水热炭化合成色氨酸衍生手性碳量子点及其手性识别性能研究  

Preparation of tryptophan-derived chiral carbon quantum dots by hydrothermal carbonization and their chiral recognition properties

作　　者：范金玥 徐明聪 李伟[1] 安邦 刘守新[1] Jinyue Fan;Mingcong Xu;Wei Li;Bang An;Shouxin Liu(Key Laboratory of Bio-based Material Science&Technology,Northeast Forestry University,Harbin 150040,China)

机构地区：[1]生物质材料科学与技术教育部重点实验室,东北林业大学,哈尔滨150040

出　　处：《中国科学：化学》2024年第6期903-915,共13页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金面上项目(编号:32371808)和国家自然科学基金重大项目(编号:31890773)资助。

摘　　要：在保留碳量子点性质的同时获得手性特征是手性碳量子点(CCQDs)合成的关键.本研究以氨基葡萄糖(N-Glu)为碳源,色氨酸对映体(L-/D-Trp)为手性源,采用水热炭化法制备出在紫外光下能够发出明亮蓝色荧光的手性碳量子点(L-/D-NCQDs).研究表明, L-/D-NCQDs的平均粒径为4.0~4.5 nm,激发波长为310和368 nm,发射波长为450 nm.圆二色光谱证实了L-NCQDs和D-NCQDs为一对对映异构体,在220、280和350 nm处呈现相反且对称的手性信号.其中, 220 nm处较强的手性信号源于表面手性残基的保留. 280和350 nm的手性中心源于手性单体在碳核中的堆叠和光学跃迁. L-NCQDs对L-/D-天冬酰胺(L-/D-Asn)和L-/D-谷氨酰胺(L-/D-Gln)对映体展示出优异的手性识别性能.左旋对映体对L-NCQDs的荧光发射强度无明显影响,而右旋对映体能够显著增强L-NCQDs荧光发射强度,在0~6.25 m M范围内具有较好的线性关系,最低检测限为0.06和0.29 mM.对映选择性(ID-I0)/(IL-I0)分别为8.7和4.0.The key to preparing chiral carbon quantum dots(CCQDs)is to preserve the properties of carbon quantum dots while endowing them with chiral characteristics.Herein,chiral carbon quantum dots(L-/D-NCQDs)were synthesized by hydrothermal carbonization method using glucosamine(N-Glu)as the carbon source and tryptophan enantiomer(L-D-Trp)as the chiral source,emitting bright blue fluorescence under UV lamp.It is showed that L-/D-NCQDs have an average diameter of 4.0-4.5 nm,a maximum excitation wavelength of 310 and 368 nm,and a maximum emission wavelength of 450 nm.Circular dichroism spectra confirms that L-NCQDs and D-NCQDs are pairs of enantiomers with opposite and symmetric chiral signals at 220,280 and 350 nm.The stronger chiral signal at 220 nm was attributed to the retention of surface chiral residues,and the chiral centers at 280 and 350 nm were attributed to the aggregates of chiral molecules and optical transitions in carbon nucleus.L-NCQDs exhibited excellent chiral recognition for L-/D-asparagine(L-/D-Asn)and L-/D-glutamine(L-/D-Gln).The fluorescence intensity of L-NCQDs had no observable change in the presence of left-handed enantiomers,but enhanced obviously in the presence of right-handed enantiomers.This method displayed a linear range of 0-6.25 mM with the detection limit of 0.06 and 0.29 mM.The enantioselectivity(lp-lo)/(lL-lo)can reach up to 8.7 and 4.0,respectively.

关 键 词：水热炭化 手性碳量子点 色氨酸 手性识别 

分 类 号：O657.3[理学—分析化学] TB383.1[理学—化学]