Visible-to-NIR-Light Activated Release: From Small Molecules to Nanomaterials

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(24), P. 13135 - 13272

Published: Oct. 30, 2020

Photoactivatable (alternatively, photoremovable, photoreleasable, or photocleavable) protecting groups (PPGs), also known as caged photocaged compounds, are used to enable non-invasive spatiotemporal photochemical control over the release of species interest. Recent years have seen development PPGs activatable by biologically and chemically benign visible near-infrared (NIR) light. These long-wavelength-absorbing moieties expand applicability this powerful method its accessibility non-specialist users. This review comprehensively covers organic transition metal-containing photoactivatable compounds (complexes) that absorb in visible- NIR-range various leaving gasotransmitters (carbon monoxide, nitric oxide, hydrogen sulfide). The text NIR-light-induced photosensitized using molecular sensitizers, quantum dots, upconversion second-harmonic nanoparticles, well via photodynamic (photooxygenation singlet oxygen) photothermal effects. Release from polymers, micelles, vesicles, photoswitches, along with related emerging field photopharmacology, is discussed at end review.

Language: Английский

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Advances and opportunities in the exciting world of azobenzenes

Nature Reviews Chemistry, Journal Year: 2021, Volume and Issue: 6(1), P. 51 - 69

Published: Nov. 18, 2021

Language: Английский

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Photoresponsive molecular tools for emerging applications of light in medicine

Chemical Science, Journal Year: 2020, Volume and Issue: 11(43), P. 11672 - 11691

Published: Jan. 1, 2020

This perspective article explores the current state of light-controlled molecular tools for medical therapy and imaging offers an outlook on clinical application scenarios optimisation strategies.

Language: Английский

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Infrared Difference Spectroscopy of Proteins: From Bands to Bonds

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(7), P. 3466 - 3576

Published: March 23, 2020

Infrared difference spectroscopy probes vibrational changes of proteins upon their perturbation. Compared with other spectroscopic methods, it stands out by its sensitivity to the protonation state, H-bonding, and conformation different groups in proteins, including peptide backbone, amino acid side chains, internal water molecules, or cofactors. In particular, detection H-bonding a time-resolved manner, not easily obtained techniques, is one most successful applications IR spectroscopy. The present review deals use perturbations designed specifically change protein between two (or more) functionally relevant states, strategy often referred as reaction-induced first half this contribution, I technique special emphasis given preparation suitable samples characterization, strategies for perturbation methodologies measurements (from nanoseconds minutes). second contribution focuses on spectral interpretation. It starts reviewing how medium polarity, coupling affect frequencies, intensities, bandwidths. followed band assignments, crucial aspect mostly performed help isotopic labeling site-directed mutagenesis, complemented integration interpretation results context studied protein, an increasingly supported calculations. Selected examples from literature, predominately but exclusively retinal are used illustrate topics covered review.

Language: Английский

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Rational Design in Photopharmacology with Molecular Photoswitches

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(30)

Published: April 7, 2023

Photopharmacology is an attractive approach for achieving targeted drug action with the use of light. In photopharmacology, molecular photoswitches are introduced into structure biologically active small molecules to allow optical control their potency. Going beyond trial and error, photopharmacology has progressively applied rational design methodologies devise light-controlled bioactive ligands. this review, we categorize photopharmacological efforts from standpoint medicinal chemistry strategies, focusing on diffusible photochromic ligands modified that operate through E-Z bond isomerization. vast majority cases, photoswitchable designed as analogs existing compounds, a variety approaches. By analyzing in detail comprehensive list instructive examples, describe state art discuss future opportunities photopharmacology.

Language: Английский

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Exploring Emergent Properties in Enzymatic Reaction Networks: Design and Control of Dynamic Functional Systems

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(5), P. 2553 - 2582

Published: March 4, 2024

The intricate and complex features of enzymatic reaction networks (ERNs) play a key role in the emergence sustenance life. Constructing such vitro enables stepwise build up complexity introduces opportunity to control activity using physicochemical stimuli. Rational design modulation network motifs enable engineering artificial systems with emergent functionalities. Such functional are useful for variety reasons as creating new-to-nature dynamic materials, producing value-added chemicals, constructing metabolic modules synthetic cells, even enabling molecular computation. In this review, we offer insights into chemical characteristics ERNs while also delving their potential applications associated challenges.

