An atomic-level mechanism for molybdenum nitrogenase. Part 1. Reduction of dinitrogen.

Abstract:

:The properties of the Fe and Mo sites of the iron-molybdenum cofactor of nitrogenase with respect to binding and activation of N(2) have been studied by molecular mechanics calculations on the local protein environment and by density functional theory (DFT) calculations on subsections of the cofactor. The DFT calculations indicate that the homocitrate ligand of the cofactor can become monodentate on reduction, allowing N(2) to bind at Mo. In addition, the neighboring Fe atom plays a crucial role in N(2) reduction by stabilizing the initial reduced N(2) species and by facilitating cleavage of the N-N bond. The various possible isomers for partially reduced N(2) intermediates have been compared by DFT, and a detailed model for the reduction of N(2) is developed based on these results, together with chemical precedents and the available biochemical data for nitrogenase.

journal_name

Biochemistry

journal_title

Biochemistry

authors

Durrant MC

doi

10.1021/bi025623z

subject

Has Abstract

pub_date

2002-11-26 00:00:00

pages

13934-45

issue

47

eissn

0006-2960

issn

1520-4995

pii

bi025623z

journal_volume

41

pub_type

杂志文章
  • Heteronuclear NMR and crystallographic studies of wild-type and H187Q Escherichia coli uracil DNA glycosylase: electrophilic catalysis of uracil expulsion by a neutral histidine 187.

    abstract::The nature of the putative general acid His187 in the reaction catalyzed by Escherichia coli uracil DNA glycosylase (UDG) was investigated using X-ray crystallography and NMR spectroscopy. The crystal structures of H187Q UDG, and its complex with uracil, have been solved at 1.40 and 1.60 A resolution, respectively. Th...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi9910880

    authors: Drohat AC,Xiao G,Tordova M,Jagadeesh J,Pankiewicz KW,Watanabe KA,Gilliland GL,Stivers JT

    更新日期:1999-09-14 00:00:00

  • Genetic polymorphism of human cytochrome P-450 (S)-mephenytoin 4-hydroxylase. Studies with human autoantibodies suggest a functionally altered cytochrome P-450 isozyme as cause of the genetic deficiency.

    abstract::The metabolism of the anticonvulsant mephenytoin is subject to a genetic polymorphism. In 2-5% of Caucasians and 18-23% of Japanese subjects a specific cytochrome P-450 isozyme, P-450 meph, is functionally deficient or missing. We have accumulated evidence that autoimmune antibodies observed in sera of patients with t...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi00399a065

    authors: Meier UT,Meyer UA

    更新日期:1987-12-15 00:00:00

  • Photosystem II of green plants: topology of core pigments and redox cofactors as inferred from electrochromic difference spectra.

    abstract::Three electrochromic difference spectra induced by the deposition of (1) a negative charge on the primary quinone acceptor, Q(A), (2) a positive charge on (or near) Tyr161 of the D1 subunit (Y(Z)), and (3) a positive charge on the manganese cluster were determined at room temperature in photosystem II (PSII) core part...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi9513057

    authors: Mulkidjanian AY,Cherepanov DA,Haumann M,Junge W

    更新日期:1996-03-05 00:00:00

  • Ca2+, Mg2+, and troponin I inhibitory peptide binding to a Phe-154 to Trp mutant of chicken skeletal muscle troponin C.

    abstract::The effects of Ca2+, Mg2+, and troponin I (TnI) inhibitory peptide (Ip) binding on the spectral properties of a Phe-154 to Trp mutant (F154W) of chicken recombinant troponin C (rTnC) have been examined. Residue 154 is positioned in the final flanking helix H of metal binding site IV. Since there are no other Tyr or Tr...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi00176a028

    authors: Chandra M,McCubbin WD,Oikawa K,Kay CM,Smillie LB

    更新日期:1994-03-15 00:00:00

  • Simultaneous binding of drugs with different chemical structures to Ca2+-calmodulin: crystallographic and spectroscopic studies.

    abstract::The modulatory action of Ca2+-calmodulin on multiple targets is inhibited by trifluoperazine, which competes with target proteins for calmodulin binding. The structure of calmodulin crystallized with two trifluoperazine molecules is determined by X-ray crystallography at 2.74 A resolution. The X-ray data together with...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi980795a

    authors: Vertessy BG,Harmat V,Böcskei Z,Náray-Szabó G,Orosz F,Ovádi J

    更新日期:1998-11-03 00:00:00

  • Structure around the cleavage site in the thrombin receptor determined by NMR spectroscopy.

