm,进液腔4-1和出液腔4-2位于腔体4-3的两侧(如图9a、c和d所示)或同一侧(如图9b所示)。进液腔4-1和出液腔4-2的结构一致,第一通道4-4和第二通道4-5的结构一致,进液腔4-1和第一通道4-4的长度和为2.5mm~2.5cm。The liquid inlet cavity 4-1, the liquid outlet cavity 4-2, the cavity 4-3, the first channel 4-4 and the second channel 4-5 together form a micro-channel, the first channel 4-4 and the second channel 4 The width of -5 is 10μm~1mm respectively, the length of the first channel 4-4 and the second channel 4-5 are 2mm-2cm respectively, the liquid inlet chamber 4-1 and the liquid outlet chamber 4-2 are located in the chamber 4-3 on both sides (as shown in Figures 9a, c and d) or on the same side (as shown in Figure 9b). The structures of the liquid inlet chamber 4-1 and the liquid outlet chamber 4-2 are the same, the structures of the first channel 4-4 and the second channel 4-5 are the same, and the lengths of the liquid inlet chamber 4-1 and the first channel 4-4 are the same as 2.5mm~2.5cm.

通孔的横截面可以为圆形、方形、椭圆形或异形等,如图9e所示,如图9e中最后一个图所示,如果第一通道4-4和第二通道4-5与腔体4-3之间存在凸出结构时,可以将该凸出结构设置成弧面。The cross-section of the through hole can be circular, square, oval or special-shaped, etc., as shown in Figure 9e, as shown in the last figure in Figure 9e, if the first channel 4-4 and the second channel 4-5 are connected with the cavity When there is a protruding structure between the bodies 4-3, the protruding structure can be set as an arc surface.

实施例3Example 3

在实施例2的基础上,还包括:与微流道组件4平行的电化学传感器区域限定组件5,电化学传感器区域限定组件5上形成有一第一开口5-1,第一开口5-1与三电极的传感区域相对设置,电化学传感器芯片6与微型超声器件2-1为平行设置或非平行设置,其中:On the basis of Embodiment 2, the method further includes: an electrochemical sensor area defining component 5 parallel to the microfluidic component 4 , a first opening 5-1 is formed on the electrochemical sensor area defining component 5, and the first opening 5-1 Opposite to the sensing area of the three electrodes, the electrochemical sensor chip 6 and the micro ultrasonic device 2-1 are arranged in parallel or non-parallel, wherein:

当为平行设置时,电化学传感器区域限定组件5可以确定裸露在腔体4-3中的三电极的传感区域的面积,待测液体能够穿过第一开口5-1与三电极的传感区域接触,第一开口5-1的尺寸大于等于三电极的传感区域的尺寸且小于等于通孔的横截面的尺寸,如图8所示,第一开口5-1的形状可以为圆形、五边形或六边形等。When arranged in parallel, the electrochemical sensor area defining component 5 can determine the area of the sensing area of the three electrodes exposed in the cavity 4-3, and the liquid to be tested can pass through the first opening 5-1 and the transmission of the three electrodes. The sensing area is in contact, and the size of the first opening 5-1 is greater than or equal to the size of the sensing area of the three electrodes and less than or equal to the size of the cross section of the through hole. As shown in FIG. 8 , the shape of the first opening 5-1 can be a circle shape, pentagon or hexagon, etc.

当为非平行设置时,如图14所示,第一开口5-1为一细缝,电化学传感器芯片6穿过第一开口5-1与待测液体接触,该电化学传感器芯片6穿过第一开口5-1并能够与待测液体接触的部分为三电极的传感区域,电化学传感器芯片6固定在电化学传感器区域限定组件5上。When the non-parallel arrangement is used, as shown in FIG. 14 , the first opening 5-1 is a slit, and the electrochemical sensor chip 6 passes through the first opening 5-1 to contact the liquid to be measured, and the electrochemical sensor chip 6 passes through the first opening 5-1. The part that passes through the first opening 5 - 1 and can be in contact with the liquid to be tested is a sensing area with three electrodes, and the electrochemical sensor chip 6 is fixed on the electrochemical sensor area defining component 5 .

电化学传感器区域限定组件5的材质为聚二甲基硅氧烷PDMS、聚甲基丙烯酸甲酯PMMA或聚对苯二甲酸乙二醇酯PET,厚度越薄越好,作为优选,电化学传感器区域限定组件5的厚度为0.0125mm~1mm,电化学传感器区域限定组件5的长度为1cm~10cm。The material of the electrochemical sensor area limiting component 5 is polydimethylsiloxane PDMS, polymethyl methacrylate PMMA or polyethylene terephthalate PET, and the thinner the thickness, the better. The thickness of the area defining component 5 is 0.0125 mm˜1 mm, and the length of the electrochemical sensor area defining component 5 is 1 cm˜10 cm.

三电极的传感区域的结构可以为结构1、结构2或结构3,结构1如图7a所示,其形状为3个间隔设置且相互平行的矩形结构;结构2如图7b所示,包括一个矩形结构以及长条形矩形结构和折形结构,折形结构为一矩形结构弯折90°后形成的结构,长条形矩形结构和折形结构间隔设置且围成一个一边敞口的长方形,矩形结构位于该长方形内且与长条形矩形结构和折形结构间隔设置;结构3如图7c所示,包括相互间隔设置的圆形结构、矩形结构和弧形结构,矩形结构和弧形结构围在圆形结构外。The structure of the three-electrode sensing area can be structure 1, structure 2 or structure 3. Structure 1 is shown in Figure 7a, and its shape is three rectangular structures arranged at intervals and parallel to each other; Structure 2 is shown in Figure 7b, including A rectangular structure, a long rectangular structure and a folded structure, the folded structure is a structure formed after a rectangular structure is bent by 90°, and the long rectangular structure and the folded structure are arranged at intervals and enclose a rectangle with one side open. , the rectangular structure is located in the rectangle and is spaced from the elongated rectangular structure and the folded structure; structure 3, as shown in Figure 7c, includes a circular structure, a rectangular structure and an arc-shaped structure that are spaced apart from each other, and the rectangular structure and the arc-shaped structure are The structure surrounds the circular structure.

