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81.
Roland Lang Arno Schrwerth Kurt Polborn Walter Ponikwar Wolfgang Beck Theodor Severin Kay Severin 《无机化学与普通化学杂志》1999,625(8):1384-1390
Organometallic Compounds with N -substituted 3-Hydroxy-2-methyl-4-pyridone Ligands: square planar Rhodium(I), Iridium(I), and Palladium(II) Complexes Reactions of [(OC)2MCl]2 (M = Rh, Ir) or [(cod)RhCl]2 with the anions of N-Aryl or N-Alkyl substituted 3-hydroxy-2-methyl-4-pyridones (O–O′) yield complexes of the general formula [L2M(O–O′)]. Compounds of this type are also available from reactions of [(OC)2Rh(acac)] with the corresponding neutral ligands. Substitution of one carbonyl-ligand of the N-phenyl complex [(OC)2Rh(C12H10NO2)] ( 2 ) with cyclooctene affords [(OC)(C8H14)Rh(C12H10NO2)] ( 8 ). The palladium complexes [(R3P)Pd(O–O′)Cl] (R = Et, Bu), [(C6H4CH2NMe2) · Pd(O–O′)] and [(Et3P)2Pd(O–O′)]BF4 ( 9 – 12 ) were synthesized from [(R3P)PdCl2]2, [(C6H4CH2NMe2)PdCl]2 or [(Et3P)PdCl2]. The structures of the N-methyl compounds [(OC)2Rh(C7H8NO2)] ( 1 ) and [(Ph3P)Pd(C7H8NO2)Cl] ( 9 ) were determined by single crystal X-ray diffraction. 相似文献
82.
Systematic Comparison of Peptidic Proteasome Inhibitors Highlights the α‐Ketoamide Electrophile as an Auspicious Reversible Lead Motif 下载免费PDF全文
Martin L. Stein Haissi Cui Philipp Beck Christian Dubiella Constantin Voss Prof. Dr. Achim Krüger Prof. Dr. Boris Schmidt Prof. Dr. Michael Groll 《Angewandte Chemie (International ed. in English)》2014,53(6):1679-1683
The ubiquitin–proteasome system (UPS) has been successfully targeted by both academia and the pharmaceutical industry for oncological and immunological applications. Typical proteasome inhibitors are based on a peptidic backbone endowed with an electrophilic C‐terminus by which they react with the active proteolytic sites. Although the peptide moiety has attracted much attention in terms of subunit selectivity, the target specificity and biological stability of the compounds are largely determined by the reactive warheads. In this study, we have carried out a systematic investigation of described electrophiles by a combination of in vitro, in vivo, and structural methods in order to disclose the implications of altered functionality and chemical reactivity. Thereby, we were able to introduce and characterize the class of α‐ketoamides as the most potent reversible inhibitors with possible applications for the therapy of solid tumors as well as autoimmune disorders. 相似文献
83.
The reaction of CuCl with WOCl3 at 400 °C leads to a mixture of Cu1?x[W2O2Cl6] ( 1 ) and Cu1?x[W4O4Cl10] ( 2 ) in form of black lustrous needles. Both compounds crystallize in space group C2/m with a = 12.7832(5) Å, b = 3.7656(2) Å, c = 10.7362(3) Å, β = 119.169(2)° for 1 and a = 12.8367(19) Å, b = 3.7715(7) Å, c = 15.955(3) Å, β = 102.736(5)° for 2 . The structures are made up of WO2Cl4 octahedra. In the case of 1 two octahedra are edge‐sharing via chlorine atoms to form pairs which are linked via the trans‐positioned oxygen atoms to form infinite double strands . In the structure of 2 two of these double strands are condensed via terminal chlorine atoms to form quadruple strands . Like for all members of the Mx[W2O2X6] structure family (X = Cl, Br) nonstochiometry with respect to the cations M was observed. The copper content of 1 and 2 was derived from the site occupation factors of the respective structure refinements. For several crystals examined the copper content varied between x = 0.27 and 0.17 for 1 and x = 0.04 for 2 . In both structures the oxochlorotungstate strands are negatively charged and connected to layers by the monovalent copper ions, which are tetrahedrally coordinated by the non‐bridging chlorine atoms of the strands. The structure models imply disorder of the Cu+ ions over closely neighboured sites. 相似文献
84.
