Journal of the American Chemical Society, Год журнала: 2024, Номер unknown
Опубликована: Дек. 11, 2024
We develop a latent biocompatible cleavage reaction involving the hitherto unexplored interaction between hydroxylamines and cyclopropenones. Our study addresses regioselectivity challenges commonly observed in asymmetric cyclopropenone transformations, substantiated by variations substrate, Density Functional Theory calculations,
Язык: Английский
ACS Catalysis, Год журнала: 2023, Номер 13(15), С. 10425 - 10434
Опубликована: Июль 25, 2023
Tetrasubstituted alkenes are one of the most important classes aggregation-induced emission luminogens with wide applications in analytical chemistry, bioimaging science, luminescent materials and cancer treatment. However, general methods for assembly tetrasubstituted alkenes, especially unsymmetrical species, remain elusive. The established typically require prefunctionalized substrates, sensitive organometallic reagents multiple-step operation. Herein, we report a dual phosphine/rhodium catalysis direct synthesis from readily available cyclopropenones, aryl halides water. This reaction was achieved highly efficient chemoselective manner by synergistic merger phosphine-mediated hydration rhodium-catalyzed arylation, furnishing diverse set carboxyl acid–based (>80 examples). resulting carboxylate groups can be employed as universal tags downstream tetraarylethenes. A range obtained compounds were demonstrated to solid-state obvious properties. success late-stage functionalization bioactive further illustrate synthetical utility this protocol material development drug discovery.
Язык: Английский
Процитировано
7
Topics in Current Chemistry, Год журнала: 2023, Номер 381(6)
Опубликована: Ноя. 22, 2023
Abstract The desire to create biomolecules modified with functionalities that go beyond nature’s toolbox has resulted in the development of biocompatible and selective methodologies reagents, each different scope limitations. In this overview, we highlight recent advances field bioconjugation from 2016 2023. First, (metal-mediated) protein functionalization by exploiting specific reactivity amino acids will be discussed, followed novel bioorthogonal reagents for biomolecules.
Язык: Английский
Процитировано
6
Angewandte Chemie, Год журнала: 2024, Номер 136(10)
Опубликована: Янв. 20, 2024
Abstract Developing fluorogenic probes for simultaneous live cell labeling of multiple targets is crucial understanding complex cellular events. The emerging [4+1] cycloaddition between tetrazine and isonitriles holds promise as a bioorthogonal tool, yet existing lack reactivity fluorogenicity. Here, we present the development series tetrazine‐functionalized probes. By incorporating pyrazole adducts into fluorophore scaffolds, post‐reacted displayed remarkable fluorescence turn‐on ratios, up to 3184‐fold. Moreover, these modifications are generalizable various fluorophores, enabling broad emission range from 473 659 nm. Quantum chemical calculations further elucidate mechanisms. These enable in cells, without need washing step. Consequently, our findings pave way advanced multiplex imaging detection techniques studies.
Язык: Английский
Процитировано
1
The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(14), С. 10093 - 10098
Опубликована: Июнь 27, 2024
A series of amides, including α-bromo hydroxamates,
Язык: Английский
Процитировано
1
Опубликована: Авг. 19, 2024
Fluorogenic bioorthogonal reagents enable facile detection in complex environments. While useful for real-time imaging, few such probes are available. Existing tools also exploit similar mechanisms signal turn-on, precluding multiplexed applications. To address these gaps, we developed a palette of cyclopropenone (CpO) scaffolds that activated by phosphines to provide coumarins. The top CpO-phosphine pairs show strong fluorescent enhancements (up 760-fold) and high quantum yields, stable aqueous CpO fluorogens exhibit unique reaction profiles, setting the stage multi-component labeling studies.
Язык: Английский
Процитировано
1
ACS Central Science, Год журнала: 2024, Номер 10(10), С. 1945 - 1959
Опубликована: Окт. 8, 2024
Fluorogenic probes that unmask fluorescence signals in response to bioorthogonal reactions are a powerful new addition biological imaging. They can significantly reduce background and minimize nonspecific signals, potentially enabling real-time, high-contrast imaging without the need wash out excess fluorophores. While diverse classes of highly refined synthetic fluorophores now readily available, integrating them into fluorogenic scheme still requires extensive design efforts customized structural alterations optimize quenching mechanisms for each specific fluorophore scaffold. Herein, we present generalizable strategy produce an efficient from essentially any available further alterations. We designed this based on macrocyclic cucurbit[7]uril (CB7) host, where is achieved by programming guest exchange reaction within cavity. employed rapidly create across visible spectrum scaffolds, which enabled no-wash live cells tissues with minimal signal. Finally, demonstrated be combined metabolic labeling detection metabolically tagged mycobacteria under conditions paired covalently clickable super-resolution multiplexed tissues.