    abstract::NMR spectroscopic experiments were performed to study the structure of synthetic peptides identical to two extracellular regions of the human thrombin receptor. The smaller molecule, comprising 14 amino acids, was biologically active and was equivalent to the "tethered ligand" exposed after cleavage of the receptor by...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi00186a005

    authors: Smith KJ,Trayer IP,Grand RJ

    更新日期:1994-05-24 00:00:00

  • Oxidative inactivation of a charge transfer complex in the medium-chain acyl-CoA dehydrogenase.

    abstract::The intense charge transfer complex between the enolate of 3-thia-octanoyl-CoA and the oxidized flavin of the medium-chain acyl-CoA dehydrogenase is discharged by the ferricenium ion with irreversible inactivation of the enzyme. Charge transfer complex formation is a necessary, but insufficient, condition for oxidativ...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi00050a025

    authors: Schaller RA,Thorpe C

    更新日期:1995-12-19 00:00:00

  • Structurally diverse chitolipooligosaccharide nod factors accumulate primarily in membranes of wild type Rhizobium leguminosarum biovar trifolii.

    abstract::The general view on Rhizobium chitolipooligosaccharides (CLOS) is that they are made in very low levels as diffusible molecules and are primarily secreted by the bacteria into the extracellular milieu where they interact with the host. However, the structural and predicted physicochemical properties of these amphiphil...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi00011a041

    authors: Orgambide GG,Lee J,Hollingsworth RI,Dazzo FB

    更新日期:1995-03-21 00:00:00

  • Diazomethyl ketone substrate derivatives as active-site-directed inhibitors of thiol proteases. Papain.

    abstract::The diazomethyl ketones of z-Phe-Phe inactivate papain by a stoichiometric reaction at the active-center thiol. Since the reagents are stable in mercaptoethanol, their reaction with papain is judged to be the result of complex formation characteristic of affinity-labeling reagents. The diazomethyl ketones react by a m...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi00645a033

    authors: Leary R,Larsen D,Watanabe H,Shaw E

    更新日期:1977-12-27 00:00:00

  • The complete amino acid sequence of ubiquitin, an adenylate cyclase stimulating polypeptide probably universal in living cells.

    abstract::The complete amino acid sequence was determined for bovine ubiquitin, and adenylate cyclase stimulating polypeptide, which is probably represented universally in living cells. Ubiquitin has a molecular weight of 8451 and consists of a single polypeptide chain containing 74 amino acid residues. It contains four argini...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi00681a026

    authors: Schlesinger DH,Goldstein G,Niall HD

    更新日期:1975-05-20 00:00:00

  • Xenopus laevis hemoglobin and its hybrids with hemoglobin A+.

    abstract::Isolated alpha and beta chains from Xenopus laevis hemoglobin have been purified. The isolation procedure yields native alpha chains whose functional behavior has been characterized and compared with that of human alpha chains. Isolated beta chains in the presence of oxygen are characterized by low stability, and henc...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi00395a022

    authors: Condò SG,Giardina B,Bellelli A,Brunori M

    更新日期:1987-10-20 00:00:00

  • Isolation and characterization of human cDNA clones encoding the alpha and the alpha' subunits of casein kinase II.

    abstract::Casein kinase II is a widely distributed protein serine/threonine kinase. The holoenzyme appears to be a tetramer, containing two alpha or alpha' subunits (or one of each) and two beta subunits. Complementary DNA clones encoding the subunits of casein kinase II were isolated from a human T-cell lambda gt10 library usi...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi00488a034

    authors: Lozeman FJ,Litchfield DW,Piening C,Takio K,Walsh KA,Krebs EG

    更新日期:1990-09-11 00:00:00

  • Radical redesign of a tandem array of four R67 dihydrofolate reductase genes yields a functional, folded protein possessing 45 substitutions.

    abstract::R67 dihydrofolate reductase (DHFR) is a plasmid-encoded, type II enzyme. Four monomers (78 amino acids long) assemble into a homotetramer possessing 222 symmetry. In previous studies, a tandem array of four R67 DHFR gene copies was fused in frame to generate a functional monomer named Quad1. This protein possessed the...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi1005943

    authors: Feng J,Grubbs J,Dave A,Goswami S,Horner CG,Howell EE

    更新日期:2010-08-31 00:00:00

  • Characterization of metal ion activation and inhibition of CTP synthetase.

    abstract::A reinvestigation of the metal ion activation and specificity of CTP synthetase was begun in order to separate effects due to binding of free metal ions and binding of nucleotide-complexed ions. Apo-CTP synthetase was prepared by dialysis against 5 mM EDTA. Analysis of apo-enzyme by atomic absorption spectroscopy reve...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi00065a032

    authors: Robertson JG,Villafranca JJ

    更新日期:1993-04-13 00:00:00

  • Decreased amyloidogenicity caused by mutational modulation of surface properties of the immunoglobulin light chain BRE variable domain.

