The organic linkers of UiO-66 MOFs play a role in stabilizing all of the species on potential energy surfaces. The linear scaling relationship also reveals the significant role of the UiO-66 active site in activating the carbonyl C═O of furfural, and strong relationships are observed between the activation free energy, the charge of the metal at the MOF active sites, and the complexation energies in reaction coordinates.The carbon starvation-induced protein D (CsiD) is a recently characterized iron(II)/α-ketoglutarate-dependent oxygenase that activates a glutarate molecule as substrate at the C2 position to exclusively produce (S)-2-hydroxyglutarate products. This selective hydroxylation reaction by CsiD is an important component of the lysine biodegradation pathway in Escherichia coli; however, little is known on the details and the origin of the selectivity of the reaction. So far, experimental studies failed to trap and characterize any short-lived catalytic cycle intermediates. As no computational studies have been reported on this enzyme either, we decided to investigate the chemical reaction mechanism of glutarate activation by an iron(IV)-oxo model of the CsiD enzyme. Cu-CPT22 In this work, we present a density functional theory study on a large active site cluster model of CsiD and investigate the glutarate hydroxylation pathways by a high-valent iron(IV)-oxo species leading to (S)-2-hydroxyglutarate, (R)-2-hydroxyglutarate, for pro-S C2-H hydrogen atom abstraction. Finally, the calculations show that irrespective of the position of the substrate and what C-H bond is closest to the metal center, the lowest energy pathway is for a selective pro-S C2-H hydrogen atom abstraction.Fluoxapiprolin is a new piperidinyl thiazole isoxazoline fungicide developed by Bayer Crop Science in 2012, but the sensitivity and resistance mechanism of fluoxapiprolin are unclear. In this study, the sensitivities of 130 Phytophthora capsici isolates to fluoxapiprolin were determined, and a unimodal distribution was observed with a mean EC50 value of 0.00043 μg/mL. Nine stable fluoxapiprolin-resistant mutants were obtained by fungicide adaption. The fitness of mutants was similar to or lower than that of the corresponding parental isolate. Seven heterozygous point mutations in the target protein PcORP1 were found in these mutants. These point mutations were confirmed in PsORP1 of P. sojae homologue positions using the CRISPR/Cas9 system. G770V and N835S+I877F do confer high fluoxapiprolin resistance (resistance factor, RF > 1000), and ΔN835, N767I, and N837T+S910C lead to low resistance (RF 100). In conclusion, the resistance risk of P. capsici to fluoxapiprolin is moderate, and multiple point mutations in PcORP1 could confer different resistance levels to fluoxapiprolin.The crystalline selenido germanates [Li4(H2O)16][Ge4Se10]·4.3H2O (1), [Li4(thf)12Ge4Se10] (2), and [Li2(H2O)8][MnGe4Se10] (3) (thf = THF = tetrahydrofuran) were obtained by an extraction of a glassy ternary phase of the nominal composition Li4Ge4Se10 (=Li2S·2GeSe2) with water (1) or THF (2) and slow evaporation of the solvent or by being layered with MnBr2 in H2O/MeOH (3), respectively. The compounds contain known selenido germanate anions, however, for the first time with Li+ counterions. This is especially remarkable for the prominent ∞3[MnGe4Se10]2- open-framework structure, which was reported to crystallize with (NMe4)+, Cs+, Rb+, and K+ counterions, but it has not yet been realized with the smallest alkali metal cation. Impedance spectroscopic studies on Li4Ge4Se10 classify the glassy solid as a moderate Li+ ion conductor.Producing more than one structure from the same set of metal and ligand precursors will grant structural diversity in metal-organic framework (MOF) systems. One of the biggest obstacles of getting structural diversity for the late transition metals is that the coordination mode is pretty much fixed by nature. Herein, we show that two different coordination modes to Cu(II) are possible for flexible ligands containing hydrophilic terminal groups through solvent guidance. It is demonstrated that trans,trans-muconic acid (H2muco) ligands coordinate to Cu(II) to form Cu(II) muconate MOFs having a 1D chain structure and a 2D plane structure in water-rich and DMF-rich water-DMF mixed solvent systems, respectively. It is suggested that the interaction between ligands and solvent is responsible for the selective coordination. A similar result was observed from the attempts using the fumaric acid ligand. Our results provide a new direction to obtain diverse secondary building units for the construction of diverse MOFs.Flavonoid-metal complexes possess more effective functional properties than flavonoids. However, the research of iso-orientin (Iso)-metal complex has rarely been reported. In this study, Iso-zinc complex (Iso-Zn, [Zn3(C21H14O11)2]·4H2O) had been synthesized and characterized. From the UV-vis spectra and IR spectra, the 4-carbonyl group in the C-ring of Iso was involved in the metal chelation besides A-ring and B-ring hydroxyl group. Thermal gravimetric analysis and the water contact angle test showed that Iso-Zn had higher thermal stability and better hydrophilicity than Iso, respectively. The radical scavenger and antibacterial potencies of Iso-Zn were significantly stronger than those of Iso. Furthermore, Iso-Zn showed lower erythrocytes hemolysis ratio and cytotoxicity. The present study demonstrated that Iso-Zn exhibited better water solubility, antioxidative and antibacterial activities, and lower cytotoxicity and provided a theoretical basis for expanding the utilization scope of Iso through enhancing its hydrophilicity.Understanding the properties of the unfolded state under folding conditions is of fundamental importance for gaining mechanistic insight into folding as well as misfolding reactions. Toward achieving this objective, the folding reaction of a small protein, monellin, has been resolved structurally and temporally, with the use of the multisite time-resolved FRET methodology. The present study establishes that the initial polypeptide chain collapse is not only heterogeneous but also structurally asymmetric and nonuniform. The population-averaged size for the segments spanning parts of the β-sheet decreases much more than that for the α-helix. Multisite measurements enabled specific and nonspecific components of the initial chain collapse to be discerned. The expanded and compact intermediate subensembles have the properties of a nonspecifically collapsed (hence, random-coil-like) and specifically collapsed (hence, globular) polymer, respectively. During subsequent folding, both the subensembles underwent contraction to varying extents at the four monitored segments, which was close to gradual in nature.