pi cation radicals of ferrous and free base isobacteriochlorins: Models for siroheme and sirohydrochlorin.

Abstract:

:Theoretical and experimental optical, redox, and paramagnetic results are presented for models of siroheme, the iron isobacteriochlorin prosthetic group of nitrite and sulfite reductases, and of sirohydrochlorin, the metal-free siroheme that is an intermediate in the biosynthetic pathway to vitamin B(12). The facile oxidation of many isobacteriochlorins, which distinguishes them from porphyrins and chlorins, suggests that the siroheme macrocycle itself may undergo oxidation in the multi-electron enzymatic cycles that reduce nitrite to ammonia and sulfite to hydrogen sulfide. Extended Hückel MO calculations (i) help rationalize the redox properties of isobacteriochlorins compared with those of porphyrins and chlorins; (ii) indicate that Fe(II) pyridine carbonyl[(py) (CO)] complexes of isobacteriochlorins, unlike those of porphyrins and chlorins, should undergo oxidation from the macrocycle rather than the metal to yield pi cation radicals; (iii) suggest that, in hexacoordinated Fe(II) isobacteriochlorin complexes, the site of oxidation-i.e., the metal or the macrocycle-will depend on the ligand field induced by the axial ligands; and (iv) predict similar unpaired spin density profiles for metal-free and (py) (CO)Fe(II) isobacteriochlorin radicals. Experimental data for three isomeric free-base and (py) (CO)Fe(II) complexes of dimethyloctaethylisobacteriochlorins support the theoretical calculations and establish the existence of Fe(II) isobacteriochlorin pi cations in vitro.

authors

Chang CK,Hanson LK,Richardson PF,Young R,Fajer J

doi

10.1073/pnas.78.5.2652

subject

Has Abstract

pub_date

1981-05-01 00:00:00

pages

2652-6

issue

5

eissn

0027-8424

issn

1091-6490

journal_volume

78

pub_type

杂志文章
  • Von Willebrand factor-binding protein is a hysteretic conformational activator of prothrombin.

    abstract::Von Willebrand factor-binding protein (VWbp), secreted by Staphylococcus aureus, displays secondary structural homology to the 3-helix bundle, D1 and D2 domains of staphylocoagulase (SC), a potent conformational activator of the blood coagulation zymogen, prothrombin (ProT). In contrast to the classical proteolytic 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.0811750106

    authors: Kroh HK,Panizzi P,Bock PE

    更新日期:2009-05-12 00:00:00

  • Isotopic evidence for large gaseous nitrogen losses from tropical rainforests.

    abstract::The nitrogen isotopic composition (15N/14N) of forested ecosystems varies systematically worldwide. In tropical forests, which are elevated in 15N relative to temperate biomes, a decrease in ecosystem 15N/14N with increasing rainfall has been reported. This trend is seen in a set of well characterized Hawaiian rainfor...

    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.0510185103

    authors: Houlton BZ,Sigman DM,Hedin LO

    更新日期:2006-06-06 00:00:00

  • Costs, needs, and integration efforts shape helping behavior toward refugees.

    abstract::Recent political instabilities and conflicts around the world have drastically increased the number of people seeking refuge. The challenges associated with the large number of arriving refugees have revealed a deep divide among the citizens of host countries: one group welcomes refugees, whereas another rejects them....

    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.1805601115

    authors: Böhm R,Theelen MMP,Rusch H,Van Lange PAM

    更新日期:2018-07-10 00:00:00

  • Characterization of tumor necrosis factor-deficient mice.

    abstract::Although tumor necrosis factor (TNF) initially came to prominence because of its anti-tumor activity, most attention is now focused on its proinflammatory actions. TNF appears to play a critical role in both early and late events involved in inflammation, from localizing the noxious agent and amplifying the cellular 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.94.15.8093

    authors: Marino MW,Dunn A,Grail D,Inglese M,Noguchi Y,Richards E,Jungbluth A,Wada H,Moore M,Williamson B,Basu S,Old LJ

    更新日期:1997-07-22 00:00:00

  • Novel opiate binding sites selective for benzomorphan drugs.

    abstract::The simultaneous addition of [D-Ala2, D-Leu5]-enkephalin and morphiceptin at concentrations at which 98% of enkephalin (delta) and morphine (mu) receptors are occupied only partially inhibits the binding of [3H]diprenorphine to rat brain membranes. These conditions, furthermore, do not affect the curves for displaceme...

