Baruah Upama, Manna Uttam
Bio-Inspired Polymeric Materials Lab, Department of Chemistry, Indian Institute of Technology-Guwahati Kamrup Assam 781039 India.
Centre for Nanotechnology, Indian Institute of Technology-Guwahati Kamrup Assam 781039 India
Chem Sci. 2020 Dec 8;12(6):2097-2107. doi: 10.1039/d0sc05166g.
In the past, chemically reactive polymeric interfaces have been considered to be of potential interest for developing functional materials for a wide range of practical applications. Furthermore, the rational incorporation of luminescence properties into such chemically reactive interfaces could provide a basis for extending the horizon of their prospective utility. In this report, a simple catalyst-free chemical approach is introduced to develop a chemically reactive and optically active polymeric gel. Branched-polyethyleneimine (BPEI)-derived, inherently luminescent carbon dots (BPEI-CDs) were covalently crosslinked with pentaacrylate (5Acl) through a 1,4-conjugate addition reaction under ambient conditions. The synthesized polymeric gel was milky white under visible light; however, it displayed fluorescence under UV light. Additionally, the residual acrylate groups in the synthesized fluorescent gel allowed its chemical functionality to be tailored through facile, robust 1,4-conjugate addition reactions with primary-amine-containing small molecules under ambient conditions. The chemical reactivity of the luminescent gel was further employed for a proof-of-concept demonstration of portable and parallel 'ON'/'OFF' toxic chemical sensing (namely, the sensing of nitrite ions as a model analyte). First, the chemically reactive luminescent gel derived from BPEI-CDs was covalently post-modified with aniline for the selective synthesis of a diazo compound in the presence of nitrite ions. During this process, the color of the gel under visible light changed from white to yellow and, thus, the colorimetric mode of the sensor was turned 'ON'. In parallel, the luminescence of the gel under UV light was quenched, which was denoted as the 'OFF' mode of the sensor. This parallel and unambiguous 'ON'/'OFF' sensing of a toxic chemical (nitrite ions, with a detection limit of 3 μM) was also achieved even in presence of other relevant interfering ions and at concentrations well below the permissible limit (65 μM) set by the World Health Organization (WHO). Furthermore, this chemically reactive luminescent gel could be of potential interest in a wide range of basic and applied contexts.
过去,化学反应性聚合物界面被认为对于开发适用于广泛实际应用的功能材料具有潜在的吸引力。此外,将发光特性合理地引入此类化学反应性界面可为拓展其潜在用途的范围提供基础。在本报告中,引入了一种简单的无催化剂化学方法来制备具有化学反应性和光学活性的聚合物凝胶。通过在环境条件下的1,4-共轭加成反应,将支化聚乙烯亚胺(BPEI)衍生的固有发光碳点(BPEI-CDs)与五丙烯酸酯(5Acl)共价交联。合成的聚合物凝胶在可见光下呈乳白色;然而,它在紫外光下显示出荧光。此外,合成的荧光凝胶中残留的丙烯酸酯基团使其化学功能能够通过在环境条件下与含伯胺的小分子进行简便、稳健的1,4-共轭加成反应来进行定制。发光凝胶的化学反应性还被用于便携式并行“开”/“关”有毒化学传感的概念验证演示(即,以亚硝酸根离子作为模型分析物进行传感)。首先,将源自BPEI-CDs的化学反应性发光凝胶用苯胺进行共价后修饰,以便在亚硝酸根离子存在的情况下选择性合成重氮化合物。在此过程中,凝胶在可见光下的颜色从白色变为黄色,从而传感器的比色模式被“打开”。同时,凝胶在紫外光下的发光被猝灭,这被表示为传感器的“关闭”模式。即使在存在其他相关干扰离子且浓度远低于世界卫生组织(WHO)设定的允许限值(65 μM)的情况下,也实现了对有毒化学物质(亚硝酸根离子,检测限为3 μM)如此并行且明确的“开”/“关”传感。此外,这种化学反应性发光凝胶在广泛的基础和应用背景中可能具有潜在的吸引力。