CN115486834A - A wearable exhaled acetone detection method and device based on MXene - Google Patents

A wearable exhaled acetone detection method and device based on MXene Download PDF

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CN115486834A
CN115486834A CN202211227767.9A CN202211227767A CN115486834A CN 115486834 A CN115486834 A CN 115486834A CN 202211227767 A CN202211227767 A CN 202211227767A CN 115486834 A CN115486834 A CN 115486834A
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acetone
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exhaled breath
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CN115486834B (en
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刘清君
李鑫
潘静莹
卢妍利
安子建
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Zhejiang University ZJU
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Abstract

The invention discloses a wearable exhaled breath acetone detection method and device based on MXene. The device includes an exhaled breath acetone detection label. The exhaled breath acetone detection label is formed by assembling an MXene acetone sensor, a flexible detection circuit board, a polydimethylsiloxane packaging layer and a light-emitting diode circuit board and is used for detecting the concentration of acetone in exhaled breath. The invention utilizes the wireless Bluetooth between the MXene device and the mobile terminal to carry out data interaction, realizes continuous and real-time monitoring of the dynamic change of the acetone concentration of the exhaled breath, reflects the intensity of lipid metabolism activities such as diet and fat burning movement and the like, and further realizes daily metabolic health management. The method provides a wearable detection platform for exhaled breath analysis, and has the advantages of non-invasiveness, continuity, real-time performance, simplicity in operation, rapidness in detection and the like.

Description

一种基于MXene的可穿戴呼出气丙酮检测方法及装置A wearable exhaled acetone detection method and device based on MXene

技术领域technical field

本发明涉及一种呼出气丙酮的检测技术,尤其涉及一种基于MXene的可穿戴呼出气丙酮检测方法及装置。The invention relates to a detection technology of acetone in exhaled gas, in particular to a wearable method and device for detecting acetone in exhaled gas based on MXene.

背景技术Background technique

呼出气丙酮是脂质代谢的重要产物,被认为是最具吸引力的脂质代谢监测对象之一。临床证据表明,丙酮是由脂肪酸在肝脏线粒体经过一系列氧化作用产生的,并主要由呼出气排出体外。因此,呼出气丙酮具有明确的代谢来源和途径,能够反映饮食习惯和体育锻炼等日常活动相关的脂质代谢情况。研究表明,健康受试者的呼出气丙酮浓度范围从数百ppb(十亿分之一)到0.9ppm(百万分之一)之间,在禁食、生酮饮食、或有氧运动后可以显著上升到数十或数百ppm。因此,呼出气丙酮检测在指导减肥,评价运动耐力,或指导酮症酸中毒治疗等领域具有极大潜力,有望应用到临床实践中。此外,相对于血酮检测生化分析,呼出气分析具有简单、无创取样的突出优点,这对被检测对象的负担更小,因此在医疗诊断和个性化保健方面具有很大的前景。Exhaled acetone is an important product of lipid metabolism and is considered to be one of the most attractive targets for monitoring lipid metabolism. Clinical evidence shows that acetone is produced by a series of oxidations of fatty acids in the mitochondria of the liver and is mainly excreted by exhaled air. Therefore, exhaled acetone has a clear source and pathway of metabolism, which can reflect the lipid metabolism related to daily activities such as dietary habits and physical exercise. Studies have shown that exhaled acetone concentrations in healthy subjects range from hundreds of ppb (parts per billion) to 0.9 ppm (parts per million) after fasting, a ketogenic diet, or aerobic exercise Can rise significantly to tens or hundreds of ppm. Therefore, the detection of acetone in exhaled breath has great potential in guiding weight loss, evaluating exercise tolerance, or guiding the treatment of ketoacidosis, and is expected to be applied in clinical practice. In addition, compared with the biochemical analysis of blood ketone detection, exhaled breath analysis has the outstanding advantages of simple and non-invasive sampling, which has less burden on the tested object, so it has great prospects in medical diagnosis and personalized health care.

目前,标准的呼出气检测常依赖台式分析仪器,如气相色谱-质谱、选择性离子流管质谱等,这类方法适合于实验室或医院检查,而难以广泛的应用到日常的个人的代谢健康监测。因此,开发便携式、穿戴式的微型化呼出气传感检测方案可作为临床标准呼出气检测的重要补充。近年来种新兴的二维过渡金属碳化物和氮化物纳米材料家族(MXenes)在传感器开发中受到了极大的关注,主要归因于其金属导电性、高化学活性表面和高信噪比等一系列优异特性。因此,MXenes在设计高灵敏度、低检测限的室温气体传感器方面具有独特的吸引力。此外,近期研究表明,日常穿戴的口罩不仅能够为个人提供防护,同时也能够与传感材料结合,实现呼出气中病毒及生化标志物的穿戴式检测。因此,针对呼出气检测中高湿度、多干扰物,以及传感器响应漂移等检测应用瓶颈,基于MXene纳米材料平台和一次性口罩开发一套集成干扰物过滤、传感器检测、响应校正及无线数据传输的呼出气丙酮检测MXene智能口罩装置和方法,对于推动穿戴式呼吸分析和日常脂质代谢管理具有重要意义。At present, standard exhaled breath testing often relies on desktop analytical instruments, such as gas chromatography-mass spectrometry, selective ion flow tube mass spectrometry, etc. These methods are suitable for laboratory or hospital inspections, but are difficult to be widely used in daily personal metabolic health monitor. Therefore, the development of portable and wearable miniaturized exhaled breath detection solutions can be used as an important supplement to clinical standard exhaled breath detection. In recent years, an emerging family of two-dimensional transition metal carbide and nitride nanomaterials (MXenes) has received great attention in sensor development, mainly due to its metallic conductivity, highly chemically active surface, and high signal-to-noise ratio. A series of excellent characteristics. Therefore, MXenes are uniquely attractive for designing room temperature gas sensors with high sensitivity and low detection limit. In addition, recent studies have shown that masks worn daily can not only provide protection for individuals, but can also be combined with sensing materials to achieve wearable detection of viruses and biochemical markers in exhaled breath. Therefore, aiming at the detection application bottlenecks such as high humidity, multiple interferers, and sensor response drift in exhaled breath detection, based on the MXene nanomaterial platform and disposable masks, a set of exhaled breath filters integrating interferent filtering, sensor detection, response correction and wireless data transmission will be developed. The gas acetone detection MXene smart mask device and method are of great significance for promoting wearable breath analysis and daily lipid metabolism management.

发明内容Contents of the invention

本发明的目的在于针对现有技术和产品的不足,提供一种基于MXene的可穿戴呼出气丙酮检测方法及装置,以实现日常生活中呼出气丙酮的连续实时穿戴式检测,反映与脂质代谢相关的饮食、运动健康管理。The purpose of the present invention is to address the deficiencies of the prior art and products, to provide a wearable exhaled acetone detection method and device based on MXene, so as to realize the continuous real-time wearable detection of exhaled acetone in daily life, reflecting the relationship with lipid metabolism Related diet, exercise and health management.

