Lyngrouse4728

The relative Fisher information can also simultaneously determine electrophilicity and nucleophilicity, and effectively describe helical structures with different homochiral and heterochiral propensities. As integral parts of the information-theoretic approach, these newly introduced quantities will provide us with more analytical tools toward the long-term goal of crafting a chemical reactivity theory in the density-based language.Triplet-triplet annihilation (TTA)-assisted photon upconversion (TTA-UC) in three dyads (DPA-Cn-DPA), comprised of two diphenylanthracene (DPA) moieties connected by nonconjugated C1, C2, and C3 linkages (Cn), has been investigated. The performance of these dyads as energy acceptors in the presence of the energy donor platinum octaethylporphyrin are characterized by longer triplet lifetimes (τT) and different TTA rate constants than those of the parent DPA. The larger τT of the linked systems, caused by "intramolecular energy hopping" in the triplet dyad 3DPA*-Cn-DPA, results in a low threshold intensity, a key characteristic of efficient TTA-UC.A new stable and functional polyzwitterion poly[1-(carboxymethyl)-4-methacrylamidopyridin-1-ium] was synthesized. The zwitterionic polymer shows its isoelectric point at a pH of 4.2, bidirectional pH responsiveness, and formation of dendritic fractal self-aggregated structures. Using this as a common intermediate, a simple, direct, and scalable single-step protocol was established to introduce various elementary anions like NO3-, HSO4-, H2PO4-, F-, Cl-, Br-, I-, CH3COO-, and HCOO- in their salt forms by reaction with the corresponding acids. FESEM studies on cross-linked polymeric hydrogels established the macroporous nature of these materials with their pore size in the range of 10-15 μm. Bidirectional swelling behavior was observed in these hydrogels from gel swelling kinetics and pH studies. Anion release studies in deionized water and buffer solutions showed ∼82 and ∼95% cumulative release for nitrate and phosphate anions, respectively, in 72 h. TH5427 NUDIX inhibitor Our studies suggest that multifunctional polyzwitterionic gels are promising intermediates in the fixation and release of anions like nitrate and phosphate with potential applications in agriculture and healthcare.We present a weighted-graph-theoretic approach to adaptively compute contributions from many-body approximations for smooth and accurate post-Hartree-Fock (pHF) ab initio molecular dynamics (AIMD) of highly fluxional chemical systems. This approach is ONIOM-like, where the full system is treated at a computationally feasible quality of treatment (density functional theory (DFT) for the size of systems considered in this publication), which is then improved through a perturbative correction that captures local many-body interactions up to a certain order within a higher level of theory (post-Hartree-Fock in this publication) described through graph-theoretic techniques. Due to the fluxional and dynamical nature of the systems studied here, these graphical representations evolve during dynamics. As a result, energetic "hops" appear as the graphical representation deforms with the evolution of the chemical and physical properties of the system. In this paper, we introduce dynamically weighted, linear combinations of graphs, where the transition between graphical representations is smoothly achieved by considering a range of neighboring graphical representations at a given instant during dynamics. We compare these trajectories with those obtained from a set of trajectories where the range of local many-body interactions considered is increased, sometimes to the maximum available limit, which yields conservative trajectories as the order of interactions is increased. The weighted-graph approach presents improved dynamics trajectories while only using lower-order many-body interaction terms. The methods are compared by computing dynamical properties through time-correlation functions and structural distribution functions. In all cases, the weighted-graph approach provides accurate results at a lower cost.The gas-phase acidity and proton affinity (PA) of 5-halouracils (5-fluorouracil, 5-chlorouracil, 5-bromouracil, and 5-iodouracil) have been examined using both theoretical and experimental methods. This work represents a comprehensive study of the thermochemical properties of these nucleobases. Other than 5-fluorouracil acidity, the intrinsic acidity and PA of these halouracils have not been heretofore measured; these new experimental data provide a benchmark for the computational values. Furthermore, we examine these 5-halouracils in the context of the enzyme thymine DNA glycosylase (TDG), which is an enzyme that protects the genome by cleaving these substrates from DNA. Our gas-phase results are compared and contrasted to TDG excision rates to afford insights into the TDG mechanism.In hydrogen production, the anodic oxygen evolution reaction (OER) limits the energy conversion efficiency and also impacts stability in proton-exchange membrane water electrolyzers. Widely used Ir-based catalysts suffer from insufficient activity, while more active Ru-based catalysts tend to dissolve under OER conditions. This has been associated with the participation of lattice oxygen (lattice oxygen oxidation mechanism (LOM)), which may lead to the collapse of the crystal structure and accelerate the leaching of active Ru species, leading to low operating stability. Here we develop Sr-Ru-Ir ternary oxide electrocatalysts that achieve high OER activity and stability in acidic electrolyte. The catalysts achieve an overpotential of 190 mV at 10 mA cm-2 and the overpotential remains below 225 mV following 1,500 h of operation. X-ray absorption spectroscopy and 18O isotope-labeled online mass spectroscopy studies reveal that the participation of lattice oxygen during OER was suppressed by interactions in the Ru-O-Ir local structure, offering a picture of how stability was improved. The electronic structure of active Ru sites was modulated by Sr and Ir, optimizing the binding energetics of OER oxo-intermediates.Recently, Ni and Ni-Cu nanoparticle-based inks have gained considerable research interest because of their high corrosion resistance as conductors in electronic devices. However, reported inks based on Cu-Ni nanoparticles need to be sintered at high temperatures above 300 °C to obtain electrodes with high conductivity on the order of 10-5 Ω·cm. This study proposes a new conductive Cu-Ni-based hybrid ink that could be sintered at only 150-180 °C for producing Cu-Ni electrodes with low electrical resistance, high oxidation resistance, and flexibility. The hybrid ink contains Cu flakes and a complex of nickel formate and 1-amino-2-propanol (NiF-AmIP complex). At 150-180 °C, the Cu flakes catalyze the self-reduction of the NiF-AmIP complex, and Cu-Ni electrodes with high conductivity (on the order of 10-5 Ω·cm) are formed on flexible polymer substrates at temperatures exceeding 150 °C. Analysis indicates that metallic Ni was decorated on the Cu flakes (especially on the edge) to improve the electrode's conductivity, oxidation resistance, and flexibility by forming bridging interconnections between the Cu flakes.