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Chemical Logic of Peptide Branching by Iterative Nonlinear Nonribosomal Peptide Synthetases.
Biochemistry
January 2025
Department of Chemistry, Washington University in St. Louis, One Brookings Drive, St. Louis, Missouri 63130, United States.
Branch-point syntheses in nonribosomal peptide assembly are rare but useful strategies to generate tripodal peptides with advantageous hexadentate iron-chelating capabilities, as seen in siderophores. However, the chemical logic underlying the peptide branching by nonribosomal peptide synthetase (NRPS) often remains complex and elusive. Here, we review the common strategies for the biosynthesis of branched nonribosomal peptides (NRPs) and present our biochemical investigation on the NRPS-catalyzed assembly of fimsbactin A, a branched mixed-ligand siderophore produced by the human pathogenic strain .
View Article and Find Full Text PDFNanomachine Networks: Functional All-Enzyme Hydrogels from Photochemical Cross-Linking of Glucose Oxidase.
Biomacromolecules
January 2025
School of Physics and Astronomy, University of Leeds, Leeds LS2 9JT, U.K.
Enzymes are attractive as catalysts due to their specificity and biocompatibility; however, their use in industrial and biomedical applications is limited by stability. Here, we present a facile approach for enzyme immobilization within "all-enzyme" hydrogels by forming photochemical covalent cross-links between the enzyme glucose oxidase. We demonstrate that the mechanical properties of the enzyme hydrogel can be tuned with enzyme concentration and the data suggests that the dimeric nature of glucose oxidase results in unusual gel formation behavior which suggests a degree of forced induced dimer dissociation and unfolding.
View Article and Find Full Text PDFEnantiocontrolled Cyclization to Form Chiral 7- and 8-Membered Rings Unified by the Same Catalyst Operating with Different Mechanisms.
J Am Chem Soc
January 2025
Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
Chiral medium-sized rings, albeit displaying attractive properties for drug development, suffer from numerous synthetic challenges due to difficult cyclization steps that must take place to form these unusually strained, atropisomeric rings from sterically crowded precursors. In fact, catalytic enantioselective cyclization methods for the formation of chiral seven-membered rings are unknown, and the corresponding eight-membered variants are also sparse. In this work, we present a substrate preorganization-based, enantioselective, organocatalytic strategy to construct seven- and eight-membered rings featuring chirality that is intrinsic to the ring in the absence of singular stereogenic atoms or single bond axes of chirality.
View Article and Find Full Text PDFUnusual presentation of a giant recurrent inguinal hernia: a case report.
J Surg Case Rep
January 2025
University Surgery Hospital "St. Naum Ohridski", Department of Urology, 11 Oktomvri 53, 1000, Skopje, North Macedonia.
The recurrence rate of inguinal hernia is 1-10%, most often in the inguinal region, and seldom in different locations. A 72-year-old man with a large soft swelling in the right ventrolateral abdominal region without swelling in the scrotum, operated on right inguinal hernia at pediatric age. Clinical findings revealed a giant right ventrolateral hernia and abdominal CT showed weakness of the abdominal wall with a 25 cm long hernial sac with an apex under the right costal arch and a base at the deep inguinal opening, that was diagnosed as a recurrent inguinal hernia with unusual presentation.
View Article and Find Full Text PDFNontraumatic right diaphragmatic hernia with malrotated left liver lobe incarceration: An unusual case report with literature review.
Radiol Case Rep
March 2025
Department of Radiology, Mohammed Vth Military hospital, Ryad street, 10010 Rabat, Morocco.
Diaphragmatic hernia is an unusual finding, especially in emergency settings and in the absence of trauma. Imaging plays a crucial role, with various CT signs of diaphragmatic rupture having been described, including the "dangling diaphragm," "absent diaphragm," "collar sign," "hump sign," "fascia sign," and "dependent viscera sign". We report an unusual case of a 53-year-old woman who presented with exertional dyspnea and asthenia.
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