本发明的目的是通过以下技术方案来实现的:The purpose of the present invention is achieved through the following technical solutions:

一种基于MXene的可穿戴呼出气丙酮检测装置,它包括:呼出气丙酮检测标签;所述呼出气丙酮检测标签包括从下到上依次组装的MXene丙酮传感器、柔性检测电路板、用于封装柔性检测电路板的聚二甲基硅氧烷封装层以及发光二极管电路板,所述发光二极管电路板由发光二极管基底、固定在发光二极管基底的发光二极管组成,所述柔性检测电路板及聚二甲基硅氧烷封装层设有开窗,使发光二极管正对MXene丙酮传感器;所述二极管电路板、MXene丙酮传感器与柔性检测电路板电气连接;其中,MXene丙酮传感器用于检测呼出气中丙酮浓度并转换为电信号,柔性检测电路板用于获取并处理MXene丙酮传感器的电信号;所述MXene丙酮传感器包括从下到上依次组装的传感器基底、金叉指电极和MXene纳米传感层、所述MXene纳米传感层表面修饰有二氧化钛纳米颗粒及短肽分子。A wearable exhaled acetone detection device based on MXene, which includes: an exhaled acetone detection label; the exhaled acetone detection label includes an MXene acetone sensor assembled sequentially from bottom to top, a flexible detection circuit board, and a flexible detection circuit board for packaging The polydimethylsiloxane encapsulation layer of the detection circuit board and the light-emitting diode circuit board, the light-emitting diode circuit board is composed of a light-emitting diode base and a light-emitting diode fixed on the light-emitting diode base, the flexible detection circuit board and polydimethylsiloxane The siloxane-based encapsulation layer is provided with a window, so that the light-emitting diode is facing the MXene acetone sensor; the diode circuit board, the MXene acetone sensor are electrically connected to the flexible detection circuit board; wherein, the MXene acetone sensor is used to detect the concentration of acetone in the exhaled air And convert it into an electrical signal, the flexible detection circuit board is used to acquire and process the electrical signal of the MXene acetone sensor; the MXene acetone sensor includes a sensor substrate, a gold interdigitated electrode and an MXene nano-sensing layer assembled sequentially from bottom to top, the The surface of the MXene nano sensing layer is modified with titanium dioxide nanoparticles and short peptide molecules.

进一步地,所述MXene纳米传感层由2质量份陶瓷相钛铝碳粉末混合2质量份氟化锂溶于40体积份浓盐酸中,在40℃下刻蚀24小时,经由去离子水清洗沉淀,采用涡旋发生器辅助超声机械剥离后喷涂于金叉指电极表面得到。Further, the MXene nano-sensing layer is composed of 2 parts by mass of ceramic phase titanium aluminum carbon powder mixed with 2 parts by mass of lithium fluoride dissolved in 40 parts by volume of concentrated hydrochloric acid, etched at 40 ° C for 24 hours, passed through deionized water Clean the precipitate, use the vortex generator to assist ultrasonic mechanical peeling, and then spray it on the surface of the gold interdigitated electrode.

进一步地,所述二氧化钛纳米颗粒通过如下方法修饰:将MXene纳米传感层与3%质量分数过氧化氢溶液混合,80℃水浴加热处理制备得到,二氧化钛纳米颗粒原位生长在MXene纳米传感层上。Further, the titanium dioxide nanoparticles are modified by the following method: the MXene nano-sensing layer is mixed with a 3% mass fraction hydrogen peroxide solution, prepared by heating in a water bath at 80°C, and the titanium dioxide nanoparticles are grown on the MXene nano-sensing layer in situ superior.

进一步地,所述短肽分子通过如下方法修饰:按质量比1:2与原位生长二氧化钛纳米颗粒的MXene纳米传感层混合溶解,并分别加入0.005质量份的1-乙基-(3-二甲基氨基丙基)碳酰二亚胺和4-二甲氨基吡啶催化剂,在100℃下搅拌3小时反应得到二氧化钛纳米颗粒与短肽分子共修饰的MXene纳米传感层。Further, the short peptide molecule is modified by the following method: mix and dissolve with the MXene nano-sensing layer of titanium dioxide nanoparticles grown in situ at a mass ratio of 1:2, and add 0.005 parts by mass of 1-ethyl-(3- Dimethylaminopropyl) carbodiimide and 4-dimethylaminopyridine catalysts were stirred at 100°C for 3 hours to obtain a MXene nanosensing layer co-modified with titanium dioxide nanoparticles and short peptide molecules.

进一步地,还包括用于过滤呼出气的基于MXene的织物过滤器;所述基于MXene的织物过滤器由铂纳米颗粒负载MXene织物与包裹在铂纳米颗粒负载MXene织物内的活性干燥剂构成,所述铂纳米颗粒负载MXene织物是通过棉织物表面静电吸附MXene,再在氯铂酸溶液中,在MXene表面原位还原负载铂纳米颗粒得到。Further, it also includes an MXene-based fabric filter for filtering exhaled air; the MXene-based fabric filter consists of a platinum nanoparticle-loaded MXene fabric and an active desiccant wrapped in a platinum nanoparticle-loaded MXene fabric, so The platinum nanoparticle-loaded MXene fabric is obtained by electrostatically adsorbing MXene on the surface of cotton fabric, and then reducing the loaded platinum nanoparticles on the MXene surface in situ in a chloroplatinic acid solution.

进一步地,所述铂纳米颗粒负载MXene织物具体通过如下方法制备获得:由经过去离子水清洗并干燥的白色棉织物浸泡在5mg/mL MXene溶液中,沉积30分钟,重复清洗干燥后浸泡在3.86mM氯铂酸溶液中,反应30分钟,利用MXene的化学活性表面实现铂纳米颗粒的原位还原。Further, the platinum nanoparticle-loaded MXene fabric is specifically prepared by the following method: the white cotton fabric washed and dried with deionized water is soaked in a 5 mg/mL MXene solution, deposited for 30 minutes, washed and dried repeatedly, soaked in 3.86 In mM chloroplatinic acid solution for 30 min, the chemically active surface of MXene was used to realize the in situ reduction of platinum nanoparticles.

进一步地,所述柔性检测电路板由检测电路基底、检测电路、二极管电路连接焊盘及传感器连接焊盘组成,检测电路基底由聚酰亚胺薄膜构成,检测电路主要包括微型低功耗芯片、外围电阻电容构成,用于获取并处理MXene丙酮传感器的电信号;通过低温焊锡分别将发光二极管电路板与MXene丙酮传感器焊接在二极管电路连接焊盘及传感器连接焊盘上,实现二极管电路板、MXene丙酮传感器与柔性检测电路板的电气连接。Further, the flexible detection circuit board is composed of a detection circuit base, a detection circuit, a diode circuit connection pad and a sensor connection pad, the detection circuit base is composed of a polyimide film, and the detection circuit mainly includes a micro low-power chip, The external resistor and capacitor are used to obtain and process the electrical signal of the MXene acetone sensor; the light-emitting diode circuit board and the MXene acetone sensor are respectively welded on the diode circuit connection pad and the sensor connection pad through low-temperature soldering tin to realize the diode circuit board and MXene acetone sensor. Electrical connection of the acetone sensor to the flex detection circuit board.

进一步地,所述检测电路由微控制器、恒流源、模数转换器、蓝牙、低通网络、场效应管、发光二极管、电池及电源管理电路、以及外围电阻电容构成。Further, the detection circuit is composed of a microcontroller, a constant current source, an analog-to-digital converter, Bluetooth, a low-pass network, a field effect transistor, a light-emitting diode, a battery and a power management circuit, and peripheral resistors and capacitors.

进一步地,还包括一次性口罩、固定在一次性口罩上的呼吸阀与呼吸阀外壳,所述呼出气丙酮检测标签固定在一次性口罩外侧的呼吸阀与呼吸阀外壳之间,基于MXene的织物过滤器固定在一次性口罩内侧的呼吸阀之上,用于过滤通过呼吸阀的呼出气。Further, it also includes a disposable mask, a breathing valve and a breathing valve shell fixed on the disposable mask, and the exhaled acetone detection label is fixed between the breathing valve and the breathing valve shell on the outside of the disposable mask, and the fabric based on MXene The filter is fixed on the breathing valve inside the disposable mask to filter the exhaled air passing through the breathing valve.

