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Carbocations02:10

Carbocations

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Carbocations are one of the reaction intermediates formed during several nucleophilic substitutions or elimination reactions. A carbocation is an electron-deficient species with the central carbon atom having six electrons and three bonded atoms. The central carbon in a carbocation is sp2 hybridized with trigonal planar geometry. It has an empty p orbital perpendicular to the plane of the structure that can accept electrons. Thus, carbocations act as strong electrophiles and may react with any...
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Once a ligand binds to a receptor, the signal is transmitted through the membrane and into the cytoplasm. The continuation of a signal in this manner is called signal transduction. Signal transduction only occurs with cell-surface receptors, which cannot interact with most components of the cell, such as DNA. Only internal receptors can interact directly with DNA in the nucleus to initiate protein synthesis. When a ligand binds to its receptor, conformational changes occur that affect the...
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Rab GTPases act in a regulated cascade during membrane fusion, helping the lipid bilayers mix. The Rab family of proteins are active when bound to GTP, and inactive when bound to GDP. Hence, they act as guanine nucleotide-dependent molecular switches. Rab-GTP recognizes and binds to long or short-range tethering proteins to capture the target vesicle. These tethers coordinate with SNAREs on the vesicle and the target membrane to assemble the trans SNARE complex that locks the mixing bilayers.
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Atoms — and the protons, neutrons, and electrons that compose them — are extremely small. For example, a carbon atom weighs less than 2 × 10−23 g. When describing the properties of tiny objects such as atoms, we use appropriately small units of measure, such as the atomic mass unit (amu). The amu was originally defined based on hydrogen, the lightest element, then later in terms of oxygen. Since 1961, it has been defined with regard to the most abundant isotope of carbon, atoms of which...
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An atomic orbital represents the three-dimensional regions in an atom where an electron has the highest probability to reside. The radial distribution function indicates the total probability of finding an electron within the thin shell at a distance r from the nucleus. The atomic orbitals have distinct shapes which are determined by l, the angular momentum quantum number. The orbitals are often drawn with a boundary surface, enclosing densest regions of the cloud.
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Carbocations: Types and Stability
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Inherent atomic mobility changes in carbocation intermediates during the sesterterpene cyclization cascade.

Hajime Sato1,2, Takaaki Mitsuhashi3, Mami Yamazaki1

  • 1Graduate School of Pharmaceutical Sciences, Chiba University, 1-8-1 Inohana, Chuo-ku, Chiba 260-8675, Japan.

Beilstein Journal of Organic Chemistry
|August 31, 2019
PubMed
Summary

Two methyl groups in geranylfarnesyl diphosphate (GFPP) carbocations are key to controlling terpene formation. Their limited mobility helps preorganize GFPP for sesterterpene biosynthesis.

Keywords:
DFTbiosynthesiscarbocationsubstrate recognitionterpene cyclase

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Area of Science:

  • Biochemistry
  • Organic Chemistry
  • Molecular Biology

Background:

  • Terpene biosynthesis relies on carbocation intermediates, whose conformations dictate product selectivity.
  • The initial conformation of geranylfarnesyl diphosphate (GFPP) influences these intermediates, but the control mechanisms remain unclear.

Purpose of the Study:

  • To analyze atomic mobility in carbocation intermediates during sesterterpene biosynthesis.
  • To identify key structural features of GFPP involved in substrate fixation and preorganization.

Main Methods:

  • Detailed analysis of inherent atomic mobility in carbocation intermediates.
  • Computational methods to study molecular dynamics during cyclization.

Main Results:

  • Identified two specific methyl groups with minimal mobility in early-stage carbocation intermediates.
  • These methyl groups are crucial for the preorganization of GFPP within the enzyme's active site.

Conclusions:

  • The limited mobility of specific methyl groups on GFPP is critical for controlling its conformation.
  • This preorganization is essential for the regioselective and stereoselective biosynthesis of sesterterpenes like sesterfisherol and quiannulatene.