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Full-Text Articles in Chemistry
Probing The Effects Of Heterogeneous Oxidative Modifications On The Stability Of Cytochrome, Victor Yin, Lars Konermann
Probing The Effects Of Heterogeneous Oxidative Modifications On The Stability Of Cytochrome, Victor Yin, Lars Konermann
Chemistry Publications
Covalent modifications by reactive oxygen species can modulate the function and stability of proteins. Thermal unfolding experiments in solution are a standard tool for probing oxidation-induced stability changes. Complementary to such solution investigations, the stability of electrosprayed protein ions can be assessed in the gas phase by collision-induced unfolding (CIU) and ion-mobility spectrometry. A question that remains to be explored is whether oxidation-induced stability alterations in solution are mirrored by the CIU behavior of gaseous protein ions. Here, we address this question using chloramine-T-oxidized cytochrome c (CT-cyt c) as a model system. CT-cyt c comprises various proteoforms that have …
Delineating Heme-Mediated Versus Direct Protein Oxidation In Peroxidase-Activated Cytochrome, Victor Yin, Derek Holzscherer, Lars Konermann
Delineating Heme-Mediated Versus Direct Protein Oxidation In Peroxidase-Activated Cytochrome, Victor Yin, Derek Holzscherer, Lars Konermann
Chemistry Publications
Oxidation of key residues in cytochrome c (cyt c) by chloramine T (CT) converts the protein from an electron transporter to a peroxidase. This peroxidase-activated state represents an important model system for exploring the early steps of apoptosis. CT-induced transformations include oxidation of the distal heme ligand Met80 (MetO, +16 Da) and carbonylation (LysCHO, -1 Da) in the range of Lys53/55/72/73. Remarkably, the 15 remaining Lys residues in cyt c are not susceptible to carbonylation. The cause of this unusual selectivity is unknown. Here we applied top-down mass spectrometry (MS) to examine whether CT-induced oxidation is catalyzed by heme. …
Cytochrome C As A Peroxidase: Activation Of The Precatalytic Native State By H, Victor Yin, Gary S Shaw, Lars Konermann
Cytochrome C As A Peroxidase: Activation Of The Precatalytic Native State By H, Victor Yin, Gary S Shaw, Lars Konermann
Chemistry Publications
In addition to serving as respiratory electron shuttle, ferri-cytochrome c (cyt c) acts as a peroxidase; i.e., it catalyzes the oxidation of organic substrates by H2O2. This peroxidase function plays a key role during apoptosis. Typical peroxidases have a five-coordinate heme with a vacant distal coordination site that permits the iron center to interact with H2O2. In contrast, native cyt c is six-coordinate, as the distal coordination site is occupied by Met80. It thus seems counterintuitive that native cyt c would exhibit peroxidase activity. The current work scrutinizes the origin of this …
Synthesis Of 5-Azaindoles Via A Cycloaddition Reaction Between Nitriles And Donor-Acceptor Cyclopropanes., Mahmoud M Abd Rabo Moustafa, Brian L Pagenkopf
Synthesis Of 5-Azaindoles Via A Cycloaddition Reaction Between Nitriles And Donor-Acceptor Cyclopropanes., Mahmoud M Abd Rabo Moustafa, Brian L Pagenkopf
Chemistry Publications
A new method for the synthesis of 5-azaindole derivatives is reported. A [3+2] dipolar cycloaddition between nitriles and a 3,4-cyclopropanopiperidine followed by SeO(2) oxidation affords the target compounds in moderate to excellent yields. The divergent nature and cost effectiveness of this method makes it very suitable for combinatorial applications in the pharmaceutical industry.
Increased Yields And Simplified Purification With A Second-Generation Cobalt Catalyst For The Oxidative Formation Of Trans-Thf Rings., Cory Palmer, Nicholas A Morra, Andrew C Stevens, Barbora Bajtos, Ben P Machin, Brian L Pagenkopf
Increased Yields And Simplified Purification With A Second-Generation Cobalt Catalyst For The Oxidative Formation Of Trans-Thf Rings., Cory Palmer, Nicholas A Morra, Andrew C Stevens, Barbora Bajtos, Ben P Machin, Brian L Pagenkopf
Chemistry Publications
The synthesis of a second-generation cobalt catalyst for the formation of trans-THF products via the Mukaiyama aerobic oxidative cyclization is reported. Two procedures have been developed with the new water-soluble catalyst that give superior yields and greatly simplify purification compared to the previous catalysts.
First Total Synthesis And Structural Reassignment Of (-)-Aplysiallene., Jian Wang, Brian L Pagenkopf
First Total Synthesis And Structural Reassignment Of (-)-Aplysiallene., Jian Wang, Brian L Pagenkopf
Chemistry Publications
The first total synthesis of (-)-aplysiallene has been completed in 16 steps and features a key sequential Mukaiyama aerobic oxidative cyclization to prepare the fused bis-THF core. The original stereochemical assignment has been revised as shown.