A clickable caging group as a new platform for modular caged compounds with improved photochemical properties

Suzuki, Akinobu; Sekine, Ryota; Takeda, Shiori; Aikawa, Ryosuke; Shiraishi, Yukiko; Hamaguchi, Tomomi; Okuno, Hiroyuki; Tamamura, Hirokazu; Furuta, Toshiaki

doi:10.1039/c8cc07981a

Cited by 13 publications

(18 citation statements)

References 27 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“… 459 The bis(carboxymethoxy) moiety of 48b conferred increased water solubility (up to 2.7 mM in acetonitrile/HEPES buffer 5:95, pH 7.2). 367 The dialkylaminomethyl C8 substituents of 49a – d ( Table 9 ) significantly reduced the acidity of the 7-OH group in 49c (p K a = 4.9) 460 and 49d (p K a = 3.8) 461 relative to the parent 40a (p K a = 6.2), presumably because the aminomethyl group forms an intramolecular hydrogen bond with the phenolic hydroxyl group, 462 leading to greater photouncaging efficiency at the lower end of the physiological pH range. The liberation of carboxylic acids, diols, amines (as carbamic acids), and phenols (as carbonic acids) from 49a – d occurred with quantum efficiencies similar to or slightly exceeding that for 40a upon both 1P (Φ r = 0.06–0.014, λ irr = 360 nm) and 2P excitation (δ unc = 0.5–1.4 GM, 755 nm).…”

Section: Photorelease From Organic Photoactivatable Compoundsmentioning

confidence: 99%

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

et al. 2020

View full text Add to dashboard Cite

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

show abstract

Section: Photorelease From Organic Photoactivatable Compoundsmentioning

confidence: 99%

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

et al. 2020

View full text Add to dashboard Cite

show abstract

“…We previously developed Bhc caged compounds of various biologically active molecules that exhibit high photolytic efficiencies 28,45,46,47 . With the aim of expanding the repertoire of Bhc caging groups, we also reported platforms of modular caged compounds that can be modified easily by the introduction of various functional units 32,40,41 . The present protocol therefore represents a method for the synthesis of a clickable precursor of Bhc caging groups that can be modified via the copper(I)-catalyzed Huisgen cyclization.…”

Section: Discussionmentioning

confidence: 99%

“…If additional properties can be installed easily into the caging groups without compromising their photosensitivity, then the repertoire of caged compounds can be expanded 34,35,36,37,38,39 . We therefore designed modular caged compounds that comprise three parts, namely the Bhc group as a photo-responsive core, chemical handles for the installation of additional functionalities, and the molecules that are to be masked 40,41 .…”

Section: Introductionmentioning

confidence: 99%

Design, Synthesis, and Photochemical Properties of Clickable Caged Compounds

Suzuki

Shiraishi

Aoki

et al. 2019

JoVE

Self Cite

View full text Add to dashboard Cite

Caged compounds enable the photo-mediated manipulation of the cell physiology with high spatiotemporal resolution. However, the limited structural diversity of currently available caging groups and the difficulties in synthetic modification without sacrificing their photolysis efficiencies are obstacles to expanding the repertoire of caged compounds for live cell applications. As the chemical modification of coumarin-type photocaging groups is a promising approach for the preparation of caged compounds with diverse physical and chemical properties, we report a method for the synthesis of clickable caged compounds that can be modified easily with various functional units via the copper(I)-catalyzed Huisgen cyclization. The modular platform molecule contains a (6-bromo-7-hydroxycoumarin-4-yl)methyl (Bhc) group as a photo-caging group, which exhibits a high photolysis efficiency compared to those of the conventional 2-nitrobenzyls. General procedures for the preparation of clickable caged compounds containing amines, alcohols, and carboxylates are presented. Additional properties such as the water solubility and cell targeting ability can be readily incorporated into clickable caged compounds. Furthermore, the physical and photochemical properties, including the photolysis quantum yield, were measured and were found to be superior to those of the corresponding Bhc caged compounds. The described protocol could therefore be considered a potential solution for the lack of structural diversity in the available caged compounds.

show abstract

“…Despite numerous reports on photocaged taxane derivatives, [177][178][179][180] their application in delivery systems has been rarely studied. Xu et al reported such a delivery system for paclitaxel using a pyramid-shaped RNA nanocage.…”

Section: Taxanementioning

confidence: 99%

Photoactivation Strategies for Therapeutic Release in Nanodelivery Systems

Choi

2020

Advanced Therapeutics

View full text Add to dashboard Cite

Control of therapeutic release constitutes one of most critical aspects considered in the design of nanoscale delivery systems. There are a variety of cellular factors and external stimuli employed for release control. Of these, use of light offers various photoactivation mechanisms that enable to effectively engage in therapeutic release. It also allows a higher degree of spatial and temporal control. Over recent decades, the application of photoactivation strategies has seen remarkable growth and made a significant impact on rapid advances in the field of drug delivery. This Review aims to summarize the fundamental concepts and practical applications demonstrated recently in numerous therapeutic areas from cancers to infectious diseases. Its scope is defined by a focus on those photoactivation strategies that occur via either linker cleavage, nanocontainer gating, or disassembly. Each of these is discussed with specific examples and underlying mechanisms that comprise linker photolysis, photoisomerization, photothermal heating, or photodynamic reactions with reactive oxygen species. In summary, this Review provides an inclusive summary of new developments and insights obtained from recent progress in photoactivation strategies and their applications in therapeutic nanodelivery.

show abstract

A clickable caging group as a new platform for modular caged compounds with improved photochemical properties

Abstract: A clickable caging group was designed, which was applied to the synthesis of caged paclitaxels with improved physical and photochemical properties.

Cited by 13 publications

References 27 publications

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

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

Design, Synthesis, and Photochemical Properties of Clickable Caged Compounds

Photoactivation Strategies for Therapeutic Release in Nanodelivery Systems

Contact Info

Product

Resources

About