Search results for " coupling"

Linking Electrostatic Effects and Protein Motions in Enzymatic Catalysis. A Theoretical Analysis of Catechol O-Methyltransferase

2014

The role of protein motions in enzymatic catalysis is the subject of a hot scientific debate. We here propose the use of an explicit solvent coordinate to analyze the impact of environmental motions during the reaction process. The example analyzed here is the reaction catalyzed by catechol O-methyltransferase, a methyl transfer reaction from S-adenosylmethionine (SAM) to the nucleophilic oxygen atom of catecholate. This reaction proceeds from a charged reactant to a neutral product, and then a large electrostatic coupling with the environment could be expected. By means of a two-dimensional free energy surface, we show that a large fraction of the environmental motions needed to attain the…

Powerful Fluoroalkoxy Molybdenum(V) Reagent for Selective Oxidative Arene Coupling Reaction

2013

We introduce the novel fluoroalkoxy molybdenum(V) reagent 1 which has superior reactivity and selectivity in comparison to MoCl5 or the MoCl5 /TiCl4 reagent mixture in the oxidative coupling reactions of aryls. Common side reactions, such as chlorination and/or oligomer formation, are drastically diminished creating a powerful and useful reagent for oxidative coupling. Theoretical treatment of the reagent interaction with 1,2-dimethoxybenzene-type substrates indicates an inner-sphere electron transfer followed by a radical cationic reaction pathway for the oxidative-coupling process. EPR spectroscopic and electrochemical studies, X-ray analyses, computational investigations, and the experim…

Output Field-Quadrature Measurements and Squeezing in Ultrastrong Cavity-QED

2015

We study the squeezing of output quadratures of an electro-magnetic field escaping from a resonator coupled to a general quantum system with arbitrary interaction strengths. The generalized theoretical analysis of output squeezing proposed here is valid for all the interaction regimes of cavity-quantum electrodynamics: from the weak to the strong, ultrastrong, and deep coupling regimes. For coupling rates comparable or larger then the cavity resonance frequency, the standard input–output theory for optical cavities fails to calculate the variance of output field-quadratures and predicts a non-negligible amount of output squeezing, even if the system is in its ground state. Here we show that…

Vibronic Relaxation Pathways in Molecular Spin Qubit Na9[Ho(W5O18)2]·35H2O under Pressure

2023

In order to explore how spectral sparsity and vibronic decoherence pathways can be controlled in a model qubit system with atomic clock transitions, we combined diamond anvil cell techniques with synchrotron-based far infrared spectroscopy and first-principles calculations to reveal the vibrational response of Na9[Ho(W5O18)2]·35H2O under compression. Because the hole in the phonon density of states acts to reduce the overlap between the phonons and f manifold excitations in this system, we postulated that pressure might move the HoO4 rocking, bending, and asymmetric stretching modes that couple with the MJ = ±5, ±2, and ±7 levels out of resonance, reducing their …

Construction of green nanostructured heterogeneous catalysts via non-covalent surface decoration of multi-walled carbon nanotubes with Pd(II) complex…

2017

Abstract Green nanostructured heterogeneous catalysts were prepared via a bottom-up strategy. Designed ligands were synthesized joining covalently an electrondeficient pyrimidine residue and a scorpiand azamacrocycle. The desired molecular properties were easily transferred to nanostructured materials in two steps: first, exploiting their spontaneous chemisorption onto multi-walled carbon nanotubes (MWCNTs) via the pyrimidinic moiety in water at room temperature, then, taking advantage of the easy coordination of Pd(II) to the azamacrocycle in the same conditions. An evenly distribution of catalytic centres was obtained on the MWCNTs surface. Catalytic properties of these materials were ass…

Inside Cover: Synthesis and Characterization of Carbazole-Linked Porphyrin Tweezers (Chem. Eur. J. 34/2015)

2015

Alkyloxy modified pyrene fluorophores with tunable photophysical and crystalline properties

2019

Novel alkyloxy modified 2,7-di-tert-butyl-4,5,9,10-tetra(arylethynyl)pyrenes were prepared through a straightforward Sonogashira coupling approach. Optical properties such as quantum yields and absorption/emission spectra of the fluorophores were investigated by UV/Vis and fluorescence measurements. Aggregation induced excimer formation of the chromophores in polar solvents and in the solid state was proved by the presence of a characteristic bathochromically shifted emission band and a decrease of the emission capability. These results strongly indicate the unexpected observation that the excimer formation of adjacent pyrene rings is not prevented by the introduction of bulky tert-butyl su…

Unique direct synthesis of cyanide-bridged Fe2Cu2 molecular squares by destruction of sodium nitroprusside

2009

Abstract The one-pot reaction of copper powder, sodium nitroprusside, ammonium thiocyanate and 2,2′-bipyridine (bpy) in acetonitrile solution at ambient conditions of air and water yields the novel heterometallic [Fe2Cu2(bpy)6(μ-CN)4(NCS)2]2[Fe(CN)5(NO)](NCS)2·5H2O complex 1, which has been structurally and magnetically characterized. The most prominent feature of this complex is the unique tetranuclear Fe 2 II Cu 2 II squares comprised [Cu(bpy)NCS]+ and [Fe(bpy)2]2+ corners with CN edges. The Cu⋯Cu and Fe⋯Fe separations are ∼6.72 and ∼7.73 A, respectively. The variable-temperature magnetic susceptibility study revealed that a very weak antiferromagnetic coupling is active between Cu(II) ce…

SBA-15/POSS-Imidazolium Hybrid as Catalytic Nanoreactor

2019

Supported imidazolium modified polyhedral oligomeric silsesquioxanes (POSS) on SBA-15 have been used as platform for Pd(II) species. The so-obtained material was firstly characterized by means of TGA, solid state NMR, TEM, XPS, SAXS, porosimetry and ICP-OES and it was successfully tested as pre-catalyst in C−C cross couplings, namely Suzuki-Miyaura and Heck reactions. In both cases, the solid proved to be highly efficient and easily recoverable from the reaction mixture. The recyclability was verified for up to seven cycles without showing any activity decrease. Interestingly, only Pd(II) was detected in the reused catalyst in the Heck reaction. Therefore, the versatility of the material w…

A dihydrogen arsenate-mediated supramolecular network: crystal structure and magnetic properties of {[(bipy)Cu(μ-H2AsO4)(H2AsO4)]2}n

2002

Treatment of an aqueous suspension of Cu(OH)2 and 2,2′-bipyridine (bipy) with either Na2HAsO4·7H2O (1∶1∶2) or As2O5 (1∶1∶1) yields single crystals of {[(bipy)Cu(μ-H2AsO4)(H2AsO4)]2}n, 1, on standing. The solid-state structure of 1 consists of a three dimensional supramolecular network, supported by a combination of coordination covalent, hydrogen bonding and face-to-face π–π interactions. Variable temperature magnetic susceptibility measurements reveal very weak antiferromagnetic coupling between Cu(II) centres across the dihydrogen arsenate bridges (J = −0.58 cm−1).