实施例4Example 4

在实施例3的基础上,还包括:位于电化学传感器芯片6上方的顶盖7和位于支撑衬底2下方的底盖1,顶盖7上形成有用于向进液腔4-1内输入待测液体的第一通孔7-1和排出出液腔4-2内待测液体的第二通孔7-2,当电化学传感器芯片6与微型超声器件2-1为非平行设置时,顶盖7上还形成有一第三开口7-3,用于穿过电化学传感器芯片6,如图14所示。On the basis of Embodiment 3, it also includes: a top cover 7 located above the electrochemical sensor chip 6 and a bottom cover 1 located below the support substrate 2, and the top cover 7 is formed with an input for feeding into the liquid inlet chamber 4-1. The first through hole 7-1 of the liquid to be measured and the second through hole 7-2 of the liquid to be measured in the discharge chamber 4-2, when the electrochemical sensor chip 6 and the micro ultrasonic device 2-1 are arranged non-parallel , a third opening 7-3 is also formed on the top cover 7 for passing through the electrochemical sensor chip 6, as shown in FIG. 14 .

电化学传感器芯片6与微型超声器件2-1为平行设置时,电化学传感器芯片6和/或电化学传感器区域限定组件5与第一通孔7-1和第二通孔7-2相对的位置形成有孔,以使第一通孔7-1能够通入进液腔4-1且第二通孔7-2能够通入出液腔4-2。When the electrochemical sensor chip 6 and the micro ultrasonic device 2-1 are arranged in parallel, the electrochemical sensor chip 6 and/or the electrochemical sensor area defining component 5 are opposite to the first through hole 7-1 and the second through hole 7-2. Holes are formed at positions so that the first through hole 7-1 can pass into the liquid inlet chamber 4-1 and the second through hole 7-2 can pass into the liquid outlet chamber 4-2.

电化学传感器芯片6与微型超声器件2-1为非平行设置时,电化学传感器区域限定组件5与第一通孔7-1和第二通孔7-2相对的位置形成有孔,以使第一通孔7-1能够通入进液腔4-1且第二通孔7-2能够通入出液腔4-2。When the electrochemical sensor chip 6 and the micro ultrasonic device 2-1 are not arranged in parallel, holes are formed in the position of the electrochemical sensor region defining component 5 opposite to the first through hole 7-1 and the second through hole 7-2, so that the The first through hole 7-1 can pass into the liquid inlet cavity 4-1 and the second through hole 7-2 can pass into the liquid outlet cavity 4-2.

顶盖和底盖能够进一步将微流控超声电化学片上实验室分析平台的紧固,从选材上来说,顶盖和底盖可以采用胶带、聚二甲基硅氧烷PDMS、聚甲基丙烯酸甲酯PMMA等材料或硬质材料,从顶盖和底盖对微流控超声电化学片上实验室分析平台的紧固方式上来说,顶盖和底盖的紧固可以采用螺栓固定、磁性吸合和胶粘合等方式。The top cover and bottom cover can further fasten the microfluidic ultrasonic electrochemical on-chip laboratory analysis platform. In terms of material selection, the top cover and bottom cover can be made of tape, polydimethylsiloxane PDMS, polymethacrylic acid For materials such as methyl ester PMMA or hard materials, from the perspective of the fastening method of the top cover and bottom cover to the microfluidic ultrasonic electrochemical on-chip laboratory analysis platform, the top cover and bottom cover can be fastened by bolts, magnetic suction bonding and gluing, etc.

实施例5Example 5

在实施例4的基础上,还包括:设置在微流道组件4和支撑衬底2之间的微流道下底板3,微流道下底板3的厚度为0.0125mm~1mm,微流道下底板3上形成有一第二开口3-1,待测液体能够通过第二开口3-1与微型超声器件2-1的振动区域接触,进液腔4-1、第一通道4-4、出液腔4-2和第二通道4-5的底面为敞口并被微流道下底板3的顶面密封,第二开口3-1的尺寸设计只要不影响待测液体与微型超声器件2-1的振动区域接触即可,作为优选,第二开口3-1的尺寸大于等于微型超声器件2-1的振动区域的尺寸且小于等于通孔的横截面的尺寸。On the basis of Embodiment 4, the method further includes: a micro-channel lower bottom plate 3 arranged between the micro-channel component 4 and the supporting substrate 2, the thickness of the micro-channel lower bottom plate 3 is 0.0125 mm to 1 mm, and the micro-channel lower plate 3 has a thickness of 0.0125 mm to 1 mm. A second opening 3-1 is formed on the lower bottom plate 3, and the liquid to be tested can contact the vibration area of the micro ultrasonic device 2-1 through the second opening 3-1. The liquid inlet cavity 4-1, the first channel 4-4, The bottom surfaces of the liquid outlet chamber 4-2 and the second channel 4-5 are open and sealed by the top surface of the lower bottom plate 3 of the microchannel. The size of the second opening 3-1 is designed as long as it does not affect the liquid to be tested and the micro ultrasonic device. The vibration area of 2-1 only needs to be in contact. Preferably, the size of the second opening 3-1 is greater than or equal to the size of the vibration area of the micro ultrasonic device 2-1 and less than or equal to the size of the cross section of the through hole.