基于相同的原理,本发明还提供了一种基于MXene的呼出气丙酮的检测方法,具体为:Based on the same principle, the present invention also provides a method for detecting acetone in exhaled breath based on MXene, specifically:

利用上述装置获取呼出气的丙酮浓度,在丙酮检测期间保持发光二极管的开启。The acetone concentration in the exhaled breath is obtained by using the above-mentioned device, and the light-emitting diode is kept turned on during the acetone detection period.

本发明检测方法中,呼出气经由基于MXene的织物过滤器过滤,通过检测电路板开窗以及封装层开窗,直接被MXene丙酮传感器检测,无需其他预处理。In the detection method of the present invention, the exhaled air is filtered through the MXene-based fabric filter, and is directly detected by the MXene acetone sensor through the window opening of the detection circuit board and the packaging layer without other pretreatment.

本发明实施例的有益效果如下:本发明提供了一种基于MXene的可穿戴呼出气丙酮检测方法及装置,可实现连续、实时的穿戴式呼出气分析。基于MXene纳米材料设计的MXene丙酮传感器具有优异的灵敏度和低检测限,与基于MXene的织物过滤器相结合的方式提高了呼出气丙酮检测的选择性和抗干扰能力。基于柔性电子技术构建的呼出气丙酮检测标签与一次性口罩结合,为无需预处理的呼出气分析提供了穿戴式检测平台。利用MXene智能口罩中的蓝牙进行无线通信,能够进一步实现呼吸曲线在移动终端上的连续实时显示,以及呼出气丙酮浓度、呼吸频率等生理生化参数的监测分析。The beneficial effects of the embodiments of the present invention are as follows: The present invention provides a wearable exhaled breath acetone detection method and device based on MXene, which can realize continuous and real-time wearable exhaled breath analysis. The MXene acetone sensor designed based on MXene nanomaterials has excellent sensitivity and low detection limit, and the combination with the MXene-based fabric filter improves the selectivity and anti-interference ability of exhaled acetone detection. The combination of exhaled acetone detection label based on flexible electronic technology and disposable masks provides a wearable detection platform for exhaled breath analysis without pretreatment. Using the Bluetooth in the MXene smart mask for wireless communication can further realize the continuous real-time display of the respiratory curve on the mobile terminal, as well as the monitoring and analysis of physiological and biochemical parameters such as acetone concentration and respiratory rate in the exhaled breath.

与气象色谱-质谱、选择性离子流管质谱等台式呼出气分析仪器相比,本发明MXene智能口罩无需人工操作、使用灵活方便、不受使用人员和场景约束。与同类便携式呼出气分析技术相比,本发明实现了穿戴式呼出气丙酮检测,使用更加方便、而且能够实现连续、实时的呼出气丙酮分析。MXene智能口罩与普通一次性口罩的佩戴体感相似,在实现日常健康防护的同时,能够进一步反映日常生活中饮食、运动等脂质代谢活动产生的呼出气丙酮浓度变化。根据以上优点,本发明的装置及方法可广泛用于日常代谢健康管理。Compared with desktop exhaled gas analysis instruments such as gas chromatography-mass spectrometry and selective ion flow tube mass spectrometry, the MXene smart mask of the present invention does not require manual operation, is flexible and convenient to use, and is not restricted by users and scenarios. Compared with similar portable exhaled gas analysis technologies, the present invention realizes wearable exhaled acetone detection, is more convenient to use, and can realize continuous and real-time exhaled acetone analysis. The MXene smart mask has a similar wearing feel to ordinary disposable masks. While achieving daily health protection, it can further reflect the changes in exhaled acetone concentration caused by lipid metabolism activities such as diet and exercise in daily life. According to the above advantages, the device and method of the present invention can be widely used in daily metabolic health management.

附图说明Description of drawings

此处所说明的附图用来提供对本申请的进一步理解,构成本申请的一部分,本申请的示意性实施例及其说明用于解释本申请,并不构成对本申请的不当限定。在附图中:The drawings described here are used to provide a further understanding of the application and constitute a part of the application. The schematic embodiments and descriptions of the application are used to explain the application and do not constitute an improper limitation to the application. In the attached picture:

图1是本发明实施例提供的MXene智能口罩装外侧示意图;Fig. 1 is a schematic diagram of the outside of the MXene smart mask provided by the embodiment of the invention;

图2是本发明实施例提供的MXene智能口罩内侧示意图;Fig. 2 is a schematic diagram of the inside of the MXene smart mask provided by the embodiment of the present invention;

图3是本发明实施例提供的呼出气丙酮检测标签分级结构图;Fig. 3 is a hierarchical structure diagram of an exhaled acetone detection label provided by an embodiment of the present invention;

图4是本发明实施例提供的呼出气丙酮检测标签装配图;Fig. 4 is an assembly diagram of an exhaled acetone detection label provided by an embodiment of the present invention;

图5是本发明实施例提供的MXene丙酮传感器修饰图;Fig. 5 is the modified figure of the MXene acetone sensor provided by the embodiment of the invention;

图6是本发明实施例提供的基于MXene的织物过滤器结构图;Fig. 6 is the structural diagram of the fabric filter based on MXene provided by the embodiment of the present invention;

图7是本发明实施例提供的基于MXene的织物过滤器修饰图;Fig. 7 is the modified figure of the fabric filter based on MXene provided by the embodiment of the present invention;

图8是本发明实施例提供的检测电路功能模块图;Fig. 8 is a functional block diagram of a detection circuit provided by an embodiment of the present invention;

图9是本发明实施例提供的丙酮检测装置丙酮检测响应图;Fig. 9 is an acetone detection response diagram of the acetone detection device provided by the embodiment of the present invention;

图10是本发明实施例提供的丙酮检测装置丙酮检测线性拟合图;Fig. 10 is a linear fitting diagram of acetone detection by the acetone detection device provided by the embodiment of the present invention;

图11是本发明实施例提供的丙酮检测装置丙酮检测重复性响应图;Fig. 11 is a response diagram of acetone detection repeatability of the acetone detection device provided by the embodiment of the present invention;

图12是本发明实施例提供的丙酮检测装置丙酮检测稳定性响应图;Fig. 12 is a response diagram of acetone detection stability of the acetone detection device provided by the embodiment of the present invention;

图13是本发明实施例提供的丙酮检测装置湿度过滤性能图;Fig. 13 is a diagram of the humidity filtration performance of the acetone detection device provided by the embodiment of the present invention;

图14是本发明实施例提供的丙酮检测装置乙醇过滤性能图;Fig. 14 is an ethanol filtration performance diagram of the acetone detection device provided by the embodiment of the present invention;

图15是本发明实施例提供的丙酮检测装置氨气过滤性能图;Fig. 15 is a diagram of the ammonia filtration performance of the acetone detection device provided by the embodiment of the present invention;

图16是本发明实施例提供的丙酮检测装置丙酮过滤性能图;Figure 16 is a diagram of the acetone filtration performance of the acetone detection device provided by the embodiment of the present invention;

图17是本发明实施例提供的丙酮检测装置丙酮检测选择性图;Figure 17 is a selectivity diagram of acetone detection by the acetone detection device provided by the embodiment of the present invention;

图18是本发明实施例提供的MXene智能口罩实施方式示意图;Figure 18 is a schematic diagram of the implementation of the MXene smart mask provided by the embodiment of the present invention;

