Complete cleavage of the N≡N triple bond by Ta2N+ via degenerate ligand exchange at ambient temperature: A perfect catalytic cycle.

Abstract:

:An unprecedented, spontaneous, and complete cleavage of the triple bond of N2 in the thermal reaction of 15N2 with Ta214N+ was observed experimentally by Fourier transform ion cyclotron resonance mass spectrometry; mechanistic aspects of the degenerate ligand exchange were addressed by high-level quantum chemical calculations. The "hidden" dis- and reassembly of N2, mediated by Ta2N+, constitutes a full catalytic cycle. A frontier orbital analysis reveals that the scission of the N2 triple bond is essentially governed by the donation of d-electrons from the 2 metal centers into antibonding π*-orbitals of N2 and by the concurrent migration of electrons from bonding π- and σ-orbitals of N2 into empty d-orbitals of the metals. This work may contribute to a rational design of catalysts in order to reduce the still enormous energy demand required for an artificial dinitrogen activation.

authors

Geng C,Li J,Weiske T,Schwarz H

doi

10.1073/pnas.1913664116

subject

Has Abstract

pub_date

2019-10-22 00:00:00

pages

21416-21420

issue

43

eissn

0027-8424

issn

1091-6490

pii

1913664116

journal_volume

116

pub_type

杂志文章
  • Iron oxides stimulate sulfate-driven anaerobic methane oxidation in seeps.

    abstract::Seep sediments are dominated by intensive microbial sulfate reduction coupled to the anaerobic oxidation of methane (AOM). Through geochemical measurements of incubation experiments with methane seep sediments collected from Hydrate Ridge, we provide insight into the role of iron oxides in sulfate-driven AOM. Seep sed...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.1412269111

    authors: Sivan O,Antler G,Turchyn AV,Marlow JJ,Orphan VJ

    更新日期:2014-10-07 00:00:00

  • Human eosinophils regulate human lung- and skin-derived fibroblast properties in vitro: a role for transforming growth factor beta (TGF-beta).

    abstract::Eosinophils have been associated with fibrosis. To investigate their direct role in fibrosis, human peripheral blood eosinophil sonicate was added to human lung or dermal fibroblasts, and proliferation ([(3)H]thymidine) and collagen synthesis ([(3)H]proline) were evaluated. Proliferation was enhanced significantly in ...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.96.17.9660

    authors: Levi-Schaffer F,Garbuzenko E,Rubin A,Reich R,Pickholz D,Gillery P,Emonard H,Nagler A,Maquart FA

    更新日期:1999-08-17 00:00:00

  • On the very rapid enhancement by D2O of the temperature-tolerance of adult Drosophila.

    abstract::Deuterium oxide, D(2)O, increases the temperature-tolerance of Drosophila pseudoobscura when it is administered to adult flies as a sucrose solution. The effect is very rapidly exerted; it is detected within 10 min after the flies have a brief (10 min) opportunity to drink. This increased resistance to heat-death sure...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.71.2.540

    authors: Pittendrigh CS,Cosbey ES

    更新日期:1974-02-01 00:00:00

  • Receptor- and heparin-binding domains of basic fibroblast growth factor.

    abstract::Two functional domains in the primary structure of basic fibroblast growth factor (FGF) have been identified on the basis of their ability to interact with the FGF receptor, bind radiolabeled heparin, and modulate the cellular response to FGF. Peptides derived from these two functional domains can act as partial agoni...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.85.7.2324

    authors: Baird A,Schubert D,Ling N,Guillemin R

    更新日期:1988-04-01 00:00:00

  • Reconstitution of paired T cell receptor alpha- and beta-chains from microdissected single cells of human inflammatory tissues.

    abstract::We describe a strategy to "revive" putatively pathogenic T cells from frozen specimens of human inflammatory target organs. To distinguish pathogenic from irrelevant bystander T cells, we focused on cells that were (i) clonally expanded and (ii) in direct morphological contact with a target cell. Using CDR3 spectratyp...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.0604247103

    authors: Seitz S,Schneider CK,Malotka J,Nong X,Engel AG,Wekerle H,Hohlfeld R,Dornmair K

    更新日期:2006-08-08 00:00:00

  • Nuclear binding of steroid receptors: comparison in intact cells and cell-free systems.

    abstract::In regulating gene expression in mammalian tissues, steroid hormones bind to cytoplasmic receptors and the resulting complex associates with the nucleus. In an attempt to study this nuclear association under more precisely controlled conditions, we examined the binding of receptor-[(3)H]steroid complexes to isolated n...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.70.12.3415

    authors: Higgins SJ,Rousseau GG,Baxter JD,Tomkins GM

    更新日期:1973-12-01 00:00:00

  • Biochemical studies on capped RNA primers identify a class of oligonucleotide inhibitors of the influenza virus RNA polymerase.

