Perfluorocarbons in Chemical Biology

Miller, Margeaux A.; Sletten, Ellen M.

doi:10.1002/cbic.202000297

Cited by 52 publications

(47 citation statements)

References 177 publications

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“…We reasoned that the increased catalytic activity of the GTs with SF 17 tagged substrates resulted from the detergent-like properties of the SF 17 , which stabilized these membrane-associated enzymes by providing a membrane-like environment. 78 Additionally, the hydrophobic portion of the SF 17 not only increased the affinity but also altered the orientation of the tagged glycans toward the enzyme active sites upon catalysis. These results demonstrated the practical application of the SF 17 tagging strategy to enzymatic glycan synthesis and highlighted that various complex para-HMOs can be prepared efficiently, yielding high-purity products.…”

Section: ■ Conclusionmentioning

confidence: 99%

Sulfo-Fluorous Tagging Strategy for Site-Selective Enzymatic Glycosylation of para-Human Milk Oligosaccharides

Huang

et al. 2021

ACS Catal.

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In this study, we developed an efficient fluorous tagging strategy for site-selective enzymatic fucosylation/sialylation in which appending a readily removable auxiliary tag (SF 17 ) to the reducing end of an acceptor provided the regioselectivity control of a given wild-type fucosyltransferase/sialyltransferase. By combining this strategy with the sequential one-pot enzymatic system of HMO production, various fucosylated para-HMOs, such as LNFP I, LNFP II, LNFP III, LNFP V, LNDFH I, LNDFH II, TF-LNT, F-pLNH I, F-pLNH IV, DF-pLNH I isomer, DF-pLNH II, TF-pLNH I, TF-pLNH II, F-pLNnH, F-pLNnH I, DF-pLNnH, TF-pLNnH, and TetraF-pLNO, were synthesized. Furthermore, the SF 17 -tagged acceptors improved the reaction rates of the enzymatic glycan chain extension. Terminal α2,6-sialylation on SF 17 -tagged pLNnH was directly achieved using wild-type α2,6-sialyltransferase from Photobacterium damsela (Pd26ST). Moreover, enzyme kinetics revealed that the catalytic efficiency (k cat/K M) of α1,4-fucosylation of Bf13FT (α1,3/4-fucosyltransferase from Bacteroides fragilis) on SF 17 -tagged LNFP V acceptors could be enhanced by 55 times compared with tagging with an azidohexyl aglycone. We developed an efficient and reliable strategy for generating complex and diverse natural HMO libraries for functional gut microbiome studies. This SF 17 -assisted glycosylation strategy provides a practical approach to harness the extreme substrate flexibility offered by readily available bacterial glycosyltransferases, which enables the site-selective fucosylation/sialylation on para-HMOs.

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Section: ■ Conclusionmentioning

confidence: 99%

Sulfo-Fluorous Tagging Strategy for Site-Selective Enzymatic Glycosylation of para-Human Milk Oligosaccharides

Huang

et al. 2021

ACS Catal.

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“…Highly fluorinated compounds, referred to as fluorous, phase separate from aqueous and organic solution, which renders them orthogonal to natural products and biomolecules , (Figure A). The noncovalent bioorthogonality , of the fluorous phase, coupled with the inertness of the C–F bond, have resulted in rising applications of perfluorocarbons in biology and medicine, including microarray assembly, antibiofouling coatings, oxygen delivery, ultrasound and magnetic resonance imaging diagnostics, and in vivo force measurements . As the utility of fluorinated materials expands, the chemical tools available to analyze and track the fluorous phase must also evolve.…”