    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.78.7.4141

    authors: Chang KJ,Hazum E,Cuatrecasas P

    更新日期:1981-07-01 00:00:00

  • Retroviral delivery of small interfering RNA into primary cells.

    abstract::RNA interference is an evolutionarily conserved process in which recognition of double-stranded RNA ultimately leads to posttranscriptional suppression of gene expression. This suppression is mediated by short (21- to 22-nt) small interfering RNAs (siRNAs), which induce degradation of mRNA based on complementary base ...

    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.242594499

    authors: Barton GM,Medzhitov R

    更新日期:2002-11-12 00:00:00

  • Adaptive evolution of cytochrome c oxidase: Infrastructure for a carnivorous plant radiation.

    abstract::Much recent attention in the study of adaptation of organismal form has centered on developmental regulation. As such, the highly conserved respiratory machinery of eukaryotic cells might seem an unlikely target for selection supporting novel morphologies. We demonstrate that a dramatic molecular evolutionary rate inc...

    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.0408092101

    authors: Jobson RW,Nielsen R,Laakkonen L,Wikström M,Albert VA

    更新日期:2004-12-28 00:00:00

  • Molecular basis of ornithine aminotransferase deficiency in B-6-responsive and -nonresponsive forms of gyrate atrophy.

    abstract::Gyrate atrophy (GA), a recessive eye disease involving progressive loss of vision due to chorioretinal degeneration, is associated with a deficiency of the mitochondrial enzyme ornithine aminotransferase (OATase; ornithine-oxo-acid aminotransferase; L-ornithine:2-oxo-acid aminotransferase, EC 2.6.1.13) with consequent...

    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.85.11.3777

    authors: Ramesh V,McClatchey AI,Ramesh N,Benoit LA,Berson EL,Shih VE,Gusella JF

    更新日期:1988-06-01 00:00:00

  • Role of cyclophilin A in the uptake of HIV-1 by macrophages and T lymphocytes.

    abstract::Cyclophilins are a family of proteins that bind cyclosporin A (CsA) and possess peptidyl-prolyl cis-trans isomerase activity. In addition, they are secreted by activated cells and act in a cytokine-like manner, presumably via signaling through a cell surface cyclophilin receptor. More recently, host-derived cyclophili...

    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.95.4.1758

    authors: Sherry B,Zybarth G,Alfano M,Dubrovsky L,Mitchell R,Rich D,Ulrich P,Bucala R,Cerami A,Bukrinsky M

    更新日期:1998-02-17 00:00:00

  • Nucleotide sequence of the Salmonella typhimurium origin of DNA replication.

    abstract::Construction of deletion derivative plasmids and cloning of restriction fragments from plasmids containing the Salmonella typhimurium origin of replication (ori) were used to locate the functional origin to within a DNA fragment of 296 base pairs between the genes uncB and asn. The nucleotide sequence of the S. typhim...

    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.77.5.2460

    authors: Zyskind JW,Smith DW

    更新日期:1980-05-01 00:00:00

  • Rigid amphipathic fusion inhibitors, small molecule antiviral compounds against enveloped viruses.

    abstract::Antiviral drugs targeting viral proteins often result in prompt selection for resistance. Moreover, the number of viral targets is limited. Novel antiviral targets are therefore needed. The unique characteristics of fusion between virion envelopes and cell membranes may provide such targets. Like all fusing bilayers, ...

    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.1010026107

    authors: St Vincent MR,Colpitts CC,Ustinov AV,Muqadas M,Joyce MA,Barsby NL,Epand RF,Epand RM,Khramyshev SA,Valueva OA,Korshun VA,Tyrrell DL,Schang LM

    更新日期:2010-10-05 00:00:00

  • Understanding, predicting, and tuning the fragility of vitrimeric polymers.

    abstract::Fragility is an empirical property that describes how abruptly a glass-forming material solidifies upon supercooling. The degree of fragility carries important implications for the functionality and processability of a material, as well as for our fundamental understanding of the glass transition. However, the microst...

    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.1912571116

    authors: Ciarella S,Biezemans RA,Janssen LMC

    更新日期:2019-12-10 00:00:00

  • Cyclophilin catalyzes protein folding in yeast mitochondria.

    abstract::Cyclophilins are a family of ubiquitous proteins that are the intracellular target of the immunosuppressant drug cyclosporin A. Although cyclophilins catalyze peptidylprolyl cis-trans isomerization in vitro, it has remained open whether they also perform this function in vivo. Here we show that Cpr3p, a cyclophilin 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.92.14.6319

    authors: Matouschek A,Rospert S,Schmid K,Glick BS,Schatz G

    更新日期:1995-07-03 00:00:00

  • Parkinson disease: a new link between monoamine oxidase and mitochondrial electron flow.

    abstract::Two factors that contribute to the progression of Parkinson disease are a brain defect in mitochondrial respiration and the generation of hydrogen peroxide (H2O2) by monoamine oxidase (MAO). Here we show that the two are linked. Metabolism of the neurotransmitter dopamine, or other monoamines (benzylamine, tyramine), ...

