Peter Michael Kroneck

Peter Michael Kroneck
Universität Konstanz | Uni-Konstanz · Department of Biology

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Publications (248)
Article
Full-text available
Since the characterization of cytochrome c 552 as a multiheme nitrite reductase, research on this enzyme has gained major interest. Today, it is known as pentaheme cytochrome c nitrite reductase (NrfA). Part of the NH 4 ⁺ produced from NO 2 ⁻ is released as NH 3 leading to nitrogen loss, similar to denitrification which generates NO, N 2 O, and N 2...
Article
Microorganisms are found in almost every conceivable niche of the Earth. They populate every habitable environment, and through their metabolic activity, affect the chemistry and physical properties of their surroundings. They are outstanding chemists and geoengineers, and they did this for billions of years, thus playing an important role in the e...
Article
Full-text available
Nitrous oxide reductase (N2OR) is the only known enzyme reducing environmentally critical nitrous oxide (N2O) to dinitrogen (N2) as the final step of bacterial denitrification. The assembly process of its unique catalytic [4Cu:2S] cluster CuZ remains scarcely understood. Here we report on a mutagenesis study of all seven histidine ligands coordinat...
Article
Copper-containing nitrous oxide reductase (N2OR) is the only known enzyme to catalyze the conversion of the environmentally critical greenhouse gas nitrous oxide (N2O) to dinitrogen (N2) as the final step of bacterial denitrification. Other than its unique tetranuclear active site CuZ, the binuclear electron entry point CuA is also utilized in othe...
Chapter
The non-metallic chemical element sulfur, 3216S , referred to in Genesis as brimstone and identified as element by Lavoisier, is the tenth most abundant element in the universe and the fifth most common element on Earth. Important inorganic forms of sulfur in the biosphere are elemental sulfur (S8), sulfate (SO2-4), and sulfide (S2-), sulfite (SO2-...
Chapter
The number of transition metal ions which are essential to life - also often called trace elements - increased steadily over the years. In parallel, the list of biological functions in which transition metals are involved, has grown, and is still growing tremendously. Significant progress has been made in understanding the chemistry operating at th...
Chapter
Cytochromes P450 (CYPs) are heme b-binding enzymes and belong to Nature's most versatile catalysts. They participate in countless essential life processes, and exist in all domains of life, Bacteria, Archaea, and Eukarya, and in viruses. CYPs attract the interest of researchers active in fields as diverse as biochemistry, chemistry, biophysics, mol...
Article
The enzymes nitrous oxide reductase (N2OR) and cytochrome c oxidase (COX) are constituents of important biological processes. N2OR is the terminal reductase in a respiratory chain converting N2O to N2 in denitrifying bacteria; COX is the terminal oxidase of the aerobic respiratory chain of certain bacteria and eukaryotic organisms transforming O2 t...
Article
The process of oxidative dehydrogenation of the pentadentate amine ligand 2,10-bis-(2'-pyridyl)-3,6,9-triazaundecane (L¹am) mediated by Cu(II) in the absence of an external oxidant led to the Cu(I) mono-imine complex, [CuIL¹im](BPh4). This complex was quite sensitive towards air oxidation, leading to the corresponding Cu(II) mono-imine complex. The...
Article
In biology, tungsten (W) is exclusively found in microbial enzymes bound to a bis-pyranopterin cofactor (bis-WPT). Previously known W enzymes catalyze redox oxo/hydroxyl transfer reactions by directly coordinating their substrates or products to the metal. They comprise the W-containing formate/formylmethanofuran dehydrogenases belonging to the dim...
Article
Full-text available
Hydrocarbons are abundant in anoxic environments and pose biochemical challenges to their anaerobic degradation by microorganisms. Within the framework of the Priority Program 1319, investigations funded by the Deutsche Forschungsgemeinschaft on the anaerobic microbial degradation of hydrocarbons ranged from isolation and enrichment of hitherto unk...
Article
In living systems, tungsten is exclusively found in microbial enzymes coordinated by the pyranopterin cofactor, with additional metal coordination provided by oxygen and/or sulfur, and/or selenium atoms in diverse arrangements. Prominent examples are formate dehydrogenase, formylmethanofuran dehydrogenase, and aldehyde oxidoreductase all of which c...