    abstract::A synthetic 67-nt RNA substrate, containing a 32P-labeled cap-1 structure (m7G32pppGm) was specifically cleaved by the influenza virus RNA polymerase (EC 2.7.7.48) to yield a single capped 11-nt fragment capable of directly priming transcription. An analysis of systematic truncations of this RNA substrate demonstrated...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.91.6.2372

    authors: Chung TD,Cianci C,Hagen M,Terry B,Matthews JT,Krystal M,Colonno RJ

    更新日期:1994-03-15 00:00:00

  • Double-stranded RNA induces mRNA degradation in Trypanosoma brucei.

    abstract::Double-stranded RNA (dsRNA) recently has been shown to give rise to genetic interference in Caenorhabditis elegans and also is likely to be the basis for phenotypic cosuppression in plants in certain instances. While constructing a plasmid vector for transfection of trypanosome cells, we serendipitously discovered tha...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.95.25.14687

    authors: Ngô H,Tschudi C,Gull K,Ullu E

    更新日期:1998-12-08 00:00:00

  • Light-stimulated inositolphospholipid turnover in Samanea saman leaf pulvini.

    abstract::Leaflets of Samanea saman open and close rhythmically, driven by an endogenous circadian clock. Light has a rapid, direct effect on the movements and also rephases the rhythm. We investigated whether light signals might be mediated by increased inositolphospholipid turnover, a mechanism for signal transduction that is...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.84.20.7075

    authors: Morse MJ,Crain RC,Satter RL

    更新日期:1987-10-01 00:00:00

  • The gene regulatory program of Acrobeloides nanus reveals conservation of phylum-specific expression.

    abstract::The evolution of development has been studied through the lens of gene regulation by examining either closely related species or extremely distant animals of different phyla. In nematodes, detailed cell- and stage-specific expression analyses are focused on the model Caenorhabditis elegans, in part leading to the view...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.1720817115

    authors: Schiffer PH,Polsky AL,Cole AG,Camps JIR,Kroiher M,Silver DH,Grishkevich V,Anavy L,Koutsovoulos G,Hashimshony T,Yanai I

    更新日期:2018-04-24 00:00:00

  • Reduction of mammalian ferritin.

    abstract::Mammalian ferritin from horse spleen undergoes an electrochemical or chemical reduction reaction in which each iron atom present is reduced by one electron (2300 electrons per ferritin molecule containing 2300 Fe3+ ions). Midpoint potentials of -190 mV, -310 mV, and -416 mV were determined at pH 7.0, 8.0, and 9.0. Thi...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.82.11.3640

    authors: Watt GD,Frankel RB,Papaefthymiou GC

    更新日期:1985-06-01 00:00:00

  • Dopamine- and cAMP-regulated phosphoprotein (DARPP-32) and dopamine DA1 agonist-sensitive Na+,K+-ATPase in renal tubule cells.

    abstract::The cellular localization of DARPP-32, a dopamine- and cAMP-regulated phosphoprotein of Mr 32,000 that appears to mediate certain actions of dopamine in the mammalian brain by acting as an inhibitor of protein phosphatase 1, was studied in the kidney of several species. DARPP-32 mRNA and DARPP-32-like immunoreactivity...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.86.20.8068

    authors: Meister B,Fryckstedt J,Schalling M,Cortés R,Hökfelt T,Aperia A,Hemmings HC Jr,Nairn AC,Ehrlich M,Greengard P

    更新日期:1989-10-01 00:00:00

  • Proteomics gives insight into the regulatory function of chloroplast thioredoxins.

    abstract::Thioredoxins are small multifunctional redox active proteins widely if not universally distributed among living organisms. In chloroplasts, two types of thioredoxins (f and m) coexist and play central roles in regulating enzyme activity. Reduction of thioredoxins in chloroplasts is catalyzed by an iron-sulfur disulfid...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.232703799

    authors: Balmer Y,Koller A,del Val G,Manieri W,Schürmann P,Buchanan BB

    更新日期:2003-01-07 00:00:00

  • Estrogen-regulated feedback loop limits the efficacy of estrogen receptor-targeted breast cancer therapy.

    abstract::Endocrine therapy resistance invariably develops in advanced estrogen receptor-positive (ER+) breast cancer, but the underlying mechanisms are largely unknown. We have identified C-terminal SRC kinase (CSK) as a critical node in a previously unappreciated negative feedback loop that limits the efficacy of current ER-t...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.1722617115

    authors: Xiao T,Li W,Wang X,Xu H,Yang J,Wu Q,Huang Y,Geradts J,Jiang P,Fei T,Chi D,Zang C,Liao Q,Rennhack J,Andrechek E,Li N,Detre S,Dowsett M,Jeselsohn RM,Liu XS,Brown M