    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.94.10.4890

    authors: Cohen G,Farooqui R,Kesler N

    更新日期:1997-05-13 00:00:00

  • Lysinuric protein intolerance mutation is expressed in the plasma membrane of cultured skin fibroblasts.

    abstract::Lysinuric protein intolerance (LPI) is an autosomal recessive phenotype consistent with impaired transport of cationic amino acids at the basolateral membrane of intestinal and renal epithelia. On the assumption that the basolateral membrane of epithelial cells and plasma membrane of parenchymal cells are functional 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.84.21.7711

    authors: Smith DW,Scriver CR,Tenenhouse HS,Simell O

    更新日期:1987-11-01 00:00:00

  • UV-endonuclease from calf thymus with specificity toward pyrimidine dimers in DNA.

    abstract::We describe the partial purification of an endonuclease from calf thymus that nicks phage PM2 DNA irradiated with UV doses producing only a few pyrimidine dimers per molecule. It has much less activity on DNA that has been subjected to enzymatic photoreactivation after UV irradiation. The calf thymus endonuclease is d...

    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.76.8.3746

    authors: Waldstein EA,Peller S,Setlow RB

    更新日期:1979-08-01 00:00:00

  • 1H-Observe/13C-decouple spectroscopic measurements of lactate and glutamate in the rat brain in vivo.

    abstract::We have used (13C)-1H NMR spectroscopy at 360.13 MHz to resolve the 13C coupled proton resonance of glutamate and lactate in the rat brain in vivo. The time required for the 13C fractional enrichment of the 4-CH2 position of brain glutamate to reach isotopic steady state was determined during a continuous infusion 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.82.6.1633

    authors: Rothman DL,Behar KL,Hetherington HP,den Hollander JA,Bendall MR,Petroff OA,Shulman RG

    更新日期:1985-03-01 00:00:00

  • Toward the therapeutic editing of mutated RNA sequences.

    abstract::If RNA editing could be rationally directed to mutated RNA sequences, genetic diseases caused by certain base substitutions could be treated. Here we use a synthetic complementary RNA oligonucleotide to direct the correction of a premature stop codon mutation in dystrophin RNA. The complementary RNA oligonucleotide wa...

    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.92.18.8298

    authors: Woolf TM,Chase JM,Stinchcomb DT

    更新日期:1995-08-29 00:00:00

  • Disregulation of leukosialin (CD43, Ly48, sialophorin) expression in the B-cell lineage of transgenic mice increases splenic B-cell number and survival.

    abstract::Leukosialin (also known as Ly48, CD43, and sialophorin) is a major cell surface sialoglycoprotein found on a variety of hematopoietically derived cells. The precise function of this molecule is poorly understood but it has been implicated in cell proliferation and intercellular adhesion. We developed a transgenic mous...

    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.92.2.626

    authors: Dragone LL,Barth RK,Sitar KL,Disbrow GL,Frelinger JG

    更新日期:1995-01-17 00:00:00

  • Force measurements on cargoes in living cells reveal collective dynamics of microtubule motors.

    abstract::Many cellular cargoes move bidirectionally along microtubules, driven by teams of plus- and minus-end-directed motor proteins. To probe the forces exerted on cargoes during intracellular transport, we examined latex beads phagocytosed into living mammalian macrophages. These latex bead compartments (LBCs) are encased ...

    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.1215462109

    authors: Hendricks AG,Holzbaur EL,Goldman YE

    更新日期:2012-11-06 00:00:00

  • Predicting free choices for abstract intentions.

    abstract::Unconscious neural activity has been repeatedly shown to precede and potentially even influence subsequent free decisions. However, to date, such findings have been mostly restricted to simple motor choices, and despite considerable debate, there is no evidence that the outcome of more complex free decisions can be pr...

    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.1212218110

    authors: Soon CS,He AH,Bode S,Haynes JD

    更新日期:2013-04-09 00:00:00

  • Multiple gene deletions within the human immunoglobulin heavy-chain cluster.

    abstract::Two subjects, of 11,000 healthy individuals screened, were found to be missing three and four immunoglobulin isotypes, respectively (IgA1, IgG2, and IgG4; IgA1, IgG2, IgG4, and IgE), and have been analyzed at the DNA level by means of Southern blotting and Ig heavy-chain-specific probes. A broad deletion within the he...

