A theoretical study of spin states in Ni-S4 complexes and models of the [NiFe] hydrogenase active site

Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry
Maurizio BruschiMatthias Stein

Abstract

We have applied density functional theory, using both pure (BP86) and hybrid (B3LYP and B3LYP*) functionals, to investigate structural parameters and reaction energies for nickel(II)-sulfur coordination compounds, as well as for small cluster models of the Ni-SI and Ni-R redox state of [NiFe] hydrogenases. Results obtained investigating experimentally well-characterized complexes show that BP86 is well suited to describe the structural features of this class of compounds. However, the singlet-triplet energy splitting and even the computed ground state are strongly dependent on the applied functional. Results for the cluster models of [NiFe] hydrogenases lead to the conclusion that in the reduced protein structures characterized by X-ray diffraction a hydride bridges the two metal centres. The energy splitting of the singlet and triplet states in Ni-R and Ni-SI models is calculated to be very small and may be overcome at room temperature to allow a spin crossover. Moreover, the relative stability of the Ni-SI and Ni-R structures adopted in the present investigation is fully compatible with their involvement in the reversible heterolytic cleavage of H(2).

References

Oct 29, 1982·Biochemical and Biophysical Research Communications·J J MouraJ LeGall
Feb 16, 1995·Nature·A VolbedaJ C Fontecilla-Camps
Jul 17, 1998·Current Opinion in Chemical Biology·S W Ragsdale
Aug 13, 1998·Immunological Reviews·G MazzaB Malissen
Sep 15, 1988·Physical Review A: General Physics·A D Becke
Jun 15, 1986·Physical Review. B, Condensed Matter·J P Perdew
Apr 17, 2001·Inorganic Chemistry·H PaulsenA X Trautwein
May 25, 2001·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·M J Maroney, P A Bryngelson
May 25, 2001·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·P E SiegbahnR H Crabtree
May 25, 2001·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·H J Fan, M B Hall
Jan 5, 2002·Chemistry : a European Journal·M ReiherB A Hess
Jan 17, 2002·Journal of the American Chemical Society·Hua-Jun Fan, Michael B Hall
Jun 1, 2002·Current Opinion in Chemical Biology·Matthias Stein, Wolfgang Lubitz
Jan 8, 2003·Journal of the American Chemical Society·Stefanie FoersterWolfgang Lubitz
May 29, 2003·Proceedings of the National Academy of Sciences of the United States of America·Victor GuallarRichard A Friesner
Oct 7, 2003·Faraday Discussions·Jeremy N Harvey, Massimiliano Aschi
Sep 17, 2004·Journal of the American Chemical Society·Robert K SzilagyiEdward I Solomon

❮ Previous
Next ❯

Citations

Sep 11, 2009·The Journal of Chemical Physics·Marcel SwartF Matthias Bickelhaupt
Mar 3, 2006·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Alejandro PardoMichael B Hall
May 1, 2007·Theoretical Chemistry Accounts·Giorgio MoroGiuseppe Zampella
Oct 12, 2012·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Mario KampaFrank Neese
Sep 26, 2013·Biochemical Society Transactions·Matthias Stein, Sandeep Kaur-Ghumaan
Mar 22, 2014·Physical Chemistry Chemical Physics : PCCP·Mickaël G DelceyUlf Ryde
Mar 20, 2008·Physical Chemistry Chemical Physics : PCCP·Prabha JayapalJoseph J W McDouall
Oct 10, 2006·Physical Chemistry Chemical Physics : PCCP·Prabha JayapalNeil A Burton
Aug 11, 2015·Nature Communications·Hideaki OgataStephen P Cramer
Dec 22, 2017·Physical Chemistry Chemical Physics : PCCP·Raffaella BregliaMaurizio Bruschi
May 11, 2017·Essays in Biochemistry·Valerie Vaissier, Troy Van Voorhis
Jun 6, 2018·Frontiers in Chemistry·Andrés M Escorcia, Matthias Stein
Oct 12, 2007·Chemical Reviews·Per E M SiegbahnMichael B Hall
Aug 30, 2017·The Journal of Physical Chemistry. a·Alexandre LebonAntony Memboeuf
Jan 8, 2014·Journal of the American Chemical Society·Maurizio BruschiLuca De Gioia
Oct 20, 2017·Journal of Chemical Theory and Computation·Terry Z H Gani, Heather J Kulik
Feb 14, 2013·Journal of the American Chemical Society·Mario KampaFrank Neese
Nov 19, 2019·Journal of Chemical Theory and Computation·Fang Liu, Heather J Kulik
Apr 1, 2020·The Journal of Physical Chemistry. a·Michael G TaylorHeather J Kulik

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.