Together with the synthesis and experimental characterization of 14 hybrid materials containing [UO2X4]2− (X=Cl− and Br−) and organic cations, we report on novel methods for determining correlation trends in their formation enthalpy (ΔHf) and observed vibrational signatures. ΔHf values were analyzed through isothermal acid calorimetry and a Density Functional Theory+Thermodynamics (DFT+T) approach with results showing good agreement between theory and experiment. Three factors (packing efficiency, cation protonation enthalpy, and hydrogen bonding energy [ ]) were assessed as descriptors for trends in ΔHf. Results demonstrated a strong correlation between and ΔHf, highlighting the importance of hydrogen bonding networks in determining the relative stability of solid‐state hybrid materials. Lastly, we investigate how hydrogen bonding networks affect the vibrational characteristics of uranyl solid‐state materials using experimental Raman and IR spectroscopy and theoretical bond orders and find that hydrogen bonding can red‐shift U≡O stretching modes. Overall, the tightly integrated experimental and theoretical studies presented here bridge the trends in macroscopic thermodynamic energies and spectroscopic features with molecular‐level details of the geometry and electronic structure. This modeling framework forms a basis for exploring 3D hydrogen bonding as a tunable design feature in the pursuit of supramolecular materials by rational design.

Solid-state uranyl hybrid structures are often formed through unique intermolecular interactions occurring between a molecular uranyl anion and a charge-balancing cation. In this work, solid-state structures of the uranyl tetrachloride anion engaged in uranyl–cation and uranyl–hydrogen interactions were studied using density functional theory (DFT). As most first-principles methods used for systems of this type focus primarily on the molecular structure, we present an extensive benchmarking study to understand the methods needed to accurately model the geometric properties of these systems. From there, the electronic and vibrational structures of the compounds were investigated through projected density of states and phonon analysis and compared to the experiment. Lastly, we present a DFT + thermodynamics approach to calculate the formation enthalpies (ΔH f) of these systems to directly relate to experimental values. Through this methodology, we were able to accurately capture trends observed in experimental results and saw good quantitative agreement in predicted ΔH f compared to the value calculated through referencing each structure to its standard state. Overall, results from this work will be used for future combined experimental and computational studies on both uranyl and neptunyl hybrid structures to delineate how varying intermolecular interaction strengths relates to the overall values of ΔH f.

Chronic kidney disease of unknown etiology (CKDu) has been recognized as a global non-communicable health issue. There are many proposed risk factors for CKDu and the exact reason is yet to be discovered. Understanding the inhibition or manipulation of vital renal enzymes by pesticides can play a key role in understanding the link between CKDu and pesticides. Even though it is very important to take metabolites into account when investigating the relationship between CKDu and pesticides, there is a lack of insight regarding the effects of pesticide metabolites towards CKDu. In this study, a computational approach was used to study the effects of pesticide metabolites on CKDu. Further, interactions of selected pesticides and their metabolites with renal enzymes were studied using molecular docking and molecular dynamics simulation studies. It was evident that some pesticides and metabolites have affinity to bind at the active site or at regulatory sites of considered renal enzymes. Another important discovery was the potential of some metabolites to have higher binding interactions with considered renal enzymes compared to the parent pesticides. These findings raise the question of whether pesticide metabolites may be a main risk factor towards CKDu.

Together with the synthesis and experimental characterization of 14 hybrid materials containing [UO 2 X 4 ] 2À (X = Cl À and Br À ) and organic cations, we report on novel methods for determining correlation trends in their formation enthalpy (ΔH f ) and observed vibrational signatures. ΔH f values were analyzed through isothermal acid calorimetry and a Density Functional Theory + Thermodynamics (DFT + T) approach with results showing good agreement between theory and experiment. Three factors (packing efficiency, cation protonation enthalpy, and hydrogen bonding energy [ E total H;norm ]) were assessed as descriptors for trends in ΔH f . Results demonstrated a strong correlation between E total H;norm and ΔH f , highlighting the importance of hydrogen bonding networks in determining the relative stability of solid-state hybrid materials. Lastly, we investigate how hydrogen bonding networks affect the vibrational characteristics of uranyl solid-state materials using experimental Raman and IR spectroscopy and theoretical bond orders and find that hydrogen bonding can red-shift U�O stretching modes. Overall, the tightly integrated experimental and theoretical studies presented here bridge the trends in macroscopic thermodynamic energies and spectroscopic features with molecular-level details of the geometry and electronic structure. This modeling framework forms a basis for exploring 3D hydrogen bonding as a tunable design feature in the pursuit of supramolecular materials by rational design.

The novel corona virus 2019 (COVID 19) is growing at an increasing rate with high mortality. Meanwhile, the cytokine storm is the most dangerous and potentially life-threatening event related to COVID 19. Phyto-compounds found in existing Ayurveda drugs have the ability to inhibit the Interleukin 6 (IL-6R) and Interleukin 1 (IL-1R) receptors. IL-6R and IL-1R receptors involve in cytokine storm and recognition of phytochemicals with proven safety profiles could open a pathway to the development of the most effective drugs against cytokine storm. In this study, we intend to perform an in silico investigation of effective phyto compounds, which can be isolated from selected medicinal herbs to avoid cytokine storm, inhibiting the IL-6 and IL-1 receptor binding process. An extensive literature survey followed by virtual screening was carried out to identify phytochemicals with potential anti-hyper-inflammatory action. Flexible docking was conducted for validated models of IL-1R and IL-6R-α with the most promising phytochemicals at possible allosteric sites using AutoDock Vina. Molecular dynamics (MD) studies were conducted for selected protein-ligand complexes using LARMD server and conformational changes were evaluated. According to the results, taepeenin J had Gibbs energy (ΔG) of -10.85 kcal/mol towards IL-1R but had limited oral bioavailability. MD analysis revealed that taepeenin J can cause significant conformational movements in IL-1R. Nortaepeenin B showed a ΔG of -8.5 kcal/mol towards IL-6R-α with an excellent oral bioavailability. MD analysis predicted that it can cause significant conformational movements in IL-6R-α. Hence, the evaluated phytochemicals are potential candidates for further in vitro studies for the development of medicine against cytokine storm on behalf of SARS-COV-2 infected patients.