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71.
Density functional theory (DFT) combined with the conductor-like solvent model (COSMO) can provide valuable atomistic level insights into CO adsorption on Cu surface interactions in liquid paraffin. The objective of this research was to investigate the solvent effect of liquid paraffin. It was found that both structural parameters and relative energies are very sensitive to the COSMO solvent model. Solvent effects can improve the stability of CO adsorption on Cu (110) and (100) surfaces and the extent of CO activation.  相似文献   
72.
Teicoplanin, a member of the “last chance” antibiotic family has a similar structure and the same mechanism of action as parent drug vancomycin, which is proved to be an effective binder of Cu(II) ions. However, the potentiometric and spectroscopic studies (UV-visible, CD, NMR) have shown that the modification of the N-terminal structure of the peptide backbone in teicoplanin affects considerably the binding ability towards Cu(II) ions. While vancomycin forms almost instantly the stable 3 N complex species involving the N-terminal and two amide nitrogen donors, in case of teicoplanin only two nitrogen donors derived from the N-terminal amino group and adjacent peptide bond are coordinated to Cu(II) ion within the whole pH range studied. The major factor influencing the binding mode is most likely the structure of the N-terminus of the peptide unit in the antibiotic ligand.  相似文献   
73.
The cellular form of the prion protein (PrPC) is found in both full-length and several different cleaved forms in vivo. Although the precise functions of the PrPC proteolytic products are not known, cleavage between the unstructured N-terminal domain and the structured C-terminal domain at Lys-109↓His-110 (mouse sequence), termed α-cleavage, has been shown to produce the anti-apoptotic N1 and the scrapie-resistant C1 peptide fragments. β-Cleavage, residing adjacent to the octarepeat domain and N-terminal to the α-cleavage site, is thought to arise from the action of reactive oxygen species produced from redox cycling of coordinated copper. We sought to elucidate the role of key members of the ADAM (a disintegrin and metalloproteinase) enzyme family, as well as Cu2+ redox cycling, in recombinant mouse PrP (MoPrP) cleavage through LC/MS analysis. Our findings show that although Cu2+ redox-generated reactive oxygen species do produce fragmentation corresponding to β-cleavage, ADAM8 also cleaves MoPrP in the octarepeat domain in a Cu2+- and Zn2+-dependent manner. Additional cleavage by ADAM8 was observed at the previously proposed location of α-cleavage, Lys-109↓His-110 (MoPrP sequencing); however, upon addition of Cu2+, the location of α-cleavage shifted by several amino acids toward the C terminus. ADAM10 and ADAM17 have also been implicated in α-cleavage at Lys-109↓His-110; however, we observed that they instead cleaved MoPrP at a novel location, Ala-119↓Val-120, with additional cleavage by ADAM10 at Gly-227↓Arg-228 near the C terminus. Together, our results show that MoPrP cleavage is far more complex than previously thought and suggest a mechanism by which PrPC fragmentation responds to Cu2+ and Zn2+.  相似文献   
74.
The genes encoding the biosynthesis of the dipeptide bacilysin and its antibiotic constituent anticapsin were isolated from several strains of Bacillus subtilis as well as B. amyloliquefaciens and B. pumilus. The ywfBCDEF genes of B. subtilis 168 were shown to carry the biosynthetic core functions and were renamed bacABCDE. Mutation of the bacD gene or transformation of the bacABC genes into a B. subtilis (ywfA-bacABCDE) deletion mutant led to the accumulation of anticapsin, which was fourfold higher after transformation of the bacABC genes into a bacD mutant. The genes bacD and bacE proved to encode the functions of amino acid ligation and self-protection to bacilysin, respectively. Amplification of the bacABCDE gene cluster in a bacAB gene-deficient host strain of B. amyloliquefaciens resulted in a tenfold bacilysin overproduction. Some host strains required distinct glucosamine and yeast extract supplements in order to prevent suicidal effects of the recombinant antibiotic production. The bac genes from different Bacillus species revealed the same arrangement and 72.6–88.6% of sequence identity.  相似文献   
75.
A novel biosensor harnessing a conducting polymer functionalized with a copper ion specific peptide proved to be highly effective for electrochemical analysis of copper ions. The developed sensor comprised a transducer based on a conducting polymer (poly(3-thiopheneacetic acid)) electrode and a probe (tripeptide, Gly–Gly–His) selectively cognitive of copper ions. For functionalization of the electrode, the carboxylic group of the polymer was covalently coupled with the amine group of the tripeptide, and its structural features were confirmed by X-ray photoelectron spectroscopy (XPS) and attenuated total reflection infrared (ATR-IR) spectroscopy. The peptide modified polythiophene biosensor was used for the electrochemical analysis of various trace metal ions by square wave voltammetry. The electrode was found to be highly sensitive and selective to Cu2+ in the range of 0.02–20 μM with almost no cross binding to other metal ions such as Ni2+ and Pb2+. Furthermore, the developed sensor exhibited a high stability and reproducibility despite the repeated use of the sensor electrode and probe. With the advent of more diverse affinity bioprobes specific towards a broad range of analytes, the demonstrated strategy harnessing peptide modified polythiophene biosensor is likely to provide an excellent platform for the selective determination of trace amount of analytes whose detection is otherwise cumbersome.  相似文献   
76.