Article
Full-text available
Oxygen has to be considered one of the most important elements on Earth. Earlier, some dispute arose as to which of the three scientists, Carl Wilhelm Scheele (Sweden), Joseph Priestley (United Kingdom) or Antoine Lavoisier (France), should get credit for the air of life. Today it is agreed that the Swede discovered it first, the fire air in 1772....
Article
Full-text available
A mechanistic study is presented for the oxidative dehydrogenation of the iron complex [FeIIIL3]3+, 1, (L3 = 1,9-bis(2′-pyridyl)-5-[(ethoxy-2′′-pyridyl)methyl]-2,5,8-triazanonane) in ethanol in the presence of molecular oxygen. The product of the reaction was identified by NMR spectroscopy and X-ray crystallography as the identical monoimine comple...
Article
Full-text available
This work is dedicated to Prof. José E. Escamilla who unfortunately passed away. The authors developed and concluded his project which now is published in his honor and memory. Abstract: Gluconacetobacter diazotrophicus is a N2-fixing bacterium endophyte from sugar cane. The oxidation of ethanol to acetic acid of this organism takes place in the pe...
Book
MILS-15 provides an up-to-date review of the metalloenzymes involved in the activation, production, and conversion of molecular oxygen as well as the functionalization of the chemically inert gases methane and ammonia. Found either in aerobes (humans, animals, plants, microorganisms) or in anaerobes (so-called “impossible bacteria”) these enzymes e...
Article
The global biogeochemical nitrogen cycle is essential for life on Earth. Many of the underlying biotic reactions are catalyzed by a multitude of prokaryotic and eukaryotic life forms whereas others are exclusively carried out by microorganisms. The last century has seen the rise of a dramatic imbalance in the global nitrogen cycle due to human beha...
Chapter
Iodine occurs as iodide in seawater and is taken up by seaweed, from which it has traditionally been extracted. This chapter discusses the manifold roles of iodine and a prominent member of the halogen element family. Emphasis is laid on bioinorganic aspects of iodine compounds including the transformation of hypoiodite by vanadium-dependent enzyme...
Article
The thiamine diphosphate (ThDP)-dependent enzyme cyclohexane-1,2-dione hydrolase (CDH) was expressed in Escherichia coli and purified by affinity chromatography (Ni-NTA). Recombinant CDH showed the same CC bond-cleavage and CC bond-formation activities as the native enzyme. Furthermore, we have shown that CDH catalyzes the asymmetric cross-benzoi...
Book
MILS-14 provides a most up-to-date view of the exciting biogeochemistry of gases in our environment as driven mostly by microorganisms. These employ a machinery of sophisticated metalloenzymes, where especially transition metals (such as Fe, Ni, Cu, Mo, W) play a fundamental role, that is, in the activation, transformation, and syntheses of gases l...
Article
Elsholtzia splendens is a copper-tolerant plant species growing on copper deposits in China. Spatially and spectrally resolved kinetics of in vivo absorbance and chlorophyll fluorescence in mesophyll of E. splendens were used to investigate the copper-induced stress from deficiency and toxicity as well as the acclimation to excess copper stress. Th...
Article
Full-text available
The metabolism of bromine in marine brown algae remains poorly understood. This contrasts with the recent finding that the accumulation of iodide in the brown alga Laminaria serves the provision of an inorganic antioxidant – the first case documented from a living system. The aim of this study was to use an interdisciplinary array of techniques to...
Article
Despite its reactivity and hence toxicity to living cells, sulfite is readily converted by various microorganisms using distinct assimilatory and dissimilatory metabolic routes. In respiratory pathways, sulfite either serves as a primary electron donor or terminal electron acceptor (yielding sulfate or sulfide, respectively), and its conversion dri...
Article
Full-text available
Sulfate-reducing bacteria and archaea are important players in the biogeochemical sulfur cycle. ATP sulfurylase, adenosine 5'-phosphosulfate reductase and dissimilatory sulfite reductase are the key enzymes in the energy conserving process of SO(4)(2-) → H(2)S reduction. This review summarizes recent advances in our understanding of the activation...
