The „Franck-Condon” (FC) excited state is the first state created when a molecule absorbs a visible photon. Here we report Stark and visible absorption spectroscopies that interrogate the FC state of rigorously diamagnetic [M(bpy)3]2+ complexes, where bpy is 2,2′-bipyridine and M = Fe, Ru, and Os. Direct singlet-to-triplet metal-to-ligand charge transfer (MLCT) transitions are evident in the 550-750 nm region of the absorbance spectrum of [Os(bpy)3]2+, yet are poorly resolved or absent for [Ru(bpy)3]2+ and [Fe(bpy)3]2+. In the presence of a strong 0.4-0.8 MV/cm electric field, well-resolved transitions are observed for all the complexes in this same spectral region. In particular, an electroabsorption feature at 633 nm (15 800 cm-1) provides compelling evidence for the direct population of a high spin [Fe(bpy)3]2+* MLCT excited state. Group theoretical considerations and Liptay analysis of the Stark spectra revealed dramatic light-induced dipole moment changes in the range [Formula see text] = 3-9 D with the triplet transitions consistently showing shorter charge transfer distances. The finding that the spin of the initially populated FC excited state differs from that of the ground state, even with a relatively light first row transition metal, is relevant to emerging applications in energy up-conversion, dye sensitization, spintronics, photoredox catalysis, and organic light emitting diodes (OLEDs).Proteins in their native states can be represented as ensembles of conformers in dynamical equilibrium. Thermal fluctuations are responsible for transitions between these conformers. Normal modes analysis (NMA) using elastic network models (ENM) provides an efficient procedure to explore global dynamics of proteins commonly associated to conformational transitions. In the present work, we present an iterative approach to explore protein conformational spaces by introducing structural distortions according to their equilibrium dynamics at room temperature. The approach can be used either to perform unbiased explorations of conformational space or to explore guided pathways connecting two different conformations, e.g., apo and holo forms. In order to test its performance, four proteins with different magnitude of structural distortions upon ligand binding have been tested. In all cases, the conformational selection model has been confirmed and the conformational space between apo and holo forms has been encompassed. Different strategies have been tested that impact either on the efficiency to achieve a desired conformational change or to achieve a balanced exploration of the protein conformational multiplicity.Eight new neo-clerodane diterpenoids (1-8) were acquired from the aerial parts of Ajuga pantantha. Spectroscopic data analysis permitted the definition of their structures, and experimental and calculated electronic circular dichroism data were used to define their absolute configurations. Compounds 2 and 4-8 were found to have NO inhibitory effects with IC50 values of 20.2, 45.5, 34.0, 27.0, 45.0, and 25.8 μM, respectively. The more potent compounds 2, 6, and 8 were analyzed to establish their anti-inflammatory mechanism, including regulation of the expression of inducible nitric oxide synthase (iNOS) and cyclooxygenase-2 (COX-2) proteins as well as their binding interactions with the two proteins.Spectrometric methods with rapid biomarker detection capacity through untargeted metabolomics are becoming essential in the clinical cancer research. Liquid chromatography-mass spectrometry (LC-MS) is a rapidly developing metabolomic-based biomarker technique due to its high sensitivity, reproducibility, and separation efficiency. However, its translation to clinical diagnostics is often limited due to long data acquisition times (∼20 min/sample) and laborious sample extraction procedures when employed for large-scale metabolomics studies. Here, we developed a segmented flow approach coupled with high-resolution mass spectrometry (SF-HRMS) for untargeted metabolomics, which has the capability to acquire data in less than 1.5 min/sample with robustness and reproducibility relative to LC-HRMS. The SF-HRMS results demonstrate the capability for screening metabolite-based urinary biomarkers associated with prostate cancer (PCa). The study shows that SF-HRMS-based global metabolomics has the potential to evolve into a rapid biomarker screening tool for clinical research.Substituent effects play critical roles in both modulating reaction chemistry and supramolecular self-assembly processes. Using substituted terephthalate dianions (p-phthalic acid dianions; PTADAs), the effect of varying the type, number, and position of the substituents was explored in terms of their ability to regulate the inherent anion complexation features of a tetracationic macrocycle, cyclo[2](2,6-di(1H-imidazol-1-yl)pyridine)[2](1,4-dimethylenebenzene) (referred to as the Texas-sized molecular box; 14+), in the form of its tetrakis-PF6- salt in DMSO. Several of the tested substituents, including 2-OH, 2,5-di(OH), 2,5-di(NH2), 2,5-di(Me), 2,5-di(Cl), 2,5-di(Br), and 2,5-di(I), were found to promote pseudorotaxane formation in contrast to what was seen for the parent PTADA system. Other derivatives of PTADA, including those with 2,3-di(OH), 2,6-di(OH), 2,5-di(OMe), 2,3,5,6-tetra(Cl), and 2,3,5,6-tetra(F) substituents, led only to so-called outside binding, where the anion interacts with 14+ on the outsi the first interaction sphere.Quantitative predictions of reaction properties, such as activation energy, have been limited due to a lack of available training data. Such predictions would be useful for computer-assisted reaction mechanism generation and organic synthesis planning. We develop a template-free deep learning model to predict the activation energy given reactant and