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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 1547-1553 
    ISSN: 1434-1948
    Keywords: Imidazaboles ; Carbene-borane adducts ; Azole-borane adducts ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation and characterization of five new imidazabole derivatives is reported: 1,5-dibenzyl-4,4,8,8-tetrahydroimidazabole (2), 4,4,8,8-tetrafluoro-1,5-dimethylimidazabole (3), 4,4-difluoro-8,8-dihydro-1,5-dimethylimidazabole (4), 4,4,8,8-tetrachloro-1,5-dimethylimidazabole (5), and 4,4,8,8-tetraethyl-1,5-dimethylimidazabole (6). The structures of compounds 2-6 as dimeric carbene-borane adducts rather than dimeric N-borane adducts are discussed on the basis of NMR (2-6) and X-ray diffraction data (2, 3, 5 and 6).
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1434-1948
    Keywords: Alkaline earth metals ; Group-13 metals ; Coordination chemistry ; Bis(3,5-di-tert-butyl-1-hydroxy-2-phenyl)amine ligand ; Nonacoordinated strontium compound ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of 3,5-di-tert-butylcatechol and aqueous ammonia with boron, aluminum, gallium, or strontium chloride, or with calcium or barium acetate produce, under oxidizing conditions, neutral complexes of stoichiometric formulae ML (M = BCl), ML2, [M = Al (2), Ga (3), Ca (4), and Ba (5)], and ML3H [M = Sr (6)] [L = different oxidation states of bis(3,5-di-tert-butyl-1-hydroxy-2-phenyl)amine]. The structures of 1 and 4-6 were established by 1H- and 13C-NMR spectroscopy and of 2, 3, and 6 by X-ray diffraction. The coordination compound ClBL (1) was obtained by transmetallation of ZnL2 with BCl3. It is a tetracyclic compound with tetracoordinated boron and nitrogen atoms, the ligand being in the reduced form, bis(hydroxyphenyl)amine. The paramagnetic complexes 2 and 3 crystallized in the triclinic system and are hexacoordinated with two orthogonal planar ligands bonded to the metal atoms. The ligands appear in two different oxidation states: one as the monoanion and another as a radical dianion. Based on their X-ray diffraction molecular structures, it is deduced that both ligands have similar structures, confirming electronic delocalization and fast interconversion of their oxidation states. Ca and Ba complexes are diamagnetic and hexacoordinated, both ligands being monoanions The strontium complex crystallized in the monoclinic system, the metal atom is nonacoordinated, having two ligands as monoanions, and a third one is a neutral protonated diquinone. Its structure is a distorted helix with three paddles in a C3 geometry and its unexpected diamagnetic behaviour is due to the presence of a reduced protonated ligand.
    Additional Material: 4 Ill.
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  • 3
    Publication Date: 2007-09-18
    Description: Antibodies play a central role in immunity by forming an interface with the innate immune system and, typically, mediate proinflammatory activity. We describe a novel posttranslational modification that leads to anti-inflammatory activity of antibodies of immunoglobulin G, isotype 4 (IgG4). IgG4 antibodies are dynamic molecules that exchange Fab arms by swapping a heavy chain and attached light chain (half-molecule) with a heavy-light chain pair from another molecule, which results in bispecific antibodies. Mutagenesis studies revealed that the third constant domain is critical for this activity. The impact of IgG4 Fab arm exchange was confirmed in vivo in a rhesus monkey model with experimental autoimmune myasthenia gravis. IgG4 Fab arm exchange is suggested to be an important biological mechanism that provides the basis for the anti-inflammatory activity attributed to IgG4 antibodies.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉van der Neut Kolfschoten, Marijn -- Schuurman, Janine -- Losen, Mario -- Bleeker, Wim K -- Martinez-Martinez, Pilar -- Vermeulen, Ellen -- den Bleker, Tamara H -- Wiegman, Luus -- Vink, Tom -- Aarden, Lucien A -- De Baets, Marc H -- van de Winkel, Jan G J -- Aalberse, Rob C -- Parren, Paul W H I -- New York, N.Y. -- Science. 2007 Sep 14;317(5844):1554-7.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Sanquin Research-AMC Landsteiner Laboratory, Department of Immunopathology, Plesmanlaan 125, 1066 CX Amsterdam, the Netherlands.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/17872445" target="_blank"〉PubMed〈/a〉
