One-step synthesis of boron-doped graphene quantum dots for fluorescent sensors and biosensor
One-step synthesis of boron-doped graphene quantum dots for fluorescent sensors and biosensor
复制标题
DOI：
10.1016/j.talanta.2019.02.098
复制
发表时间：
2019-07-01
期刊：
影响因子：
6.1
通讯作者：
Dong, Xiaoping
中科院分区：
文献类型：
--
作者：
Ge, Shuyan;He, Jingbo;Dong, Xiaoping
杂原子掺杂可以赋予石墨烯量子点（GQD）各种新的或改进的结构、光学和物理化学性质。与广泛报道的GQD中的氧、氮或硫掺杂相反，具有高产率和量子产率的硼掺杂GQD（B-GQD）的简单且可规模化的合成仍然是挑战。本工作一步合成了B-GQD，并将其作为荧光探针用于制备Fe 3+或磷酸根（Pi）的传感器以及细胞色素C（Cyt C）的生物传感器。在水热条件下，利用1，3，6-三硝基芘和三硝基甲苯在氢氧化钠溶液中自下而上的一步分子融合反应，合成了B-GQD。合成可以使用大体积高压釜（500 ml）进行，具有71%的高产率，表明B-GQD的克级生产的可能性。所制备的B-GQD具有单层或双层石墨烯结构、高结晶度、尺寸均匀、明亮（绝对光致发光量子产率为16.8%）和非激发依赖的绿色荧光（最大激发波长和发射波长分别为480 nm和520 nm）。GQD晶格中B原子的成功掺杂使得能够实现对Fe 3+的高选择性。基于Fe 3+对B-GQD荧光的猝灭（关闭模型），证明了对Fe 3+（检测限-LOD为31.2 nM）和富Fe 3+细胞色素C（LOD为5.9 g/m1）的检测。由于Pi可以恢复B-GQD的Fe 3+淬灭荧光（关闭-打开模型），因此也可以实现Pi的间接荧光检测，LOD为340 nM。此外，实现了对真实的样品中Fe 3+、Cyt C和Pi的检测。
Heteroatom doping can endow graphene quantum dots (GQDs) with various new or improved structural, optical and physicochemical properties. In contrast to the widely reported oxygen, nitrogen or sulfur doping in GQDs, simple and scalable synthesis of boron-doped GQDs (B-GQDs) with high yield and quantum yields remains challenge. In this work, B-GQDs are one-step synthesized and serve as the fluorescence probes for the fabrication of sensors towards Fe3+ ion or phosphate (Pi) as well as biosensor towards cytochrome C (Cyt C). The B-GQDs are facile synthesized using one-step bottom-up molecular fusion between 1,3,6-trinitropyrene and borax in sodium hydroxide under hydrothermal process. The synthesis can be performed using large volume autoclave (500 ml) with a high yield of 71%, indicating possibility for gram-scale production of B-GQDs. The as-prepared B-GQDs exhibit single or bilayer graphene structure, high crystallinity, uniform size, bright (absolute photoluminescence quantum yield of 16.8%) and excitation-independent green fluorescence (maximum excitation wavelength and emission wavelength of 480 nm and 520 nm, respectively). Successful doping of B atoms in the lattice of GQDs enables high selectivity towards Fe3+. Based on quenching of fluorescence of B-GQDs by Fe3+ (turn-off model), detection of Fe3+ (with limit of detection-LOD of 31.2 nM) and Fe3+-rich Cyt C (with LOD of 5.9 g/m1) are demonstrated. As Pi can recover Fe3+-quenched fluorescence of B-GQDs (turn-off-on model), indirect fluorescent detection of Pi is also achieved with LOD of 340 nM. In addition, detection of Fe3+, Cyt C and Pi in real samples is achieved.