Are Methylaluminoxane Activators Sheets?
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ABSTRACT:
SUBMITTER: Collins S
PROVIDER: S-EPMC8362195 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Methylaluminoxane (MAO) activators have sheet structures which form ion-pairs on reaction of neutral donors such as octamethyltrisiloxane (OMTS). The ion-pairs can be detected by electrospray ionization mass spectrometry (ESI-MS) in polar media. The growth of these reactive precursors during hydrolysis of Me3 Al can be monitored using ESI-MS. Density functional theory, combined with numerical simulation of growth, indicates that this process involves rapid formation of low MW oligomers, followed by assembly of these species into low MW sheets. These can grow through further addition of low MW oligomers or by fusion into larger sheets. The mechanism of these growth processes leads to the prediction that even-numbered sheets should be favored, and this surprising result is confirmed by ESI-MS monitoring experiments of both activator growth and MAO aging.
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Project description:Ethylene tetramerization catalyst systems comprising a Cr(III) complex containing PNP ligands and methylaluminoxane (MAO) are useful for the production of 1-octene. However, a concern with these systems is the use of expensive MAO in excess. Herein, we report a catalytic system that avoids the use of MAO. Metathesis of CrCl3(THF)3 and [(CH3CN)4Ag]+[B(C6F5)4]- afforded [L4CrIIICl2]+[B(C6F5)4]- (L = CH3CN or tetrahydrofuran (THF)), which was converted to [(PNP)CrCl2L2]+[B(C6F5)4]-, where PNP is iPrN(PPh2)2 (1) or [CH3(CH2)16]2CHN(PPh2)2 (2). The molecular structures of [(THF)4CrIIICl2]+[B(C6F5)4]- and [1-CrCl2(THF)2]+[B(C6F5)4]- were unambiguously determined by X-ray crystallography. The cationic (PNP)CrIII complexes paired with [B(C6F5)4]- anions, that is, [(PNP)CrCl2(CH3CN)2]+[B(C6F5)4]-, exhibited high activity in chlorobenzene when activated with common trialkylaluminum species (Me3Al, Et3Al, and iBu3Al). The activities and selectivity were comparable to those of the original MAO-based Sasol system (1-CrCl3/MAO). When activated with Et3Al or iBu3Al, the Cr complex, [2-CrCl2(CH3CN)2]+[B(C6F5)4]-, which bears long alkyl chains, showed high activity in the more desirable methylcyclohexane solvent (89 kg/g-Cr/h) and much higher activity in cyclohexene (168 kg/g-Cr/h). Other advantages of the [2-CrCl2(CH3CN)2]+[B(C6F5)4]-/Et3Al system in cyclohexene were negligible catalyst deactivation, formation of only a negligible amount of polyethylene side product (0.3%), and formation of fewer unwanted side products above C10. The [B(C6F5)4]- anion is compatible with trialkylaluminum species once it is not paired with a trityl cation. Hence, [(PNP)CrCl2(CH3CN)2]+[B(C6F5)4]-/Et3Al exhibited a significantly higher activity than that of a previously reported system composed of [Ph3C]+[B(C6F5)4]-, that is, 1/CrCl3(THF)3/[Ph3C]+[B(C6F5)4]-/Et3Al.
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Project description:In single-site olefin polymerization catalysis, a large excess of cocatalyst is often required for the generation of highly active catalysts, but the reason for this is unclear. In this work, fundamental insight into the multifaceted role of cocatalyst methylaluminoxane (MAO) in the activation, deactivation, and stabilization of group 4 metallocenes in the immobilized single-site olefin polymerization catalyst was gained. Employing probe molecule FT-IR spectroscopy, it was found that weak Lewis acid sites, inherent to the silica-supported MAO cocatalyst, are the main responsible species for the genesis of active metallocenes for olefin polymerization. These weak Lewis acid sites are the origin of AlMe2+ groups. Deactivation of metallocenes is caused by the presence of silanol groups on the silica support. Interaction of the catalyst precursor with these silanol groups leads to the irreversible formation of inactive metallocenes. Importantly, a high concentration of MAO (14 wt% Al) on the silica support is necessary to keep the metallocenes immobilized, hence preventing metallocene leaching and consequent reactor fouling. Increasing the loading of the MAO cocatalyst leads to larger amounts of AlMe2+, fewer silanol groups, and less metallocene leaching, which all result in higher olefin polymerization activity.
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Project description:The established model cluster (AlOMe)16(AlMe3)6 for methylaluminoxane (MAO) cocatalyst has been studied by density functional theory, aiming to rationalize the different behaviors of unmodified MAO and TMA-depleted MAO/BHT (TMA = trimethylaluminum; BHT = 2,6-di-tert-butyl-4-methylphenol), highlighted in previous experimental studies. The tendency of the three model Lewis acidic sites A-C to release neutral Al fragments (i.e., AlMe2R; R = Me or bht) or transient aluminum cations (i.e., [AlMeR]+) has been investigated both in the absence and in the presence of neutral N-donors. Sites C are most likely responsible for the activation capabilities of TMA-rich MAO, but TMA depletion destabilizes them, possibly inducing structural rearrangements. The remaining sites A and B, albeit of lower Lewis acidity, should be still able to release cationic Al fragments when TMA-depleted modified MAOs are treated with N-donors (e.g. [AlMe(bht)]+ from MAO/BHT). These findings provide tentative interpretations for earlier observations of donor-dependent ionization tendencies of MAO and MAO/BHT and how TMA depleted MAOs can still be potent activators.