    Keywords: Allergens/immunology ; Animals ; Antibodies, Bispecific/immunology ; Antibodies, Monoclonal/immunology ; Antigens, CD20/immunology ; Antigens, Plant ; Autoantibodies/immunology ; Glycoproteins/immunology ; Humans ; Immunoglobulin Constant Regions/chemistry ; Immunoglobulin Fab Fragments/*chemistry/*immunology/metabolism ; Immunoglobulin G/*chemistry/*immunology/metabolism ; Immunoglobulin Heavy Chains ; Macaca mulatta ; Mice ; Mutation ; Myasthenia Gravis, Autoimmune, Experimental/immunology/prevention & control ; Protein Processing, Post-Translational ; Receptor, Epidermal Growth Factor/immunology ; Receptors, Cholinergic/immunology
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 4
    Electronic Resource
    Electronic Resource
    Amsterdam : Elsevier
    Peptides 14 (1993), S. 1083-1089 
    ISSN: 0196-9781
    Keywords: Angiotensin-converting enzyme ; Captopril ; Dipeptidyl carboxypeptidases ; Enzymatic hydrolysis ; HPLC ; Met-enkephalin ; Mice ; Novelty ; Opioid peptides ; Phosphoramidon
    Source: Elsevier Journal Backfiles on ScienceDirect 1907 - 2002
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 217-224 
    ISSN: 1434-1948
    Keywords: Reaction mechanisms ; Cyclopalladation ; Acetic acid ; Pd-C bond stability ; Polynuclear species ; Palladium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The processes operating during the synthetic cyclopalladation reactions of imines in acetic acid have been studied from a kinetico-mechanistic point of view. These reactions include a fast initial coordination to the palladium through the N-donor atom of the imine, followed by the proper C-H bond activation to produce the acetato bridged dimeric species. At this point, the lability of the bridging acetato groups, the hydrolysis of the C-Pd bonds, and/or the hydrolysis of C=N exo bonds contribute to the generation of dark red polynuclear compounds. The processes occurring after the C-H activation have been followed kinetically, both from palladium acetate plus imine, and the synthetically pure isolated acetato dimers as starting materials. The kinetic and activation parameters have been found identical within experimental error whatever the starting material was (k323 = 1.5 × 10-4 s-1; ΔH# = 51 kJ mol-1; ΔS# = -163 JK-1 mol-1 ΔV# = +19 cm3 mol-1 for the 4-ClC6H4-CH=N-CH2-C6H5 imine derivative 1a). Acidolysis of C-Pd bonds has been found to occur in these polynuclear species. When alternative monomeric Cbenzylic-Pd bond-containing complexes are possible follow ups of the reactions produce them as final dead-end complexes (k323 = 2.2 × 10-5 s-1; ΔH# = 61 kJ mol-1; ΔS# = JK-1 mol-1 ΔV# ≈ 0 cm3 cm-1 for the [2,4,6-(CH3)3]C6H2-CH=N-CH2-[2-(CH3]C6[H4] imine derivative 3d). The same study has been carried out with primary amines in order to check the validity of the data if C=N bond hydrolysis is taking place in the imine derivatives with exo C=N bonds. For complexes with similar type of metallacycles, the results agree reasonably well with the proposed mechanism [k323 = 1.2·10-4 s-1, ΔH# = 46 kJ·mol-1, ΔS# = -180 J·K-1mol-1, ΔV# = -16 cm3·mol-1 for the polynuclear formation of the C6H5-CH2-NH2 derivative 4e; k323 = 3.0·10-4 s-1, ΔH# = 55 kJ·mol-1, ΔS
    Additional Material: 1 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 3 (1997), S. 1017-1024 
    ISSN: 0947-6539
    Keywords: autocatalysis ; coiled coil ; kinetics ; peptides ; self-replication ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A 32-residue α-helical peptide with a sequence similiar to that of the GCN4 leucine zipper region is shown to catalyze its own formation by accelerating the amide bond formation of a 17-residue peptide, preactivated as a thiobenzyl ester, and a 15-residue peptide with a N-terminal cysteine. The self-replication process displays parabolic growth characteristics as revealed by a detailed kinetic analysis. Control reactions with single-mutant peptides strongly support a mechanism in which a ternary and/or quaternary complex of the product with both peptide fragments act(s) as the catalytically active intermediate(s). Furthermore, these experiments reveal a remarkable sequence selectivity, as evidenced by the loss of autocatalytic activity as a result of a single replacement of leucine or valine residues with an alanine at the recognition interface.