    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.81.18.5811

    authors: Migone N,Oliviero S,de Lange G,Delacroix DL,Boschis D,Altruda F,Silengo L,DeMarchi M,Carbonara AO

    更新日期:1984-09-01 00:00:00

  • Host-gene control of type-C RNA tumor virus expression and tumorigenesis in inbred mice.

    abstract::We analyzed the relationship of genetic factors determining the expression of endogenous type-C RNA tumor viruses and other host-gene markers to tumorigenesis. A hybridization experiment was performed with mice of strains AKR/J and C57L, the first filial (F(1)) generation hybrids, the second filial (F(2)) generation h...

    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.70.5.1450

    authors: Meier H,Taylor BA,Cherry M,Buebner RJ

    更新日期:1973-05-01 00:00:00

  • Phosphorylation of eukaryotic initiation factor-2{alpha} promotes the extracellular survival of obligate intracellular parasite Toxoplasma gondii.

    abstract::While seeking a new host cell, obligate intracellular parasites, such as the protozoan Toxoplasma gondii, must be able to endure the stress of an extracellular environment. The mechanisms Toxoplasma use to remain viable while deprived of a host cell are not understood. We have previously shown that phosphorylation 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.1007610107

    authors: Joyce BR,Queener SF,Wek RC,Sullivan WJ Jr

    更新日期:2010-10-05 00:00:00

  • Relationship between somatic mutation and neoplastic transformation.

    abstract::Somatic mutation and neoplastic transformation of diploid Syrian hamster embryo cells were examined concomitantly. Mutations induced by benzo[a]pyrene and N-methyl-N'-nitro-N-nitrosoguanidine were quantitated at the hypoxanthine phosphoribosyltransferase and Na(+)/K(+) ATPase loci and compared to phenotypic transforma...

    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.75.7.3297

    authors: Barrett JC,Ts'o PO

    更新日期:1978-07-01 00:00:00

  • Role for Plk1 phosphorylation of Hbo1 in regulation of replication licensing.

    abstract::In a search for Polo-like kinase 1 (Plk1)-interacting proteins using a yeast two-hybrid system, we have identified histone acetyltransferase binding to the origin recognition complex 1 (Hbo1) as a potential Plk1 target. Here, we show that the interaction between Plk1 and Hbo1 is mitosis-specific and that Plk1 phosphor...

    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.0712063105

    authors: Wu ZQ,Liu X

    更新日期:2008-02-12 00:00:00

  • Adhesive-cohesive model for protein compressibility: an alternative perspective on stability.

    abstract::As a dynamic property of folded proteins, protein compressibility provides important information about the forces that govern structural stability. We relate intrinsic compressibility to stability by using molecular dynamics to identify a molecular basis for the variation in compressibility among globular proteins. We...

    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.2434157100

    authors: Dadarlat VM,Post CB

    更新日期:2003-12-09 00:00:00

  • A splicing variant of a death domain protein that is regulated by a mitogen-activated kinase is a substrate for c-Jun N-terminal kinase in the human central nervous system.

    abstract::The mitogen-activated kinase activating death domain protein (MADD) that is differentially expressed in neoplastic vs. normal cells (DENN) was identified as a substrate for c-Jun N-terminal kinase 3, the first demonstration of such an activity for this stress-activated kinase that is predominantly expressed in the bra...

    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.95.5.2586

    authors: Zhang Y,Zhou L,Miller CA

    更新日期:1998-03-03 00:00:00

  • Human thiopurine S-methyltransferase pharmacogenetics: variant allozyme misfolding and aggresome formation.

    abstract::Thiopurine S-methyltransferase (TPMT) catalyzes the S-methylation of thiopurine drugs. TPMT genetic polymorphisms represent a striking example of the potential clinical value of pharmacogenetics. Subjects homozygous for TPMT*3A, the most common variant allele for low activity, an allele that encodes a protein with two...

    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.0502352102

    authors: Wang L,Nguyen TV,McLaughlin RW,Sikkink LA,Ramirez-Alvarado M,Weinshilboum RM

    更新日期:2005-06-28 00:00:00

  • Identification of a pathogenic epitope involved in initiation of Heymann nephritis.

    abstract::Heymann nephritis is an experimental autoimmune disease model for human membranous nephropathy. We have recently identified a pathogenic epitope, clone 14 (C14), responsible for formation and deposition of glomerular immune complexes that is contained within the small subunit of the Heymann nephritis antigenic complex...

    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.89.23.11179

    authors: Kerjaschki D,Ullrich R,Diem K,Pietromonaco S,Orlando RA,Farquhar MG

    更新日期:1992-12-01 00:00:00