图19是本发明实施例提供的MXene智能口罩进行呼出气丙酮检测结果与血酮检测相关性图;Figure 19 is a correlation diagram between the detection results of exhaled acetone and blood ketone detection by the MXene smart mask provided by the embodiment of the present invention;

图中:一次性口罩1,呼吸阀2,呼吸阀外壳3,呼出气丙酮检测标签4,基于MXene的织物过滤器5,MXene丙酮传感器41,柔性检测电路板42,检测电路板开窗421,聚二甲基硅氧烷封装层43,封装层开窗431,发光二极管电路板44,发光二极管基底441,发光二极管442,检测电路基底422,检测电路423,二极管电路连接焊盘424,传感器连接焊盘425,传感器基底411,金叉指电极412,MXene纳米传感层413,二氧化钛纳米颗粒414,短肽分子415,活性干燥剂51,铂纳米颗粒负载MXene织物52,MXene智能口罩11,移动终端12,实时呼吸曲线显示功能区13,呼吸结果分析功能区14。In the figure: disposable mask 1, breathing valve 2, breathing valve housing 3, exhaled acetone detection label 4, MXene-based fabric filter 5, MXene acetone sensor 41, flexible detection circuit board 42, detection circuit board window 421, Polydimethylsiloxane encapsulation layer 43, encapsulation layer opening 431, light-emitting diode circuit board 44, light-emitting diode substrate 441, light-emitting diode 442, detection circuit substrate 422, detection circuit 423, diode circuit connection pad 424, sensor connection Pad 425, sensor substrate 411, gold interdigitated electrode 412, MXene nano-sensing layer 413, titanium dioxide nanoparticles 414, short peptide molecules 415, active desiccant 51, platinum nanoparticles loaded MXene fabric 52, MXene smart mask 11, mobile Terminal 12, real-time respiratory curve display functional area 13, respiratory result analysis functional area 14.

具体实施方式detailed description

以下将参考附图详细说明本公开的实施例、特征和方面,但并不是限制本发明。基于本发明实施例所扩展的任何一项实施例,在没有做出创造性劳动的前提下,对于本领域普通技术人员所获得的所有其他实施例,均属于本发明保护的范围。附图中相同的标记表示相同或者功能相似的元件。尽管在附图中展示了实施例的各种方面,但是除非特别指出,不必按照比例绘制附图。Embodiments, features, and aspects of the present disclosure will be described in detail below with reference to the accompanying drawings, but do not limit the present invention. Based on any embodiment extended from the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative work shall fall within the protection scope of the present invention. Like numbers in the figures indicate identical or functionally similar elements. While various aspects of the embodiments are shown in the drawings, the drawings are not necessarily drawn to scale unless specifically indicated.

另外,为了更好的说明本公开,在下文的具体实施方式中给出了众多的具体细节,在本领域的技术人员应当理解,没有某些具体细节,本公开同样也可以实施,在一些本领域人员熟知的方法和手段,元器件使用上不作详细描述,以便凸显本公开的主旨。In addition, in order to better illustrate the present disclosure, numerous specific details are given in the following specific embodiments. Those skilled in the art should understand that the present disclosure can also be implemented without certain specific details. The methods and means well known to those in the art, and the use of components are not described in detail in order to highlight the gist of the present disclosure.

本发明实施例提供一种基于MXene的可穿戴呼出气丙酮检测装置,它主要包括:呼出气丙酮检测标签4,所述呼出气丙酮检测标签4用于检测呼出气中丙酮浓度。An embodiment of the present invention provides a wearable exhaled acetone detection device based on MXene, which mainly includes: an exhaled acetone detection label 4, and the exhaled acetone detection label 4 is used to detect the concentration of acetone in the exhaled air.

图3展示了呼出气丙酮检测标签4的分级结构图。该呼出气丙酮检测标签4由发光二极管电路板44、聚二甲基硅氧烷封装层43、柔性检测电路板42及MXene丙酮传感器41自上而下组装而成。其中,聚二甲基硅氧烷封装层43通过溶液热固化的方法对柔性检测电路板42进行顶层封装,并采用激光切割对聚二甲基硅氧烷封装层43及柔性检测电路板42进行开窗加工,封装层开窗431与检测电路板开窗421的尺寸与MXene丙酮传感器41保持一致。该设计有利于位于呼出气丙酮检测标签4底层的MXene丙酮传感器41与呼出气的直接接触,以实现呼出气丙酮检测。聚二甲基硅氧烷封装层43起到对柔性检测电路板42的保护作用,同时作为间隔器固定发光二极管电路板44与MXene丙酮传感器41之间的工作距离。通过调节聚二甲基硅氧烷封装层43的厚度,可以控制不同的光照工作距离。光照工作距离与传感器接收功率密度相关,本实施例为1.5mm。Figure 3 shows the hierarchical structure diagram of the exhaled acetone detection label 4. The breath acetone detection label 4 is assembled from top to bottom by a light emitting diode circuit board 44 , a polydimethylsiloxane encapsulation layer 43 , a flexible detection circuit board 42 and an MXene acetone sensor 41 . Among them, the polydimethylsiloxane encapsulation layer 43 encapsulates the flexible detection circuit board 42 on the top layer by solution thermal curing, and uses laser cutting to encapsulate the polydimethylsiloxane encapsulation layer 43 and the flexible detection circuit board 42. Window processing, the size of the window 431 in the packaging layer and the window 421 in the detection circuit board are consistent with the size of the MXene acetone sensor 41 . This design is conducive to the direct contact between the MXene acetone sensor 41 located at the bottom of the exhaled acetone detection label 4 and the exhaled gas, so as to realize the exhaled acetone detection. The polydimethylsiloxane encapsulation layer 43 protects the flexible detection circuit board 42 and serves as a spacer to fix the working distance between the LED circuit board 44 and the MXene acetone sensor 41 . By adjusting the thickness of the polydimethylsiloxane encapsulation layer 43 , different working distances of light can be controlled. The working distance of illumination is related to the received power density of the sensor, which is 1.5 mm in this embodiment.

图4展示了呼出气丙酮检测标签4的装配图。所述柔性检测电路板42由检测电路基底422、检测电路423、二极管电路连接焊盘424及传感器连接焊盘425组成。发光二极管442固定在发光二极管基底441上,进一步组装在聚二甲基硅氧烷封装层43之上,通过封装层开窗431及检测电路板开窗421与MXene丙酮传感器41对齐,以固定光照工作距离,并通过低温焊锡与二极管电路连接焊盘424焊接,与柔性检测电路板42的电气连接。MXene丙酮传感器41包含传感器基底411与金叉指电极412,并通过低温焊锡与传感器连接焊盘425焊接,实现与呼出气丙酮检测标签4的电气连接。FIG. 4 shows an assembly diagram of the breath acetone detection label 4 . The flexible detection circuit board 42 is composed of a detection circuit substrate 422 , a detection circuit 423 , a diode circuit connection pad 424 and a sensor connection pad 425 . The light-emitting diode 442 is fixed on the light-emitting diode substrate 441, further assembled on the polydimethylsiloxane encapsulation layer 43, and aligns with the MXene acetone sensor 41 through the encapsulation layer opening 431 and the detection circuit board opening 421 to fix the light. Working distance, and through low-temperature soldering and diode circuit connection pad 424 welding, and the electrical connection with the flexible detection circuit board 42 . The MXene acetone sensor 41 includes a sensor substrate 411 and a gold interdigitated electrode 412, and is welded to the sensor connection pad 425 by low-temperature soldering to realize the electrical connection with the exhaled acetone detection label 4 .