Stephan Schrölkamp Alfons Völkl Thomas Lügger F. Ekkehardt Hahn Wolfgang Beck Wolf Peter Fehlhammer Prof. Dr. 《无机化学与普通化学杂志》2008,634(15):2940-2947
Palladium, Platinum, and Diiron Complexes with Isocyanoacetate: Ring Closure, Acid‐Induced Ring Opening, Diprotonation Substitution by isocyanoacetate (CNCH2CO2?) of one chloro ligand in trans‐[MCl2(PPh3)2] (M = Pd, Pt) results in the Δ2‐oxazolin‐5‐on‐2‐ato complexes 4a , b , i.e. immediate cyclization occurs in contact with these metal(II) species. In contrast, the open‐chain form of the functional isocyanide is retained in [K(18‐crown‐6][Fe2Cp2(CNCH2CO2)(CO)3] ( 16 ) in which it occupies a terminal position. Protonation (alkylation) of the platinum complex 4b proceeds with ring cleavage and formation of isocyano acetic acid 11 (ethyl isocyanoacetate 12 ) stabilized by metal ion coordination. Protonation of 16 requires two equivalents of acid to yield the aminocarbyne‐bridged complex [{μ‐C=N(H)CH2CO2H}Fe2Cp2(CO)3](BF4) ( 17 ) as the only isolable product. Here isocyanoacetate displays a third kind of reactivity pattern in addition to that at PdII/PtII and that at Cr0/W0 where the primary species [M(CO)5CNCH2CO2]? and [M(CO)5CNCH2CO2H] proved to be the most stable. All of the proposed structures are substantiated by analytical and the usual spectroscopic (IR, NMR{1H, 13C, 31P}, FAB‐MS) data, that of 4b also by an X‐ray structure determination which reveals a practically perpendicular arrangement of the coordination and the ring plane, and a long C2‐O bond as the predetermined breaking point of the heterocycle. 相似文献
85.
Talib J Green C Davis KJ Urathamakul T Beck JL Aldrich-Wright JR Ralph SF 《Dalton transactions (Cambridge, England : 2003)》2008,(8):1018-1026
Electrospray ionisation mass spectrometry (ESI-MS) and circular dichroism (CD) spectroscopy were used to compare the binding of mononuclear nickel, ruthenium and platinum complexes to double stranded DNA (dsDNA) and quadruplex DNA (qDNA). CD studies provided evidence for the binding of intact complexes of all three metal ions to qDNA. ESI mass spectra of solutions containing platinum or ruthenium complexes and qDNA showed evidence for the formation of non-covalent complexes consisting of intact metal molecules bound to DNA. However, the corresponding spectra of solutions containing nickel complexes principally contained ions consisting of fragments of the initial nickel molecule bound to qDNA. In contrast ESI mass spectra of solutions containing nickel, ruthenium or platinum complexes and dsDNA only showed the presence of ions attributable to intact metal molecules bound to DNA. The fragmentation observed in mass spectral studies of solutions containing nickel complexes and qDNA is attributable to the lower thermodynamic stability of the former metal complexes relative to those containing platinum or ruthenium, as well as the slightly harsher instrumental conditions required to obtain spectra of qDNA. This conclusion is supported by the results of tandem mass spectral studies, which showed that ions consisting of intact nickel complexes bound to qDNA readily undergo fragmentation by loss of one of the ligands initially bound to the metal. The ESI-MS results also demonstrate that the binding affinity of each of the platinum and ruthenium complexes towards qDNA is significantly less than that towards dsDNA. 相似文献
86.