product graphs and train the model on a new, diverse data set of gas-phase quantum chemistry reactions. We demonstrate that our model achieves accurate predictions and agrees with an intuitive understanding of chemical reactivity. With the continued generation of quantitative chemical reaction data and the development of methods that leverage such data, we expect many more methods for reactivity prediction to become available in the near future.Lead-free tin halide perovskite solar cells (PSCs) have attracted great attention because of their low toxicity, ideal band gap, and high carrier mobilities. However, the efficiency and reproducibility of tin halide PSCs has been limited because of the facile oxidation of Sn2+ to Sn4+. Herein, liquid formic acid (LFA) was introduced as a reducing solvent in the FASnI3 (FA formamidinium) perovskite precursor solution. Unlike solid reducing additives, the LFA solvent is volatile, so no residual LFA remained in the FASnI3 perovskite film. Use of the LFA solvent resulted in production of the FASnI3 perovskite film with high crystallinity, low Sn4+ content, reduced background doping, and low electronic trap density. As a result, an efficiency of over 10% was obtained for lead-free tin halide PSCs with improved reproducibility.Cationic antimicrobial peptides (CAMPs) are potent therapeutics for drug-resistant bacterial infections. However, the clinical application of CAMPs is hampered by its poor proteolytic stability and hemolytic activity toward eukaryotic cells. Great efforts have been made to design and generate derivatives of CAMPs with improved pharmacological properties. Here, we report a novel stapling protocol, which tethers two ε-amino groups of the lysine residue by the N-alkylation reaction on the hydrophilic face of amphiphilic antimicrobial peptides. A series of lysine-tethered stapled CAMPs were synthesized, employing the antimicrobial peptide OH-CM6 as a model. Biological screening of the stapled CAMPs provided an analogue with strong antimicrobial activity, high proteolytic stability, and low hemolytic activity. This novel stapling approach offers an important chemical tool for developing CAMP-based antibiotics.The reactivities of phosphanylphosphinidene complexes [(DippN)2W(Cl)(η2-P-PtBu2)]- (1), [(pTol3P)2Pt(η2-P═PtBu2)] (2), and [(dppe)Pt(η2-P═PtBu2)] (3) toward dihaloalkanes and methyl iodide were investigated. The reactions of the anionic tungsten complex (1) with stochiometric Br(CH2)nBr (n = 3, 4, 6) led to the formation of neutral complexes with a tBu2PP(CH2)3Br ligand or neutral dinuclear complexes with unusual tetradentate tBu2PP(CH2)nPPtBu2 ligands (n = 4, 6). The methylation of platinum complexes 2 and 3 with MeI yielded neutral or cationic complexes bearing side-on coordinated tBu2P-P-Me moieties. The reaction of 2 with I(CH2)2I gave a platinum complex with a tBu2P-P-I ligand. When the same dihaloalkane was reacted with 3, the P-P bond in the phosphanylphosphinidene ligand was cleaved to yield tBu2PI, phosphorus polymers, [(dppe)PtI2] and C2H4. Furthermore, the reaction of 3 with Br(CH2)2Br yielded dinuclear complex bearing a tetraphosphorus tBu2PPPPtBu2 ligand in the coordination sphere of the platinum. The molecular structures of the isolated products were established in the solid state and in solution by single-crystal X-ray diffraction and NMR spectroscopy. DFT studies indicated that the polyphosphorus ligands in the obtained complexes possess structures similar to free phosphenium cations tBu2P+═P-R (R = Me, I) or (tBu2P+═P)2.In this study, the synergistic behavior of Ni species and bimodal mesoporous undoped SnO2 is investigated in oxygen evolution reaction (OER) under alkaline conditions without any other modification of the compositional phases or using noble metals. An efficient and environmentally friendly hydrothermal method to prepare bimodal mesoporous undoped SnO2 with very high surface area (>130 m2 g-1) and a general deposition-precipitation methodology of well-dispersed Ni-species on undoped SnO2 is reported. The powders have been characterized by adsorption-desorption isotherms, TG-DTA, XRD, SEM, TEM, Raman, TPR-H2, and XPS. The best NiSn composite generates, under certain experimental conditions, a very high TOF value of 1.14 s-1 and a mass activity higher than 370 A g-1, which are remarkable results considering the low amount of Ni deposited on the electrode (3.78 ng). Moreover, in 1M NaOH electrolyte this material produces more than 24 mA cm-2 at an overpotential value of approx. +0.33 V, with only 5 wt. % Ni species. This performance steams from the dual role of undoped SnO2, on the one hand as support for active and well dispersed Ni species and on the other hand as an active player through oxygen vacancies generated upon Ni deposition.The garnet-type Li7La3Zr2O12 (LLZO) solid electrolyte is of particular interest because of its good chemical stability under atmospheric condition, suitable for practical all-solid-state batteries (ASSBs). However, recent works observed electrochemical instability at the LLZO/Li interfaces. Herein, we have revealed the origin of the instability by performing a comprehensive first-principles investigation with a high-throughput interface structure search scheme, based on the density functional theory framework. Based on the constructed phase diagrams of low-index surfaces, we found that the coordinatively unsaturated (i.e. coordination number less then 6) Zr sites exist widely on the low-energy LLZO surfaces. These undercoordinated Zr sites are reduced once the LLZO surface is in contact with the Li metal, leading to chemical instability of the LLZO/Li interface. Besides, the calculated formation and adhesion energies of interfaces suggest that the Li wettability on the LLZO surface is dependent on the termination structure.