电化学传感器区域限定组件5的下表面和上表面具有粘接性,微流道下底板3的下表面和上表面具有粘接性。电化学传感器区域限定组件5和微流道下底板3两面的粘接性可以实现对微流控超声电化学片上实验室分析平台的紧固,可以在实现紧固的同时实现减小微流控超声电化学片上实验室分析平台的厚度。The lower surface and the upper surface of the electrochemical sensor area defining component 5 have adhesiveness, and the lower surface and upper surface of the microchannel lower bottom plate 3 have adhesiveness. The adhesiveness between the two sides of the electrochemical sensor area defining component 5 and the lower bottom plate 3 of the microfluidic channel can realize the fastening of the microfluidic ultrasonic electrochemical on-chip laboratory analysis platform, and can realize the reduction of microfluidic control while realizing the fastening. Thickness of the sonoelectrochemical on-chip laboratory analysis platform.

将实施例5所得微流控超声电化学片上实验室分析平台进行测试,在测试时,微型超声器件2-1与功率放大器连接,功率放大器与信号发生器连接,电化学传感器芯片6连接电化学工作站。具体的,实施例5获得的微流控超声电化学片上实验室分析平台的产品如下:The microfluidic ultrasonic electrochemical on-chip laboratory analysis platform obtained in Example 5 was tested. During the test, the micro ultrasonic device 2-1 was connected to the power amplifier, the power amplifier was connected to the signal generator, and the electrochemical sensor chip 6 was connected to the electrochemical device. workstation. Specifically, the products of the microfluidic ultrasonic electrochemical on-chip laboratory analysis platform obtained in Example 5 are as follows:

产品1:Product 1:

电化学传感器芯片6与微型超声器件2-1为平行设置。顶盖7和底盖1的材料为聚甲基丙烯酸甲酯PMMA,顶盖7和底盖1的紧固方式为胶粘合。微型超声器件2-1为smr(固态装配型谐振器(solidly mounted resonator,smr))。支撑衬底为evb板(电学测试板(electrical valuation board,evb)),支撑衬底的厚度为2mm。微型超声器件2-1的振动区域为图6c所示的五边形区域,五边形边长100um。微型超声器件2-1的长度为几百微米。The electrochemical sensor chip 6 is arranged in parallel with the micro ultrasonic device 2-1. The material of the top cover 7 and the bottom cover 1 is polymethyl methacrylate PMMA, and the fastening method of the top cover 7 and the bottom cover 1 is glue bonding. The micro ultrasonic device 2-1 is an smr (solidly mounted resonator (smr)). The supporting substrate is an evb board (electrical valuation board (evb)), and the thickness of the supporting substrate is 2 mm. The vibration area of the micro ultrasonic device 2-1 is the pentagonal area shown in Fig. 6c, and the side length of the pentagon is 100um. The length of the micro ultrasonic device 2-1 is several hundreds of micrometers.

微流道下底板3上第二开口3-1的直径为5mm,微流道下底板3的厚度为0.5mm。The diameter of the second opening 3-1 on the lower bottom plate 3 of the microchannel is 5 mm, and the thickness of the lower bottom plate 3 of the microchannel is 0.5 mm.

微流道组件4的选材为聚甲基丙烯酸甲酯PMMA,厚度为3mm。微流道形状采用图9d,进液腔4-1和出液腔4-2位于腔体4-3的两侧,第一通道4-4和第二通道4-5位于同一直线上,并通过腔体中心。通孔的横截面为直径5mm的圆形,高度为3mm。第一通道4-4和第二通道4-5的宽度为0.8mm。第一通道4-4和第二通道4-5的长度为1cm。进液腔4-1和第一通道4-4的长度和为1.2cm。The material of the micro-channel component 4 is polymethyl methacrylate PMMA, and the thickness is 3 mm. The shape of the microchannel adopts Fig. 9d, the liquid inlet chamber 4-1 and the liquid outlet chamber 4-2 are located on both sides of the chamber 4-3, the first channel 4-4 and the second channel 4-5 are located on the same straight line, and through the center of the cavity. The cross section of the through hole is a circle with a diameter of 5mm and a height of 3mm. The width of the first channel 4-4 and the second channel 4-5 is 0.8 mm. The length of the first channel 4-4 and the second channel 4-5 is 1 cm. The sum of the lengths of the liquid inlet chamber 4-1 and the first channel 4-4 is 1.2 cm.

电化学传感器区域限定组件5的第一开口5-1的形状为图8b所示圆形。电化学传感器区域限定组件5的选材为聚对苯二甲酸乙二醇酯PET,其厚度为0.5mm,电化学传感器区域限定组件5的长度为3cm。第一开口5-1的直径3mm。The shape of the first opening 5-1 of the electrochemical sensor area defining assembly 5 is a circle as shown in FIG. 8b. The material of the electrochemical sensor area defining component 5 is polyethylene terephthalate PET, the thickness of which is 0.5 mm, and the length of the electrochemical sensor area defining component 5 is 3 cm. The diameter of the first opening 5-1 is 3 mm.

