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61.
A series of low-coordinate, paramagnetic iron complexes in a tris(thioether) ligand environment have been prepared. Reduction of ferrous {[PhTt(tBu)]FeCl}2 [1; PhTt(tBu) = phenyltris((tert-butylthio)methyl)borate] with KC8 in the presence of PR3(R = Me or Et) yields the high-spin, monovalent iron phosphine complexes [PhTt(tBu)]Fe(PR3) (2). These complexes provide entry into other low-valent derivatives via ligand substitution. Carbonylation led to smooth formation of the low-spin dicarbonyl [PhTt(tBu)]Fe(CO)2 (3). Alternatively, replacement of PR 3 with diphenylacetylene produced the high-spin alkyne complex [PhTt(tBu)]Fe(PhCCPh) (4). Lastly, 2 equiv of adamantyl azide undergoes a 3 + 2 cycloaddition at 2, yielding high-spin dialkyltetraazadiene complex 5. 相似文献
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Ina Puscasu Christian Mock Michael Rauterkus Axel Rndigs Gesche Tallen Suman Gangopadhyay Johannes E. A. Wolff Bernt Krebs 《无机化学与普通化学杂志》2001,627(6):1292-1298
The reactions of [Pt(dpma)(H2O)2]2+ (dpma = 2,2′‐dipyridylmethylamine) and [Pt(dpk)(H2O)2]2+ (dpk = 2,2′‐dipyridylketone) with the model nucleobases 1‐methylthymine (1‐MeT) and 1‐methyluracil (1‐MeU) were studied. Reaction products were characterized by 195Pt NMR spectroscopy and by X‐ray structure analysis. The symmetric dpma and dpk diaqua complexes form dinuclear complexes with 1‐methylthymine, acting as secondary bridging ligand via its N3 and O4 donor atoms. [Pt2(dpma)2(1‐MeT)2](ClO4)2 · H2O ( 5 ) and [Pt2(dpk)(dpk · H2O)(1‐MeT)2](PF6)2 · 4 H2O ( 6 ) both show a head‐to‐head arrangement. Biological tests show a significant in vitro antitumor activity of [Pt(dpk)Cl2] against the human glioma cell line U 87. 相似文献
64.
Helane?MS?Costa Augusto?CV?Freitas Júnior Ian?PG?Amaral Izaura?Y?Hirata Patrícia?MG?Paiva Luiz?B?CarvalhoJr Vitor?Oliveira Ranilson?S?BezerraEmail author 《Chemistry Central journal》2013,7(1):166
Background
Over the past decades, the economic development and world population growth has led to increased for food demand. Increasing the fish production is considered one of the alternatives to meet the increased food demand, but the processing of fish leads to by-products such as skin, bones and viscera, a source of environmental contamination. Fish viscera have been reported as an important source of digestive proteases with interesting characteristics for biotechnological processes. Thus, the aim of this study was to purify and to characterize a trypsin from the processing by-products of crevalle jack (Caranx hippos) fish.Results
A 27.5 kDa trypsin with N-terminal amino acid sequence IVGGFECTPHVFAYQ was easily purified from the pyloric caeca of the crevalle jack. Its physicochemical and kinetic properties were evaluated using N-α-benzoyl-DL-arginine-p-nitroanilide (BApNA) as substrate. In addition, the effects of various metal ions and specific protease inhibitors on trypsin activity were determined. Optimum pH and temperature were 8.0 and 50°C, respectively. After incubation at 50°C for 30 min the enzyme lost only 20% of its activity. K m , kcat, and k cat /K m values using BApNA as substrate were 0.689 mM, 6.9 s-1, and 10 s-1 mM-1, respectively. High inhibition of trypsin activity was observed after incubation with Cd2+, Al3+, Zn2+, Cu2+, Pb2+, and Hg2+ at 1 mM, revealing high sensitivity of the enzyme to metal ions.Conclusions
Extraction of a thermostable trypsin from by-products of the fishery industry confirms the potential of these materials as an alternative source of these biomolecules. Furthermore, the results suggest that this trypsin-like enzyme presents interesting biotechnological properties for industrial applications.65.