Complexes of general formula [{CuX}2(YNC10H14O)] (X = Cl; Y = NHMe, NH2 or X = Br; Y = NH2) were synthesised from camphor hydrazone ligands (YNC10H14O) by reaction with the suitable copper(I) halide. Structural analysis by X-rays performed on a red crystal of [{CuCl}2(Me2NNC10H14O)] revealed that the complex is a one-dimensional copper polymer formed by two rather different copper units bridged by chloride. One of the copper units displays a tetrahedral geometry while the other is linear. Although the geometries and neighbourhoods of the two copper units are very different the oxidation state of the metal is the same, i.e. Cu(I) as corroborated by magnetic and electrochemical measurements.The ability of [{CuCl}2(Me2NNC10H14O)] to promote the activation of 4-pentyn-1-ol towards cyclization was studied under homogeneous or heterogeneous experimental conditions. The best results were obtained under homogeneous conditions at 40 °C.  相似文献   
77.
Three new copper(I) complexes with tricyclohexylphosphine (PCy3) and different diimine ligands, [Cu(phen)(PCy3)]BF4 (1) (phen = 1,10′-phennanthroline), [Cu(bpy)(PCy3)2]BF4 (2) (bpy = 2,2′-bipyridine) and [Cu(MeO-CNN)(PCy3)]BF4 (3) (MeO-CNN = 6-(4-methoxyl)phenyl-2,2′-bipyridine), have been synthesized and characterized. X-ray structure reveals that complexes 1 and 3 are three-coordinated with trigonal geometry, while complex 2 adopts distorted tetrahedron geometry. Complexes 1 and 3 exhibit ligand redistribution reactions in chloromethane solution by addition of excess amount of PCy3, in which three-coordinated 1 changes into four-coordinated [Cu(phen)(PCy3)2]+, and 3 leads to form [Cu(PCy3)2]BF4 and CNN-OMe. All the three complexes display yellow 3MLCT emissions in solid state at room temperature with λmax at 558, 564 and 582 nm for 1, 2 and 3, respectively, and red-shift to 605, 628 and 643 nm at 77 K in dichloromethane solution.  相似文献   
78.
Abstract The effects of recent fire frequency and time‐since‐fire on plant community composition and species abundance in open‐forest and woodland vegetation in Girraween National Park, south‐east Queensland, Australia, were examined. Cover‐abundance data were collected for shrub and vine species in at least 10 400‐m2 plots in each of four study areas. Study areas were within one community type and had burnt most recently either 4 or 9 years previously. Variations in fire frequency allowed us to compare areas that had burnt at least three times in the previous 25 years with less frequently burnt areas, and also woodlands that had experienced a 28‐year interfire interval with more frequently burnt areas. Although species richness did not differ significantly with either time‐since‐fire or fire frequency, both these factors affected community composition, fire frequency being the more powerful. Moisture availability also influenced floristics. Of the 67 species found in five or more plots, six were significantly associated with time‐since‐fire, whereas 11 showed a significant difference between more and less frequently burnt plots in each of the two fire‐frequency variables. Most species, however, did not vary in cover‐abundance with the fire regime parameters examined. Even those species that showed a marked drop in cover‐abundance when exposed to a particular fire regime generally maintained some presence in the community. Five species with the capacity to resprout after fire were considered potentially at risk of local extinction under regimes of frequent fire, whereas two species were relatively uncommon in long‐unburnt areas. Variable fire regimes, which include interfire intervals of at least 15 years, could be necessary for the continuity of all species in the community.  相似文献   
79.
Summary Boron, copper, iron, manganese and zinc concentrations were measured in sunflower leaves from plants grown hydroponically in a closed continuous flow system and with boron concentrations ranging from deficient to toxic. Leaves were analyzed at the stage of flower development. There was a highly significant inverse correlation between B concentration in solution and Mn concentration in leaves. Cu, Fe and Zn concentrations in the leaves were not changed by the different B levels, although the B concentration in leaves increased with an increasing concentration in solution, showing a close correlation each other.  相似文献   
80.
We have previously shown that vitamin C (ascorbic acid) can initiate hydroxyl radical formation in copper contaminated household drinking water. In the present study, we have examined the stability of vitamin C in copper and bicarbonate containing household drinking water. In drinking water samples, contaminated with copper from the pipes and buffered with bicarbonate, 35% of the added vitamin C was oxidized to dehydroascorbic acid within 15 min. After 3 h incubation at room temperature, 93% of the added (2 mM) ascorbic acid had been oxidized. The dehydroascorbic acid formed was further decomposed to oxalic acid and threonic acid by the hydrogen peroxide generated from the copper (I) autooxidation in the presence of oxygen. A very modest oxidation of vitamin C occurred in Milli-Q water and in household water samples not contaminated by copper ions. Moreover, addition of vitamin C to commercially sold domestic bottled water samples did not result in vitamin C oxidation. Our results demonstrate that ascorbic acid is rapidly oxidized to dehydroascorbic acid and further decomposed to oxalic- and threonic acid in copper contaminated household tap water that is buffered with bicarbonate. The impact of consuming ascorbic acid together with copper and bicarbonate containing drinking water on human health is discussed.  相似文献   
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