Hydrophobic tagging of biomolecules has been reported by our group and others to increase their ionization efficiency during electrospray ionization and facilitate their detection by mass spectrometry. As such, hydrophobic tagging should provide a viable method for augmenting MS-based quantification of low abundance proteins by decreasing their detection limits. Herein we have evaluated two commercial alkylation reagents and several newly synthesized hydrophobic alkylation reagents for their utility in quantifying B-type Natriuretic Peptide, a low abundance cardiac biomarker, by protein cleavage isotope dilution mass spectrometry. For the cysteine containing tryptic peptide evaluated, a approximately 3.5-fold decrease in the detection limit was observed for the best performing hydrophobic reagent, 2-iodo-N-octylacetamide, relative to the commonly used alkylation reagent, iodoacetamide. Additionally, we have evaluated the use of nonpolar surface areas as a metric for assessing the effectiveness of the alkylation reagents in improving ESI response.
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http://dx.doi.org/10.1039/b919484c | DOI Listing |
Org Lett
December 2024
State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004, China.
A visible light-driven, intermolecular interrupted Barton reaction has been developed for radical-relay sulfonyloximation of alkenes with alkyl nitrites, using DABSO as a trapping reagent. This method overcomes the challenges of competing normal Barton reactions and polarity mismatches by rapidly and irreversibly capturing alkyl radicals, preventing unwanted side reactions. The resulting polarity-reversed sulfonyl radicals undergo highly selective addition to alkenes, yielding α-alkylsulfonyl ketoximes tethered to hydroxyl or ketone groups.
View Article and Find Full Text PDFSmall
December 2024
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC, V6T 1Z1, Canada.
Cellulose nanocrystals (CNCs) are known to self-assemble into a left-handed chiral nematic lyotropic liquid crystalline phase in water. When captured in the solid state, this structure can impart films with photonic properties that make them promising candidates in photonics, sensing, security, and other areas. Unfortunately, the intrinsic hydrophilicity of CNCs renders these iridescent films susceptible to moisture, thereby limiting their practicality.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
University of Edinburgh, Chemistry, South Bridge, EH8 9YL, Edinburgh, UNITED KINGDOM OF GREAT BRITAIN AND NORTHERN IRELAND.
Organofluorine compounds are vital across multiple sectors, hence highly selective methods to install fluorine are of considerable importance. The deoxyfluorination of alcohols is a key approach to prepare organofluorine compounds, however, a highly secondary (2°)-selective deoxyfluorination of alcohols has not been realized to date. Herein, we report that borane-mediated deoxyfluorination results in high 2°-selectivity in inter- and intra-molecular competition reactions versus primary (1°), tertiary (3°) and even benzylic (Bn) alcohols.
View Article and Find Full Text PDFACS Omega
December 2024
Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, Hachioji, Tokyo 192-0397, Japan.
CO chemisorption using amine-based sorbents is one of the most effective techniques for carbon capture and storage. Solid CO sorbents with amines immobilized on their surface have been attracting attention due to the easy collection of sorbents and reusability. In this study, we developed a solid CO adsorbent by co-condensation of a silanizing reagent having a chloroalkyl group and tetraethyl ethoxysilane, followed by alkylation of the chloroalkyl group with diamine.
View Article and Find Full Text PDFOrg Lett
December 2024
Department of Biophysical Chemistry, Graduate School of Pharmaceutical Science, Tohoku University, AobaSendai 980-8578, Japan.
In this paper, we report that the use of an alkyl silyl carbonate reagent combined with CsF and 18-crown-6 facilitates efficient direct carboxylations of (hetero)aromatic C-H bonds. This system also enables benzylic carboxylation of a toluene derivative and double carboxylation of methyl heteroarene. The carbonate reagent is characterized by its ease of handling and storage.
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