Iminoboronates are efficient intermediates for selective, rapid and reversible N-terminal cysteine functionalisation

Faustino, Hélio; Silva, Maria J. S. A.; Veiros, Luı́s F.; Bernardes, Gonçalo J. L.; Góis, Pedro M. P.

doi:10.1039/c6sc01520d

Cited by 106 publications

(112 citation statements)

References 42 publications

(25 reference statements)

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“…Their recognition was envisioned with dynamic covalent bonds between boronic acids and diols ( Scheme ) . There is massive evidence for the power of dynamic covalent boronate esters in functional supramolecular systems in general, including fluorescent probes, sensors, bioorthogonal labeling, covalent organic frameworks, carriers, pores, photosystems, and so on. Sialic acid‐boronate interactions have been used before for cellular uptake …”

Section: Introductionmentioning

confidence: 99%

Ganglioside‐Selective Mechanosensitive Fluorescent Membrane Probes

Straková

Soleimanpour

Diez-Castellnou

et al. 2018

Helvetica Chimica Acta

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The development of fluorescent probes to image forces in cells is an important challenge in chemistry and biology. Planarizable push‐pull probes have been introduced recently for this purpose. To provide most valuable information on forces in complex systems, these mechanosensitive ‘flipper’ probes will have to be localized by molecular recognition of targets of interest. Here we report fluorescent flippers that selectively recognize gangliosides on the surface of lipid bilayer membranes by formation of dynamic covalent boronate esters. The original flipper probes were equipped with 2‐fluorophenyl boronic acids and benzoboroxoles using consecutive triazole and oxime ligation. Evaluation was done in large unilamellar vesicles composed of EYPC/SM/CL/GM 40:40‐x:20:x to obtain mixed membranes with separate liquid‐disordered (Ld) and ganglioside (GM) containing liquid‐ordered (Lo) domains. With increasing GM concentration, fluorescence intensities increased and excitation maximum shifted to the red. Deconvolution of the spectra confirmed that these changes originate from a migration of the flipper probes from Ld to Lo domains upon binding to the gangliosides and thus the planarization in the more ordered environment. Control mechanophores without boronic acids failed to show the same response, and fructose partially inhibited the ganglioside sensitivity. These results demonstrate that it is possible to selectively accumulate mechanosensitive flipper probes in Lo domains and, more generally, that probe localization in complex membranes is possible and matters.

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Section: Introductionmentioning

confidence: 99%

Ganglioside‐Selective Mechanosensitive Fluorescent Membrane Probes

Straková

Soleimanpour

Diez-Castellnou

et al. 2018

Helvetica Chimica Acta

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“…8e). 30,121 The N-terminus has also been converted to a reactive ketone via transamination mediated by pyridoxal-5′phosphate (PLP); however, this method cannot be applied to some N-terminal residues (Lys and Gln) because of side reactions (Fig. 8f ).…”

Section: •6 N-and C-terminimentioning

confidence: 99%

Recent Progress in Chemical Modification of Proteins

Sakamoto

Hamachi

2018

ANAL. SCI.

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Chemical modification of proteins is important for creating a myriad of engineered proteins and for elucidating the function and dynamics of proteins in live cells. A wide variety of chemical protein modification methods have been developed and can be categorized into three classes: (i) modification of proteins using the reactivity of naturally occurring amino acids; (ii) modification by bioorthogonal reactions using unnatural amino acids, most of which can be siteselectively incorporated into proteins-of-interest using genetic codon expansion techniques; and (iii) recognition driven chemical modification, which is the only approach that allows modification of endogenous proteins without any genetic manipulation even under heavily crowded and multi-molecular conditions, as in live cells and organisms. All of these approaches have merits and limitations. In this review, we summarize these approaches and discuss their characteristics with respect to specificity, reaction rate and versatility.