David N. Stephens Prof. Robert K. Szilagyi Paige N. Roehling Dr. Navamoney Arulsamy Prof. Michael T. Mock 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(1):e202213462
We report a nickel complex for catalytic oxidation of ammonia to dinitrogen under ambient conditions. Using the aryloxyl radical 2,4,6-tri-tert-butylphenoxyl (tBu3ArO⋅) as a H atom acceptor to cleave the N−H bond of a coordinated NH3 ligand up to 56 equiv of N2 per Ni center can be generated. Employing the N-oxyl radical 2,2,6,6-(tetramethylpiperidin-1-yl)oxyl (TEMPO⋅) as the H-atom acceptor, up to 15 equiv of N2 per Ni center are formed. A bridging Ni-hydrazine product identified by isotopic nitrogen (15N) studies and supported by computational models indicates the N−N bond forming step occurs by bimetallic homocoupling of two paramagnetic [Ni]−NH2 fragments. Ni-mediated hydrazine disproportionation to N2 and NH3 completes the catalytic cycle. 相似文献
66.
Ultra-small-angle X-ray scattering was performed on suspensions of anisotropic polystyrene particles of varying degrees of anisotropy. The wave vector dependence of particle form factors is well described by a model developed by Debye for the scattering from fused spheres. As volume fraction is raised, all suspensions undergo a disorder/order phase transition. The scattering from disordered and ordered suspensions of anisotropic particles is the same as that of spheres up to volume fractions of 0.45, suggesting that, in the dilute crystalline phase, the anisotropic particles order into a rotator or plastic crystal phase, where the particle centers of mass are ordered, but the particle directors are randomly distributed. Further increase in particle volume fraction leads to differences in scattering between homonuclear dicolloids and spheres, implying that the homonuclear dicolloids form a body-centered tetragonal phase with both positional and directional order. This conclusion is supported by real-space imaging of dried films of the particles. 相似文献
67.
Sanford TW Jennings CA Rochau GA Rosenthal SE Sarkisov GS Sasorov PV Stygar WA Bennett LF Bliss DE Chittenden JP Cuneo ME Haines MG Leeper RJ Mock RC Nash TJ Peterson DL 《Physical review letters》2007,98(6):065003
Axial symmetry in x-ray radiation of wire-array z pinches is important for the creation of dynamic hohlraums used to compress inertial-confinement-fusion capsules. We present the first evidence that this symmetry is directly correlated with the magnitude of the negative radial electric field along the wire surface. This field (in turn) is inferred to control the initial energy deposition into the wire cores, as well as any current shorting to the return conductor. 相似文献
68.
Michael M. Coleman Marissa Mock Paul C. Painter 《Journal of Macromolecular Science: Physics》2013,52(4):403-417
Oxidation reactions are one of the main reasons for the failure of polymeric materials. Antioxidants, compounds designed to protect against oxidation, must meet three main requirements for success: (1) an efficient antioxidative mechanism, (2) compatibility with the oxidizing polymer, and (3) permanence Within the oxidizing polymer. Common antioxidants are low molecular weight materials that can easily diffuse, leach, or evaporate from the polymer they are designed to protect. An increase in the molecular weight of the antioxidant not only decreases diffusion and volatility, but also decreases compatibility since most high molecular weight polymers will not mix. Selective sterically hindered phenolics, however, are concurrently antioxidants and “compatibilizers” through hydrogen bond formation. Carefully designed copolymers containing a small percentage of 2,6-diisopropyl-4-vinylphenol were found to mix intimately with two readily oxidizing polyethers and to protect them against oxidation. 相似文献
69.
Sandip N.Gavade Ravi S.Balaskar Madhav S.Mane Pramod N.Pabrekar Murlidhar S.Shingare Dhananjay V.Mane 《中国化学快报》2011,22(6):675-678
The coupling reaction of phenylurea with different functionalized aryl halides in the presence of air stable CuI,N,N-dimethylethylenediamine as a ligand,and K3PO4 as a base gives symmetrical and unsymmetrical diarylureas in relatively high yields.This method is milder than the palladium catalyzed arylation and avoids the use of toxic phosphine ligands. 相似文献
70.