Supramolecular regulation of bioorthogonal catalysis in cells using nanoparticle-embedded transition metal catalysts

Tonga, Gülen Yesilbag; Jeong, Youngdo; Duncan, Bradley; Mizuhara, Tsukasa; Mout, Rubul; Das, Rahul; Kim, Sung Tae; Yeh, Yi‐Cheun; Yan, Bo; Hou, Singyuk; Rotello, Vincent M.

doi:10.1038/nchem.2284

Cited by 402 publications

(343 citation statements)

References 58 publications

(51 reference statements)

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“…The latest advances in bioorthogonal chemistry1 demonstrate how organometallic compounds and inorganic materials are capable of catalyzing the activation of profluorescent substrates and prodrugs with remarkable efficiency in biological environments 2, 3, 4, 5, 6, 7, 8, 9, 10. These selective catalysts carry out non‐natural reactions dodging the interference of biological molecules, in some cases with endogenous cellular components as co‐reactants 3, 9…”

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confidence: 99%

Bioorthogonal Catalytic Activation of Platinum and Ruthenium Anticancer Complexes by FAD and Flavoproteins

et al. 2018

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Recent advances in bioorthogonal catalysis promise to deliver new chemical tools for performing chemoselective transformations in complex biological environments. Herein, we report how FAD (flavin adenine dinucleotide), FMN (flavin mononucleotide), and four flavoproteins act as unconventional photocatalysts capable of converting PtIV and RuII complexes into potentially toxic PtII or RuII−OH2 species. In the presence of electron donors and low doses of visible light, the flavoproteins mini singlet oxygen generator (miniSOG) and NADH oxidase (NOX) catalytically activate PtIV prodrugs with bioorthogonal selectivity. In the presence of NADH, NOX catalyzes PtIV activation in the dark as well, indicating for the first time that flavoenzymes may contribute to initiating the activity of PtIV chemotherapeutic agents.

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confidence: 99%

Bioorthogonal Catalytic Activation of Platinum and Ruthenium Anticancer Complexes by FAD and Flavoproteins

et al. 2018

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“…[85,86] A first attempt on a therapeutic systems was presented by Rotello, Isaacs and coworkers. [109,111] A diaminohexane functionalized cytotoxic gold nanoparticle surface was covered with CB [7], which lead to a reduced toxicity. After cell uptake a competing adamantane guest was added and removed the CB [7] cover from the gold nanoparticle, which induces apoptosis due to its cytotoxicity.…”

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confidence: 99%

Stimuli‐Responsive Cucurbit[n]uril‐Mediated Host‐Guest Complexes on Surfaces

Wiemann

Jonkheijm

2017

Israel Journal of Chemistry

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Supramolecular functional surfaces are at the heart of many materials and medical applications. Increasing interest can be seen for devising new supramolecular functionalization strategies of surfaces. In this review we place particular emphasis on the use of cucurbit[n]urilmediated host-guest complexation as surface functionalization strategy. The state of the art of cucurbit[n]uril-mediated host-guest complexes on surfaces is reviewed. Cucurbit [n] urils (CB[n]) are able to form strong host-guest complexes with affinities that span several orders of magnitudes up to the regime of the biotin-streptavidin pair and that can be modulated by applying remote stimuli provided suitably sensitive guests were selected. Strategies to fabricate stimuliresponsive surfaces creates versatile supramolecular systems and several applications of these types of surfaces are outlined.

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“…However, full electrochemical control over catalytic activity is achieved only when catalyst activation is a reversible process. [24,25] The reversibility of the electrochemical activation of the system was investigated using Cu 2+ (Figure 4 a). As before, Cu 2+ was released from a prepared electrode into a buffered solution containing Au NP 1 and HPNPP after which the rate of PNP- Figure S9).…”

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Reversible Electrochemical Modulation of a Catalytic Nanosystem

et al. 2016

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A catalytic system based on monolayer-functionalized gold nanoparticles (Au NPs) that can be electrochemically modulated and reversibly activated is reported. The catalytic activity relies on the presence of metal ions (Cd 2+ and Cu 2+ ), which can be complexed by the nanoparticle-bound monolayer. This activates the system towards the catalytic cleavage of 2-hydroxypropyl-p-nitrophenyl phosphate (HPNPP), which can be monitored by UV/Vis spectroscopy. It is shown that Cu 2+ metal ions can be delivered to the system by applying an oxidative potential to an electrode on which Cu 0 was deposited. By exploiting the different affinity of Cd 2+ and Cu 2+ ions for the monolayer, it was also possible to upregulate the catalytic activity after releasing Cu 2+ from an electrode into a solution containing Cd 2+ . Finally, it is shown that the activity of this supramolecular nanosystem can be reversibly switched on or off by oxidizing/reducing Cu/Cu 2+ ions under controlled conditions. Complexityisemergingasamajorthemeinchemistry. [1] Notonly does it mark a shift from the study of relatively simple molecules to complex molecular structures similar to those found in nature, but it also marks a shift from the study of single molecules to networks of molecules. [2][3][4] Within the subfield of catalysis, [5] the emergence of nanozymes, defined as nanomaterials with enzyme-like activity, nicely illustrates this development. [6] Nanozymes are prepared following a bottom-up strategy relying on the use of simple synthetic components for the formation of structures with a size and structural complexity similar to that of enzymes. [7,8] Their high stability, uniformity, and ease of modification is favoring applications in the fields of sensing, [9] materials science, [10] and systems chemistry. [11] The observation that nanozymes can exhibit an emerging property such as cooperativity is indeed a sign that significant progress has been made in the design of functional complex systems. [12] However, whereas nature has gained exquisite control over the complex biological machinery by using specific triggers to up-and down-regulate catalytic processes, similar regulatory pathways are still largely inexistent for nanozymes. Herein, we present a simple setup for the reversible activation and modulation of nanozymes using an electronic input. The electrochemical activation is highly attractive because of its ease of implementation, cleanliness, precision, and rapid response. [13][14][15][16] The availability of this kind of regulatory mechanism will strongly determine the success of chemists in constructing synthetic networks for studying complexity on the systems level.The main component of our system is Au NP 1, which are gold nanoparticles (d = 1.5 AE 0.3 nm) covered with C9-thiols terminating with a 1,4,7-triazacyclononane (TACN) head group (Figure 1 a). [11] Such nanoparticle-bound TACN moieties are able to coordinate Zn 2+ -metal ions forming a supra-

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Supramolecular regulation of bioorthogonal catalysis in cells using nanoparticle-embedded transition metal catalysts

Cited by 402 publications

References 58 publications

Bioorthogonal Catalytic Activation of Platinum and Ruthenium Anticancer Complexes by FAD and Flavoproteins

Bioorthogonal Catalytic Activation of Platinum and Ruthenium Anticancer Complexes by FAD and Flavoproteins

Stimuli‐Responsive Cucurbit[n]uril‐Mediated Host‐Guest Complexes on Surfaces

Reversible Electrochemical Modulation of a Catalytic Nanosystem

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