Language: Английский

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General Principles for the Design of Visible‐Light‐Responsive Photoswitches: Tetra‐ortho‐Chloro‐Azobenzenes

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(48), P. 21663 - 21670

Published: Aug. 28, 2020

Molecular photoswitches enable reversible external control of biological systems, nanomachines, and smart materials. Their development is driven by the need for low energy (green-red-NIR) light switching, to allow non-invasive operation with deep tissue penetration. The lack clear design principles adaptation optimization such systems limits further applications. Here we provide a rulebook tetra-ortho-chloroazobenzenes, an emerging class visible-light-responsive photochromes, elucidating role that substituents play in defining their key characteristics: absorption spectra, band overlap, photoswitching efficiencies, half-lives unstable cis isomers. This achieved through joint photochemical theoretical analyses representative library molecules featuring varying electronic nature. A set guidelines presented enables tuning properties desired application informed photochrome engineering.

Language: Английский

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Iminothioindoxyl as a molecular photoswitch with 100 nm band separation in the visible range

Nature Communications, Journal Year: 2019, Volume and Issue: 10(1)

Published: June 3, 2019

Light is an exceptional external stimulus for establishing precise control over the properties and functions of chemical biological systems, which enabled through use molecular photoswitches. Ideal photoswitches are operated with visible light only, show large separation absorption bands functional in various solvents including water, posing unmet challenge. Here we a class fully-visible-light-operated photoswitches, Iminothioindoxyls (ITIs) that meet these requirements. ITIs band 100 nm, isomerize on picosecond time scale thermally relax millisecond scale. Using combination advanced spectroscopic computational techniques, provide rationale switching behavior influence structural modifications environment, aqueous solution, their photochemical properties. This research paves way development improved photo-controlled systems wide variety applications require fast responsive functions.

Language: Английский

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Spatiotemporal Control of Biology: Synthetic Photochemistry Toolbox with Far-Red and Near-Infrared Light

ACS Chemical Biology, Journal Year: 2021, Volume and Issue: 17(12), P. 3255 - 3269

Published: Sept. 13, 2021

The complex network of naturally occurring biological pathways motivates the development new synthetic molecules to perturb and/or detect these processes for fundamental research and clinical applications. In this context, photochemical tools have emerged as an approach control activity drug or probe at high temporal spatial resolutions. Traditional tools, particularly photolabile protecting groups (photocages) photoswitches, rely on high-energy UV light that is only applicable cells transparent model animals. More recently, such designs evolved into visible near-infrared regions with deeper tissue penetration, enabling photocontrol study biology in animal contexts. This Review highlights recent developments far-red photocages photoswitches their current potential applications interface chemistry biology.

Language: Английский

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Computational Design, Synthesis, and Photochemistry of Cy7‐PPG, an Efficient NIR‐Activated Photolabile Protecting Group for Therapeutic Applications**

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(27)

Published: Feb. 19, 2022

Photolabile Protecting Groups (PPGs) are molecular tools used, for example, in photopharmacology the activation of drugs with light, enabling spatiotemporal control over their potency. Yet, red-shifting PPG wavelengths into NIR range, which penetrates deepest tissue, has often yielded inefficient or insoluble molecules, hindering use PPGs clinic. To solve this problem, we report herein a novel concept design, by transforming clinically-applied NIR-dyes suitable orbital configurations new NIR-PPGs using computational approaches. Using method, demonstrate how Cy7, class dyes possessing ideal properties (NIR-absorption, high absorptivity, excellent aqueous solubility) can be successfully converted Cy7-PPG. We facile synthesis towards Cy7-PPG from accessible precursors and confirm its as most redshifted oxygen-independent NIR-PPG to date (λ

Language: Английский

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