电化学传感器芯片的长度为2.5cm,电化学传感器芯片6的传感区域的结构为图7c所示的结构,工作电极为圆形结构。电化学传感器芯片6的工作电极为Au电极、对比电极为Pt电极、参比电极为Ag/AgCl电极,工作电极的直径1.2mm。电化学传感器芯片的衬底为聚对苯二甲酸乙二醇酯PET。电化学传感器芯片6的工作电极、对比电极、参比电极的三电极的总体工作区域的尺寸约为6mm2,总体工作区域单向长度为3mm。The length of the electrochemical sensor chip is 2.5 cm, the structure of the sensing area of the electrochemical sensor chip 6 is the structure shown in FIG. 7c, and the working electrode is a circular structure. The working electrode of the electrochemical sensor chip 6 is an Au electrode, the reference electrode is a Pt electrode, and the reference electrode is an Ag/AgCl electrode, and the diameter of the working electrode is 1.2 mm. The substrate of the electrochemical sensor chip is polyethylene terephthalate PET. The size of the overall working area of the working electrode, the reference electrode and the reference electrode of the electrochemical sensor chip 6 is about 6 mm 2 , and the unidirectional length of the overall working area is 3 mm.

信号发生器和功率放大器不向上述产品中的微型超声器件添加任何信号。待测液体为1mM的二茂铁甲醇溶液,电化学工作站测得该待测液体的循环伏安曲线。The signal generator and power amplifier do not add any signal to the miniature ultrasonic devices in the above products. The liquid to be tested is a 1mM ferrocene methanol solution, and the cyclic voltammetry curve of the liquid to be tested is measured by the electrochemical workstation.

产品2:Product 2:

与产品1相同,不同之处仅在于测试环境:信号发生器向微型超声器件smr施加2.56GHz的工作频率,功率放大器件向微型超声器件smr施加0.7W功率。The same as product 1, the difference is only in the test environment: the signal generator applies a working frequency of 2.56 GHz to the micro ultrasonic device smr, and the power amplifier device applies 0.7W of power to the micro ultrasonic device smr.

产品3:Product 3:

与产品1相同,不同之处仅在于测试环境:信号发生器和功率放大器件向本产品的微型超声器件smr施加2.56GHz的工作频率,1W功率。The same as product 1, the difference is only in the test environment: the signal generator and the power amplifier apply 2.56GHz operating frequency and 1W power to the miniature ultrasonic device smr of this product.

产品4:Product 4:

与产品1基本相同,产品4的不同之处仅在于:微流道组件4的厚度为1mm(通孔的高度为1mm)。信号发生器和功率放大器件向上述产品的微型超声器件smr施加2.56GHz的工作频率,1W功率。It is basically the same as product 1, and the difference of product 4 is only that: the thickness of the microfluidic channel component 4 is 1 mm (the height of the through hole is 1 mm). The signal generator and the power amplifier device apply an operating frequency of 2.56GHz and a power of 1W to the miniature ultrasonic device smr of the above product.

产品5:Product 5:

与产品1基本相同,产品5的不同之处仅在于:微流道组件4的厚度为5mm(通孔的高度为5mm)。信号发生器和功率放大器件向上述产品的微型超声器件smr施加2.56GHz的工作频率,1W功率。It is basically the same as Product 1, and the difference of Product 5 is only that the thickness of the microfluidic channel component 4 is 5 mm (the height of the through hole is 5 mm). The signal generator and the power amplifier device apply an operating frequency of 2.56GHz and a power of 1W to the miniature ultrasonic device smr of the above product.

产品6:Product 6:

与产品1基本相同,产品6的不同之处仅在于:微流道下底板3上第二开口3-1直径为3mm,通孔的横截面为直径3mm的圆形,信号发生器和功率放大器件向上述产品的微型超声器件smr施加2.56GHz的工作频率,0.7W功率。Basically the same as product 1, the only difference of product 6 is: the diameter of the second opening 3-1 on the bottom plate 3 of the microchannel is 3mm, the cross section of the through hole is a circle with a diameter of 3mm, the signal generator and the power amplifier The device applies an operating frequency of 2.56GHz and a power of 0.7W to the miniature ultrasonic device smr of the above product.

产品7:Product 7:

与产品1基本相同,产品7的不同之处仅在于:微流道下底板3上第二开口3-1直径为8mm,通孔的横截面为直径8mm的圆形,信号发生器和功率放大器件向上述产品的微型超声器件smr施加2.56GHz的工作频率,0.7W功率。It is basically the same as product 1, the only difference of product 7 is: the diameter of the second opening 3-1 on the bottom plate 3 of the microchannel is 8mm, the cross-section of the through hole is a circle with a diameter of 8mm, the signal generator and the power amplifier The device applies an operating frequency of 2.56GHz and a power of 0.7W to the miniature ultrasonic device smr of the above product.

产品8:Product 8:

与产品1基本相同,不同之处仅在于:电化学传感器芯片6与微型超声器件2-1为垂直设置(非平行设置),电化学传感器区域限定组件5的第一开口5-1的形状为细缝(长条状),细缝的长为4mm,宽为0.5mm,其大小刚好满足电化学传感器芯片垂直于电化学传感器区域限定组件5从第一开口5-1中插入。It is basically the same as the product 1, the only difference is that the electrochemical sensor chip 6 and the micro ultrasonic device 2-1 are arranged vertically (non-parallel arrangement), and the shape of the first opening 5-1 of the electrochemical sensor region defining component 5 is The slit (long strip), the length of the slit is 4mm and the width is 0.5mm, the size of the slit is just enough for the electrochemical sensor chip to be inserted from the first opening 5-1 perpendicular to the electrochemical sensor area defining component 5.

产品9:Product 9:

与产品8相同,不同之处仅在于测试环境:信号发生器和功率放大器件向产品的微型超声器件smr施加2.56GHz的工作频率,0.3W功率。The same as Product 8, the difference is only in the test environment: the signal generator and the power amplifier device apply a working frequency of 2.56GHz and a power of 0.3W to the miniature ultrasonic device smr of the product.

