Mills Andrew, McDonnell Lauren, Yusufu Dilidaer
School of Chemistry and Chemical Engineering, Queens University Belfast, David Keir Building, Stranmillis Road, Belfast BT95AG, U.K.
Acc Mater Res. 2023 Jun 19;4(7):570-579. doi: 10.1021/accountsmr.2c00226. eCollection 2023 Jul 28.
Carbon dioxide, CO, is an essential part of life, in that through green plant photosynthesis it is used to generate food and fuel and is generated in both aerobic and anaerobic respiration. Industrially, it is used in fire extinguishers, supercritical fluid extractions, and food packaging. Environmentally, it is in the atmosphere, hydrosphere, and biosphere and is responsible for global warming and the acidification of the oceans. The monitoring of CO in the gas phase is usually carried out using FTIR spectroscopy, whereas the measurement of dissolved CO usually involves an electrochemical device. Excitingly, the most recent forms of CO indicators appear to offer significant advantages over current methods, such as simplicity, low cost, and portability. This Account highlights the work of the Mills group on transforming CO colorimetric indicator technology from the usual water-based (i.e., "wet") indicator form to dry CO-sensitive inks, pigments, plastics, and adhesives. Initially, the basic theory associated with colorimetric CO indicators is described, and the simple relationship between indicator absorbance and the partial pressure of CO, , established. The early work on CO-sensitive inks is then described, where such inks comprise a hydrophilic pH-sensitive dye anion, coupled with a lipophilic quaternary ammonium cation, dissolved in a nonaqueous solution of a polymer which, when cast, forms a dry ink film that gives a reversible color response when exposed to CO both in the gas phase and dissolved in solution. The ability to tune the sensitivity of a CO ink film to the desired application through the judicious choice of the pH indicator dye and base concentration is described. The dependence of the sensitivity of a CO ink film on temperature is used to create a temperature indicator, and the ability to tune the ink, to respond to high levels of CO, is used to create a fizziness indicator for carbonated drinks. Very sensitive CO inks are used to make a vacuum and a general air-pressure indicator. The more recent development in CO indicator technology is described in which CO inks are used to coat silica particles to make a range of different CO-sensitive pigments, which, when incorporated into a plastic, through extrusion, produce a range of novel CO-sensitive plastic films that have many notable advantages over their ink film counterparts. Examples are then given of such plastic films being used for dissolved CO measurements in salt water, for food packaging, and as an early wound-infection indicator. Finally, the recent incorporation of a CO-sensitive pigment into a pressure sensitive adhesive to make an after opening freshness tape is described briefly. Although most commercial CO indicators are assessed by eye and so are limited to qualitative analysis, this work shows that colorimetric CO indicators can be used for quantitative analysis through absorbance measurements. Nowadays, such measurements can be readily made using just a digital camera and color analysis software via digital camera colorimetry, DCC, which is likely to have a significant impact on the widespread use of the CO indicators described herein, their commercial viability, and their potential areas of application.
二氧化碳(CO₂)是生命的重要组成部分,通过绿色植物的光合作用,它被用于生产食物和燃料,并且在有氧呼吸和无氧呼吸过程中都会产生。在工业上,它被用于灭火器、超临界流体萃取和食品包装。在环境方面,它存在于大气圈、水圈和生物圈中,是全球变暖和海洋酸化的原因。气相中CO₂的监测通常使用傅里叶变换红外光谱法,而溶解态CO₂的测量通常涉及电化学装置。令人兴奋的是,最新形式的CO₂指示剂似乎比现有方法具有显著优势,如操作简单、成本低和便于携带。本综述重点介绍了米尔斯团队在将CO₂比色指示剂技术从常见的水基(即“湿”)指示剂形式转变为对CO₂敏感的干油墨、颜料、塑料和粘合剂方面的工作。首先,描述了与比色CO₂指示剂相关的基本理论,并建立了指示剂吸光度与CO₂分压之间的简单关系。接着介绍了早期对CO₂敏感油墨的研究,这类油墨包含一种亲水性pH敏感染料阴离子和一种亲脂性季铵阳离子,溶解在聚合物的非水溶液中,当浇铸时形成干油墨膜,在气相和溶解态CO₂存在时会产生可逆的颜色变化。阐述了通过明智地选择pH指示剂染料和碱浓度来调节CO₂油墨膜对特定应用的灵敏度的能力。利用CO₂油墨膜灵敏度对温度的依赖性制作温度指示剂,以及通过调节油墨使其对高浓度CO₂作出响应来制作碳酸饮料的气泡感指示剂。非常灵敏的CO₂油墨被用于制作真空和通用气压指示剂。文中还介绍了CO₂指示剂技术的最新进展,即使用CO₂油墨包覆二氧化硅颗粒制成一系列不同的CO₂敏感颜料,通过挤出工艺将其掺入塑料中,可生产出一系列新型的CO₂敏感塑料薄膜,与相应的油墨膜相比具有许多显著优点。随后列举了此类塑料薄膜用于盐水中溶解态CO₂测量、食品包装以及作为早期伤口感染指示剂的实例。最后简要介绍了最近将CO₂敏感颜料掺入压敏胶中制成开封后新鲜度胶带的情况。尽管大多数商业CO₂指示剂是通过肉眼评估的,因此仅限于定性分析,但这项工作表明,比色CO₂指示剂可通过吸光度测量用于定量分析。如今,借助数码相机比色法(DCC),仅使用数码相机和颜色分析软件就能轻松进行此类测量,这可能会对本文所述CO₂指示剂的广泛应用、商业可行性及其潜在应用领域产生重大影响。