Article
Full-text available
Abstract The tetranuclear CuZ cluster is the unique active site of nitrous oxide reductase, the enzyme that catalyzes the reduction of nitrous oxide to dinitrogen as the final reaction in bacterial denitrification. Three-dimensional structures of orthologs of the enzyme from a variety of different bacterial species were essential steps in the eluci...
Article
Silencing prion: Copper-catalyzed transformations of prion protein (PrP) lead to the production of reactive oxygen species (ROS), PrP oxidation, and cleavage and aggregation in transmissible spongiphorm encephalopathies. Zn(7) MT-3 efficiently targets Cu(II) bound in different coordination modes to PrP-Cu(II) . By an unusual redox-dependent metal-s...
Article
The thiamine diphosphate (ThDP) dependent flavoenzyme cyclohexane-1,2-dione hydrolase (CDH) (EC 3.7.1.11) catalyses a key step of a novel anaerobic degradation pathway for alicyclic alcohols by converting cyclohexane-1,2-dione (CDO) to 6-oxohexanoate and further to adipate using NAD+ as electron acceptor. To gain insights into the molecular basis o...
Article
The membrane‐bound alcohol dehydrogenase of Gluconacetobacter diazotrophicus contains one pyrroloquinoline quinone moiety (PQQ), one [2Fe‐2S] cluster, and four c‐type cytochromes. Here, we describe a novel and inactive enzyme. ADHi, similarly to ADHa, is a heterodimer of 72‐ and 44‐kDa subunits and contains the expected prosthetic groups. However,...
Article
The membrane-bound alcohol dehydrogenase of Gluconacetobacter diazotrophicus contains one pyrroloquinoline quinone moiety (PQQ), one [2Fe-2S] cluster, and four c-type cytochromes. Here, we describe a novel and inactive enzyme. ADHi, similarly to ADHa, is a heterodimer of 72- and 44-kDa subunits and contains the expected prosthetic groups. However,...
Chapter
The tungsten-iron-sulfur enzyme acetylene hydratase is a rather unique enzyme within the class of tungsten/molybdenum enzymes in the sense that it catalyzes a nonredox reaction, the addition of one molecule of water to the CC bond of acetylene to form acetaldehyde. Its crystal structure (1.26 Å) reveals a close to octahedral, or trigonal antiprisma...
Article
Full-text available
Alicyclic compounds with hydroxyl groups represent common structures in numerous natural compounds, such as terpenes and steroids. Their degradation by microorganisms in the absence of dioxygen may involve a C-C bond ring cleavage to form an aliphatic intermediate that can be further oxidized. The cyclohexane-1,2-dione hydrolase (CDH) (EC 3.7.1.11)...
Article
Full-text available
Nitrous oxide (N(2)O) is generated by natural and anthropogenic processes and has a critical role in environmental chemistry. It has an ozone-depleting potential similar to that of hydrochlorofluorocarbons as well as a global warming potential exceeding that of CO(2) 300-fold. In bacterial denitrification, N(2)O is reduced to N(2) by the copper-dep...
Article
TcHMA4 (GenBank no. AJ567384), a Cd/Zn transporting ATPase of the P(1B)-type (=CPx-type) was isolated and purified from roots of the Cd/Zn hyperaccumulator Thlaspi caerulescens. Optimisation of the purification protocol, based on binding of the natural C-terminal His-tag of the protein to a Ni-IDA metal affinity column, yielded pure, active TcHMA4...
Article
Full-text available
The soluble tungsten, iron-sulfur enzyme acetylene hydratase (AH) from mesophilic Pelobacter acetylenicus is a member of the dimethyl sulfoxide (DMSO) reductase family. It stands out from its class as it catalyzes a nonredox reaction, the addition of H2O to acetylene (H—C≡C—H) to form acetaldehyde (CH3CHO). Caught in its active W(IV) state, the hig...
Chapter
Dissimilatory sulfite reductase (dSiR) belongs to the group of oxidoreductases and is a key enzyme of the biogeochemical sulfur cycle. The enzyme is organized as a heterotetrameric α2β2, or a heterohexameric α2β2γ2 complex, and catalyzes the reduction of sulfite (SO32−) to hydrogen sulfide (H2S) in a six-electron transfer process as the final step...