如图5所示,所述MXene丙酮传感器41在金叉指电极412上修饰了MXene纳米传感层413、二氧化钛纳米颗粒414及短肽分子415,短肽分子415可以改善检测性能,本发明中短肽分子可以使用如苯丙氨酸-丝氨酸-赖氨酸、甲硫氨酸-半胱氨酸-组氨酸、色氨酸-丙氨酸-亮氨酸等但不限于此。所述MXene纳米传感层413由盐酸/氟化锂溶液刻蚀陶瓷相钛铝碳制备得到。具体地,将2质量份氟化锂溶于40体积份浓盐酸(质量分数为36%~38%)中,在室温下搅拌30分钟,制备出蚀刻液。然后将2质量份陶瓷相钛铝碳粉末缓慢加入溶液中,在40℃下搅拌反应24小时。反应完成后,取混合溶液以3500转/分钟速度离心,去上清液后以去离子水洗涤,采用涡旋发生器进行机械振荡,并再次以3500转/分钟速度离心,再次去上清液。重复以上步骤,直到黑色沉淀膨胀并明显分层。收集黑色沉淀并用去离子水分散,使用超声法进一步剥离MXene多层膜,以得到MXene纳米传感层413。将所得的MXene纳米传感层413配置成合适浓度,并与3%质量分数过氧化氢按不同体积比混合,80℃水浴加热处理5分钟,制备得到负载有不同浓度二氧化钛纳米颗粒414的MXene纳米传感层413。将上述材料按质量比1:2与短肽分子415(苯丙氨酸-丝氨酸-赖氨酸)混合溶解,室温下搅拌5分钟,得到均匀分散的溶液,随后分别加入0.005质量份的1-乙基-(3-二甲基氨基丙基)碳酰二亚胺和4-二甲氨基吡啶,在100℃下搅拌3小时。将所得溶液在8000转/分钟速度下离心,沉积物经去离子水冲洗后重新分散成合适浓度,得到二氧化钛纳米颗粒与短肽共修饰的MXene纳米传感层,使用喷枪喷涂在等离子体清洗过的传感器基底411与金叉指电极412上,干燥后最终得到MXene丙酮传感器41。As shown in Figure 5, the MXene acetone sensor 41 has modified the MXene nano-sensing layer 413, titanium dioxide nanoparticles 414 and short peptide molecules 415 on the gold interdigitated electrode 412, and the short peptide molecules 415 can improve the detection performance. In the present invention Short peptide molecules such as phenylalanine-serine-lysine, methionine-cysteine-histidine, tryptophan-alanine-leucine, etc. can be used, but are not limited thereto. The MXene nano-sensing layer 413 is prepared by etching ceramic phase titanium aluminum carbon with hydrochloric acid/lithium fluoride solution. Specifically, 2 parts by mass of lithium fluoride was dissolved in 40 parts by volume of concentrated hydrochloric acid (36%-38% by mass), and stirred at room temperature for 30 minutes to prepare an etching solution. Then slowly add 2 parts by mass of ceramic phase titanium aluminum carbon powder into the solution, and stir and react at 40° C. for 24 hours. After the reaction is completed, take the mixed solution and centrifuge at a speed of 3500 rpm, remove the supernatant, wash with deionized water, use a vortex generator for mechanical oscillation, and centrifuge again at a speed of 3500 rpm, and remove the supernatant again . Repeat the above steps until the black precipitate swells and visibly separates. The black precipitate was collected and dispersed with deionized water, and the MXene multilayer film was further peeled off by ultrasonic method to obtain the MXene nano-sensing layer 413 . The obtained MXene nano-sensing layer 413 is configured to a suitable concentration, mixed with 3% mass fraction hydrogen peroxide in different volume ratios, and heated in a water bath at 80°C for 5 minutes to prepare MXene nano-particles 414 loaded with different concentrations of titanium dioxide nanoparticles. Sensing layer 413 . Mix and dissolve the above materials with the short peptide molecule 415 (phenylalanine-serine-lysine) at a mass ratio of 1:2, stir at room temperature for 5 minutes to obtain a uniformly dispersed solution, and then add 0.005 parts by mass of 1- Ethyl-(3-dimethylaminopropyl)carbodiimide and 4-dimethylaminopyridine were stirred at 100°C for 3 hours. The resulting solution was centrifuged at a speed of 8,000 rpm, and the sediment was washed with deionized water and redispersed to a suitable concentration to obtain a MXene nanosensing layer co-modified with titanium dioxide nanoparticles and short peptides, which was sprayed with a spray gun after plasma cleaning. The sensor substrate 411 and the gold interdigitated electrodes 412 are dried and finally the MXene acetone sensor 41 is obtained.

装置的检测系统功能模块如图8所示。检测电路423主要由微控制器、恒流源、低通网络、模数转换器、蓝牙、场效应管、电池及电源管理电路,以及外围电阻电容构成。其中,微控制器实现信号调制,数据处理等功能,具体为恒流源提供参考电压Vref、通过I2C等总线获取模数转换器采样信号、与蓝牙进行数据传输、以及控制场效应管通断,等等。恒流源根据参考电压Vref输出恒定的测试电流Imeasure,经过MXene丙酮传感器41后产生电压信号并通过低通网络滤波去除工频噪声干扰,最后被模数转换器转换生成采样信号。微处理器产生控制信号调节场效应管通断,实现发光二极管442的开关,以控制对MXene丙酮传感器41的光辐照时间。蓝牙通过无线通信与移动终端进行信号传输,在移动终端进行数据处理和显示。系统通过电池及电源管理模块供能,提供供电电压Vcc驱动检测电路423。为实现紧凑小型化的电路设计,检测电路423均可采用微型低功耗芯片,包括但不限于MSP430FR2632微处理器芯片、AD8605运算放大器芯片、ADS1115模数转换芯片等。The functional modules of the detection system of the device are shown in Figure 8. The detection circuit 423 is mainly composed of a microcontroller, a constant current source, a low-pass network, an analog-to-digital converter, Bluetooth, a field effect transistor, a battery and a power management circuit, and peripheral resistors and capacitors. Among them, the microcontroller realizes signal modulation, data processing and other functions, specifically provides reference voltage Vref for constant current source, obtains analog-to-digital converter sampling signal through bus such as I2C, performs data transmission with Bluetooth, and controls field effect tube on and off, wait. The constant current source outputs a constant test current Imeasure according to the reference voltage Vref. After passing through the MXene acetone sensor 41, a voltage signal is generated, filtered by a low-pass network to remove power frequency noise interference, and finally converted by an analog-to-digital converter to generate a sampling signal. The microprocessor generates a control signal to adjust the on-off of the field effect tube to realize the switch of the light-emitting diode 442 to control the light irradiation time of the MXene acetone sensor 41 . Bluetooth performs signal transmission with the mobile terminal through wireless communication, and performs data processing and display on the mobile terminal. The system is powered by the battery and the power management module, which provides the power supply voltage Vcc to drive the detection circuit 423 . In order to achieve a compact and miniaturized circuit design, the detection circuit 423 can use micro-chips with low power consumption, including but not limited to MSP430FR2632 microprocessor chips, AD8605 operational amplifier chips, ADS1115 analog-to-digital conversion chips, and the like.

