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The peroxo adducts of hemes are pivotal intermediates generated in the active site of heme enzymes, which catalyze dioxygen activation.
These pivotal intermediates can also phosphorylate the AF-1 domain on estrogen receptor (ER) protein, transforming the tamoxifen ER complex into a positive nuclear transcription factor [ 13].
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The GnGn glycoform constitutes the pivotal intermediate for the formation of complex-type N-glycans in all higher eukaryotes.
Pyruvate is the pivotal intermediate metabolite of the entire central carbon metabolism and determines the carbon fluxes to the TCA cycle or to ethanol formation.
The methylglycoside was calculated to have a slower forward rate (0.3 μs−1) and a more stable C1 conformer (0.2 kcal mol−1), suggesting that pivotal 3D intermediates (particularly SO, S5 and B2,5) increased in energy, and water was implicated as a major cause.
The synthesis features a three-step cascade reaction involving highly stereoselective Michael addition, anion-oxidative hydroxylation, and oxygen anion cyclization to construct the pivotal butyrolactonimidate intermediate.
The synthetic route starting from commercially available carbohydrates yielded a pivotal lactone intermediate with excellent stereochemical control which subsequently could be diversified at the P1-position.
This iterative interdisciplinary approach, identification of pivotal kinetic 3D intermediates and concomitant-directed chemical modification of equilibrium conformer populations and exchange kinetics, has great potential to revolutionize glycan design.
As part of our broader DOS strategy, we have developed a synthesis of pivotal allenic amino-ester intermediates by utilizing a Claisen rearrangement of amino-acid propar-gyl esters.
It was found that titanocene reagents were clearly superior due to their low Lewis acidity, high reduction tendency towards epoxides, and low reduction tendency towards the pivotal β-metal oxy radical intermediates.
Cytoplasmic vesicular DEC1 proteins appear to localise to the Golgi and ER Golgi intermediate compartment, providing a pivotal clue for further study into the detailed molecular mechanism of DEC1 in oesophageal SCC development.
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