87.
The thermal conductivities of several nanofluids (dispersions of alumina nanoparticles in ethylene glycol) were measured at temperatures ranging from 298 to 411 K using a liquid metal transient hot wire apparatus. Our measurements span the widest range of temperatures that have been investigated to date for any nanofluid. A maximum in the thermal conductivity versus temperature behavior was observed at all mass fractions of nanoparticles, closely following the behavior of the base fluid (ethylene glycol). Our results confirm that additional temperature contributions inherent in Brownian motion models are not necessary to describe the temperature dependence of the thermal conductivity of nanofluids. Our results also show that the effect of mass or volume fraction of nanoparticles on the thermal conductivity of nanofluids can be correlated using the Hamilton and Crosser or Yu and Choi models with one adjustable parameter (the shape factor in the Hamilton and Crosser model, or the ordered liquid layer thickness in the Yu and Choi model). 相似文献
88.
Locked by Design: A Conformationally Constrained Transglutaminase Tag Enables Efficient Site‐Specific Conjugation 下载免费PDF全文
Dr. Vanessa Siegmund Dr. Stefan Schmelz Stephan Dickgiesser Jan Beck Aileen Ebenig Heiko Fittler Dr. Holm Frauendorf Dr. Birgit Piater Dr. Ulrich A. K. Betz Dr. Olga Avrutina Dr. Andrea Scrima Prof. Dr. Hans‐Lothar Fuchsbauer Prof. Dr. Harald Kolmar 《Angewandte Chemie (International ed. in English)》2015,54(45):13420-13424
Based on the crystal structure of a natural protein substrate for microbial transglutaminase, an enzyme that catalyzes protein crosslinking, a recognition motif for site‐specific conjugation was rationally designed. Conformationally locked by an intramolecular disulfide bond, this structural mimic of a native conjugation site ensured efficient conjugation of a reporter cargo to the therapeutic monoclonal antibody cetuximab without erosion of its binding properties. 相似文献
89.
The high pressure behaviour of InI is studied by DFT‐calculations and compared with experimental data. The existence of a 5s2 electron pair in In+ represents an unfavourable bonding situation for high symmetry structures because of effective closed shell repulsion. Since cations with a ns2 electron pair are highly polarizable and the electronic situation is more favourable in the low symmetry structure InI prefers a TlI‐type structure at ambient pressure. A pressure induced transition to the more densely packed high symmetry CsCl‐type structure takes place at about 19 GPa according to our calculations. At ambient pressure the interactions are predominantly ionic. However with increasing pressure the distances between In+ cations in the TlI‐type structure diminish drastically, mainly due to the changing space requirement of the lone electron pair. Apart from ionic interactions further bonding interactions between the In+ cations occur. At elevated pressure the electron localization function (ELF) as well as the band structure diagrams suggest metallic bonding between the In+ within the zigzag chain, i. e. increasing bonding interactions between the In+ cations due to the electron pair and its s‐p‐mixing. At ambient pressure In‐In interactions are rather weak and the space requirement of the lone electron pair mainly determines the characteristic arrangement of the ions. At elevated pressure the In‐In interactions become stronger and stabilise themselves additionally the specific structural arrangement. 相似文献
90.
Jeremy P. Scott Deborah C. Hammond Elizabeth M. Beck Karel M.J. Brands Antony J. Davies Ulf-H. Dolling Derek J. Kennedy 《Tetrahedron letters》2004,45(17):3345-3348
The efficient preparation of 4-aryl-4-phenylsulfonyl cyclohexanones, containing a quaternary sulfone-bearing carbon centre, is described. Their synthesis proceeds in 38-78% overall yield by way of three steps: (i) sulfinate alkylation; (ii) methylenation; and (iii) regioselective Diels-Alder condensation with 2-trimethylsiloxybutadiene. The scope and limitations of the one-pot Mannich-type methylenation described were examined. 相似文献