本发明装置可对0.5-50ppm浓度的呼出气丙酮进行实时监测,在使用前进行标定。标定实验中使用标准丙酮气(100ppm)与标准空气进行混合配置得到不同浓度丙酮气,标准丙酮气通过无水丙酮在标准空气中完全挥发配置得到。The device of the invention can monitor the exhaled acetone at a concentration of 0.5-50 ppm in real time, and perform calibration before use. In the calibration experiment, standard acetone gas (100ppm) is mixed with standard air to obtain different concentrations of acetone gas. The standard acetone gas is obtained by completely volatilizing anhydrous acetone in standard air.

由于MXene丙酮传感器41存在不可逆的丙酮吸附现象,为实现重复性良好、可定量分析的丙酮传感检测,本发明引入发光二极管442对MXene丙酮41传感器进行光辐照。由于所述MXene丙酮传感器41中包含二氧化钛纳米颗粒414与MXene纳米传感层413构成的光电响应异质界面在光辐照条件下能产生光生载流子,改善丙酮脱附情况,因此在丙酮检测期间保持发光二极管442的开启,以校正MXene丙酮传感器41的响应。Since the MXene acetone sensor 41 has an irreversible acetone adsorption phenomenon, in order to realize acetone sensing and detection with good repeatability and quantitative analysis, the present invention introduces a light-emitting diode 442 to irradiate the MXene acetone 41 sensor with light. Since the photoelectric response heterogeneous interface composed of titanium dioxide nanoparticles 414 and MXene nano-sensing layer 413 in the MXene acetone sensor 41 can generate photogenerated carriers under light irradiation conditions, and improve the acetone desorption situation, so in acetone detection During this period, keep the LED 442 turned on to correct the response of the MXene acetone sensor 41 .

如图9所示,当通入丙酮气时,MXene丙酮传感器41产生正向的归一化电阻响应,表明传感器电阻随丙酮通入而增大。当重新通入空气后丙酮响应恢复到基线值,表明光辐照条件下丙酮响应完全可逆,且随着丙酮浓度增加响应值依次增大。此外,图9表明所述的MXene丙酮传感器41具有较快的丙酮响应和恢复速度,有利于进一步缩短呼出气分析时间。对同一批次的MXene丙酮传感器41进行三次独立重复实验,将所得结果绘制散点图并使用分段线性拟合。如图10所示,丙酮响应在0.5-2ppm以及2-50ppm浓度范围分别呈现线性相关,其中,在0.5-2ppm范围内线性相关系数R2为0.98,灵敏度为0.672%/ppm;在2-50ppm范围内线性相关系数R2为0.97,灵敏度为0.145%/ppm。独立重复测试的结果具有较好的一致性,表现为图10中较小的误差条。As shown in FIG. 9 , when acetone gas is fed, the MXene acetone sensor 41 produces a positive normalized resistance response, indicating that the sensor resistance increases with the acetone gas being fed. The acetone response returned to the baseline value after the air was reintroduced, indicating that the acetone response was completely reversible under light irradiation, and the response value increased sequentially with the increase of the acetone concentration. In addition, FIG. 9 shows that the MXene acetone sensor 41 has a faster acetone response and recovery speed, which is beneficial to further shorten the time for exhaled gas analysis. Three independent repeated experiments were performed on the same batch of MXene acetone sensor 41, and the obtained results were plotted as scatter plots and piecewise linear fitting was used. As shown in Figure 10, the acetone response presents a linear correlation in the concentration ranges of 0.5-2ppm and 2-50ppm respectively, wherein the linear correlation coefficient R in the range of 0.5-2ppm is 0.98, and the sensitivity is 0.672%/ppm; The linear correlation coefficient R2 in the range is 0.97, and the sensitivity is 0.145%/ppm. The results of independent repeated tests have good agreement, as shown by the smaller error bars in Figure 10.

本实施例对MXene丙酮传感器41的检测重复性及长期稳定性进行了测试。如图11-12所示,MXene丙酮传感器41在连续多个周期的5ppm丙酮响应-恢复中表现出良好的可逆性,且响应幅度保持良好一致。连续15天的稳定性测试表明MXene丙酮传感器41具有较好的长期稳定性,在较小的响应衰减下能够应用于长期的呼出气丙酮检测。In this embodiment, the detection repeatability and long-term stability of the MXene acetone sensor 41 are tested. As shown in Figures 11-12, the MXene acetone sensor 41 exhibits good reversibility in the response-recovery of 5ppm acetone for multiple consecutive cycles, and the response amplitude remains well consistent. The stability test for 15 consecutive days shows that the MXene acetone sensor 41 has good long-term stability, and can be applied to long-term exhaled breath acetone detection with a small response attenuation.

针对呼出气中存在的湿度、呼出乙醇、氨等典型干扰物,作为一种优选实施方案,本发明提出一种能够抑制呼吸干扰基于MXene的织物过滤器5,基于MXene的织物过滤器5由铂纳米颗粒负载MXene织物52与活性干燥剂51构成,如图6所示。活性干燥剂51可采用对人体无害的颗粒形干燥剂,包括但不限于活性氧化铝、变色硅胶等。铂纳米颗粒负载MXene织物52由两步溶液处理法制备得到,如图7所示。首先将经过去离子水清洗并干燥的白色棉织物浸泡在5mg/mL MXene溶液中,沉积30分钟。利用MXene与棉织物表面丰富的含氧官能团形成氢键网络,实现MXene在棉织物上稳定的静电吸附。采用去离子水冲洗未吸附的MXene并干燥。重复上述步骤直到得到黑色的MXene织物。将所得MXene织物浸泡在3.86nM氯铂酸溶液中,反应30分钟,利用MXene的化学活性表面实现铂纳米颗粒的原位还原,制备得到铂纳米颗粒负载MXene织物52。将活性干燥剂51填充到铂纳米颗粒负载MXene织物52之间,使用透气性良好的聚二甲基硅氧烷胶水对铂纳米颗粒负载MXene织物52进行封装粘合,得到基于MXene的织物过滤器5。Typical interfering substances such as humidity, exhaled ethanol, ammonia, etc. that exist in the exhaled air, as a preferred embodiment, the present invention proposes a fabric filter 5 based on MXene that can suppress respiratory interference, and the fabric filter 5 based on MXene is made of platinum The nanoparticle-loaded MXene fabric 52 is composed of an active desiccant 51, as shown in FIG. 6 . The active desiccant 51 can be a granular desiccant that is harmless to the human body, including but not limited to activated alumina, color-changing silica gel, and the like. Platinum nanoparticles loaded MXene fabric 52 was prepared by a two-step solution processing method, as shown in Fig. 7 . First, white cotton fabrics washed and dried in deionized water were soaked in 5 mg/mL MXene solution and deposited for 30 min. The stable electrostatic adsorption of MXene on cotton fabric was realized by utilizing the hydrogen bond network formed by MXene and abundant oxygen-containing functional groups on the surface of cotton fabric. The unadsorbed MXene was rinsed with deionized water and dried. Repeat the above steps until you get a black MXene fabric. The obtained MXene fabric was soaked in a 3.86 nM chloroplatinic acid solution and reacted for 30 minutes. The chemically active surface of MXene was used to realize the in situ reduction of platinum nanoparticles, and the platinum nanoparticle-loaded MXene fabric 52 was prepared. The active desiccant 51 is filled between the platinum nanoparticle-loaded MXene fabrics 52, and the platinum nanoparticle-loaded MXene fabric 52 is encapsulated and bonded with polydimethylsiloxane glue with good air permeability to obtain an MXene-based fabric filter 5.

