Lakekromann8376

Regarding ionic conductivities, a relative maximum was observed at 40 °C for a mesopore diameter of 10 nm for the AIL with 0.5 M lithium, while it was not clearly visible for the PIL. These differences are discussed in view of the charge balance at the interface between silanols and ILs the presence of a PIL, contrary to an AIL, is expected to modify the acidity of the silica. Raman data showed that the coordination number of lithium by TFSI is reduced upon AIL confinement, although this was not observed for PILs. At last, this work highlights the impact of the acidity of a PIL on the chemistry occurring at the interface of the host network within ionogels.Water oxidation catalysts (WOCs) create electrons that allow generating H2 from water and sunlight, a promising process for the production of clean energy. The mechanism of water oxidation mediated by Ru(2,2'-bipyridine-6,6'-diphosphonato)(4-picoline)2 has been studied computationally to comprehend the results obtained in the experiments performed by the Concepcion and Grotjahn groups. Our study was performed at pH = 8 and 1. At pH = 8, the phosphonates are fully deprotonated and the catalysis, which is shown to be more energetically costly than that of the dicarboxylato Ru catalyst counterpart, takes place through a mechanism that involves a bimolecular interaction between two metal-oxo units (I2M). At pH = 1, only one of the phosphonates of the catalyst can deprotonate. After testing all possible pathways and comparing with experimental data, we conclude that the catalysis proceeds neither through a water nucleophilic attack nor via I2M, but rather we hypothesize that the rate-determining step involves both the catalyst and the ceric ammonium nitrate.Platinum-based antineoplastic agents play a major role in the treatment of numerous types of cancer. A new bulky, lipophilic, and chiral ligand based on 1,2-diaminodiamantane in both of its enantiomeric forms was employed for the preparation of new platinum(ii) complexes with chloride and oxalate ligands. The dichloride complexes have a higher solubility and were evaluated as anti-proliferation agents for human ovarian cancer cell lines A2780 and cisplatin-resistant A2780cis. Its R,R-enantiomer showed increased efficacy compared to cisplatin for both cancer cell lines. A chromatographic approach was used to estimate the solvent partition coefficient of the dichloride complex. The binding of diamondoid-based platinum complexes to nucleotides was tested for both enantiomers with guanosine monophosphate (GMP) and deoxyguanosine monophosphate (dGMP) and occurs at a similar or faster rate for both isomers compared to cisplatin despite greatly increased steric demand. These findings highlight the potential in 1,2-diaminodiamantane as a viable pharmacophore.A class of unimolecular channels formed by pillararene-gramicidin hybrid molecules are presented. The charge status of the peptide domain in these channels has a significant impact on their ion transport and antimicrobial activity. These channels exhibited different membrane-association abilities between microbial cells and mammalian cells. One of the channels displayed a higher antimicrobial activity towards S. aureus (IC50 = 0.55 μM) and negligible hemolytic toxicity, showing potential to serve as a systemic antibiotic.Regulation of the catalytic activity of enzymes immobilized on carbon nanotube electrodes was achieved by changing their local pH environment using electrochemical reactions. Reduction of oxygen increased the interfacial pH while oxidation of ascorbate decreased it, thus allowing changing rates of enzymatic reactions of electrode-immobilized amyloglucosidase and trypsin enzymes over a wide activity range.The normal boiling point (NBP) is a fundamental property of liquids and marks the intersection of the Gibbs energies of the liquid and the gas-phase at ambient pressure. This work provides the first comprehensive demonstration of the calculation of boiling points of atomic liquids through first-principles molecular-dynamics simulations. To this end, thermodynamic integration (TDI) and perturbation theory (TPT) are combined with a density-functional theory (DFT) Hamiltonian, which provides absolute Gibbs energies, internal energies, and entropies of atomic liquids with an accuracy of a few meV/atom. Linear extrapolation to the intersection with the Gibbs energy of a non-interacting gas-phase eventually pins-down the NBPs. Lomeguatrib While these direct results can already be quite accurate, they are susceptible to a systematic over or underbinding of the employed density functional. It is shown how this dependency can be strongly reduced and the robustness of the method increased through a simple linear correction termed λ-scaling. Eventually, by carefully tuning of the technical parameters of the approach, the walltime per element is reduced from weeks to about a day (10-20k core-hours), enabling extensive testing for B, Al, Na, K, Ca, Sr, Ba, Mn, Cu, Xe, and Hg. This comprehensive benchmark demonstrates the excellent performance and robustness of the approach with a mean absolute deviation (MAD) of less than 2% from experimental NBPs and very similar accuracy for liquid entropies (MAD 2.3 J (mol K)-1, 2% relative). In some cases, the uncertainties in the predictions are several times smaller than the variation between literature values, allowing us to clear out long-standing ambiguities in the NBPs of B and Ba.Studies on the vibrational spectra of various ammonium-centered clusters under different solvation environments have raised interest over the last thirty years. The gas-phase infrared photodissociation spectroscopy (IRPD) experiments showed that these NH4+Xn clusters exhibit rich spectral features from 2600 to 3400 cm-1. In this work, we have simulated the vibrational spectra and analyzed couplings among vibrational quantum states in the aforementioned frequency range using ab initio anharmonic algorithms. Originating from the anharmonic couplings between NH stretching fundamentals and bending overtones, Fermi resonance (FR) is a common feature in these spectra, and its extent is determined by the magnitude of couplings and the energy matching conditions between relevant states, which are governed by the proton affinity, number, and bonding configuration of the solvation species. For weakly bound clusters consisting of rare gas atoms, FR is insignificant but not negligible; for strongly bound clusters, such as ammonium-water clusters, the hydrogen-bonded NH stretching fundamentals redshift and reach a better resonance condition, and thus light up the bending overtones as prominent FR bands.