    abstract::Amyloid formation by immunoglobulin light chain (LC) proteins is associated with amyloid light chain (AL) amyloidosis. Destabilization of the native state of the variable domain of the LC (VL) is known to be one of the critical factors in promoting the formation of amyloid fibrils. However, determining the key residue...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi5007892

    authors: Kobayashi Y,Tsutsumi H,Abe T,Ikeda K,Tashiro Y,Unzai S,Kamikubo H,Kataoka M,Hiroaki H,Hamada D

    更新日期:2014-08-12 00:00:00

  • Electrophoretic analysis of substrate-attached proteins from normal and virus-transformed cells.

    abstract::The proteins which have been left tightly bound to the tissue culture substrate after ethylenebis (oxyethyl-enenitrilo) tetraacetic acid (EGTA)-mediated removal of normal, virus-transformed, and revertant mouse cells and which have been implicated in the substrate adhesion process have been analyzed by slab sodium dod...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi00663a028

    authors: Culp LA

    更新日期:1976-09-07 00:00:00

  • Solution structure of the biologically relevant G-quadruplex element in the human c-MYC promoter. Implications for G-quadruplex stabilization.

    abstract::The nuclease hypersensitivity element III(1) (NHE III(1)) of the c-MYC promoter strongly controls the transcriptional activity of the c-MYC oncogene. The purine-rich strand of the NHE III(1) element has been shown to be a silencer element for c-MYC transcription upon formation of a G-quadruplex structure. We have dete...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi048242p

    authors: Ambrus A,Chen D,Dai J,Jones RA,Yang D

    更新日期:2005-02-15 00:00:00

  • Steady-state FTIR spectra of the photoreduction of QA and QB in Rhodobacter sphaeroides reaction centers provide evidence against the presence of a proposed transient electron acceptor X between the two quinones.

    abstract::In the reaction center (RC) of the photosynthetic bacterium Rhodobacter sphaeroides, two ubiquinone molecules, QA and QB, play a pivotal role in the conversion of light energy into chemical free energy by coupling electron transfer to proton uptake. In native RCs, the transfer of an electron from QA to QB takes place ...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi700297b

    authors: Breton J

    更新日期:2007-04-17 00:00:00

  • Effect of pH on the active site of an Arg121Cys mutant of the metallo-beta-lactamase from Bacillus cereus: implications for the enzyme mechanism.

    abstract::The zinc-dependent metallo-beta-lactamases are a group of bacterial enzymes that pose a threat to the future efficacy of present-day antibiotics. Their mechanism is poorly understood, and there are no clinically useful inhibitors. While most members of the group contain two tightly bound zinc ions in their active site...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi047709t

    authors: Davies AM,Rasia RM,Vila AJ,Sutton BJ,Fabiane SM

    更新日期:2005-03-29 00:00:00

  • Kinetic mechanism of the Escherichia coli UDPMurNAc-tripeptide D-alanyl-D-alanine-adding enzyme: use of a glutathione S-transferase fusion.

    abstract::The D-alanyl-D-alanine-adding enzyme encoded by the murF gene catalyzes the ATP-dependent formation of UDP-N-acetylmuramyl-L-gamma-D-Glu-meso-diaminopimelyl-D-Ala-D-Ala (UDP-MurNAc-tripeptide). MurF has been cloned from Escherichia coli and expressed as a glutathione S-transferase (GST) fusion using the tac promoter-b...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi961872+

    authors: Anderson MS,Eveland SS,Onishi HR,Pompliano DL

    更新日期:1996-12-17 00:00:00

  • Extracellular labeling of growing secreted polypeptide chains in Bacillus subtilis with diazoiodosulfanilic acid.

    abstract::Studies of the mechanism of protein secretion in a Gram-positive bacterium, Bacillus subtilis, yielded results very similar to those previously obtained with a Gram-negative organism: nascent chains protruding from protoplasts could be labeled extracellularly; the labeled chains could be recovered on polysomes isolate...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi00568a030

    authors: Smith WP,Tai PC,Davis BD

    更新日期:1979-01-09 00:00:00

  • Structural Insights into the Inhibitory Mechanism of Insulin Secretagogues on the Pancreatic ATP-Sensitive Potassium Channel.

    abstract::Sulfonylureas and glinides are commonly used oral insulin secretagogues (ISs) that act on the pancreatic ATP-sensitive potassium (KATP) channel to promote insulin secretion in order to lower the blood glucose level. Physiologically, KATP channels are inhibited by intracellular ATP and activated by Mg-ADP. Therefore, t...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/acs.biochem.9b00692

    authors: Wu JX,Ding D,Wang M,Chen L

    更新日期:2020-01-14 00:00:00

  • Intestinal absorption of dietary cholesteryl ester is decreased but retinyl ester absorption is normal in carboxyl ester lipase knockout mice.

