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  • Holocene  (2)
  • Key words Metallothionein  (2)
  • Springer  (4)
  • Molecular Diversity Preservation International
  • PANGAEA
  • 1995-1999  (4)
Collection
Keywords
Publisher
  • Springer  (4)
  • Molecular Diversity Preservation International
  • PANGAEA
Years
  • 1995-1999  (4)
Year
  • 1
    Electronic Resource
    Electronic Resource
    Kinetics of reversible N-ethylmaleimide alkylation of metallothionein and the subsequent metal release (1997)
    Springer
    JBIC 2 (1997), S. 65-73 
    Details
    ISSN: 1432-1327
    Keywords: Key words Metallothionein ; N-Ethylmaleimide ; Alkylation ; Kinetics and mechanism ; 111Cd-NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract  The model alkylating agent N-ethylmaleimide (NEM) reacts reversibly at the metal-bound thiolates of Zn7MT and Cd7MT. An unprecedented feature of this reaction is that it approaches equilibrium and requires a large excess of NEM (〉1 mM for 3 μM protein) to drive it to completion. The complex kinetics of the reaction can be followed by monitoring the release of bound metal ions using the metallochromic dyes Zincon (ZI) for Zn7MT and pyridylazoresorcinol for Cd7MT. An initial lag phase is followed by more rapid release of zinc ions. The observed pseudo-first-order rate constants for the two phases are independent of the ZI and Zn7MT concentrations. The complex NEM concentration dependence of each phase, k f, obs=k f 1+k f 2 [NEM] and k s, obs=k s 1+k s 2 [NEM], demonstrates that the forward reactions are second order and the reverse reactions are first order. The alkylation can be reversed using 2-mercaptoethanol to compete for the protein-bound NEM and regenerate the Zn-binding capability of alkylated MT. An explanation of these observations, based on the reversibility of cysteine alkylation by NEM, was developed and tested. The reactions of Cd7MT are less complete than those of Zn7MT and occur more slowly. 111Cd-NMR studies of the partially alkylated 111Cd7MT reveal that reaction with only four equivalents of NEM completely alters the cluster structure and eliminates the spectral signatures of the α and β clusters, although very little cadmium has been removed from the protein. This finding substantiates the proposed kinetic intermediate, a partially alkylated MT with complete or nearly complete retention of the metal ions, and rules out the possibility of cooperative reactions at either cluster.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s007750050107
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  • 2
    Electronic Resource
    Electronic Resource
    Characterization of the cadmium complex of peptide 49–61: a putative nucleation center for cadmium-induced folding in rabbit liver metallothionein IIA (1999)
    Springer
    JBIC 4 (1999), S. 495-507 
    Details
    ISSN: 1432-1327
    Keywords: Key words Metallothionein ; Peptide-metal complexes ; 111Cd NMR ; Protein folding ; Molecular mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract  The synthetic peptide fragment containing residues 49–61 of rabbit liver metallothionein II (MT-II) (Ac-Ile-Cys-Lys-Gly-Ala-Ser-Asp-Lys-Cys-Ser-Cys-Cys-Ala-COOH), which includes the only sequential four cysteines bound to the same metal ion in Cd7MT, forms a stable, monomeric Cd-peptide complex with 1 : 1 stoichiometry (Cd:peptide) via Cd-thiolate interactions. This represents the first synthesis of a single metal-binding site of MT independent of the domains. The 111Cd NMR chemical shift at 716 ppm indicates that the 111Cd2+ in the metal site is terminally coordinated to four side-chain thiolates of the cysteine residues. The pH of half dissociation for this Cd-peptide derivative, ∼3.3, demonstrates an affinity similar to that for Cd7MT. Molecular mechanics calculations show that the thermodynamically most stable folding for this isolated Cd2+ center has the same counterclockwise chirality (Λ or S) observed in the native holo-protein. These properties are consistent with its proposed role as a nucleation center for cadmium-induced protein folding. However, the kinetic reactivity of the CdS4 structure toward 5,5′-dithiobis(5-nitrobenzoate) (DTNB) and EDTA is greatly increased compared to the complete cluster (α-domain or holo-protein). The rate law for the reaction with DTNB is rate=(k uf +k 1,f +k 2,f [DTNB])[peptide], where k uf=0.15 s–1, k 1,f=2.59×10–3 s–1, and k 2,f=0.88 M–1 s–1. The ultrafast step (uf), observable only by stopped-flow measurement, is unprecedented for mammalian (M7MT) and crustacean (M6MT) holo-proteins or the isolated domains. The accommodation of other metal ions by the peptide indicates a rich coordination chemistry, including stoichiometries of M-peptide for Hg2+, Cd2+, and Zn2+, M2-peptide for Hg2+ and Au+, and (Et3PAu)2-peptide.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s007750050335
