Previous work has shown that the essential R210 of subunit a in the Escherichia coli ATP synthase can be switched with a conserved glutamine Q252 with retention of a moderate level of function, that a third mutation P204T enhances this function, and that the arginine Q252R can be replaced by lysine without total loss of activity. In this study, the roles of P204T and R210Q were examined. It was concluded that the threonine in P204T is not directly involved in function since its replacement by alanine did not significantly affect growth properties. Similarly, it was concluded that the glutamine in R210Q is not directly involved with function since replacement by glycine results in significantly enhanced function. Not only did the rate of ATP-driven proton translocation increase, but also the sensitivity of ATP hydrolysis to inhibition by N,N'-dicyclohexylcarbodiimide (DCCD) rose to more than 50%. Finally, mutations at position E219, a residue near the proton pathway, were used to test whether the Arginine-switched mutant uses the normal proton pathway. In a wild type background, the E219K mutant was confirmed to have greater function than the E219Q mutant, as has been shown previously. This same unusual result was observed in the triple mutant background, P204T/R210Q/Q252R, suggesting that the Arginine-switched mutants are using the normal proton pathway from the periplasm.
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http://dx.doi.org/10.1016/j.bbabio.2009.03.022 | DOI Listing |
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January 2025
Department of Physics, Dongguk University, Seoul, 04620, Republic of Korea.
The hydrogen spillover phenomenon provides an expeditious reaction pathway via hydrogen transfer from a strong H adsorption site to a weak H adsorption site, enabling a cost-efficient hydrogen evolution reaction (HER) analogous to platinum with moderate H adsorption energy. Here, a high-entropy oxychalcogenide (HEOC) comprising Co, Ni, Mo, W, O, Se, and Te is prepared by a two-step electrochemical deposition for hydrogen spillover-enhanced HER in acidic and alkaline water electrolysis. The anodic-cathodic reversal current enables the co-deposition of cations and aliovalent anions, facilitating a glass structure with multiple active sites for hydrogen spillover.
View Article and Find Full Text PDFChem Sci
January 2025
Department of Chemistry and Biochemistry, University of California Los Angeles California 90095-1569 USA
Group 13 aminoxy complexes of the form (L)E(TEMPO) (TEMPO = 2,2,6,6-tetramethylpiperidine 1-oxyl; L = THF (tetrahydrofuran) or Py (pyridine); E = Al, Ga, In) were prepared and structurally characterized. The complexes (THF)Ga(TEMPO) (1·THF) and (Py)In(TEMPO) (2·Py) are shown to heterolytically cleave H under mild conditions (3 atm, 20 °C, ≤ 1 h). 1·THF reacts reversibly with H to form a formal H-adduct that bears a Ga(iii) hydride site and a protonated TEMPO ligand with concomitant loss of THF, consistent with Ga(iii) and TEMPO functioning as Lewis acid and base, respectively.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, University of California Davis, Davis, California 95616, United States.
[FeFe]-hydrogenases are enzymes that catalyze the redox interconversion of H and H using a six-iron active site, known as the H-cluster, which consists of a structurally unique [2Fe] subcluster linked to a [4Fe-4S] subcluster. A set of enzymes, HydG, HydE, and HydF, are responsible for the biosynthesis of the [2Fe] subcluster. Among them, it is well established that HydG cleaves tyrosine into CO and CN and forms a mononuclear [Fe(II)(Cys)(CO)(CN)] complex.
View Article and Find Full Text PDFJ Exp Biol
January 2025
Department of Biological Sciences, University of Alberta, 116 St and 85 Ave, Edmonton, AB T6G 2R3, Canada.
Acidification is a key component of digestion throughout metazoans. The gut digestive fluid of many invertebrates is acidified by the vesicular-type H+-ATPase (VHA). In contrast, vertebrates generate acidic gut fluids using the gastric H+/K+-ATPase (HKA); an evolutionary innovation linked with the appearance of a true stomach that greatly improves digestion, absorption, and immune function.
View Article and Find Full Text PDFCatal Sci Technol
January 2025
Department of Chemistry and Chemical Biology, Stevens Institute of Technology 1 Castle Point Terrace Hoboken NJ 07030 USA
Engineered heme proteins possess excellent biocatalytic carbene N-H insertion abilities for sustainable synthesis, and most of them have His as the Fe axial ligand. However, information on the basic reaction mechanisms is limited, and ground states of heme carbenes involved in the prior computational mechanistic studies are under debate. A comprehensive quantum chemical reaction pathway study was performed for the heme model with a His analogue as the axial ligand and carbene from the widely used precursor ethyl diazoacetate with aniline as the substrate.
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