Institute for Advanced Study, Shenzhen University, 3688 Nanhai Road, Shenzhen, Guangdong 518060, P.R. China.
Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, Illinois 61801, United States.
Acc Chem Res. 2021 Feb 16;54(4):950-960. doi: 10.1021/acs.accounts.0c00671. Epub 2020 Dec 17.
How does one tell the difference between one molecule or mixture of molecules from another? Chemical sensing seeks to probe physical or chemical properties of molecular or ionic species (i.e., analytes) and transform that information into a useful and distinguishable output. The olfactory system of animals is the prototype of chemical sensing. Even for human beings (who are generally more visual than olfactory creatures), the sense of smell is one of our most basic capabilities, and we can discriminate among many thousands, and possibly even billions, of different odors. The chemical specificity of the olfactory system does not come from specific receptors for specific analytes (i.e., the traditional lock-and-key model of enzyme-substrate interactions), but rather olfaction uses pattern recognition of the combined responses of several hundred olfactory receptors.In analogy to olfaction, colorimetric sensor arrays provide high dimensional data from the color changes of chemically responsive colorants as they are exposed to analytes. These colorants include pH responsive dyes, Lewis acid/base indicators, redox dyes, vapochromics, and surface-modified silver nanoparticles. The color difference maps so created provide chemical sensing with high sensitivity (often down to ppb levels), impressive discrimination among very similar analytes, and exquisite fingerprinting of extremely similar mixtures over a wide range of analyte types, both in the gas and liquid phases. Such colorimetric arrays probe a wide range of the chemical reactivity of analytes, rather than the limited dimensionality of physical properties (e.g., mass) or physisorption (e.g., traditional electronic noses). Our sensor arrays are disposable and simple to produce by either inkjet or robotic dip-pen printing onto the surface of porous polymer membranes or even paper.Design of both sensor arrays and optical readers for their analysis has advanced to a fully self-contained pocket-sized instrument, the optoelectronic nose. Quantitative analysis requires appropriate chemometric methods for pattern recognition of data with inherently high dimensionality, e.g., hierarchical cluster analysis and support vector machines. A wide range of applications for the colorimetric sensor arrays has been developed, including personal dosimetry of toxic industrial chemicals, detection of explosives or fire accelerants, monitoring pollutants for artwork and cultural heritage preservation, quality control of foods and beverages, rapid identification of bacteria and fungi, and detection of disease biomarkers in breath or urine. The development of portable, high-accuracy instrumentation using standard imaging devices with the capability of onboard, real-time analysis has had substantial progress and increasingly meets the expectations for real-world use.
如何区分一个分子或分子混合物与另一个分子或分子混合物?化学传感旨在探测分子或离子种类(即分析物)的物理或化学性质,并将该信息转化为有用且可区分的输出。动物的嗅觉系统是化学传感的原型。即使对于人类(通常比嗅觉动物更具视觉性),嗅觉也是我们最基本的能力之一,我们可以区分成千上万种,甚至可能数十亿种不同的气味。嗅觉系统的化学特异性不是来自于特定的分析物特定受体(即酶-底物相互作用的传统锁钥模型),而是嗅觉系统使用数百个嗅觉受体的组合反应的模式识别。类似地,比色传感器阵列通过暴露于分析物时化学响应着色剂的颜色变化提供高维数据。这些着色剂包括 pH 响应染料、路易斯酸碱指示剂、氧化还原染料、蒸气变色剂和表面修饰的银纳米粒子。如此创建的颜色差异图为化学传感提供了高灵敏度(通常低至 ppb 水平)、对非常相似的分析物进行令人印象深刻的区分,以及对极相似混合物的精美指纹识别,范围广泛的分析物类型,无论是在气相还是液相中。这种比色阵列探测分析物的化学反应性范围很广,而不是物理性质(例如质量)或物理吸附(例如传统的电子鼻)的有限维度。我们的传感器阵列是一次性的,通过喷墨或机器人蘸笔印刷到多孔聚合物膜甚至纸张的表面上,非常简单地制作。传感器阵列和光学读取器的设计都已经发展到了完全独立的袖珍仪器,即光电鼻。定量分析需要适当的化学计量学方法来对固有高维数据进行模式识别,例如层次聚类分析和支持向量机。比色传感器阵列已经开发出了广泛的应用,包括有毒工业化学品的个人剂量测定、爆炸物或火灾促进剂的检测、艺术品和文化遗产保护用污染物监测、食品和饮料的质量控制、细菌和真菌的快速识别以及呼吸或尿液中疾病生物标志物的检测。使用具有板载实时分析能力的标准成像设备开发便携式、高精度仪器已经取得了实质性进展,并且越来越符合实际使用的期望。