本发明对其干扰过滤性能进行标定。如图13-16所示,实验用模拟呼出气(5%二氧化碳,79%氮,16%氧)分别混合10ppm氨气、乙醇、丙酮以及90%相对湿度,得到未过滤标准气。使用MXene丙酮传感器41测试未过滤的干扰物响应,并分别使用商业湿度计标定湿度,气象色谱标定氨气、乙醇、丙酮浓度。同时,将包含干扰物的模拟呼出气通过基于MXene的织物过滤器5,过滤后的模拟呼出气由MXene丙酮传感器41测试响应,并用气袋收集尾气再次进行商业湿度计标定湿度,气象色谱标定氨气、乙醇、丙酮浓度。图13-16表明,所述基于MXene的织物过滤器5对氨气、乙醇、湿度均有良好的过滤效果,对丙酮有一定的过滤作用,但MXene丙酮传感器41仍然保持较高的丙酮响应。因此,所述基于MXene的织物过滤器5能够改善呼出气丙酮检测的选择性。The invention calibrates its interference filtering performance. As shown in Figures 13-16, the experimental simulated exhaled air (5% carbon dioxide, 79% nitrogen, 16% oxygen) was mixed with 10ppm ammonia, ethanol, acetone and 90% relative humidity to obtain unfiltered standard gas. Use the MXene acetone sensor 41 to test the unfiltered interference response, and use a commercial hygrometer to calibrate the humidity, and a gas chromatograph to calibrate the concentrations of ammonia, ethanol, and acetone. Simultaneously, the simulated exhaled air containing interfering substances is passed through the fabric filter 5 based on MXene, the filtered simulated exhaled air is tested for response by the MXene acetone sensor 41, and the tail gas is collected with an air bag to calibrate the humidity of the commercial hygrometer again, and the gas chromatograph calibrates the ammonia Gas, ethanol, acetone concentration. Figures 13-16 show that the MXene-based fabric filter 5 has a good filtering effect on ammonia, ethanol, and humidity, and has a certain filtering effect on acetone, but the MXene acetone sensor 41 still maintains a high response to acetone. Therefore, the MXene-based fabric filter 5 can improve the selectivity of exhaled acetone detection.

进一步地,本发明装置能够在干扰物存在的情况下实现选择性的呼出气丙酮检测。如图17所示,实验配置了分别混合10ppm丙酮、氨气、乙醇、己烷、异戊二烯的90%RH湿度模拟呼出气,测试结果表明,本发明装置对丙酮产生了最高的响应,对极性和非极性的呼出气干扰物均具有明显的抑制,从选择性方面看能够满足呼出气复杂环境中的丙酮检测需求。Further, the device of the present invention can realize selective detection of acetone in exhaled breath in the presence of interfering substances. As shown in Figure 17, the experiment was configured with 90% RH humidity simulated exhaled air mixed with 10ppm acetone, ammonia, ethanol, hexane, and isoprene respectively. The test results showed that the device of the present invention produced the highest response to acetone. It has obvious suppression of polar and non-polar exhaled breath interferers, and can meet the requirements of acetone detection in the complex environment of exhaled breath from the perspective of selectivity.

为了实现稳定检测,作为一优选实施方案,该装置还包括一次性口罩1、呼吸阀2、呼吸阀外壳3,构成MXene智能口罩11,其中,所述呼出气丙酮检测标签4固定在一次性口罩1外侧的呼吸阀2与呼吸阀外壳3之间,用于检测呼出气中丙酮浓度。基于MXene的织物过滤器5固定在一次性口罩1内侧的呼吸阀2之上,用于过滤通过呼吸阀2的呼出气,如图1-2所示。In order to achieve stable detection, as a preferred embodiment, the device also includes a disposable mask 1, a breathing valve 2, and a breathing valve housing 3 to form an MXene smart mask 11, wherein the exhaled acetone detection label 4 is fixed on the disposable mask 1 between the outer respiration valve 2 and the respiration valve housing 3 for detecting the concentration of acetone in the exhaled air. The fabric filter 5 based on MXene is fixed on the breathing valve 2 inside the disposable mask 1, and is used to filter the exhaled air passing through the breathing valve 2, as shown in Figure 1-2.

图18是本发明实施例提供的MXene智能口罩11的一种实施方式示意图。将基于MXene的织物过滤器5装配在一次性口罩1紧贴呼吸阀2的内表面,将呼出气丙酮检测标签4装配在一次性口罩1外侧呼吸阀2与呼吸阀外壳3之间,利用蓝牙无线传输实现用于呼出气丙酮检测MXene智能口罩11与移动终端12之间的数据通信及后续数据显示处理。呼出气经由基于MXene的织物过滤器5过滤,通过检测电路板开窗421以及封装层开窗431,直接被MXene丙酮传感器41检测,无需其他预处理。移动终端12根据接收到的数据绘制连续实时的呼吸曲线,并在实时呼吸曲线显示功能区13展示呼吸活动引起的呼出气节律和呼出气丙酮浓度变化,呼吸结果分析功能区14展示计算出的呼出气丙酮浓度和每分钟的呼息速率。Fig. 18 is a schematic diagram of an implementation of the MXene smart mask 11 provided by the embodiment of the present invention. The MXene-based fabric filter 5 is assembled on the inner surface of the disposable mask 1 close to the breathing valve 2, and the exhaled acetone detection label 4 is assembled between the breathing valve 2 on the outer side of the disposable mask 1 and the breathing valve shell 3. Wireless transmission realizes data communication and subsequent data display processing between the MXene smart mask 11 and the mobile terminal 12 for exhaled acetone detection. The exhaled air is filtered through the MXene-based fabric filter 5, passes through the detection circuit board opening 421 and the packaging layer opening 431, and is directly detected by the MXene acetone sensor 41 without other pretreatment. The mobile terminal 12 draws a continuous real-time respiratory curve according to the received data, and displays the exhaled breath rhythm and the change of exhaled acetone concentration caused by breathing activity in the real-time respiratory curve display functional area 13, and the respiratory result analysis functional area 14 displays the calculated exhaled breath. Gas acetone concentration and breath rate per minute.

进一步地,本实施例招募了5位志愿者对本发明所述的MXene智能口罩11进行在体呼吸测试验证,并检测了5位志愿者血酮浓度变化作为呼出气丙酮浓度变化的标准参考。血酮测试是临床常用的酮体测试方法,也是呼出气丙酮检测的常用参考值。实验过程中,志愿者按照实验人员的引导,穿戴用于呼出气丙酮检测MXene智能口罩11进行5分钟以内的呼出气丙酮测试,同时采集指尖血并进行血酮水平检测。采血前利用酒精棉片为指尖消毒,采血时使用采血笔和一次性微创采血针,利用标准生化试纸检测血酮水平作为参照。计一次呼出气丙酮测试和一次血酮水平检测为一次标准测试。其中,两位志愿者参加饮食试验,在三天内分别摄入均衡饮食,生酮饮食,以及高碳水饮食,第一天晚上五点半和八点半分别进行标准测试一次,第二天从早上八点半到晚上八点半每3小时标准测试一次,第三天从早上八点半到晚上五点半每3小时标准测试一次,每人总计11次标准测试。另外三位志愿者参加运动试验,在工作日进行两次半小时的单车骑行运动,总计一个小时运动,实验控制受试者运动负载,并监测心输出量作为运动强度参考,随后志愿者需要静坐休息共两个小时,实验持续总计三个小时。试验期间,在第0、30、90、120、180分钟进行标准测试,每人总计5次标准测试。Further, in this embodiment, 5 volunteers were recruited to carry out in-body breathing test verification on the MXene smart mask 11 described in the present invention, and the blood ketone concentration changes of the 5 volunteers were detected as a standard reference for the change of acetone concentration in exhaled breath. Blood ketone test is a commonly used clinical method for ketone body testing, and it is also a common reference value for exhaled acetone testing. During the experiment, the volunteers followed the guidance of the experimenters, wore the MXene smart mask 11 for exhaled acetone detection, and performed the exhaled acetone test within 5 minutes, and at the same time collected fingertip blood and tested the blood ketone level. Alcohol swabs were used to sterilize fingertips before blood collection, blood collection pens and disposable minimally invasive blood collection needles were used during blood collection, and blood ketone levels were detected with standard biochemical test strips as a reference. A breath acetone test and a blood ketone level test count as one standard test. Among them, two volunteers participated in the diet experiment, and they ate a balanced diet, a ketogenic diet, and a high-carbohydrate diet within three days. They performed a standard test at 5:30 and 8:30 on the first day, and the second day from the morning A standard test was performed every 3 hours from 8:30 to 8:30 pm, and a standard test was performed every 3 hours from 8:30 am to 5:30 pm on the third day, with a total of 11 standard tests per person. The other three volunteers participated in the exercise test. They had two half-hour cycling exercises on weekdays, totaling an hour of exercise. The experiment controlled the exercise load of the subjects, and monitored the cardiac output as a reference for exercise intensity. Then the volunteers needed to There was a total of two hours of sitting and rest, and the experiment lasted a total of three hours. During the test period, standard tests were performed at 0, 30, 90, 120, and 180 minutes, and each person had a total of 5 standard tests.