Язык: Английский
Процитировано
1
ACS Chemical Biology, Год журнала: 2024, Номер unknown
Опубликована: Дек. 6, 2024
RNA sequences encode structures that impact protein production and other cellular processes. Misfolded RNAs can also potentiate disease, but a complete picture is lacking. To establish more comprehensive accurate structure–function relationships, new methods are needed to interrogate in native environments. Existing tools rely primarily on electrophiles constitutively "on" or triggered by UV light, often resulting high background. Here we describe an alternative, chemically approach cross-link using bioorthogonal cyclopropenones (CpOs). These reagents selectively react with phosphines provide ketenes─electrophiles trap neighboring nucleophiles forge covalent cross-links. As proof-of-concept, conjugated CpO motif thiazole orange (TO-1). TO-1–CpO bound model aptamer (Mango) nanomolar affinity, as confirmed fluorescence turn-on. After phosphine administration, cross-links were formed between the RNA. Cross-linking was both time dose dependent. We further applied under biologically relevant conditions. Collectively, this work expands toolkit of probes for studying its conformations.
Язык: Английский
Процитировано
1
Israel Journal of Chemistry, Год журнала: 2022, Номер 63(1-2)
Опубликована: Дек. 5, 2022
Abstract Bioorthogonal chemistry traces its roots to a seminal report by Saxon and Bertozzi, who described modified Staudinger reaction between organic azides triaryl phosphines. This finding not only inspired several biological pursuits, but also launched an entire field of discovery. Over the years, much effort has been directed at identifying alternative bioorthogonal transformations with azides; less work focused on leveraging phosphines for new development. The landscape changed in recent generation faster‐reacting probes novel classes reagents. perspective covers newly developed phosphine‐based chemistries their application settings. We focus, particular, reactions cyclopropenones related analogs. These feature unique mechanisms that are broadening scope reactivity.
Язык: Английский
Процитировано
7
Chemistry - An Asian Journal, Год журнала: 2022, Номер 17(17)
Опубликована: Июль 12, 2022
Aryl azide and diaryl tetrazole are both photoactive molecules, which can form nitrene nitrile imine intermediates respectively by photolysis. Depending on the new finding that suppress photolysis of in azide-tetrazole conjugated system, we developed aryl probes for photoactivatable fluorogenic alkyne click (PFAAC) reaction, were not phoroactivatable itself, but triazole products after reaction prefluorophore be activated light. Therefore, PFAAC chemistry, fluorescent two orthogonal events: azide-alkyne light, leads to spatiotemporal resolution high signal-to-noise ratio. This process was proved vitro copper-catalyzed or strain-promoted reactions live cells spatiotemporally controlled organelle imaging. By incorporation a linker conjugate, this chemistry could covalently label extra biomolecules detecting photoinduced fluorescence.
Язык: Английский
Процитировано
5
Physical Chemistry Chemical Physics, Год журнала: 2022, Номер 25(1), С. 304 - 313
Опубликована: Ноя. 22, 2022
Time resolved fluorescence spectroscopic investigation of four Schiff base anions has established that their excited state dynamics is governed by several solvent properties: polarity, viscosity and hydrogen bond donating ability. With viscous protic solvents like glycerol, lifetimes have been found to be markedly longer than those in ethanol, implying conformational relaxation molecules plays a key role nonradiative relaxation. Surprisingly, the less aprotic solvents, acetonitrile, are even longer. The only plausible rationalization this observation light bond-assisted phenomena operative solvents. This contention draws support from time evolution emission red end spectrum low moderately with regard an absence such rise strongly viz., 2,2,2-trifluoroethanol. Rudimentary quantum chemical calculations provide preliminary idea about nature redistribution involved process.
Язык: Английский
Процитировано
3