Montoyaroy0684

One-dimensional zigzag cyanido-bridged coordination polymers have been prepared as a result of self-assembly of lanthanide(III) ions with octacyanidotungstate(V) anions in the presence of N,N-dimethylacetamide (dma). All compounds crystallized in noncentrosymmetric space group P21 with a molecular formula of [LnIII(dma)5][WV(CN)8] [Ln = Gd (1), Tb (2), Dy (3), Ho (4), Er (5), Tm (6), Yb (7), Lu (8), or Y (9)]. Magnetic studies revealed weak antiferromagnetic interactions through LnIII-NC-WV bridges and the formation of ferrimagnetically coupled chains at very low temperatures. Moreover, temperature dependencies of magnetic susceptibilities were fitted using the crystal field parameters for Ln(III) ions, determined by the ab initio calculations, yielding magnetic coupling constants in the range of -1 to -5 cm-1. The wide optical transparency of 1-9 has been determined using solid state absorption spectroscopy. Samples exhibited second harmonic (SH) generation properties with SH susceptibilities ranging from 4.7 × 10-12 to 9.4 × 10-11 esu due to the presence of nonlinear optical susceptibility tensor elements (χijk) χzxx, χzyy, χzzz, χzxy, χyyz, χyzx, χxyz, and χxzx, corresponding to space group P21. The determined values were also compared with the results of theoretical calculations and previous reports, indicating a potential relationship between the type of lanthanide ion and the SH intensity.Groundwater contamination and transport of viruses and bacteria in aquifers are a major concern worldwide. To ascertain the ability of these aquifers to remove pathogens, tracer tests with microbial surrogates are carried out. These tests are laborious and may require special permits, and therefore, column tests are often done instead. Unfortunately, results from column tests tend to grossly overestimate removal rates when compared to the field scale, which can lead to an underestimation of groundwater contamination risks. Scale is an important consideration when examining pathogen transport through porous media, as pathogen removal is rarely a linear process. In this study, field tests were carried out with endospores of Bacillus subtilis and coliphage phiX174 over a distance of 25 m in an alluvial gravel aquifer near Vienna, Austria. The sandy gravel material from the field site was also used in column tests with the same tracers. Both attachment-detachment and colloid filtration theory were used to model these tests, as well as log-removal rates per meter. The results show that the spatial removal rate (log/m) is approximately 2 orders of magnitude higher on the column scale, when compared to the field. A comparison with the literature showed a correlation between the heterogeneity of the porous media and the difference in removal rates between the column and field scale.The negative ion photoelectron spectroscopy (NIPES) has been proven to be a powerful technique to reveal the electronic structures and spectroscopic properties of various cluster anions/radicals with very high precision. However, direct comparisons of the theoretical NIPES with experimental measurements remain challenging. Particularly the nuclear vibration effect and the ionization probability are typically ignored in reproducing NIPES. In this work, the NIPES of three representative anions (NaS5-, P2N3-, and HCPN3-) with significantly different spectral features were simulated by combining the nuclear ensemble approach (NEA) and Dyson orbitals (DOs). Overall, the simulated NIPES are in good agreement with the experimentally determined ones, confirming the robustness of such a strategy. The analysis of frontier molecular orbitals (MOs) and DOs further suggests the similar mixed characters for the first ionized doublet (D0) and adjacent D1 states of NaS5- with distributions on the side sulfur atoms. And the D0 of P2N3* is confirmed as the lowest energy σ radical state; however, the D0 of HCPN3* should possess a mixture of π and σ electrons by taking into account the nuclear vibration effect. Next, the broader vibrational distribution and stronger main vibration modes of P2N3- and HCPN3- explain why the nuclear vibration possesses a more pronounced influence in reproducing their NIPES while it has little effect on NaS5-. Last, the limitations based on the double-harmonic approximation model and density of state method were also discussed, highlighting that the ionization probability and orbital relaxation effect during the ionization process should be reasonably considered.In this study, proton-irradiated tungsten targets, up to 2.6 GeV, were investigated for the purpose of the experimental cross-section measurements. Radiochemical separation methods were applied to isolate the residual long-lived alpha-emitters 148Gd, 154Dy, and 146Sm and the beta-emitters 129I and 36Cl from proton-irradiated tungsten targets. The molecular plating technique has been applied to prepare 148Gd, 154Dy, and 146Sm samples for alpha-spectrometry. Production cross-sections of 129I and 36Cl were determined by means of accelerator mass spectrometry. The results are compared with theoretical predictions, obtained with the INCL++-ABLA07 codes, showing good agreement for 36Cl and 148Gd, while a factor of 4 difference was observed for 154Dy, similar to the results obtained for tantalum targets.High-valent multimetallic-oxo/oxyl species have been implicated as intermediates in oxidative catalysis involving proton-coupled electron transfer (PCET) reactions, but the reactive nature of these oxo species has hindered the development of an in-depth understanding of their mechanisms and multimetallic character. The mechanism of C-H oxidation by previously reported RuCo3O4 