Fluorescence switching via competitive ESIPT and spirolactam ring opening in a multifunctional rhodamine B probe for selective detection of Cu2+ and OCl−: theoretical insights with anticancer and biosensor activity†

IF 4.7 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY
Vishnu S, Avijit Kumar Das, Gouri Karan and Sujata Maiti Choudhury
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Abstract

A multifunctional ESIPT-based rhodamine-derived probe (BHS) was synthesized and developed as a colorimetric and fluorometric sensor for the selective detection of copper (Cu2+) and hypochlorite (OCl) in aqueous solutions. Initially, BHS exhibits intense whitish blue fluorescence due to the active excited-state intramolecular proton transfer (ESIPT) mechanism within the molecule. However, upon interaction with Cu2+ and OCl, noticeable changes in absorption and fluorescence occur, attributed to the inhibition of ESIPT resulting from analyte binding with BHS, leading to spirolactam ring opening. Furthermore, significant Stokes shifts in absorption (Δλ = 34 nm and 170 nm for Cu2+, and 163 nm for OCl) and emission (Δλ = 67 nm for both Cu2+ and OCl) further confirm this transformation. The spirolactam ring opening is induced by Cu2+ coordination, whereas for OCl, it is triggered by oxidative cleavage. To explore potential biological applications, fluorescence titration experiments were conducted to study the interactions of the BHS–Cu2+ complex with ct-DNA and the transport protein bovine serum albumin (BSA). Additionally, molecular docking studies were performed to assess these interactions, while DFT calculations were employed to optimize the structures of BHS and its Cu2+ complex. The fluorescence changes of BHS in the presence of Cu2+ and OCl in biological samples have been examined by the anticancer and biosensor activity of BHS in HCT-116 colorectal cancer cells.

Abstract Image

通过竞争性ESIPT和螺内酰胺环开口在多功能罗丹明B探针中进行荧光切换,用于选择性检测Cu2+和OCl−:抗癌和生物传感器活性的理论见解†
合成了一种基于esipd的多功能罗丹明衍生探针(BHS),用于选择性检测水溶液中的铜(Cu2+)和次氯酸盐(OCl−)。最初,由于分子内活跃的激发态分子内质子转移(ESIPT)机制,BHS表现出强烈的白蓝色荧光。然而,当与Cu2+和OCl−相互作用时,吸收和荧光发生明显变化,这是由于分析物与BHS结合导致ESIPT抑制,导致螺内酰胺环打开。此外,吸收(Cu2+ Δλ = 34 nm, OCl−170 nm, OCl−163 nm)和发射(Cu2+和OCl−Δλ = 67 nm)的显著Stokes位移进一步证实了这一转变。螺内酰胺的开环是由Cu2+配位引起的,而OCl−的开环是由氧化裂解引起的。为了探索潜在的生物学应用,采用荧光滴定实验研究了BHS-Cu2 +配合物与ct-DNA和运输蛋白牛血清白蛋白(BSA)的相互作用。此外,通过分子对接研究来评估这些相互作用,同时采用DFT计算来优化BHS及其Cu2+配合物的结构。利用BHS在HCT-116结直肠癌细胞中的抗癌和生物传感器活性,研究了生物样品中Cu2+和OCl−存在下BHS的荧光变化。
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来源期刊
Materials Advances
Materials Advances MATERIALS SCIENCE, MULTIDISCIPLINARY-
CiteScore
7.60
自引率
2.00%
发文量
665
审稿时长
5 weeks
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