产品10:Product 10:

与产品1基本相同,产品10的不同之处仅在于:产品中采用低频的微型超声器件pMUT,信号发生器和功率放大器件向产品的微型超声器件pMUT施加2.5MHz的工作频率,0.7W功率。Basically the same as product 1, the only difference of product 10 is that a low-frequency micro-ultrasonic device pMUT is used in the product, and the signal generator and power amplifier device apply 2.5MHz operating frequency and 0.7W power to the product's micro-ultrasonic device pMUT.

产品11:Product 11:

与产品1基本相同,产品11的不同之处仅在于:产品采用的电化学传感器芯片6的工作电极为石墨烯电极,电极形貌采用图7a所示,工作电极为矩形结构,其尺寸为0.5mm×2mm,信号发生器和功率放大器件向产品的微型超声器件smr施加2.56GHz的工作频率,0.5W功率。It is basically the same as product 1, and the difference between product 11 is only that the working electrode of the electrochemical sensor chip 6 used in the product is a graphene electrode, the electrode morphology is shown in Figure 7a, the working electrode is a rectangular structure, and its size is 0.5 mm×2mm, the signal generator and the power amplifier device apply a working frequency of 2.56GHz and a power of 0.5W to the miniature ultrasonic device smr of the product.

产品12:Product 12:

与产品11基本相同,不同之处仅在于:电化学传感器芯片6的工作电极尺寸为1mm×2mm。It is basically the same as the product 11, except that the size of the working electrode of the electrochemical sensor chip 6 is 1 mm×2 mm.

产品13:Product 13:

与产品1基本相同,不同之处仅在于:产品中采用的待测液体为浓度100ppb重金属离子Cu2+水溶液,其中包含0.1M醋酸钠作为缓冲液。电化学方法采用方波阳极溶出伏安法,沉积电势-0.5V,沉积时间60s,溶出电势-0.5~0.6V。It is basically the same as product 1, the only difference is that the liquid to be tested used in the product is an aqueous solution of heavy metal ions Cu 2+ with a concentration of 100ppb, which contains 0.1M sodium acetate as a buffer. The electrochemical method adopts square wave anodic stripping voltammetry, the deposition potential is -0.5V, the deposition time is 60s, and the stripping potential is -0.5~0.6V.

产品14:Product 14:

与产品13相同,不同之处仅在于测试环境:信号发生器和功率放大器件向产品的微型超声器件smr施加2.56GHz的工作频率,0.5W功率。The same as product 13, the difference is only in the test environment: the signal generator and the power amplifier device apply the working frequency of 2.56GHz and the power of 0.5W to the micro ultrasonic device smr of the product.

产品15:Product 15:

与产品1基本相同,不同之处仅在于:微流道组件4的微流道形状采用图9a,信号发生器和功率放大器件向上述产品的微型超声器件smr施加2.56GHz的工作频率,0.7W功率。It is basically the same as product 1, the only difference is: the micro-channel shape of the micro-channel component 4 adopts Fig. 9a, the signal generator and the power amplifier part apply the working frequency of 2.56GHz to the micro ultrasonic device smr of the above product, 0.7W power.

产品16:Product 16:

与产品1基本相同,不同之处仅在于:微流道组件4的微流道形状采用图9b,信号发生器和功率放大器件向上述产品的微型超声器件smr施加2.56GHz的工作频率,0.7W功率。It is basically the same as product 1, the only difference is: the micro-channel shape of the micro-channel component 4 adopts Fig. 9b, the signal generator and the power amplifier part apply the working frequency of 2.56GHz to the micro ultrasonic device smr of the above product, 0.7W power.

产品17:Product 17:

与产品1基本相同,不同之处仅在于:微流道组件4的微流道形状采用图9c,信号发生器和功率放大器件向上述产品的微型超声器件smr施加2.56GHz的工作频率,0.7W功率。Basically the same as product 1, the only difference is: the micro-channel shape of the micro-channel component 4 adopts Fig. 9c, the signal generator and the power amplifier part apply the working frequency of 2.56GHz to the micro ultrasonic device smr of the above product, 0.7W power.

经过对产品1~17进行测试,获得以下结论:After testing products 1 to 17, the following conclusions were obtained:

1、超声刺激对电化学检测灵敏度具有显著的影响,产品1、产品2、产品3分别添加了0W、0.7W、1W的功率,图10为其循环伏安曲线图,产品2、产品3的极限电流分别为18uA、24uA,产品1的阳极峰值电流约为7uA,可见,产品2,产品3的极限电流分别约为产品1的峰值电流的2.6倍,3.4倍。由此可见,超声刺激引起被检测液流动,增强了物质传输过程,显著提高了电化学传感灵敏度。1. Ultrasound stimulation has a significant impact on the sensitivity of electrochemical detection. Product 1, Product 2, and Product 3 were added with 0W, 0.7W, and 1W of power, respectively. Figure 10 is the cyclic voltammetry curve. The limiting currents are 18uA and 24uA, respectively, and the anode peak current of product 1 is about 7uA. It can be seen that the limiting currents of product 2 and product 3 are about 2.6 times and 3.4 times the peak current of product 1, respectively. It can be seen that the ultrasonic stimulation causes the liquid to be detected to flow, which enhances the material transfer process and significantly improves the sensitivity of electrochemical sensing.

