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调节氟化腙类开关的激活 pH 值─通往多功能 F 磁共振成像对比剂的途径。

Tuning the pH of Activation of Fluorinated Hydrazone-Based Switches─A Pathway to Versatile F Magnetic Resonance Imaging Contrast Agents.

机构信息

Department of Chemical Organic Technology and Petrochemistry, Silesian University of Technology, Krzywoustego 4, 44-100Gliwice, Poland.

出版信息

ACS Sens. 2023 Feb 24;8(2):721-727. doi: 10.1021/acssensors.2c02251. Epub 2023 Jan 25.


DOI:10.1021/acssensors.2c02251
PMID:36695323
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9972467/
Abstract

Molecular switches have become an area of great interest in recent years. They are explored as high-density data storage and organic diodes in molecular electronics as well as chemosensors due to their ability to undergo a transition between well-defined structures under the action of external stimuli. One of the types of such switches is hydrazones. They work by changing the configuration from E to Z under the influence of pH or light. The change in configuration is accompanied by a change in the absorption band and changes in the nuclear magnetic resonance (NMR) spectrum. In this publication, the structure-property relationship of fluorinated hydrazone switches was established. A linear relationship between the Hammett substituent constants and the pH where the switching occurs was found. Introduction of strong electron-donating groups allowed obtaining a hydrazone switch of p = 6 suitable for application in F MRI as contrast agents.

摘要

近年来,分子开关已经成为一个非常热门的研究领域。由于它们在外来刺激的作用下能够在明确定义的结构之间进行转换,因此它们被探索用于高密度数据存储和分子电子学中的有机二极管以及化学传感器。这类开关之一是腙。在 pH 值或光的影响下,它们通过改变构型从 E 变为 Z 来工作。构型的变化伴随着吸收带的变化和核磁共振(NMR)谱的变化。在本出版物中,建立了氟化腙开关的结构-性质关系。发现了取代基常数与发生开关的 pH 值之间的线性关系。引入强供电子基团可以得到 p = 6 的腙开关,适用于作为 F MRI 中的造影剂。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7dc0/9972467/ef28e0a6f517/se2c02251_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7dc0/9972467/aaeca7506be4/se2c02251_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7dc0/9972467/477ee1c4f48d/se2c02251_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7dc0/9972467/4a08bfb325ef/se2c02251_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7dc0/9972467/e982eebd5af0/se2c02251_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7dc0/9972467/c8e2079d8f4e/se2c02251_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7dc0/9972467/ef28e0a6f517/se2c02251_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7dc0/9972467/aaeca7506be4/se2c02251_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7dc0/9972467/477ee1c4f48d/se2c02251_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7dc0/9972467/4a08bfb325ef/se2c02251_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7dc0/9972467/e982eebd5af0/se2c02251_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7dc0/9972467/c8e2079d8f4e/se2c02251_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7dc0/9972467/ef28e0a6f517/se2c02251_0007.jpg

相似文献

[1]
Tuning the pH of Activation of Fluorinated Hydrazone-Based Switches─A Pathway to Versatile F Magnetic Resonance Imaging Contrast Agents.

ACS Sens. 2023-2-24

[2]
Ratiometric pH-Responsive F Magnetic Resonance Imaging Contrast Agents Based on Hydrazone Switches.

Anal Chem. 2022-3-1

[3]
Hydrazone Molecular Switches with Paramagnetic Center as F Magnetic Resonance Imaging Relaxation Enhancement Agents for pH Imaging.

ACS Sens. 2023-5-26

[4]
Spectroscopic and quantum chemical investigations of substituent effects on the azo-hydrazone tautomerism and acid-base properties of arylazo pyridone dyes.

Spectrochim Acta A Mol Biomol Spectrosc. 2013-12-17

[5]
Simple hydrazone building blocks for complicated functional materials.

Acc Chem Res. 2014-4-25

[6]
A pH activated configurational rotary switch: controlling the E/Z isomerization in hydrazones.

J Am Chem Soc. 2009-12-30

[7]
3D Hydrazone-Functionalized Covalent Organic Frameworks as pH-Triggered Rotary Switches.

Small. 2021-10

[8]
A switching cascade of hydrazone-based rotary switches through coordination-coupled proton relays.

Nat Chem. 2012-7-29

[9]
Switchable MRI contrast agents based on morphological changes of pH-responsive polymers.

Bioorg Med Chem. 2011-12-8

[10]
Isomerization mechanism in hydrazone-based rotary switches: lateral shift, rotation, or tautomerization?

J Am Chem Soc. 2011-6-2

引用本文的文献

[1]
Study on the Photoinduced Isomerization Mechanism of Hydrazone Derivatives Molecular Switch.

ACS Omega. 2025-4-23

[2]
How to 19F MRI: applications, technique, and getting started.

BJR Open. 2023-9-29

[3]
Hydrazone Molecular Switches with Paramagnetic Center as F Magnetic Resonance Imaging Relaxation Enhancement Agents for pH Imaging.

ACS Sens. 2023-5-26

本文引用的文献

[1]
Manipulating extracellular tumour pH: an effective target for cancer therapy.

RSC Adv. 2018-6-19

[2]
Ratiometric pH-Responsive F Magnetic Resonance Imaging Contrast Agents Based on Hydrazone Switches.

Anal Chem. 2022-3-1

[3]
Potentiometric pH Nanosensor for Intracellular Measurements: Real-Time and Continuous Assessment of Local Gradients.

Anal Chem. 2021-11-30

[4]
F MRI Probes for Multimodal Imaging.

Chemistry. 2022-1-24

[5]
Recent advances in the fabrication of pH-sensitive indicators films and their application for food quality evaluation.

Crit Rev Food Sci Nutr. 2023

[6]
Multiresponsive Nanoprobes for Turn-On Fluorescence/F MRI Dual-Modal Imaging.

Anal Chem. 2020-9-1

[7]
Paramagnetic Cobalt(II) Complexes with Cyclam Derivatives: Toward F MRI Contrast Agents.

Inorg Chem. 2020-7-7

[8]
Activatable probes for diagnosis and biomarker detection by MRI.

J Mater Chem B. 2017-6-21

[9]
Role of pH Value in Clinically Relevant Diagnosis.

Diagnostics (Basel). 2020-2-16

[10]
Design of Collective Motions from Synthetic Molecular Switches, Rotors, and Motors.

Chem Rev. 2019-12-23

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