Section: Introductionmentioning

confidence: 99%

Fluorous Soluble Cyanine Dyes for Visualizing Perfluorocarbons in Living Systems

et al. 2020

Self Cite

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The bioorthogonal nature of perfluorocarbons provides a unique platform for introducing dynamic nano-and microdroplets into cells and organisms. To monitor the localization and deformation of the droplets, fluorous soluble fluorophores that are compatible with standard fluorescent protein markers and applicable to cells, tissues, and small organisms are necessary. Here, we introduce fluorous cyanine dyes that represent the most red-shifted fluorous soluble fluorophores to date. We study the effect of covalently appended fluorous tags on the cyanine scaffold and evaluate the changes in photophysical properties imparted by the fluorous phase. Ultimately, we showcase the utility of the fluorous soluble pentamethine cyanine dye for tracking the localization of perfluorocarbon nanoemulsions in macrophage cells and for measurements of mechanical forces in multicellular spheroids and zebrafish embryonic tissues. These studies demonstrate that the red shifted cyanine dyes offer spectral flexibility in multiplexed imaging experiments and enhanced precision in force measurements.

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“…For example, avagacestat ( A ), a γ‐secretase inhibitor used in the treatment of Alzheimer disease, contains the residue of ( S )‐2‐amino‐5,5,5‐trifluoropentanoic acid; [12] fluorinated leucine is presented in odanacatib ( B ) – the cathepsin K inhibitor; [13] a selective induced nitric oxide synthase inhibitor ( C ) is based on 4,4‐difluorinated l ‐lysine; [14] trifluoromethylglutamic acid ( D ) is an important building block for the synthesis of modified calcium‐dependent antibiotics (CDAs) ( Figure 1). [15,16] Moreover, the perfluoroalkylated AAs (PFAAs) are incorporated into peptides and proteins for their study and to modify and fine‐tune their structures and physicochemical properties [17,18] …”

Section: Introductionmentioning

confidence: 99%

“…[15,16] Moreover, the perfluoroalkylated AAs (PFAAs) are incorporated into peptides and proteins for their study and to modify and fine-tune their structures and physicochemical properties. [17,18] To date, there exist a plethora of methods for the synthesis of FAAs, [19][20][21][22][23] however, the approaches for obtaining of PFAAs are still rare, especially in an enantioselective manner. [24,25] As a consequence, only several selective examples of asymmetric synthesis of PFAAs have been reported to date.…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Synthesis of Perfluoroalkylated α‐Amino Acids through Generated Radicals Using a Chiral Ni(II) Complex

Stoletova

Moshchenkov

Smol’yakov

et al. 2020

Helvetica Chimica Acta

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Dedicated to our friend and colleague Prof. Antonio Togni on the occasion of his 65th birthday Perfluoroalkylated α-amino acids (PFAAs) are a unique class of compounds for biochemistry and pharmaceutical science. In this context, we report the successful intermolecular coupling of the Belokon's chiral dehydroalanine Ni(II) complex with a variety of perfluoroalkyl iodides. A 4-cyanopyridine/B 2 Pin 2 catalytic system generates perfluoroalkyl radicals, which after trapping by the ligand sphere of a chiral Ni(II) complex provide the diastereomeric complexes with up to > 20 : 1 dr (seven examples). The obtained major (S,S)-diastereomers were easily isolated by simple silica column chromatography in 33-54 % yields. The perfluoroalkylated α-AA was subsequently released from the obtained Ni(II) complex through aqueous HCl treatment. The chiral auxiliary ligand ((S)-BPB = (S)-2-(N-benzylprolyl)aminobenzophenone) can be easily recycled after the acidic complex decomposition and reused for the synthesis of the starting dehydroalanine Ni(II) complex.

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Perfluorocarbons in Chemical Biology

Cited by 52 publications

References 177 publications

Sulfo-Fluorous Tagging Strategy for Site-Selective Enzymatic Glycosylation of para-Human Milk Oligosaccharides

Sulfo-Fluorous Tagging Strategy for Site-Selective Enzymatic Glycosylation of para-Human Milk Oligosaccharides

Fluorous Soluble Cyanine Dyes for Visualizing Perfluorocarbons in Living Systems

Asymmetric Synthesis of Perfluoroalkylated α‐Amino Acids through Generated Radicals Using a Chiral Ni(II) Complex

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