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  • 3
    Electronic Resource
    Electronic Resource
    Upland vegetation in the north-west Iberian peninsula after the last glaciation: Forest history and deforestation dynamics (1997)
    Springer
    Vegetation history and archaeobotany 6 (1997), S. 215-233 
    Details
    ISSN: 1617-6278
    Keywords: Pollen analysis ; Late-glacial ; Holocene ; Iberian peninsula
    Source: Springer Online Journal Archives 1860-2000
    Topics: Archaeology , Biology
    Notes: Abstract This paper presents the results of pollen analyses from organic sediments of seven cores (299 spectra) in a mountainous area of the north-west Iberian peninsula. The pollen diagrams, supported by seven14C dates, are used to construct a regional pollen sequence covering the main stages of vegetation dynamics, from the last phases of the Late-glacial until the present. During the Late-glacial Interstadial an important development of cryophilous forests (Betula andPinus) was recorded, although various mesophilous and thermophilous tree elements were also present. The Younger Dryas, palynologically clearly defined, is characterized by an important reduction in tree pollen percentages and the expansion of steppe formations (Poaceae andArtemisia). At the beginning of the Holocene, there was an expansion ofQuercus and a spread of other trees, which combined to give a vegetation cover of varied composition but dominated by mixed deciduous forests. Such forest formations prevailed in these mountains until 3000 years ago, when successive deforestation phases are recorded at various times as a result of increased farming activity. The results are compared with data from other mountainous areas in the northern Iberian peninsula and southern France.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01370443
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  • 4
    Electronic Resource
    Electronic Resource
    Differences in the vegetation of the North Iberian Peninsula during the last 16,000 years (1998)
    Springer
    Plant ecology 138 (1998), S. 41-62 
    Details
    ISSN: 1573-5052
    Keywords: Holocene ; Lateglacial ; North Iberian Peninsula ; Pollen analysis ; Vegetation development
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The dynamics of vegetation in the North Iberian Peninsula have been historically established from peaty and lacustrine records obtained in strongly continental mountainous areas. Pollen records located in areas with a more oceanic climate, have allowed a more precise evaluation of the changes and differences in the vegetation development of the various biogeographical areas in the North Iberian Peninsula, during the Late-glacial and Holocene. It was found that: (1) The vegetation of the Cantabrian–Atlantic province in northern Iberian Peninsula responded to climatic changes during the last 16000 years. (2) Tree vegetation declined during the Oldest Dryas, with steppe vegetation in the interior and cryophilous vegetation along the coast. (3) During the time of the Lateglacial Interestadial, lowlands, arboreal vegetation was dominant in the landscape (Pinus, Betula, Quercus, Corylus). (4) During the Younger Dryas the differences between coast and interior are less obvious. (5) During the Holocene oceanic decidious forests of Quercus robur, Corylus avellana, Tilia sp. and Fagus sylvatica were present along the coast. At low altitudes, in the interior, forests of Quercus robur / pyrenaica, enclaves of pine woods and Mediterranean types of forest (Quercus ilex, Olea europea) were present. At higher altitudes Pinus (P. sylvestris and P. uncinata) or mixed forests of Pinus and Betula were dominant.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1009736432739
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