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This functional form also results by implementing a simple mechanistic explanation via the cooperative free volume (CFV) rate model, which assumes that dynamic relaxation is both thermally activated and that it requires molecular segmental cooperativity. With the degree of the latter, and thus the activation energy, being determined by the availability of free volume, the new route we demonstrate here for determination of Vfree expands the potential for understanding and predicting local dynamic relaxation in glass-forming materials.[RuCl2(p-cymene)]2/AgNO3-catalyzed intramolecular double hydrofunctionalization of internal alkynes having nitrogen and oxygen nucleophilic groups at appropriate positions provided a series of spirocyclic hemiaminal ether derivatives in good to excellent yields. The product spiro-hemiaminal ethers underwent Lewis acid-mediated chemoselective cleavage, and in situ-generated iminium/oxocarbenium ions could be trapped with nucleophiles to afford a range of nitrogen and oxygen heterocycles.The plasmonic properties of carboxylated gold nanostars distributed on amidoximated polyacrylonitrile (AO PAN) electrospun polymer films scale with surface-enhanced Raman scattering (SERS) intensities for coordinated uranium(VI) oxide (uranyl) species. This two-step plasmonic sensor first isolates uranyl from solution using functionalized polymers; then carboxylated gold nanostars are subsequently deposited for SERS. Spatially resolved localized surface plasmon resonance (LSPR) and SERS facilitate correlated nanostar optical density and uranyl quantification. To reduce sampling bias, gold nanostars are deposited in an inverted drop-coating geometry and measurements are conducted inside resulting nanoparticle coffee rings that form on the polymer substrates. This approach naturally preserves the plasmonic properties of gold nanostars while reducing the deposition of nanoparticle aggregates in active sensing regions, thereby maximizing both the accuracy and the precision of SERS measurements. Several advances aased sensor for uranyl.Previous structural and electron paramagnetic resonance (EPR) results are combined with new theoretical chemistry calculations on a series of copper-containing Tutton salts to investigate the influence of the host crystal electric field on the copper unpaired wave function and dynamics. Density functional theory (DFT) computations were performed on clusters centered on the host structure metal-hexahydrate complex to provide a model of atomic charges, which in turn were used to determine the electric fields and potentials at points along coordinate bonds of the complex. A significantly higher electric potential at the metal-water bonds is found for those Tutton salt systems having a greater copper EPR temperature dependency. Such a dependency has long been interpreted to arise from the averaging of tensor coupling parameters of the copper-hexahydrate complex due to a dynamic Jahn-Teller effect. However, the correlation found here reinforces a recent view that the coupling of the copper complex to the surrounding crystal lattice is the major determinant of these dynamics. The lattice potentials lack any significant temperature dependency and thus do not appear to be responsible for changes in the EPR patterns. A trend also appears between unbalanced spin in the compressed d-orbital lobe of the unpaired wave function and the magnitude of the potential. Hence, the lattice field is an important factor in defining both the electronic and dynamic characteristics of the copper-hexahydrate complex in these systems.Trace detection based on surface-enhanced Raman scattering (SERS) has attracted considerable attention, and exploiting efficient strategies to stretch the limit of detection and understanding the mechanisms on molecular level are of utmost importance. In this work, we use ionic liquids (ILs) as trace additives in a protein-TiO2 system, allowing us to obtain an exceptionally low limit of detection down to 10-9 M. The enhancement factors (EFs) were determined to 2.30 × 104, 6.17 × 104, and 1.19 × 105, for the three systems one without ILs, one with ILs in solutions, and one with ILs immobilized on the TiO2 substrate, respectively, corresponding to the molecular forces of 1.65, 1.32, and 1.16 nN quantified by the atomic force microscopy. The dissociation and following hydration of ILs, occurring in the SERS system, weakened the molecular forces but instead improved the electron transfer ability of ILs, which is the major contribution for the observed excellent detection. The weaker diffusion of the hydrated IL ions immobilized on the TiO2 substrate did provide a considerably greater EF value, compared to the ILs in the solution. This work clearly demonstrates the importance of the hydration of ions, causing an improved electron transfer ability of ILs and leading to an exceptional SERS performance in the field of trace detection. Our results should stimulate further development to use ILs in SERS and related applications in bioanalysis, medical diagnosis, and environmental science.We present a practical approach to treat static and dynamical correlation accurately in large multiconfigurational systems. The static correlation is taken into account by using the spin-flip approach, which is well-known for capturing static correlation accurately at low-computational expense. Unlike previous approaches to add dynamical correlation to spin-flip models which use perturbation theory or coupled-cluster theory, we explore the ability to use the on-top pair-density functional theory approaches recently developed by Gagliardi and co-workers (J. Selleckchem TPEN Comput. Theor. Chem., 2014, 10, 3669). External relaxations are performed in the spin-flip calculations through a restricted active space framework for which a truncation scheme for the orbitals used in the external excitation is presented. The performance of the approach is demonstrated by computing energy gaps between ground and excited states for diradicals, triradicals, and linear polyacene chains ranging from naphthalene to dodecacene. Accurate results are obtained using the new approach for these challenging open-shell molecular systems.
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