如图19所示,本发明实施例提供的MXene智能口罩11用于呼出气丙酮检测,所得结果与志愿者血酮水平做相关性分析。通过线性回归得到呼出气丙酮与血酮的皮尔森相关系数为0.911,证明所述用于MXene智能口罩11能够用于可靠的呼出气丙酮检测。As shown in Figure 19, the MXene smart mask 11 provided by the embodiment of the present invention is used to detect acetone in exhaled breath, and the correlation analysis between the obtained results and the blood ketone level of volunteers is carried out. The Pearson correlation coefficient between exhaled acetone and blood ketone obtained by linear regression is 0.911, which proves that the MXene smart mask 11 can be used for reliable exhaled acetone detection.

需要说明的是,以上所述仅为本发明的优选实施例,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。在没有做出创造性劳动的前提下,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。It should be noted that the above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. On the premise of no creative work, any modification, equivalent replacement, improvement, etc. should be included in the protection scope of the present invention.

Claims (10)

1. The utility model provides a wearable exhaled breath acetone detection device based on MXene which characterized in that, it includes: an exhaled breath acetone detection label (4); the exhaled breath acetone detection label (4) comprises an MXene acetone sensor (41), a flexible detection circuit board (42), a polydimethylsiloxane packaging layer (43) for packaging the flexible detection circuit board (42) and a light-emitting diode circuit board (44) which are sequentially assembled from bottom to top, wherein the light-emitting diode circuit board (44) comprises a light-emitting diode substrate (441) and a light-emitting diode (442) fixed on the light-emitting diode substrate (441), and windows are arranged on the flexible detection circuit board (42) and the polydimethylsiloxane packaging layer (43) so that the light-emitting diode (442) is opposite to the MXene acetone sensor (41); the diode circuit board (44) and the MXene acetone sensor (41) are electrically connected with the flexible detection circuit board (42); the MXene acetone sensor (41) is used for detecting the concentration of acetone in the exhaled breath and converting the acetone into an electric signal, and the flexible detection circuit board (42) is used for acquiring and processing the electric signal of the MXene acetone sensor (41); the MXene acetone sensor (41) comprises a sensor substrate (411), a gold interdigital electrode (412) and an MXene nano sensing layer (413) which are sequentially assembled from bottom to top, wherein titanium dioxide nanoparticles (414) and short peptide molecules (415) are modified on the surface of the MXene nano sensing layer (413).
2. The device according to claim 1, wherein the MXene nano sensing layer (413) is prepared by mixing 2 parts by mass of ceramic phase titanium aluminum carbon powder, 2 parts by mass of lithium fluoride and 40 parts by volume of concentrated hydrochloric acid, etching at 40 ℃ for 24 hours, cleaning precipitate by deionized water, and spraying the mixture on the surface of the gold interdigital electrode (412) after ultrasonic mechanical stripping assisted by a vortex generator.
3. The device according to claim 1, characterized in that the titanium dioxide nanoparticles (414) are modified by: mixing the MXene nano sensing layer (413) with 3% of hydrogen peroxide solution by mass fraction, and heating in a water bath at 80 ℃ to obtain the nano sensing material, wherein the titanium dioxide nano particles (414) grow on the MXene nano sensing layer (413) in situ.
4. The device of claim 1, wherein the short peptide molecule (415) is modified by: mixing and dissolving the MXene nano sensing layer (413) of the in-situ grown titanium dioxide nanoparticles (414) according to the mass ratio of 1.
5. The device according to claim 1, further comprising an MXene-based fabric filter (5) for filtering exhaled breath; the MXene-based fabric filter (5) is composed of a platinum nanoparticle-loaded MXene fabric (52) and an active drying agent (51) wrapped in the platinum nanoparticle-loaded MXene fabric (52), wherein the platinum nanoparticle-loaded MXene fabric (52) is obtained by performing electrostatic adsorption on MXene on the surface of cotton fabric and performing in-situ reduction on the loaded platinum nanoparticles on the MXene surface in a chloroplatinic acid solution.
6. The device according to claim 5, characterized in that the platinum nanoparticle loaded MXene fabric (52) is prepared in particular by: the white cotton fabric which is washed by deionized water and dried is soaked in 5mg/mL MXene solution, deposition is carried out for 30 minutes, the white cotton fabric is repeatedly washed and dried and then soaked in 3.86mM chloroplatinic acid solution, reaction is carried out for 30 minutes, and the in-situ reduction of the platinum nanoparticles is realized by utilizing the chemical active surface of MXene.
7. The device according to claim 1, wherein the flexible detection circuit board (42) is composed of a detection circuit substrate (422), a detection circuit (423), a diode circuit connection pad (424) and a sensor connection pad (425), the detection circuit substrate (422) is composed of a polyimide film, the detection circuit (423) mainly comprises a miniature low-power chip and a peripheral resistor-capacitor, and is used for acquiring and processing the electric signal of the MXene acetone sensor (41); and respectively welding the light-emitting diode circuit board (44) and the MXene acetone sensor (41) on the diode circuit connecting pad (424) and the sensor connecting pad (425) through low-temperature soldering tin, so that the electrical connection between the diode circuit board (44), the MXene acetone sensor (41) and the flexible detection circuit board (42) is realized.
8. The device according to claim 7, characterized in that the detection circuit (423) is composed of a microcontroller, a constant current source, an analog-to-digital converter, bluetooth, a low-pass network, a field effect transistor, a light emitting diode, a battery and power management circuit, and a peripheral resistor-capacitor.
9. The device according to any one of claims 1 to 8, further comprising a disposable mask (1), a breather valve (2) and a breather valve housing (3) fixed on the disposable mask (1), wherein the exhaled breath acetone detection label (4) is fixed between the breather valve (2) and the breather valve housing (3) on the outside of the disposable mask (1), and an MXene-based fabric filter (5) is fixed on the breather valve (2) on the inside of the disposable mask (1) for filtering the exhaled breath passing through the breather valve (2).
10. A detection method of exhaled breath acetone based on MXene is characterized by comprising the following steps:
use of the device of any of claims 1-9 to obtain the acetone concentration of exhaled breath, keeping the light emitting diode (442) on during the acetone detection.
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