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Strain-Modulated Reactivity: An Acidic Silane.

ABSTRACT: Compounds of main-group elements such as silicon are attractive candidates for green and inexpensive catalysts. For them to compete with state-of-the-art transition-metal complexes, new reactivity modes must be unlocked and controlled, which can be achieved through strain. Using a tris(2-skatyl)methylphosphonium ([TSMPH₃ ]⁺ ) scaffold, we prepared the strained cationic silane [TSMPSiH]⁺ . In stark contrast with the generally hydridic Si-H bond character, it is acidic with an experimental pK_a ^DMSO within 4.7-8.1, lower than in phenol, benzoic acid, and the few hydrosilanes with reported pK_a values. We show that ring strain significantly contributes to this unusual acidity along with inductive and electrostatic effects. The conjugate base, TSMPSi, activates a THF molecule in the presence of CH-acids to generate a highly fluxional alkoxysilane via trace amounts of [TSMPSiH]⁺ functioning as a strain-release Lewis acid. This reaction involves a formal oxidation-state change from Si^II to Si^IV , presenting intriguing similarities with transition-metal-mediated processes.

SUBMITTER: Tretiakov S

PROVIDER: S-EPMC8252520 | biostudies-literature | 2021 Apr

REPOSITORIES: biostudies-literature

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Strain-Modulated Reactivity: An Acidic Silane.

Tretiakov Serhii S Witteman Léon L Lutz Martin M Moret Marc-Etienne ME

Angewandte Chemie (International ed. in English) 20210312 17

Compounds of main-group elements such as silicon are attractive candidates for green and inexpensive catalysts. For them to compete with state-of-the-art transition-metal complexes, new reactivity modes must be unlocked and controlled, which can be achieved through strain. Using a tris(2-skatyl)methylphosphonium ([TSMPH3 ]+ ) scaffold, we prepared the strained cationic silane [TSMPSiH]+ . In stark contrast with the generally hydridic Si-H bond character, it is ac ...[more]

PMID: 33476423

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Project description:BackgroundThe extracellular pH (pH e ) is known to be acidic. We investigated the effect of mild (pH e 6.8) and severe (pH e 5.9) acidosis on gene expression in mouse B16-BL6 melanoma cells using cDNA microarray analysis and compared them with the acidic pH e dependence of human tumors.MethodsB16-BL6 cells were treated with pH e 7.4 (control), pH e 6.8, and pH e 5.9. The mRNA expression was analyzed by using the cDNA microarray. Heat map, volcano plot, and gene ontology enrichment analysis were performed. The data were compared with the gene signatures of published data GSE52031 and GSE8401 and compared with the pathological staging by GEPIA2, and the prognostic signature of proteins was searched by the Human Protein Atlas database. If the acidic pH e -induced and -reduced genes were correlated with shortened and prolonged survival times, respectively, and also correlated with pathological staging, we defined it as "hit" and counted the sum of hit points of eight types of tumors such as breast, colorectal, prostate, gastric, liver, prostate, lung, and head and neck and melanoma.ResultsGene expression was differentially and commonly regulated by both pH e s. The number of genes upregulated fourfold or more at pH e 6.8 and 5.9 only for 25 and 131 genes, respectively, and 85 genes were common. The number of genes downregulated fourfold or less at pH e 6.8 and 5.9 only for 63 and 82 genes, respectively, and 118 genes were common. Compared with human mRNA expression data (GSE8401), there is no correlation with the overall pattern of the signature. In seven types of cancer (breast, colorectal, gastric, liver, prostate, lung, and head and neck) and melanoma, the relationship between acidic pH e -modulated gene expression and overall survival was evaluated. As a result, acidic pH e dependency contributing to prognosis was higher in colorectal, lung, and head and neck cancers and lower in prostate cancer.ConclusionTumor classification based on response to extracellular acidic pH e will provide new insights into chemotherapy strategy for patients with tumors.

Project description:Streptococcus mutans, a major etiological agent of dental caries, causes demineralization of the tooth tissue due to the formation of acids from dietary carbohydrates. Dominant among the virulence determinants of this organism are aciduricity and acidogenicity, the abilities to grow at low pH and to produce acid, respectively. The mechanisms underlying the ability of S. mutans to survive and proliferate at low pH are currently under investigation. In this study we cultured S. mutans at pH 5.2 or 7.0 and extracted soluble cellular proteins. These were analyzed using high-resolution two-dimensional gel electrophoresis, and replicate maps of proteins expressed under each of the two conditions were generated. Proteins with modulated expression at low pH, as judged by a change in the relative integrated optical density, were excised and digested with trypsin by using an in-gel protocol. Tryptic digests were analyzed using matrix-assisted laser desorption ionization mass spectrometry to generate peptide mass fingerprints, and these were used to assign putative functions according to their homology with the translated sequences in the S. mutans genomic database. Thirty individual proteins exhibited altered expression as a result of culture of S. mutans at low pH. Up-regulated proteins (n = 18) included neutral endopeptidase, phosphoglucomutase, 60-kDa chaperonin, cell division proteins, enolase, lactate dehydrogenase, fructose bisphosphate aldolase, acetoin reductase, superoxide dismutase, and lactoylglutathione lyase. Proteins down-regulated at pH 5.2 (n = 12) included protein translation elongation factors G, Tu, and Ts, DnaK, small-subunit ribosomal protein S1P, large-subunit ribosomal protein L12P, and components of both phosphoenolpyruvate:protein phosphotransferase and multiple sugar binding transport systems. The identification of proteins differentially expressed following growth at low pH provides new information regarding the mechanisms of survival and has identified new target genes for mutagenesis studies to further assess their physiological significance.

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Strain-Modulated Reactivity: An Acidic Silane.

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Strain-Modulated Reactivity: An Acidic Silane.

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