Search results for "coupling"
showing 10 items of 1862 documents
DctA- and Dcu-independent transport of succinate in Escherichia coli : contribution of diffusion and of alternative carriers
2001
Quintuple mutants of Escherichia coli deficient in the C4-dicarboxylate carriers of aerobic and anaerobic metabolism (DctA, DcuA, DcuB, DcuC, and the DcuC homolog DcuD, or the citrate/succinate antiporter CitT) showed only poor growth on succinate (or other C4-dicarboxylates) under oxic conditions. At acidic pH (pH 6) the mutants regained aerobic growth on succinate, but not on fumarate. Succinate uptake by the mutants could not be saturated at physiological succinate concentrations (≤5 mM), in contrast to the wild-type, which had a K m for succinate of 50 µM and a V max of 35 U/g dry weight at pH 6. At high substrate concentrations, the mutants showed transport activities (32 U/g dry weigh…
Testing mode-coupling theory for a supercooled binary Lennard-Jones mixture
1995
Abstract We have performed a molecular dynamics computer simulation study to investigate the dynamical behavior of a supercooled simple liquid for comparison with the predictions of mode-coupling theory (MCT). By scaling the intermediate scattering function by the α-relaxation time r we find that the correlators fall onto a master curve extending over several decades in time. Thus we find that the time temperature superposition principle holds. In the late β-relaxation regime this master curve can be fitted very well by a master curve predicted by the idealized version MCT. However, there is no evidence for the presence of the critical decay predicted by the theory for the early part of the…
Over-Oxidation as the Key Step in the Mechanism of the MoCl5-Mediated Dehydrogenative Coupling of Arenes.
2015
Molybdenum pentachloride is an unusually powerful reagent for the dehydrogenative coupling of arenes. Owing to the high reaction rate using MoCl5, several labile moieties are tolerated in this transformation. The mechanistic course of the reaction was controversially discussed although indications for a single electron transfer as the initial step were found recently. Herein, based on a combined study including synthetic investigations, electrochemical measurements, EPR spectroscopy, DFT calculations, and mass spectrometry, we deduct a highly consistent mechanistic scenario: MoCl5 acts as a one-electron oxidant in the absence of TiCl4 and as two-electron oxidant in the presence of TiCl4, bu…
Unusual redox play of Mo(V/IV) during oxidative aryl–aryl coupling
2012
The oxidative treatment of a suitable 1,3-diarylpropene precursor by MoCl5 causes a series of redox steps yielding a dimer of dibenzo[a,c]cycloheptene. After the oxidative aryl–aryl bond formation, a C,H activation occurs providing a tropylium intermediate. Upon aqueous workup the metal waste acts as reductive media generating the dimer in an almost quantitative manner. The oxidative generation of the tropylium species as well as the subsequent redox play by the metal waste is unique and unprecedented. The dimeric compound can be oxidatively cleaved and subsequently decarboxylated providing the key intermediate of a previous synthesis of metasequirin-B derivatives.
Gold based plasmonic stripes co-integrated with low loss Si3N4 platform in aqueous environment
2018
We demonstrate a butt-coupled interface between LPCVD Si 3 N 4 and gold based plasmonic waveguides in aqueous environment, exhibiting 2.3dB coupling loss and 75μm propagation length at 1550nm, towards future employment in biosensing applications.
[Mnii2(bpym)(H2O)8]4+ and [Miv(CN)8]4– (M = Mo and W) as building blocks in designing bpym- and cyanide-bridged bimetallic three-dimensional networks…
2002
One-pot reaction between the dinuclear [MnII2(bpym)(H2O)8]4+ complex and the mononuclear [MIV(CN)8]4− unit (M = Mo and W; bpym = 2,2′-bipyrimidine) in aqueous solution yields the novel heterobimetallic complexes of formula {(μ-bpym)[Mn(H2O)]2-(μ-NC)6M(CN)2} with M = Mo (1) and W (2). 1 and 2 are isostructural three-dimensional compounds where the manganese atoms are bridged by bisbidentate bpym and hexakismonodentate octacyanometalate units. Variable-temperature magnetic susceptibility data of 1 and 2 show the occurrence of a significant antiferromagnetic coupling between the high spin manganese(II) ions through bridging bpym (Jca. −1.1 cm−1, the exchange Hamiltonian being defined as H = −J…
Ferromagnetic coupling through a carbonate bridge in the copper (II) chain [Cu(CO3)(4-apy)2] · H2O (4-apy = 4-aminopyridine)
1999
Abstract Atmospheric CO2 fixation by aqueous solutions containing copper(II) bromide and 4-aminopyridine (4-apy) yields the first carbonatobridged copper(II) chain of formula [Cu(CO3)(4-apy)2] · H2O that exhibits an intrachain ferromagnetic coupling.
Oxidative transformation of aryls using molybdenum pentachloride.
2012
Molybdenum pentachloride combines a strong Lewis acid character with an unusually high oxidation potential creating a powerful reagent for oxidative transformations. Since the oxidative coupling reaction of aryls is induced at an extraordinarily high reaction rate, a variety of labile groups, e.g. iodo, tert-alkyl, etc., are tolerated on the aromatic core. Furthermore, the co-formed molybdenum salts can either be exploited for template effects to obtain uncommon geometries in a preferred manner, or redox-play starts after aqueous workup. Therefore MoCl(5) represents a unique and easily available reagent.
Single Molecule Spectroscopy of Oriented Recombinant Trimeric Light Harvesting Complexes of Higher Plants
2002
The bleaching dynamics of reconstituted single light-harvesting chlorophyll a/b investigated. The complexes containing one histidine6 tag per monomeric subunit were immobilised predominantly in a defined orientation with their symmetry axis perpendicular to a Ni-ion-containing surface allowing for the first time the examination of single LHCIIb in an aqueous environment. Most complexes exhibit photobleaching in one step, indicating coupling between the monomeric subunits leading to an energy transfer between adjacent subunits. Differences in bleaching behaviour between these and previous observations with single LHCIIb are discussed.
Intersystem crossing in Fe(II) coordination compounds
1994
Fe(II) spin-crossover systems can be quantitatively converted from the low-spin (LS) to the high-spin (HS) state well below the thermal transition temperature by irradiating either into the metal-ligand charge transfer or d-d absorption bands, and even in low-spin systems a transient population of the HS state can be achieved. This fact can be made use of to determine HS → LS relaxation rate constants for a wide variety of Fe(II) spin-crossover and low-spin systems. The HS → LS relaxation shows strong deviations from an Arrhenius behaviour, with nearly temperature-independent tunnelling below ∼70 K and a thermally activated process above ∼100 K. The range of more than 12 orders of magnitude…