Search results for "dynamics"
showing 10 items of 9782 documents
Theoretical Study on the Photo-Oxidation and Photoreduction of an Azetidine Derivative as a Model of DNA Repair
2021
Photocycloreversion plays a central role in the study of the repair of DNA lesions, reverting them into the original pyrimidine nucleobases. Particularly, among the proposed mechanisms for the repair of DNA (6-4) photoproducts by photolyases, it has been suggested that it takes place through an intermediate characterized by a four-membered heterocyclic oxetane or azetidine ring, whose opening requires the reduction of the fused nucleobases. The specific role of this electron transfer step and its impact on the ring opening energetics remain to be understood. These processes are studied herein by means of quantum-chemical calculations on the two azetidine stereoisomers obtained from photocyc…
Thermodynamic parameters of the interaction between Co(II) bovine carbonic anhydrase and anionic inhibitors
1992
The pH dependence of the apparent affinity constants of perchlorate for cobalt(II)bovine carbonic anhydrase II has been measured by electronic absorption spectroscopy. The obtained data have been analyzed in terms of the ionization of two acidic groups of CoBCAII, and the affinity of perchlorate for the two water-containing species of the enzyme have been estimated. Furthermore, the affinity constants of nitrate, perchlorate, and azide for CoBCAII in the temperature range 5 degrees C-30 degrees C have been determined by spectrophotometric titrations at pH 7. The affinity constants for these ligands decrease with increasing temperatures. The temperature dependence of binding was used to esti…
Water Structure Recovery in Chaotropic Anion Recognition: High-Affinity Binding of Dodecaborate Clusters to γ-Cyclodextrin
2015
Dodecaborate anions of the type B12X12(2-) and B12X11Y(2-) (X=H, Cl, Br, I and Y=OH, SH, NH3(+), NR3(+)) form strong (K(a) up to 10(6) L mol(-1), for B12Br12(2-)) inclusion complexes with γ-cyclodextrin (γ-CD). The micromolar affinities reached are the highest known for this native CD. The complexation exhibits highly negative enthalpies (up to -25 kcal mol(-1)) and entropies (TΔS up to -18.4 kcal mol(-1), both for B12I12(2-)), which position these guests at the bottom end of the well-known enthalpy-entropy correlation for CDs. The high driving force can be traced back to a chaotropic effect, according to which chaotropic anions have an intrinsic affinity to hydrophobic cavities in aqueous …
Liquid structure of a water-in-salt electrolyte with a remarkably asymmetric anion
2021
Water-in-salt systems, i.e., super-concentrated aqueous electrolytes, such as lithium bis(trifluoromethanesulfonyl)imide (21 mol/kgwater), have been recently discovered to exhibit unexpectedly large electrochemical windows and high lithium transference numbers, thus paving the way to safe and sustainable charge storage devices. The peculiar transport features in these electrolytes are influenced by their intrinsically nanoseparated morphology, stemming from the anion hydrophobic nature and manifesting as nanosegregation between anions and water domains. The underlying mechanism behind this structure-dynamics correlation is, however, still a matter of strong debate. Here, we enhance the apol…
Micro magnetofluidics: droplet manipulation of double emulsions based on paramagnetic ionic liquids
2013
The ability to control and manipulate discrete fluid droplets by magnetic fields offers new opportunities in microfluidics. A surfactant-free and easy to realize technique for the continuous generation of double emulsion droplets, composed of an organic solvent and a paramagnetic ionic liquid, is applied. The inner phase of the emulsion droplet consists of imidazolium-based ionic liquids with either iron, manganese, nickel or dysprosium containing anions which provide paramagnetic behaviour. The double emulsion droplets are dispersed in a continuous phase of FC-40. All substances - the organic phase, the paramagnetic ionic liquid and the continuous phase -are immiscible. The magnetic proper…
Borate-driven gatelike scaffolding using mesoporous materials functionalised with saccharides.
2009
We report the development of an MCM-41 mesoporous support that is functionalised with saccharides at the pore outlets and contains the dye [Ru(bipy)(3)](2+) in the pores (solid S1; bipy = 2,2'-bipyridyl). For this hybrid system, the inhibition of mass transport of the dye from the pore voids to the bulk solution in the presence of borate is demonstrated in water at neutral pH. The formation of the corresponding boroester derivative is related to the selective reaction of borate with the appended saccharides. This control is selective and only anion borate, among several anions and cations, can act as a molecular tap and inhibit the delivery of the entrapped guest. Additionally, the S1-borat…
Dimensionless Analysis Of Slurry Photocatalytic Reactors Using Two-Flux And Six-Flux Radiation Absorption-Scattering Models
2007
Photocatalytic oxidation (PCO) over titanium dioxide (TiO2) is a "green" sustainable process for the treatment and purification of water and wastewater. However,the application of PCO for wastewater treatment on an industrial scale is currently hindered by a lack of simple mathematical models that can be readily applied to reactor design. Current models are either too simplistic or too rigorous to be useful in photocatalytic reactor design, scale-up, and optimization. In this paper a simple mathematical model is presented for slurry, annular, photocatalytic reactors that still retains the essential elements of a rigorous approach while providing simple solutions. The model extends the appli…
Exact non-Markovian dynamics of Gaussian quantum channels: Finite-time and asymptotic regimes
2018
We investigate the Markovian and non-Markovian dynamics of Gaussian quantum channels, exploiting a recently introduced necessary and sufficient criterion and the ensuing measure of non-Markovianity based on the violation of the divisibility property of the dynamical map. We compare the paradigmatic instances of Quantum Brownian motion (QBM) and Pure Damping (PD) channels, and for the former we find that the exact dynamical evolution is always non-Markovian in the finite-time as well as in the asymptotic regimes, for any nonvanishing value of the non-Markovianity parameter. If one resorts to the rotating wave approximated (RWA) form of the QBM, that neglects the anomalous diffusion contribut…
Fractional-order constitutive equations in mechanics and thermodynamics
2019
This chapter is devoted to the application of fractional calculus in mechanics of materials and thermodynamics. The use of fractional calculus in mechanics is related to the definition of fractional-order constitutive equations leading to the class of fractional hereditariness. In this regard, a brief description of the classical rheological models of material hereditariness and a comparison with the fractional elements are reported. It is shown that a rheological hierarchy corresponding to the fractional order stress-strain relation may be defined. Such a model provides a multi-scale mechanical picture of the power-law hereditariness and it leads toward an unique definition of material fre…
Extraordinary tuning of a nanocavity by a near-field probe
2011
Abstract We report here an experimental observation of an extraordinary near-field interaction between a local probe and a small-volume solid-state nanocavity. We directly compare the normally observed near-field interaction regime driven by the perturbation theory and then report the extraordinary interaction regime. Subsequently, we show that the cavity can take up to 2 min to recover from this interaction after removing the probe and that leads to an extraordinary blue-shift of the cavity resonance wavelength (∼15 nm) which depends on the probe motion above the cavity and not the position. The reasons for this effect are not fully understood yet but we try to give some explanations.