Chapter
The iron-sulfur flavoenzyme adenosine-5′-phosphosulfate reductase (APSR) catalyzes the reductive cleavage of APS (adenosine-5′-phosphosulfate) to sulfite plus AMP and the reverse reaction, both important reactions within the biogeochemical sulfur cycle. The structure of the dissimilatory enzyme from the hyperthermophilic sulfate reducer Archaeoglob...
Article
Full-text available
Nitrous oxide reductase (N(2)OR) from Pseudomonas stutzeri catalyzes the final step in denitrification: the two-electron reduction of nitrous oxide to molecular dinitrogen. Crystals of the enzyme were grown under strict exclusion of dioxygen by sitting-drop vapour diffusion using 2R,3R-butanediol as a cryoprotectant. N(2)OR crystallized in either s...
Article
A vital process in the biogeochemical sulfur cycle is the dissimilatory sulfate reduction pathway in which sulfate (SO₄⁻²) is converted to hydrogen sulfide (H₂S). Dissimilatory sulfite reductase (dSir), its key enzyme, hosts a unique siroheme-[4Fe-4S] cofactor and catalyzes the six-electron reduction of sulfite (SO₃²⁻) to H₂S. To explore this react...
Article
Full-text available
Natural rubber [poly-(cis-1,4-isoprene)] is cleaved to 12-oxo-4,8-dimethyltrideca-4,8-diene-1-al (ODTD) by rubber oxygenase A (RoxA) isolated from Xanthomonas sp. RoxA has two c-type haem centres that show two distinct alpha-bands at 549 and 553 nm in the dithionite-reduced state. A well-resolved midpoint potential (E(0)') of -65 mV was determined...
Article
Gluconacetobacter diazotrophicus stands out among the acetic acid bacteria as it fixes dinitrogen and is a true endophyte. It has a set of constitutive enzymes to oxidize ethanol and acetaldehyde which is upregulated during N(2)-dependent growth. The membrane-bound alcohol dehydrogenase (ADH) is a heterodimer (subunit I approximately 72 kDa, subuni...
Chapter
1Introduction2Types of Biological Copper Centers3Copper Proteins with Mononuclear Copper Sites4Copper Proteins with Multinuclear Copper Sites5Outlook6AcknowledgmentsKeywords:biochemistry of organocopper compounds;types of biological copper centers;copper proteins with mononuclear copper sites;copper proteins with multinuclear copper sites;nitrous o...
Article
Alicyclic alcohols are naturally occurring compounds which can be degraded by microorganisms via cleavage of the ring C–C bond. Denitrifying Azoarcus sp. strain 22Lin grows on cyclohexane-1,2-diol which serves as electron donor and carbon source. The diol is converted to cyclohexane-1,2-dione followed by hydrolysis to the corresponding semialdehyde...
Article
Full-text available
The cadmium/zinc hyperaccumulator Thlaspi caerulescens is sensitive toward copper (Cu) toxicity, which is a problem for phytoremediation of soils with mixed contamination. Cu levels in T. caerulescens grown with 10 microm Cu(2+) remained in the nonaccumulator range (<50 ppm), and most individuals were as sensitive toward Cu as the related nonaccumu...
Article
Kinetic and structural data are presented for the iron-promoted dehydrogenation of the amine, [Fe(III)L3]3+ (1), L3 = 1,9-bis(2'-pyridyl)-5-[(ethoxy-2''-pyridyl)methyl]-2,5,8-triazanonane. Spectroscopic and electrochemical experiments under the exclusion of dioxygen helped to identify reaction intermediates and the final product, the Fe(II)-monoimi...
Article
Since the early discovery of Prussian Blue, cyano transition metal complexes have played a fundamental role in coordination chemistry. They represent important compounds with fascinating chemical and physical properties which turn them into valuable tools for both chemists and biologists. HCN as a precursor in prebiotic chemistry has gained interes...
Chapter
The tungsten-iron-sulfur enzyme acetylene hydratase is a rather unique enzyme within the class of tungsten/molybdenum enzymes in the sense that it catalyzes a nonredox reaction, the addition of one molecule of water to the CC bond of acetylene to form acetaldehyde. Its crystal structure (1.26 Å) reveals a close to octahedral, or trigonal antiprisma...
