Solid-phase fluorescent BODIPY–peptide synthesis via in situ dipyrrin construction

Abstract

Traditional fluorescent peptide chemical syntheses hinge on the use of limited fluorescent/dye-taggable unnatural amino acids and entail multiple costly purifications. Here we describe a facile and efficient protocol for in...

A review on marine plastisphere: biodiversity, formation, and role in degradation

“…The large amount of MPs in the ocean has an impact on the ecology of the ocean and the food chain. In the ocean, MPs could affect the photosynthesis and growth of phytoplankton [40] , slow down the swimming of zooplankton and thus reduce their reproductive efficiency [41] , and may also impact the ocean carbon stock [42] . In addition, floating MPs could become a transport vehicle for microorganisms and even some pathogenic microorganisms, accelerating the spread of infectious diseases [43] .…”

Rationales Design von Phe‐BODIPY‐Aminosäuren als fluorogene Bausteine für den peptidbasierten Nachweis von Candida‐Infektionen im Harntrakt

“…The borondipyrromethene (BODIPY) scaffold is an attractive fluorophore for the development of imaging probes due to its excellent photophysical properties. [16] Current approaches for synthesizing BODIPY-peptide conjugates include classical CuAAC [17] and SPAAC [18] methods using pre-functionalised intermediates, total solid-phase approaches for in situ dipyrrin construction on N-terminal/Lys sites [19] and the use of BODIPYbearing FlAAs, [12a] with the latter enabling site-selective fluorophore incorporation without disrupting the native biomolecular properties of peptides. Among the different BODIPY structures reported for the construction of FlAAs, the fluorogenic Trp-BODIPY (4, Figure 1a) stands out for its utility in wash-free imaging of biological systems.…”

Solid‐Phase Peptide Macrocyclization and Multifunctionalization via Dipyrrin Construction

“…The commercially available orthoesters were used for constructing dipyrrins with hydrogen, methyl or ethyl groups at the meso position effectively (Method A, 1 a-1 c) with the aid of POCl 3 in CH 2 Cl 2 . With our previously established protocol, [24] the two pyrroles on-resin can be condensed with various commercially available aldehydes (e.g., polarity-sensitive pyrene and AIEgen tetraphenylethene) under the catalysis of BF 3 •OEt 2 in DMF, and the resulting dipyrrin-cyclopeptides could be obtained with high percent conversions (all > 80 %) after DDQ oxidation and global cleavage and deprotection (Method B, 1 d-1 h). In essence, when 4-carboxybenzaldehyde was used, COOHcontaining dipyrrin cyclopeptide could be obtained (1 h) with very high percent conversion (94 %), and continued SPPS with it afforded 1 i to have an additional peptide chain, which may accomplish other functions or serve as anchors for further manipulations.…”

“…Very recently, our group has disclosed a facile, efficient, and purification-economical Fmoc-based solid-phase synthetic method for fluorescent boron-dipyrromethene (BODIPY)-peptide conjugates via in situ dipyrrin construction. [24] We then speculated that such solid-phase dipyrrin assembly reaction can also be compatibly utilized for peptide macrocyclization and stapling, i.e., the dipyrrin as a new multifunctional staple linker, to obtain highly sought-after either fluorescent BODIPY-containing, or metal-chelating thus light-emissive macrocyclic peptides. Herein, we unleash the potential of a new multi-functional dipyrrin staple linker and introduce our solid-phase peptide macrocyclization and multifunctionalization strategy via dipyrrin coupling and manipulation (Figure 1 c).…”