2、电化学传感器芯片与微型超声器件相对距离影响超声刺激增强电化学检测灵敏度的效果。产品3、产品4、产品5中电化学传感器芯片与微型超声器件的相对距离分别为3mm、1mm、5mm,添加功率1W,产品1相对距离3mm,添加功率为0W,如图11所示循环伏安图,产品1的阳极峰值电流7uA,产品3、产品4、产品5的极限电流分别约为22uA、24uA、33uA。可见,产品4,产品3,产品5的极限电流分别约产品1峰值电流的4.7倍,3.4倍,3.1倍。由此可见,电化学传感器芯片与微型超声器件的相对距离大小影响电化学传感灵敏度高低,距离越小,检测灵敏度越高。2. The relative distance between the electrochemical sensor chip and the micro ultrasonic device affects the effect of ultrasonic stimulation on enhancing the sensitivity of electrochemical detection. In product 3, product 4, and product 5, the relative distance between the electrochemical sensor chip and the micro ultrasonic device is 3mm, 1mm, and 5mm, respectively, and the added power is 1W. The relative distance of product 1 is 3mm, and the added power is 0W, as shown in Figure 11. Antu, the anode peak current of product 1 is 7uA, and the limit currents of product 3, product 4, and product 5 are about 22uA, 24uA, and 33uA, respectively. It can be seen that the limit current of product 4, product 3 and product 5 is about 4.7 times, 3.4 times and 3.1 times of the peak current of product 1 respectively. It can be seen that the relative distance between the electrochemical sensor chip and the micro ultrasonic device affects the sensitivity of electrochemical sensing. The smaller the distance, the higher the detection sensitivity.

3、研究用于检测待测液体的腔体大小对超声电化学检测灵敏度的影响,产品6、产品2、产品7的腔体直径分别为3mm、5mm、8mm。添加功率均为0.7W,获得的循环伏安曲线显示产品6、产品2、产品7的极限电流基本相同,约为18uA。由此可见,腔体直径对检测结果影响不大。3. To study the influence of the cavity size used to detect the liquid to be tested on the ultrasonic electrochemical detection sensitivity, the cavity diameters of product 6, product 2, and product 7 are 3mm, 5mm, and 8mm, respectively. The added power is all 0.7W, and the obtained cyclic voltammetry curve shows that the limiting current of product 6, product 2, and product 7 is basically the same, about 18uA. It can be seen that the cavity diameter has little effect on the detection results.

4、微型超声器件工作平面与电化学传感器芯片的工作平面可以以多种角度组合,产品1是以相互平行的方式组合。产品8、产品9是以相互垂直的方式组合的,产品8不添加功率,产品9添加0.3W的功率。如图12循环伏安曲线所示,产品9的阳极峰值电流44uA稍大于产品8的峰值电流40uA。由此可见,微型超声器件工作平面与电化学传感器芯片的工作平面以相互垂直的方式组合时,超声刺激可以增强电化学传感灵敏度,在实际应用中,可根据应用需求灵活改变两个工作平面的组合角度。4. The working plane of the micro ultrasonic device and the working plane of the electrochemical sensor chip can be combined at various angles, and the product 1 is combined in a parallel manner. Product 8 and Product 9 are combined in a mutually perpendicular manner. Product 8 does not add power, and Product 9 adds 0.3W of power. As shown in the cyclic voltammetry curve of Fig. 12, the anode peak current 44uA of product 9 is slightly larger than the peak current 40uA of product 8. It can be seen that when the working plane of the micro ultrasonic device and the working plane of the electrochemical sensor chip are combined in a mutually perpendicular manner, ultrasonic stimulation can enhance the sensitivity of electrochemical sensing. In practical applications, the two working planes can be flexibly changed according to application requirements. combination angle.

5、本发明可满足多种频率段的微型超声器件的应用,产品2采用的是高频的微型超声器件smr,其工作频率为2.58GHz,添加功率0.7W,产品10采用低频的微型超声器件pMUT,其工作频率为2.5MHz,添加功率0.7W。在循环伏安曲线中,产品10的极限电流约为13uA,可见产品2、产品10的极限电流分别是产品1的峰值电流的2.6倍、1.9倍。由此可见,本发明中,微型超声器件可根据应用需求灵活改变。5. The invention can meet the application of micro ultrasonic devices in various frequency bands. Product 2 uses a high-frequency micro ultrasonic device smr, its operating frequency is 2.58GHz, and the added power is 0.7W. Product 10 uses a low-frequency micro ultrasonic device. The pMUT, which operates at 2.5MHz, adds 0.7W of power. In the cyclic voltammetry curve, the limit current of product 10 is about 13uA, it can be seen that the limit current of product 2 and product 10 is 2.6 times and 1.9 times of the peak current of product 1, respectively. It can be seen that, in the present invention, the micro ultrasonic device can be flexibly changed according to application requirements.

6、本发明可采用多种电化学传感器芯片,产品11、产品12采用与其他产品不同的石墨烯材料电极,电极形状为长条状,尺寸分别为0.5mm×2mm,1mm×2mm。产品11的极限电流约为16uA,产品12的极限电流约为31uA,产品12的峰值电流约为产品11的1.9倍。由此可见,本发明中,电化学传感器芯片的材料、形状、尺寸可以根据应用需求灵活改变。6. The present invention can use a variety of electrochemical sensor chips. Product 11 and Product 12 use graphene material electrodes that are different from other products. The electrodes are elongated in shape and have dimensions of 0.5mm×2mm and 1mm×2mm respectively. The limit current of product 11 is about 16uA, the limit current of product 12 is about 31uA, and the peak current of product 12 is about 1.9 times that of product 11. It can be seen that, in the present invention, the material, shape and size of the electrochemical sensor chip can be flexibly changed according to application requirements.