    abstract::Carboxyl ester lipase (CEL; EC 3.1.1.13) hydrolyzes cholesteryl esters and retinyl esters in vitro. In vivo, pancreatic CEL is thought to liberate cholesterol and retinol from their esters prior to absorption in the intestine. CEL is also a major lipase in the breast milk of many mammals, including humans and mice, an...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi981679a

    authors: Weng W,Li L,van Bennekum AM,Potter SH,Harrison EH,Blaner WS,Breslow JL,Fisher EA

    更新日期:1999-03-30 00:00:00

  • Kinetics of the subtransition in dipalmitoylphosphatidylcholine.

    abstract::The kinetics of the interconversions of the subgel and gel phases in dipalmitoylphosphatidylcholine have been studied by using differential dilatometry, differential scanning calorimetry (DSC), and neutral buoyancy centrifugation as a function of incubation temperature and deuteriation of the solvent. As seen by other...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi00388a016

    authors: Tristram-Nagle S,Wiener MC,Yang CP,Nagle JF

    更新日期:1987-07-14 00:00:00

  • Aminophosphonate inhibitors of dialkylglycine decarboxylase: structural basis for slow binding inhibition.

    abstract::The kinetics of inhibition of dialkylglycine decarboxylase by five aminophosphonate inhibitors are presented. Two of these [(R)-1-amino-1-methylpropanephosphonate and (S)-1-aminoethanephosphonate] are slow binding inhibitors. The inhibitors follow a mechanism in which a weak complex is rapidly formed, followed by slow...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi026318g

    authors: Liu W,Rogers CJ,Fisher AJ,Toney MD

    更新日期:2002-10-15 00:00:00

  • Rapid intrachain binding of histidine-26 and histidine-33 to heme in unfolded ferrocytochrome C.

    abstract::Time-resolved spectroscopic studies of unfolded horse iron(II) cytochrome c have suggested that the imidazole side chains of His26 and His33 bind transiently to the heme iron on microsecond time scales, after photodissociation of a carbon monoxide ligand from the heme. Our studies of four variants of cytochrome c (hor...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi011371a

    authors: Hagen SJ,Latypov RF,Dolgikh DA,Roder H

    更新日期:2002-01-29 00:00:00

  • Protein kinase C acylation by palmitoyl coenzyme A facilitates its translocation to membranes.

    abstract::Protein kinase C (PKC) translocation to specific subcellular membrane loci after cellular stimulation is mediated, in part, through its interaction with diacylglycerol, phosphatidylserine, and calcium. Herein, we present multiple lines of evidence which demonstrate that purified rabbit brain PKC undergoes specific acy...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi980565w

    authors: Ford DA,Horner CC,Gross RW

    更新日期:1998-08-25 00:00:00

  • Mechanism of oligonucleotide loop formation in solution.

    abstract::We have studied the tridecadeoxynucleotide CGCGAATTACGCG (I), which contains an additional A at position 9 compared to the dodecanucleotide of which the crystal structure has been determined. Sequence I exhibits no distinct melting curve and also has a concentration-dependent pattern of peaks on reverse-phase chromato...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi00371a025

    authors: Roy S,Weinstein S,Borah B,Nickol J,Appella E,Sussman JL,Miller M,Shindo H,Cohen JS

    更新日期:1986-11-18 00:00:00

  • Chemical modification of the bovine mitochondrial bc1 complex reveals critical acidic residues involved in the proton pumping activity.

    abstract::Bovine heart ubiquinol-cytochrome c reductase (bc1 complex) was modified with N-(ethoxycarbonyl)-2-ethoxy-1,2-dihydroquinoline (EEDQ), which is a selective reagent for buried carboxyl groups. EEDQ treatment caused a loss of the proton pumping activity of liposome-reconstituted bc1 complex, without effect on the passiv...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi9724164

    authors: Cocco T,Di Paola M,Papa S,Lorusso M

    更新日期:1998-02-17 00:00:00

  • Substitution of active site tyrosines with tryptophan alters the free energy for nucleotide flipping by human alkyladenine DNA glycosylase.

    abstract::Human alkyladenine DNA glycosylase (AAG) locates and excises a wide variety of structurally diverse alkylated and oxidized purine lesions from DNA to initiate the base excision repair pathway. Recognition of a base lesion requires flipping of the damaged nucleotide into a relatively open active site pocket between two...

    journal_title:Biochemistry

    pub_type: 杂志文章

    doi:10.1021/bi101856a

    authors: Hendershot JM,Wolfe AE,O'Brien PJ

    更新日期:2011-03-22 00:00:00