The cell membrane of (hyper)thermophilic archaea, including the thermoacidophile Sulfolobus acidocaldarius, incorporates dibiphytanylglycerol tetraether lipids. The hydrophobic cores of such tetraether lipids can include up to eight cyclopentane rings. Presently, nothing is known of the biosynthesis of these rings. In this study, a series of S. acidocaldarius mutants deleted of genes currently annotated as encoding proteins involved in sugar/polysaccharide processing were generated and their glycolipids were considered. Whereas the glycerol-dialkyl-glycerol tetraether core of a S. acidocaldarius tetraether glycolipid considered here mostly includes four cyclopentane rings, in cells where the Saci_0421 or Saci_1201 genes had been deleted, species containing zero, two or four cyclopentane rings were observed. At the same time, in cells lacking Saci_0201, Saci_0275, Saci_1101, Saci_1249 or Saci_1706, lipids containing mostly four cyclopentane rings were detected. Although Saci_0421 and Saci_1201 are not found in proximity to other genes putatively involved in lipid biosynthesis, homologs of these sequences exist in other Archaea containing cyclopentane-containing tetraether lipids. Thus, Saci_0421 and Saci_1201 represent the first proteins described that somehow contribute to the appearance of cyclopentane rings in the core moiety of the S. acidocaldarius glycolipid considered here.
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http://dx.doi.org/10.1093/femsle/fnx250 | DOI Listing |
Molecules
November 2024
Dipartimento di Chimica, Università degli Studi di Roma "La Sapienza", 00185 Rome, Italy.
In this work, the first review paper about -iridoids was presented. In particular, their detailed occurrence, chemophenetic evaluation and biological activities were reported. To the best of our knowledge, two hundred and eighty-eight -iridoids have been evidenced so far, bearing different structural features, with the link between two -iridoids sub-units as the major one.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Department of Materials and Environmental Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden.
The structure of novel large pore borosilicate zeolite EMM-59 (|CHN|[BSiO]) with localized framework boron sites was determined by using three-dimensional electron diffraction (3D ED) and scanning transmission electron microscopy (STEM) imaging. EMM-59 was synthesized using 2,2-(cyclopentane-1,1-diyl)bis(,-diethyl--methylethan-1-aminium) as an organic structure-directing agent (OSDA). The framework has a three-dimensional intersecting channel system delimited by 12 × 10 × 10-ring openings and contains 28 T and 60 oxygen atoms in the asymmetric unit, making it the most complex monoclinic zeolite.
View Article and Find Full Text PDFOrg Lett
December 2024
Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang, Hubei 443002, China.
An unexpected phosphine-catalyzed controllable three-component domino reaction involving [1 + 2 + 2] annulation and [1 + 2 + 2]/[3 + 2] sequential annulation reaction of 2-arylmethylidene cyanoacetates/malononitriles with Morita-Baylis-Hillman (MBH) carbonates has been developed. A broad range of densely functionalized cyclopentanes and diquinanes bearing five or four consecutive stereogenic centers, including two all-carbon quaternary stereocenters, were smoothly acquired in moderate to excellent yields under mild reaction conditions from readily available materials. Moreover, this divergent transformation enables the simultaneous generation of three or four new C-C bonds and one or two carbocyclic rings in only one step.
View Article and Find Full Text PDFJ Org Chem
November 2024
Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran 14115-175, Iran.
Herein, we present a green cascade approach for synthesizing a range of chemoselective polysubstituted pyrano[3',4':3,4]cyclopenta[1,2-]chromenes containing a chiral stereocenter. The strategy involves a metal-free nucleophilic reaction between dialkyl (2)-2-{2-oxo-3-[(2)-3-aryl-2-propenoyl]-2-chromen-4-yl}-2-butenedioates and α,α-dicyanoolefins under reflux conditions in ethanol solvent. Mechanistic studies have shown that the reaction proceeds via a cascade of steps, including Michael addition, intramolecular C- and -cyclization, intramolecular trans-esterification, [1,2]- and [1,5]-methoxy- and ethoxy carbonyl shift, and finally aromatization to yield the desired product.
View Article and Find Full Text PDFJ Am Chem Soc
September 2024
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China.
To date, it remains challenging to precisely and efficiently construct structurally intriguing polycarbocycles with densely packed stereocenters in organic synthesis. Niduterpenoid B, a naturally occurring ERα inhibitor, exemplifies this complexity with its intricate polycyclic network comprising 5 cyclopentane and 1 cyclopropane rings, featuring 13 contiguous stereocenters, including 4 all-carbon quaternary centers. In this work, we describe the first total synthesis of niduterpenoid B using a structural reorganization strategy.
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