    Additional Material: 11 Ill.
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  • 7
    ISSN: 1434-1948
    Keywords: Trinuclear triangulo palladium complex ; 2-Hydroxyacetophenone N4-ethylthiosemicarbazone ; Dimethylformamide aggregation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The X-ray crystal structure of a palladium(II) complex of 2-hydroxyacetophenone N4-ethylthiosemicarbazone (H2Ap4E) shows it to be a triangular,trinuclear complex with bridging thiosemicarbazonato sulfur atoms. This species can be formed from a monomer on dissolution in DMF or directly from Li2PdCl4 and the thiosemicarbazone in methanol-ammonia solution.
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  • 8
    ISSN: 1434-1948
    Keywords: Palladium ; Platinum ; Aryl rotation ; Through-space coupling interactions ; Turnstile mechanism ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The square-planar complexes [MR2L2] (M = Pd, Pt; R = 3,5-C6Cl2F3) [L2 = OPPyPh2 (Py = 2-pyridyl); SPPyPh2; OPPy2Ph; DMBI (3,3′-dimethyl-2,2′-biindazole); OPPyPh(NHTol-p); p-TolNPPy2Ph] have been prepared by treating cis-[MR2(THF)2] (THF = tetrahydrofuran) with the appropriate chelate ligands. The 19F-NMR spectra of these complexes show the presence of intramolecular through-space F-F couplings between ortho-fluorine atoms of nonequivalent R groups, which provide information for the assignment of the different ortho-fluorine signals and can be used to study the dynamic behavior of the mentioned complexes such as: a) Rotation of the R group in either Pd or Pt complexes, at the same or at different rates for each R groups depending on the neutral ligand; and b) exchange of the coordination sites of the chelating ligand, either by Berry or by turnstile mechanisms. The activation parameters for some of the processes are given.
    Additional Material: 9 Ill.
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  • 9
    ISSN: 1434-1948
    Keywords: Ruthenium ; Thiolate ligands ; Dithiolate ligands ; Substitution reactions ; Electrophilic additions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The known dithiolate-bridged ruthenium(I) complex [Ru2(μ-bdt)(CO)6] (1) (bdt = benzene-1,2-dithiolate) has been prepared in fair yield (55%) by the sequential treatment of RuCl3·nH2O with carbon monoxide, benzene-1,2-dithiol and zinc in a one-pot reaction. Complex 1 reacts readily with monodentate phosphanes to give, stepwise, the penta- and tetracarbonyl derivatives [Ru2(μ-bdt)(CO)6-n(PR3)n] (n = 1, 2; R = Ph, Cy, iPr). However, the reaction of 1 with one equivalent of bis(diphenylphosphanyl)methane (dppm) affords a mixture of complex 1 and the disubstituted derivative [Ru2(μ-bdt)(CO)4(η1-dppm)2], in which the dppm ligands are monodentate. This mixture is subsequently transformed into a polymeric material of formula [{Ru2(μ-bdt)(CO)4}(μ-dppm)]n, which consists of binuclear {Ru2(μ-bdt)(CO)4} units linked to each other by bridging dppm ligands. The use of two equivalents of dppm leads to [Ru2(μ-bdt)(CO)4(η1-dppm)2] in quantitative yield. The X-ray diffraction structure of [Ru2(μ-bdt)(CO)4(PiPr3)2] (3c) confirms that the phosphane ligands are located in axial positions, cis to both sulfur atoms, and that the Ru-Ru distance is short [2.6753(7) Å]. A comparative study of the reactivity of complexes 1 and 3c with the electrophiles H+, [Au(PPh3)]+, and HgCl2 has allowed the isolation of the derivatives [Ru2(μ-H)(μ-bdt)(CO)6-n(PiPr3)n][BF4] (n = 0, 2), [Ru2Au(μ-bdt)(CO)6-n(PiPr3)n(PPh3)][BF4] (n = 0, 2) and [Ru2HgCl2(μ-bdt)(CO)6-n(PiPr3)n] (n = 0, 2), respectively.
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  • 10
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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