The cyclopropanation of unsaturated lipid acyl chains of some bacterial cell membranes is an important survival strategy to protect the same against drastic cooling. To elucidate the role of cyclopropane ring-containing lipids, we have simulated the lipid membrane of () and two modified membranes by replacing the cyclopropane rings with either single or double bonds at widely different temperatures. It has been observed that the cyclopropane rings provide more rigid kinks in the lipid acyl chain compared to the double bonds and therefore further reduce the packing density of the membrane and subsequently enhance the membrane fluidity at low temperatures. They also inhibit the close packing of other lipids and deleterious phase separation by strongly interacting with them. Therefore, this study has explained why bacterial strain, susceptible to freezing environments, relies on the cyclopropanation of an unsaturated chain.
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http://dx.doi.org/10.1021/acs.jpcb.3c00541 | DOI Listing |
J Microbiol Biotechnol
November 2024
Hanyang University ERICA, Ansan 15588, Republic of Korea.
Previous studies showed no improvement in bacterial biomass for Puniceispirillum marinum IMCC1322 under light regimes. Nevertheless, in nutrient-replete cultures with higher inoculating cell densities, strain IMCC1322 exhibited proteorhodopsin photoheterotrophy. Increasing both inoculum size and the amino acid pool can eliminate quorum sensing and starvation responses in strain IMCC1322.
View Article and Find Full Text PDFMicrob Pathog
January 2025
Department of Epidemiology and Health Statistics, College of Public Health, Zhengzhou University, Zhengzhou, China.
Wide-ranging sophisticated physiological activities of cell membranes are associated with changes in fatty acid structure and composition. The cfa gene is a core regulator of cell membrane fatty acid cyclopropanation reaction. Its encoded cyclopropane fatty acid synthase (CFA synthase) catalyzes the binding of unsaturated fatty acid (UFA) to methylene groups, which undergoes cyclopropanation modification to produce cyclopropane fatty acids (CFAs).
View Article and Find Full Text PDFOrg Lett
January 2025
Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712, United States.
We disclose a broad platform for copper-catalyzed atom transfer radical addition (ATRA) of electron-deficient olefins. Catalytic Cu(dtbbpy)(OTf) enables radical addition of electron-deficient alkyl halides to acrylates, acrylamides, and vinyl sulfones in fair to excellent yields. The resultant ATRA products can be used in a variety of telescoped reactions, including substitution with basic amine nucleophiles to afford α-amino esters.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Department of Chemistry, Indian Institute of Technology Jammu, Jagti, NH-44, Nagrota Bypass, Jammu J&K, 181221, India.
The development of Michael addition reactions to conjugated cyclopropenes is a challenge in organic synthesis due to the fleeting and reactive nature of such strained Michael acceptor systems. Herein, the development of a photochemical approach towards such conjugated cyclopropenes is reported that serves as a strategic entry point to densely functionalized cyclopropanes in a diastereoselective fashion. The process involves the light-mediated generation of transient cyclopropenyl α,β-unsaturated esters from vinyl diazo esters, followed by an organic base catalyzed nucleophilic addition of N-heterocycles to directly access β-N-heterocyclic cyclopropanoic esters.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Laboratory of Catalysis and Organic Synthesis, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, CH-1015, Lausanne, Switzerland.
We report herein our studies on the direct photoactivation of carbonyl cyclopropanes to give biradical intermediates, leading to selective cleavage of the more substituted carbon-carbon bond. Depending on the substrate structure, extended alkenes were isolated or directly reacted in a photo-Nazarov process to give bicyclic products. Based on these results, a unified reductive ring-opening reaction was developed by using diphenyl disulfide as a hydrogen atom transfer (HAT) reagent.
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