Article
Conservation of energy based on the reduction of sulfate is of fundamental importance for the biogeochemical sulfur cycle. A key enzyme of this ancient anaerobic process is the dissimilatory sulfite reductase (dSir), which catalyzes the six-electron reduction of sulfite to hydrogen sulfide under participation of a unique magnetically coupled sirohe...
Article
A mutant of mouse prion protein (PrPC) carrying a deletion of residues 114-121 (PrPDelta114-121) has previously been described to lack convertibility into the scrapie-associated isoform of PrP (PrPSc) and to exhibit a dominant-negative effect on the conversion of wild-type PrPC into PrPSc in living cells. Here we report the characterization of reco...
Article
Full-text available
Brown algae of the Laminariales (kelps) are the strongest accumulators of iodine among living organisms. They represent a major pump in the global biogeochemical cycle of iodine and, in particular, the major source of iodocarbons in the coastal atmosphere. Nevertheless, the chemical state and biological significance of accumulated iodine have remai...
Article
Pentaheme cytochrome c nitrite reductase (ccNiR) catalyzes the six-electron reduction of nitrite to ammonia as the final step in the dissimilatory pathway of nitrate ammonification. It has also been shown to reduce sulfite to sulfide, thus forming the only known link between the biogeochemical cycles of nitrogen and of sulfur. We have found the sul...
Article
We report here the first purification of a P(1B) type ATPase, a group of transporters that occurs in bacteria, plants and animals incl. humans, from a eukaryotic organism in native state. TcHMA4 is a P(1B) type ATPase that is highly expressed in the Cd/Zn hyperaccumulator plant Thlaspi caerulescens and contains a C-terminal 9-histidine repeat. Afte...
Chapter
The reduction of sulfate to sulfide and the reverse reaction are widespread biological processes. Hereby, microorganisms play a central role. Plants also reduce sulfate for the purpose of biosynthesis, and both plants and animals convert reduced sulfur compounds to sulfate. Sulfate respiration is used for energy conservation by strictly anaerobic b...
Article
Full-text available
Nervous system development and plasticity require regulation of cell proliferation, survival, neurite outgrowth and synapse formation by specific extracellular factors. The EF-hand protein S100B is highly expressed in human brain. In the extracellular space, it promotes neurite extension and neuron survival via the receptor RAGE (receptor for advan...
Article
Human S100A2 is an EF-hand calcium-binding S100 protein that is localized mainly in the nucleus and functions as tumor suppressor. In addition to Ca2+ S100A2 binds Zn2+ with a high affinity. Studies have been carried out to investigate whether Zn2+ acts as a regulatory ion for S100A2, as in the case of Ca2+. Using the method of competition with the...
Article
Full-text available
The tungsten-iron-sulfur enzyme acetylene hydratase stands out from its class because it catalyzes a nonredox reaction, the hydration of acetylene to acetaldehyde. Sequence comparisons group the protein into the dimethyl sulfoxide reductase family, and it contains a bis-molybdopterin guanine dinucleotide-ligated tungsten atom and a cubane-type [4Fe...
Chapter
Nickel is an essential ultra-micronutrient for higher plants and some cyanobacteria. The best known function in higher plants is its role in the active center of the enzyme urease, but at least one by now well-known additional function is the deterrence of herbivores in Ni hyperaccumulator plants. In cyanobacteria, Ni has additional enzymatic funct...
Article
N2O is a potent greenhouse gas and stratospheric reactant that has been steadily on the rise since the beginning of industrialization. It is an obligatory inorganic metabolite of denitrifying bacteria, and some production of N2O is also found in nitrifying and methanotrophic bacteria. We focus this review on the respiratory aspect of N2O transforma...
Article
RAGE is a multi-ligand receptor involved in various human diseases including diabetes, cancer or Alzheimer's disease. Engagement of RAGE by its ligands triggers activation of key cellular signalling pathways such as the MAP kinase and NF-kappaB pathways. Whereas the main isoform of RAGE is a transmembrane receptor with both extra- and intracellular...