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Project description:The development of peptide beta-hairpins is problematic, because folding depends on the amino acid sequence and changes to the sequence can significantly decrease folding. Robust beta-hairpins that can tolerate such changes are attractive tools for studying interactions involving protein beta-sheets and developing inhibitors of these interactions. This paper introduces a new class of peptide models of protein beta-sheets that addresses the problem of separating folding from the sequence. These model beta-sheets are macrocyclic peptides that fold in water to present a pentapeptide beta-strand along one edge; the other edge contains the tripeptide beta-strand mimic Hao [JACS 2000, 122, 7654] and two additional amino acids. The pentapeptide and Hao-containing peptide strands are connected by two delta-linked ornithine (deltaOrn) turns [JACS 2003, 125, 876]. Each deltaOrn turn contains a free alpha-amino group that permits the linking of individual modules to form divalent beta-sheets. These "cyclic modular beta-sheets" are synthesized by standard solid-phase peptide synthesis of a linear precursor followed by solution-phase cyclization. Eight cyclic modular beta-sheets 1a-1h containing sequences based on beta-amyloid and macrophage inflammatory protein 2 were synthesized and characterized by 1H NMR. Linked cyclic modular beta-sheet 2, which contains two modules of 1b, was also synthesized and characterized. 1H NMR studies show downfield alpha-proton chemical shifts, deltaOrn delta-proton magnetic anisotropy, and NOE cross-peaks that establish all compounds but 1c and 1g to be moderately or well folded into a conformation that resembles a beta-sheet. Pulsed-field gradient NMR diffusion experiments show little or no self-association at low (</=2 mM) concentrations. Changes to the residues in the Hao-containing strands of 1c and 1g improve folding and show that folding of the structures can be enhanced without altering the sequence of the pentapeptide strand. Well-folded cyclic modular beta-sheets 1a, 1b, and 1f each have a phenylalanine directly across from Hao, suggesting that cyclic modular beta-sheets containing aromatic residues across from Hao are better folded.
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Project description:The properties of conventional materials result from the arrangement of and the interaction between atoms at the nanoscale. Metamaterials have shifted this paradigm by offering property control through structural design at the mesoscale, thus broadening the design space beyond the limits of traditional materials. A family of mechanical metamaterials consisting of soft sheets featuring a patterned array of reconfigurable bistable domes is reported here. The domes in this metamaterial architecture can be reversibly inverted at the local scale to generate programmable multistable shapes and tunable mechanical responses at the global scale. By 3D printing a robotic gripper with energy-storing skin and a structure that can memorize and compute spatially-distributed mechanical signals, it is shown that these metamaterials are an attractive platform for novel mechanologic concepts and open new design opportunities for structures used in robotics, architecture, and biomedical applications.
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Project description:Eukaryotic transcription activation domains (ADs) are not well defined on the proteome scale. We systematicallly tested approximately 6000 yeast proteins for transcriptional activity using a yeast one-hybrid system and identified 451 transcriptional activators. We then determined their transcription activation strength using fusions to the Gal4 DNA-binding domain and a His3 reporter gene which contained a promoter with a Gal4-binding site. Among the 132 strongest activators 32 are known transcription factors while another 35 have no known function. Although zinc fingers, helix-loop-helix domains and several other domains are highly overrepresented among the activators, only few contain characterized ADs. We also found some striking correlations: the stronger the activation activity, the more acidic, glutamine-rich, proline-rich or asparagine-rich the activators were. About 29% of the activators have been found previously to specifically interact with the transcription machinery, while 10% are known to be components of transcription regulatory complexes. Based on their transcriptional activity, localization and interaction patterns, at least six previously uncharacterized proteins are suggested to be bona fide transcriptional regulators (namely YFL049W, YJR070C, YDR520C, YGL066W/Sgf73, YKR064W and YCR082W/Ahc2).
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Project description:Transcriptional profiling of adult forestomach epithelium comparing K5-CreER controsl with K5-CreER;Rosa26Sox2/Sox2 mutants. Two doses of tamoxifen were given and four weeks later the epithelal sheets were harvested for RNA extraction. Goal was to determine the effects of Sox2 overexpression on epithelial phenotypic changes.
2012-05-09 | GSE37857 | GEO
Project description:Interactions among ?-sheets occur widely in protein quaternary structure, protein-protein interaction, and protein aggregation and are central in Alzheimer's and other amyloid-related diseases. This Perspective looks at the structural biology of these important yet under-appreciated interactions from a supramolecular chemist's point of view. Common themes in the supramolecular interactions of ?-sheets are identified and richly illustrated though examples from proteins, amyloids, and chemical model systems. ?-Sheets interact through edge-to-edge hydrogen bonding to form extended layers and through face-to-face hydrophobic or van der Waals interactions to form layered sandwich-like structures. Side chains from adjacent layers can fit together through simple hydrophobic contacts or can participate in complementary interdigitation or knob-hole interactions. The layers can be aligned, offset, or rotated. The right-handed twist of ?-sheets provides additional opportunities for stabilization of edge-to-edge contacts and rotated layered structures.
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