cubane complexes bearing a terminal RuV-oxo ligand, with significant oxyl radical character, was investigated. The rate-determining step involves H atom abstraction (HAA) from an organic substrate to generate a Ru-OH species and a carbon-centered radical. Radical intermediates are subsequently trapped by another equivalent of the terminal oxo to afford isolable radical-trapped cubane complexes. Density functional theory (DFT) reveals a barrierless radical combination step that is more favorable than an oxygen-rebound mechanism by 12.3 kcal mol-1. This HAA reactivity to generate organic products is influenced by steric congestion and the C-H bond dissociation energy of the substrate. Tuning the electronic properties of the cubane (i.e., spin density localized on terminal oxo, basicity, and redox potential) by varying the donor ability of ligands at the Co sites modulates C-H activations by the RuV-oxo fragment and enables construction of structure-activity relationships. These results reveal a mechanistic pathway for C-H activation by high-valent metal-oxo species with oxyl radical character and provide insights into cooperative effects of multimetallic centers in tuning PCET reactivity.We developed hybrid liver-specific three-dimensional (3D) printed scaffolds using a solubilized native decellularized liver (DCL) matrix and silk fibroin (SF) and investigated their ability to support functional cultures of hepatic cells. Rat livers were decellularized by perfusing detergents via the portal vein, solubilized using pepsin to form DCL, and characterized. SF blended with gelatin (8% w/v) was optimized with varying percentages of DCL to obtain silk gelatin-DCL bioink (SG-DCL). Different compositions of SG-DCL were studied by rheology for optimum versatility and print fidelity. 3D printed six-layered scaffolds were fabricated using a sophisticated direct-write 3D bioprinter. Huh7 cells were cultured on the 3D printed scaffolds for 3 weeks. 3D printed SG scaffolds without DCL along with 2D films (SG and SG-DCL) and 2D culture on tissue culture Petri dish control were used for comparative studies. The DCL matrix showed the absence of cells in histology and SEM. The combined SG-DCL ink at all of the 3D SG-DCL on day 7 of culture. Hence, the SG-DCL 3D printed scaffolds provide a conducive microenvironment for elevating differentiation and functions of hepatic cells possibly through an involvement of the Wnt/β-catenin signaling pathway.Controlling and tuning surface properties of a catalyst have always been a prime challenge for efficient hydrogen production via water splitting. Here, we report a facile method for tuning both charger transfer and sorption-desorption properties of NiFe layered double hydroxide (LDH) by intercalating a conductive polymer of polypyrrole (ppy) via an interlayer confined polymerization synthesis (ICPS) process. Ex situ characterizations and in situ electrochemical quartz-crystal microbalance with dissipation (EQCM-D) tracking experiments showed that the intercalated ppy not only improved the charge transfer property of the resulting hybrid catalyst LDH-ppy but also made it more flexible and adaptive for quick and reversible sorption-desorption of reactants and intermediates during the oxygen evolution reaction (OER) process. Consequently, the as-prepared LDH-ppy exhibited a doubled catalytic current density over the bare LDH, as visualized by in situ scanning electrochemical microscopy (SECM) at the subnanometer scale. This work sheds light on orchestrating the charge and sorbate transfer abilities of catalysts for efficient water splitting by smartly combining inorganic and organic layers.While additives play an important role in the reactions of samarium iodide, ligand-SmI2 complexation constants are scarce. Here, VIS spectroscopy was harnessed along with NMR to determine the first complexation constant for most of the alcohols and amines used in SmI2 reactions. The second equilibrium constant was determined for selected ligands. In cases where both methods could be applied, in general, a good correlation between the equilibrium constants was obtained.Hydrogen production from the electrolysis of seawater and domestic sewage is more attractive than that from pure water, especially in regions where freshwater resources are scarce. However, under such harsh conditions, higher requirements are put forward for the catalytic activity and adaptability of a catalytic electrode. Herein, we advance an ultrasimple dipping-and-heating method to engineer the surface of Ni foam (NF) into an interface-rich FeNi oxide layer and realize an exceptional oxygen evolution reaction (OER) performance. It only requires overpotentials of 182 and 267 mV to achieve current densities of 10 and 1000 mA cm-2 in 1 M KOH, respectively, which are significantly lower than those of the recently reported catalysts. The as-prepared FNE300||MoNi4/MoO2 electrolyzer realizes the industrial demand of 500 mA cm-2 at low voltages of ∼1.75 V for overall alkaline natural seawater and domestic sewage electrolysis, as well as satisfactory stability. 1-PHENYL-2-THIOUREA molecular weight Density functional theory (DFT) calculations indicate that modifying the electronic structure so as to optimize the intermediate adsorption is well achieved by constructing the interfaces between NiO and Fe2O3. The interaction of Fe with oxygen intermediates can be optimized by e--e- repulsion between Ni2+ and oxygen intermediates. This work provides a facile approach to fabricate an electrocatalyst for seawater and domestic sewage electrolysis, which is of great significance to the synergetic development of hydrogen economy and environmental science.