7、采用本发明检测100ppb浓度的重金属离子Cu2+溶液,产品13不添加功率,产品14添加0.5W功率,电化学检测方法采用方波阳极溶出伏安法,如图13所示为获得的方波阳极溶出伏安曲线图,产品13的溶出电流约为9uA,产品14的溶出电流约为78uA,产品14测得的溶出电流约为产品13溶出电流的8.7倍。由此可见,超声刺激显著提高了重金属离子Cu2+检测的灵敏度。7. Using the present invention to detect the heavy metal ion Cu 2+ solution with a concentration of 100ppb, no power is added to product 13, and 0.5W power is added to product 14. The electrochemical detection method adopts square wave anode stripping voltammetry, as shown in Figure 13. The square wave anode stripping voltammetry curve shows that the stripping current of product 13 is about 9uA, the stripping current of product 14 is about 78uA, and the measured stripping current of product 14 is about 8.7 times that of product 13. It can be seen that ultrasonic stimulation significantly improves the sensitivity of heavy metal ion Cu 2+ detection.

8、本发明的微沟道组件4的微流道形状较为灵活,可以有多种组合方式。产品15、产品16、产品17、产品2分别采用图9a、图9b、图9c、图9d的微流道形状,添加0.7W,实验结果显示,产品15、产品16、产品17、产品2获得相似的可逆的循环伏安曲线,由此可见,这四种微流道形状对电化学检测的影响较小。8. The shape of the micro-channel of the micro-channel component 4 of the present invention is relatively flexible, and can be combined in various ways. Product 15, Product 16, Product 17, and Product 2 use the micro-channel shapes shown in Figure 9a, Figure 9b, Figure 9c, and Figure 9d, respectively, and add 0.7W. The experimental results show that Product 15, Product 16, Product 17, and Product 2 obtained Similar reversible cyclic voltammetry curves, it can be seen that the four microchannel shapes have less influence on electrochemical detection.

上述产品的厚度如下:The thicknesses of the above products are as follows:

序号serial number 产品1Product 1 产品2Product 2 产品3Product 3 产品4Product 4 产品5Product 5 产品6Product 6 厚度(mm)Thickness(mm) 88 88 88 66 1010 88 序号serial number 产品7Product 7 产品8Product 8 产品9Product 9 产品10Product 10 产品11Product 11 产品12Product 12 厚度(mm)Thickness(mm) 88 88 88 88 88 88 序号serial number 产品13Product 13 产品14Product 14 产品15Product 15 产品16Product 16 产品17Product 17 -- 厚度(mm)Thickness(mm) 88 88 88 88 88 --

以上对本发明做了示例性的描述,应该说明的是,在不脱离本发明的核心的情况下,任何简单的变形、修改或者其他本领域技术人员能够不花费创造性劳动的等同替换均落入本发明的保护范围。The present invention has been exemplarily described above. It should be noted that, without departing from the core of the present invention, any simple deformation, modification or other equivalent replacements that can be performed by those skilled in the art without creative effort fall into the scope of the present invention. the scope of protection of the invention.

Claims (10)

