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有机硅烷功能化碳量子点及其在“开-关-开”式铬酸盐和抗坏血酸荧光测定以及白光发光器件中的应用。

Organosilane-functionalized carbon quantum dots and their applications to "on-off-on" fluorometric determination of chromate and ascorbic acid, and in white light-emitting devices.

机构信息

Key laboratory of Bio-based Material Science and Technology of Ministry of Education, Northeast Forestry University, Harbin, 150040, People's Republic of China.

出版信息

Mikrochim Acta. 2019 Jul 6;186(8):516. doi: 10.1007/s00604-019-3603-6.

DOI:10.1007/s00604-019-3603-6
PMID:31280375
Abstract

Organosilane-functionalized carbon quantum dots (Si-CQDs) were synthesized by reacting glucosamine and 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane in acetone. The surface morphology, crystal structure, functional groups, elemental composition, and optical properties of the Si-CQDs were characterized using TEM (HRTEM), XRD, FT-IR, XPS, UV-vis absorption and fluorescence spectroscopy. They show that N-containing groups including C=N and C-N, and Si-containing groups including Si-O-C and Si-O-Si have been formed on the surface of Si-CQDs. The element doping and surface functionalization of Si-CQDs endow their novel chemical, physical and optical properties. The Si-CQDs dispersed in acetone are almost monodisperse with an average particle diameter of 3.6 nm. The Si-CQDs dispersed in acetone display blue fluorescence (excitation/emission maxima of 380/460 nm). In contrast, the solid-state Si-CQDs exhibited yellow fluorescence (with excitation/emission maxima of 470/595 nm). The fluorescence emission spectra of acetone-suspended Si-CQDs are concentration-dependent, and the emission peak becomes red-shifted as the concentration is increased. The Si-CQDs are sensitive and selective fluorescent "on off on" nanoprobes for chromate [Cr(VI)] and ascorbic acid (AA). Fluorescence is quenched by Cr(VI) via an inner filter effect from the absorption of Si-CQDs excitation at 380 nm by Cr(VI). Upon addition of AA, fluorescence is restored because of reduction of Cr(VI) by AA. Under optimal conditions (excitation/emission wavelength of 380/460 nm), the response is linear in the 0.4-160 μM Cr(VI) concentration range, and the detection limit is 34 nM. The respective data for AA are 1-80 μM and 84.6 nM. The practical use of the nanoprobe for Cr(VI) determination in real river water samples is also demonstrated successfully. Their concentration-dependent fluorescence, good thermal stability and self-crosslinking behavior also make the Si-CQDs a candidate material for white light-emitting diodes that displays color conversion and can act as an encapsulation layer in a blue light-emitting diode (LED) chip. Graphical abstract One-pot solvothermal synthesis of organosilane-functionalized carbon quantum dots (Si-CQDs) with blue fluorescence in solution, yellow fluorescence in solid state and concentration-dependent fluorescence property, and their applications for chromate (Cr(VI)) and ascorbic acid dual determinations and white light-emitting device. Graphical Abstract contains poor quality and small text inside the artwork. Please do not re-use the file that we have rejected or attempt to increase its resolution and re-save. It is originally poor, therefore, increasing the resolution will not solve the quality problem. We suggest that you provide us the original format. We prefer replacement figures containing vector/editable objects rather than embedded images. Preferred file formats are eps, ai, tiff and pdf.We have changed the poor quality graphical abstract into the jpg and pdf.

摘要

通过在丙酮中反应氨基葡萄糖和 3-[2-(2-氨乙基氨基)乙基氨基]丙基三甲氧基硅烷,合成了有机硅烷功能化的碳量子点(Si-CQDs)。使用 TEM(HRTEM)、XRD、FT-IR、XPS、UV-vis 吸收和荧光光谱法对 Si-CQDs 的表面形态、晶体结构、官能团、元素组成和光学性质进行了表征。结果表明,Si-CQDs 表面形成了包括 C=N 和 C-N 在内的含氮基团,以及包括 Si-O-C 和 Si-O-Si 在内的含硅基团。Si-CQDs 的元素掺杂和表面功能化赋予了它们新颖的化学、物理和光学性质。分散在丙酮中的 Si-CQDs 几乎呈单分散性,平均粒径为 3.6nm。分散在丙酮中的 Si-CQDs 显示蓝色荧光(激发/发射最大值为 380/460nm)。相比之下,固态 Si-CQDs 表现出黄色荧光(激发/发射最大值为 470/595nm)。丙酮悬浮的 Si-CQDs 的荧光发射光谱与浓度有关,随着浓度的增加,发射峰发生红移。Si-CQDs 是对重铬酸盐[Cr(VI)]和抗坏血酸(AA)敏感且选择性的荧光“开启-关闭-开启”纳米探针。Cr(VI) 通过 Si-CQDs 对 380nm 激发光的吸收的内滤效应使荧光猝灭。加入 AA 后,由于 AA 将 Cr(VI)还原,荧光恢复。在最佳条件下(激发/发射波长为 380/460nm),Cr(VI) 的浓度范围在 0.4-160μM 内呈线性响应,检测限为 34nM。AA 的相应数据分别为 1-80μM 和 84.6nM。还成功地证明了纳米探针在实际河水样品中 Cr(VI)测定中的实际应用。它们的浓度依赖性荧光、良好的热稳定性和自交联行为也使 Si-CQDs 成为一种候选材料,可用于显示颜色转换的白光发光二极管,并可用作蓝光发光二极管(LED)芯片的封装层。

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