    更新日期:2018-07-31 00:00:00

  • Tropical amphibian populations experience higher disease risk in natural habitats.

    abstract::Habitat loss and disease are main drivers of global amphibian declines, yet the interaction between them remains largely unexplored. Here we show that paradoxically, habitat loss is negatively associated with occurrence, prevalence, and infection intensity of the chytrid fungus Batrachochytrium dendrobatidis (Bd) in a...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.1014497108

    authors: Becker CG,Zamudio KR

    更新日期:2011-06-14 00:00:00

  • Quantification and rationalization of the higher affinity of sodium over potassium to protein surfaces.

    abstract::For a series of different proteins, including a structural protein, enzyme, inhibitor, protein marker, and a charge-transfer system, we have quantified the higher affinity of Na+ over K+ to the protein surface by means of molecular dynamics simulations and conductivity measurements. Both approaches show that sodium bi...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.0606959103

    authors: Vrbka L,Vondrásek J,Jagoda-Cwiklik B,Vácha R,Jungwirth P

    更新日期:2006-10-17 00:00:00

  • A cation binding motif stabilizes the compound I radical of cytochrome c peroxidase.

    abstract::Cytochrome c peroxidase reacts with peroxide to form compound I, which contains an oxyferryl heme and an indolyl radical at Trp-191. The indolyl free radical has a half-life of several hours at room temperature, and this remarkable stability is essential for the catalytic function of cytochrome c peroxidase. To probe ...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.91.23.11118

    authors: Miller MA,Han GW,Kraut J

    更新日期:1994-11-08 00:00:00

  • AtVPS41-mediated endocytic pathway is essential for pollen tube-stigma interaction in Arabidopsis.

    abstract::In flowering plants, extensive male-female interactions are required for successful fertilization in which various signaling cascades are involved. Prevacuolar compartments (PVC) and vacuoles are two types of subcellular compartments that terminate signal transduction by sequestrating signaling molecules in yeast and ...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.1602757113

    authors: Hao L,Liu J,Zhong S,Gu H,Qu LJ

    更新日期:2016-05-31 00:00:00

  • Underdeveloped uterus and reduced estrogen responsiveness in mice with disruption of the estrogen-responsive finger protein gene, which is a direct target of estrogen receptor alpha.

    abstract::The biological roles of estrogen-responsive finger protein (efp) in vivo were evaluated in mice carrying a loss-of-function mutation in efp by gene-targeted mutagenesis. Although efp homozygous mice were viable and fertile in both sexes, the uterus that expressed abundant estrogen receptor alpha exhibited significant ...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.96.21.12027

    authors: Orimo A,Inoue S,Minowa O,Tominaga N,Tomioka Y,Sato M,Kuno J,Hiroi H,Shimizu Y,Suzuki M,Noda T,Muramatsu M

    更新日期:1999-10-12 00:00:00

  • Selective fertilization with phosphite allows unhindered growth of cotton plants expressing the ptxD gene while suppressing weeds.

    abstract::Weeds, which have been the bane of agriculture since the beginning of civilization, are managed manually, mechanically, and, more recently, by chemicals. However, chemical control options are rapidly shrinking due to the recent rise in the number of herbicide-resistant weeds in crop fields, with few alternatives on th...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.1804862115

    authors: Pandeya D,López-Arredondo DL,Janga MR,Campbell LM,Estrella-Hernández P,Bagavathiannan MV,Herrera-Estrella L,Rathore KS

    更新日期:2018-07-17 00:00:00

  • Liver-targeted disruption of Apc in mice activates beta-catenin signaling and leads to hepatocellular carcinomas.

    abstract::Although inappropriate activation of the Wnt/beta-catenin pathway has been implicated in the development of hepatocellular carcinoma (HCC), the role of this signaling in liver carcinogenesis remains unclear. To investigate this issue, we constructed a mutant mouse strain, Apc(lox/lox), in which exon 14 of the tumor-su...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.0404761101

    authors: Colnot S,Decaens T,Niwa-Kawakita M,Godard C,Hamard G,Kahn A,Giovannini M,Perret C

    更新日期:2004-12-07 00:00:00

  • Yin6, a fission yeast Int6 homolog, complexes with Moe1 and plays a role in chromosome segregation.

    abstract::The INT6 gene has been implicated in human breast cancer formation, but its function is unknown. We isolated an Int6 homolog from fission yeast, Yin6, by its binding to a conserved protein in the Ras pathway, Moe1. Yin6 and Moe1 converge on the same protein complex to promote microtubule instability/disassembly. Yin6 ...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.97.26.14370

    authors: Yen HC,Chang EC

    更新日期:2000-12-19 00:00:00

  • Purification of kidney epithelial cell growth inhibitors.