1. A laboratory analysis platform on microfluidic ultrasonic electrochemical chip is characterized by comprising: an electrochemical sensor chip (6), a micro-channel component (4) and a supporting substrate (2) which are arranged in parallel, the electrochemical sensor chip (6), the micro-channel component (4) and the supporting substrate (2) are arranged from top to bottom in sequence, wherein the top surface of the supporting substrate (2) is provided with a micro ultrasonic device (2-1), a through hole is formed on the micro-channel component (4), the hole wall of the through hole is enclosed into a cavity (4-3) with the top end and the bottom end open, the cavity (4-3) is communicated with the outside of a laboratory analysis platform on the microfluidic ultrasonic electrochemical chip, so that the liquid to be measured can be discharged into and out of the cavity (4-3), and the liquid to be measured in the cavity (4-3) can be contacted with the three electrodes of the electrochemical sensor chip (6) and the vibration area of the miniature ultrasonic device (2-1).
2. The microfluidic ultrasonic electrochemical on-chip laboratory analysis platform according to claim 1, wherein a liquid inlet chamber (4-1) and a liquid outlet chamber (4-2) are formed in the microchannel assembly (4), the liquid inlet chamber (4-1) is communicated with the chamber (4-3) through a first channel (4-4), the liquid outlet chamber (4-2) is communicated with the chamber (4-3) through a second channel (4-5), and the chamber (4-3) is communicated with the outside of the microfluidic ultrasonic electrochemical on-chip laboratory analysis platform through the liquid inlet chamber (4-1) and the liquid outlet chamber (4-2).
3. The microfluidic ultrasonic-electrochemical on-chip laboratory analysis platform of claim 2, wherein the height of the through hole is 10 μm to 10mm, and the width of the through hole is 1mm to 10 mm.
4. The microfluidic ultrasonic-electrochemical on-chip laboratory analysis platform according to claim 3, wherein the liquid inlet chamber (4-1), the liquid outlet chamber (4-2), the chamber body (4-3), the first channel (4-4) and the second channel (4-5) together form a microchannel, the widths of the first channel (4-4) and the second channel (4-5) are respectively 10 μm to 1mm, the lengths of the first channel (4-4) and the second channel (4-5) are respectively 2mm to 2cm, and the liquid inlet chamber (4-1) and the liquid outlet chamber (4-2) are located on two sides or the same side of the chamber body (4-3).
5. The microfluidic ultrasonic-electrochemical on-chip laboratory analysis platform according to claim 4, wherein the structures of the liquid inlet cavity (4-1) and the liquid outlet cavity (4-2) are consistent, the structures of the first channel (4-4) and the second channel (4-5) are consistent, and the sum of the lengths of the liquid inlet cavity (4-1) and the first channel (4-4) is 2.5 mm-2.5 cm;
the length of the electrochemical sensor chip (6) is 1.5 cm-5 cm.
6. The microfluidic sonoelectrochemical on-chip laboratory analytical platform of claim 5, wherein the micro flow channel component (4) is Polydimethylsiloxane (PDMS), Polymethylmethacrylate (PMMA), or paper;
the length of the micro ultrasonic device (2-1) is 100 um-10 mm, and the length of the vibration area of the micro ultrasonic device (2-1) is 10 mu m-10 mm.
7. The microfluidic sonoelectrochemical on-chip laboratory analysis platform of claim 6, further comprising: an electrochemical sensor area defining component (5) parallel to the micro flow channel component (4), wherein a first opening (5-1) is formed on the electrochemical sensor area defining component (5), the electrochemical sensor chip (6) and the micro ultrasonic device (2-1) are arranged in parallel or not, and when the electrochemical sensor chip and the micro ultrasonic device are arranged in parallel, the liquid to be measured can pass through the first opening (5-1) to be in contact with the sensing area of the three electrodes; when the sensor chip is arranged in a non-parallel mode, the electrochemical sensor chip (6) penetrates through the first opening (5-1) to be in contact with the liquid to be measured.
8. The microfluidic ultrasonic-electrochemical on-chip laboratory analysis platform according to claim 7, wherein when the electrochemical sensor chip (6) and the micro-ultrasonic device (2-1) are disposed in a non-parallel manner, the electrochemical sensor chip (6) is fixed on the electrochemical sensor area defining assembly (5) and the sensing area of the three electrodes of the electrochemical sensor chip (6) passes through the first opening (5-1) and can be contacted with the liquid to be measured;
when the electrochemical sensor chip (6) and the micro ultrasonic device (2-1) are arranged in a non-parallel mode, the first opening (5-1) is a slit; when the electrochemical sensor chip (6) and the micro ultrasonic device (2-1) are arranged in parallel, the size of the first opening (5-1) is larger than or equal to that of a sensing area of the three electrodes and smaller than or equal to that of the cross section of the through hole.
9. The microfluidic sonoelectrochemical lab-on-a-chip analysis platform of claim 8, further comprising: the electrochemical sensor chip comprises a top cover (7) and is located above an electrochemical sensor chip (6), wherein a first through hole (7-1) for inputting liquid to be detected into a liquid inlet cavity (4-1) and a second through hole (7-2) for discharging the liquid to be detected from a liquid outlet cavity (4-2) are formed in the top cover (7), and when the electrochemical sensor chip (6) and the miniature ultrasonic device (2-1) are arranged in a non-parallel mode, a third opening (7-3) is formed in the top cover (7) and is used for penetrating through the electrochemical sensor chip (6).
10. The microfluidic ultrasonic-electrochemical on-chip laboratory analysis platform according to claim 9, wherein when the electrochemical sensor chip (6) and the micro-ultrasonic device (2-1) are arranged in parallel, the electrochemical sensor chip (6) and/or the electrochemical sensor area defining assembly (5) is formed with holes at positions opposite to the first through hole (7-1) and the second through hole (7-2); when the electrochemical sensor chip (6) and the micro ultrasonic device (2-1) are arranged in a non-parallel mode, holes are formed in the electrochemical sensor area limiting assembly (5) at positions opposite to the first through hole (7-1) and the second through hole (7-2), so that the first through hole (7-1) can be communicated with the liquid inlet cavity (4-1) and the second through hole (7-2) can be communicated with the liquid outlet cavity (4-2);
further comprising: the micro-channel lower bottom plate (3) is arranged between the micro-channel assembly (4) and the supporting substrate (2), a second opening (3-1) is formed in the micro-channel lower bottom plate (3), the liquid to be detected can be in contact with a vibration area of the micro-ultrasonic device (2-1) through the second opening (3-1), and the bottom surfaces of the liquid inlet cavity (4-1), the first channel (4-4), the liquid outlet cavity (4-2) and the second channel (4-5) are open and sealed by the top surface of the micro-channel lower bottom plate (3);
in the above technical solution, the method further comprises: a bottom cover (1) located below the support substrate (2);
in the technical scheme, the liquid inlet cavity (4-1) and the liquid outlet cavity (4-2) are positioned at two sides or the same side of the cavity (4-3);
the thickness of the supporting substrate (2) is 0.1 mm-2 mm;
the thickness of the lower bottom plate (3) of the micro-channel is 0.0125 mm-1 mm;
the thickness of the electrochemical sensor area limiting assembly (5) is 0.0125 mm-1 mm;
the laboratory analysis platform on the microfluidic ultrasonic electrochemical chip is fastened and glued by a bolt or attracted by magnetic force;
the lower surface of the electrochemical sensor area defining component (5) has adhesive property;
the upper surface of the lower micro-channel bottom plate (3) has adhesiveness;
the upper surface of the electrochemical sensor area limiting component (5) has adhesive property;
the lower surface of the lower micro-channel bottom plate (3) has adhesiveness;
the material of the electrochemical sensor area limiting component (5) is polydimethylsiloxane PDMS, polymethyl methacrylate PMMA or polyethylene terephthalate PET;
the length of the electrochemical sensor area limiting assembly (5) is 1 cm-10 cm;
the size of the second opening (3-1) is larger than or equal to that of a vibration area of the micro ultrasonic device (2-1) and smaller than or equal to that of the cross section of the through hole.
CN202010556972.4A 2020-06-18 2020-06-18 Laboratory analysis platform on microfluidic ultrasonic electrochemical chip Pending CN112191284A (en)

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