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氧化石墨烯上锌(II)酞菁的界面组装:稳定的“关-开”纳米平台用于检测 G-四链体 (G4)。

Interfacial assembly of zinc(II) phthalocyanines on graphene oxide (GO): Stable "turn-off-on" nanoplatforms to detect G-quadruplexes (G4).

机构信息

CICECO, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal; LAQV-REQUIMTE, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal.

LAQV-REQUIMTE, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal.

出版信息

J Colloid Interface Sci. 2022 Dec;627:900-912. doi: 10.1016/j.jcis.2022.07.075. Epub 2022 Jul 16.

Abstract

HYPOTHESIS

The aggregation of phthalocyanines (Pcs) enfeebles their suitability as G-quadruplex (G4) ligands over time. It is hypothesized that the interfacial assembly of Pcs on graphene oxide (GO) influences intermolecular interactions, thereby affecting their physicochemical properties and inducing stabilization of Pcs in solution. Hence, the stacking of Pcs on GO could be tuned to create nanosystems with the ability to detect G4 for longer periods through a slow release of Pcs.

EXPERIMENTS

Four cationic structurally-related zinc(II) phthalocyanines (ZnPc) were non-covalently assembled on GO by ultrasonic exfoliation. A comprehensive characterization of ZnPcs@GO was carried out by spectroscopic techniques and electron microscopy to understand the organization of ZnPcs on GO. The fluorescence of ZnPcs@GO was studied in the presence of G4 (TGT) and duplex ds26 through spectrofluorimetric titrations and monitored along time.

FINDINGS

GO induced a re-organization of the ZnPcs mostly to J-aggregates and quenched their original fluorescence up to 98 % ("turn-off"). In general, ZnPcs@GO recovered their fluorescence ("turn-on") after the titrations and showed affinity to G4 (K up to 1.92 μM). This is the first report that highlights the contribution of GO interfaces to assemble ZnPcs and allow their slow and controlled release to detect G4 over longer periods.

摘要

假设

聚酞菁(Pcs)的聚集会随着时间的推移削弱它们作为 G-四链体(G4)配体的适用性。假设 Pcs 在氧化石墨烯(GO)上的界面组装会影响分子间相互作用,从而影响它们的物理化学性质,并诱导 Pcs 在溶液中稳定。因此,通过缓慢释放 Pcs,可以调节 Pcs 在 GO 上的堆叠,以创建具有更长时间检测 G4 能力的纳米系统。

实验

通过超声剥离,将四种阳离子结构相关的锌(II)酞菁(ZnPc)非共价组装在 GO 上。通过光谱技术和电子显微镜对 ZnPcs@GO 进行了全面的表征,以了解 ZnPcs 在 GO 上的组织。通过荧光光谱滴定法研究了 ZnPcs@GO 在 G4(TGT)和双链 ds26 存在下的荧光,并随时间进行监测。

结果

GO 诱导 ZnPcs 重新组织,主要形成 J-聚集体,并猝灭其原始荧光高达 98%(“关闭”)。通常,ZnPcs@GO 在滴定后会恢复荧光(“打开”),并显示对 G4 的亲和力(K 高达 1.92 μM)。这是首次报道强调了 GO 界面在组装 ZnPcs 并允许其缓慢和受控释放以更长时间检测 G4 方面的贡献。

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