    abstract::Two high molecular weight growth inhibitors have been isolated from the culture medium of BSC-1 cells, epithelial cells of African green monkey kidney. The purified kidney epithelial cell growth inhibitors, at ng/ml concentrations, reversibly arrest the growth of BSC-1 cells in the G1 phase of the cell cycle. Their ac...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.77.10.5989

    authors: Holley RW,Böhlen P,Fava R,Baldwin JH,Kleeman G,Armour R

    更新日期:1980-10-01 00:00:00

  • Interferon regulatory factor 4 differentially regulates the production of Th2 cytokines in naive vs. effector/memory CD4+ T cells.

    abstract::Interferon regulatory factor (IRF) 4 is a member of the IRF family of transcription factors and plays critical roles in the development of CD4(+) T cells into Th2 and Th17 cells. Using the infection model of Nippostrongyrus brasiliensis, we have confirmed the critical roles of IRF-4 in Th2 development in vivo by using...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.0803171105

    authors: Honma K,Kimura D,Tominaga N,Miyakoda M,Matsuyama T,Yui K

    更新日期:2008-10-14 00:00:00

  • Conformations of arsanilazotyrosine-248 carboxypeptidase A alpha, beta, gamma, comparison of crystals and solution.

    abstract::The spectra of the alpha, beta, and gamma forms of zinc monoarsanilazotyrosine-248 carboxypeptidase A are indistinguishable. At pH 8.2 their crystals are yellow, while their solutions are red, lambda(max) 510 nm. Absorption and circular dichroism-pH titrations of the modified zinc and apoenzymes demonstrate that the a...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.70.7.2006

    authors: Johansen JT,Vallee BL

    更新日期:1973-07-01 00:00:00

  • TOR dynamically regulates plant cell-cell transport.

    abstract::The coordinated redistribution of sugars from mature "source" leaves to developing "sink" leaves requires tight regulation of sugar transport between cells via plasmodesmata (PD). Although fundamental to plant physiology, the mechanisms that control PD transport and thereby support development of new leaves have remai...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.1919196117

    authors: Brunkard JO,Xu M,Scarpin MR,Chatterjee S,Shemyakina EA,Goodman HM,Zambryski P

    更新日期:2020-03-03 00:00:00

  • Atomistic structure and dynamics of the human MHC-I peptide-loading complex.

    abstract::The major histocompatibility complex class-I (MHC-I) peptide-loading complex (PLC) is a cornerstone of the human adaptive immune system, being responsible for processing antigens that allow killer T cells to distinguish between healthy and compromised cells. Based on a recent low-resolution cryo-electron microscopy (c...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.2004445117

    authors: Fisette O,Schröder GF,Schäfer LV

    更新日期:2020-08-25 00:00:00

  • Adsorption from a one-dimensional lattice gas and the Brunauer-Emmett-Teller equation.

    abstract::An exact treatment of adsorption from a one-dimensional lattice gas is used to eliminate and correct a well-known inconsistency in the Brunauer-Emmett-Teller (B.E.T.) equation-namely, Gibbs excess adsorption is not taken into account and the Gibbs integral diverges at the transition point. However, neither model shoul...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.93.25.14328

    authors: Hill TL

    更新日期:1996-12-10 00:00:00

  • Systematic mapping of free energy landscapes of a growing filamin domain during biosynthesis.

    abstract::Cotranslational folding (CTF) is a fundamental molecular process that ensures efficient protein biosynthesis and minimizes the formation of misfolded states. However, the complexity of this process makes it extremely challenging to obtain structural characterizations of CTF pathways. Here, we correlate observations of...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.1716252115

    authors: Waudby CA,Wlodarski T,Karyadi ME,Cassaignau AME,Chan SHS,Wentink AS,Schmidt-Engler JM,Camilloni C,Vendruscolo M,Cabrita LD,Christodoulou J

    更新日期:2018-09-25 00:00:00

  • IFNalpha kinoid vaccine-induced neutralizing antibodies prevent clinical manifestations in a lupus flare murine model.

    abstract::A major involvement of IFNalpha in the etiopathogenesis of systemic lupus erythematosus has been suggested by clinical observations, including the increase of serum levels of this cytokine in patients with active disease. Supporting this hypothesis, we have shown that expression of IFNalpha from a recombinant adenovir...

    journal_title:Proceedings of the National Academy of Sciences of the United States of America

    pub_type: 杂志文章

    doi:10.1073/pnas.0900615106

    authors: Zagury D,Le Buanec H,Mathian A,Larcier P,Burnett R,Amoura Z,Emilie D,Peltre G,Bensussan A,Bizzini B,Gallo RC,Koutouzov S

    更新日期:2009-03-31 00:00:00