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“…[65,66] Die TzB-Bildung ist fürd as zentrenselektive Labeling natürlicher,p roteinogener Aminosäuren sehr vorteilhaft, da unter anderem keine Notwendigkeit besteht, eine nichtnatürliche Aminosäure in das POI einzuführen. [65,66] Die TzB-Bildung ist fürd as zentrenselektive Labeling natürlicher,p roteinogener Aminosäuren sehr vorteilhaft, da unter anderem keine Notwendigkeit besteht, eine nichtnatürliche Aminosäure in das POI einzuführen.…”

Section: Reversible Thiazolidinboronat(tzb)-bildungunclassified

“…[71] In jüngsten Verçffentlichungen widmen sich Gao und Mitarbeiter dieser Problemstellung,i ndem sie das stabilere und harmloses Hydrazinderivat Semicarbazid verwendeten, welches bei neutralem pH-Wert stabile Konjugate mit 2-FBBAo der 2-ABBAb ildet. [ [65,66] die schnelle Bildung eines Thiazolidinboronats (TzB) zwischen 2-FBBAund N-terminalem Cystein in Peptiden und Proteinen bei neutralem pH-Wert (Schema 12). Gao und Mitarbeiter beobachteten dies als Nebenreaktion in ihren Studien der Diazaborinbildung zwischen 2-FBBAund Semicarbazid in der Gegenwart von S. aureus-Zelllysaten, bei denen N-terminale Cysteinketten reichlich vorhanden sind.…”

Section: Reversible Thiazolidinboronat(tzb)-bildungunclassified

Boronsäuren als bioorthogonale Sonden für zentrenselektives Protein‐Labeling

Akgun¹,

Hall²

2018

Angewandte Chemie

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In den vergangenen zwei Jahrzehnten hat sich die bioorthogonale Chemie zu einem beliebten Hilfsmittel entwickelt, um zentrenselektive Modifikationen an Proteinen zu erzielen. Dennoch sind nur einige wenige bioorthogonale Reaktionen bekannt, die zudem Limitierungen aufweisen können, wie etwa geringe Reaktionsgeschwindigkeiten, die Verwendung instabiler oder zytotoxischer Reagenzien und das Auftreten von Nebenreaktionen. Folglich besteht ein großes Interesse an der Erweiterung der Methodik in der bioorthogonalen Chemie. In diesem Zusammenhang wurden kürzlich Boronsäuren in den Bereich der bioorthogonalen Chemie eingeführt, welche in drei verschiedenen Strategien zum Einsatz kommen: 1) Bildung eines Boronsäureesters zwischen der Boronsäure und einem 1,2‐cis‐Diol; 2) Bildung eines Iminoboronates zwischen 2‐Acetyl‐/Formyl‐Arylboronsäure und Hydrazin‐/Hydroxylamin‐/Semicarbazid‐Derivaten; 3) Verwendung einer Boronsäure als Transfergruppe in einer Suzuki‐Miyaura‐Kreuzkupplung oder einer anderen Reaktion, in deren Verlauf die Boronylgruppe das Intermediat verlässt. In diesem Aufsatz fassen wir die Fortschritte der Anwendung von Boronsäuren in der bioorthogonalen Chemie zusammen, welche das zentrenspezifische Labeling von Proteinen ermöglicht, und vergleichen diese Methoden mit den gängigsten bioorthogonalen Reaktionen.

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Iminoboronates are efficient intermediates for selective, rapid and reversible N-terminal cysteine functionalisation

Abstract: Formyl benzeno boronic acids rapidly and selectively react with N-terminal cysteines to yield a reversible boronated thiazolidine that may be used in the interactive orthogonal modification of peptides.

Cited by 106 publications

References 42 publications

Ganglioside‐Selective Mechanosensitive Fluorescent Membrane Probes

Ganglioside‐Selective Mechanosensitive Fluorescent Membrane Probes

Recent Progress in Chemical Modification of Proteins

Boronsäuren als bioorthogonale Sonden für zentrenselektives Protein‐Labeling

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