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The acute toxicity test of EECS showed that there was no mouse died at the highest dose, indicating safe for the mice. The subacute toxicity based on the histology data showed no significant difference in the liver and kidney of mice between the tested group and the healthy group. The histological and enzymatic effect of EECS in mice infected with P. berghei showed the histological and enzymatic effect that improved liver function and the histopathological effect on kidneys with the highest activity at a dose of 200 mg/kg BW compared with the negative control. The results showed the EECS was not toxic in mice and repaired the liver and kidney functions of P. berghei ANKA-infected mice, indicating a good candidate for antimalarial drug development.[This corrects the article DOI 10.1039/D1SC06035J.].Control over chemo- and regioselectivity is a critical issue in the heterobiaryl synthesis via C-H oxidative coupling. To address this challenge, a strategy to invert the normal polarity of indoles in the heterobiaryl coupling was developed. With N-carboxyindoles as umpoled indoles, an exclusively ortho-selective coupling with phenols has been realized, employing a Brønsted acid- or Cu(i)-catalyst (as low as 0.01 mol%). A range of phenols and N-carboxyindoles coupled with exceptional efficiency and selectivity at ambient temperature and the substrates bearing redox-active aryl halides (-Br and -I) smoothly coupled in an orthogonal manner. Notably, preliminary examples of atropselective heterobiaryl coupling have been demonstrated, based on a chiral disulfonimide or a Cu(i)/chiral bisphosphine catalytic system. The reaction was proposed to occur through SN2' substitution or a Cu(i)-Cu(iii) cycle, with Brønsted acid or Cu(i) catalysts, respectively.An efficient asymmetric synthesis of isochromanone derivatives was realized through Z-selective-1,3-OH insertion/aldol cyclization reaction involving acyclic carboxylic oxonium ylides. The combination of achiral dirhodium salts and chiral N,N'-dioxide-metal complexes, along with the use of α-diazoketones instead of α-diazoesters, enables the cascade reaction efficiently. A variety of benzo-fused δ-lactones bearing vicinal quaternary stereocenters were obtained with good to excellent enantioselectivity, bypassing the competitive 1,1-OH insertion and racemic background aldol reaction.Optical properties are central to molecular design for many applications, including solar cells and biomedical imaging. A variety of ab initio and statistical methods have been developed for their prediction, each with a trade-off between accuracy, generality, and cost. Existing theoretical methods such as time-dependent density functional theory (TD-DFT) are generalizable across chemical space because of their robust physics-based foundations but still exhibit random and systematic errors with respect to experiment despite their high computational cost. Statistical methods can achieve high accuracy at a lower cost, but data sparsity and unoptimized molecule and solvent representations often limit their ability to generalize. Here, we utilize directed message passing neural networks (D-MPNNs) to represent both dye molecules and solvents for predictions of molecular absorption peaks in solution. Additionally, we demonstrate a multi-fidelity approach based on an auxiliary model trained on over 28 000 TD-DFT calculations that further improves accuracy and generalizability, as shown through rigorous splitting strategies. selleck compound Combining several openly-available experimental datasets, we benchmark these methods against a state-of-the-art regression tree algorithm and compare the D-MPNN solvent representation to several alternatives. Finally, we explore the interpretability of the learned representations using dimensionality reduction and evaluate the use of ensemble variance as an estimator of the epistemic uncertainty in our predictions of molecular peak absorption in solution. The prediction methods proposed herein can be integrated with active learning, generative modeling, and experimental workflows to enable the more rapid design of molecules with targeted optical properties.Mechanochemistry offers a new route to polyoxometalates (POMs) under mild conditions. The molybdenum isoPOM heptamolybdate and the molybdenum heteroPOMs of the Strandberg- and Keggin-type could be achieved from grinding together molybdenum oxide, potassium or ammonium carbonate and phosphate. The reactions were controlled by the stoichiometric ratio of the starting materials and the liquid used, with reaction times between 30 min and 3 h. In situ investigations of the syntheses reveal the formation of intermediates during the reactions. Their identification helps explaining the mechanism of formation of the intermediates as well as the final POMs.Helicenes are chiral polycyclic aromatic hydrocarbons (PAHs) of significant interest, e.g. in supramolecular chemistry, materials science and asymmetric catalysis. Herein an enhanced N-directed electrophilic C-H borylation methodology has been developed that provides access to azaborine containing helicenes (BN-helicenes). This borylation process proceeds via protonation of an aminoborane with bistriflimidic acid. DFT calculations reveal the borenium cation formed by protonation to be more electrophilic than the product derived from aminoborane activation with BBr3. The synthesised helicenes include BN-analogues of archetypal all carbon [5]- and [6]helicenes. The replacement of a CC with a BN unit (that has a longer bond) on the outer helix increases the strain in the BN congeners and the racemization half-life for a BN-[5]helicene relative to the all carbon [5]helicene. BN incorporation also increases the fluorescence efficiency of the helicenes, a direct effect of BN incorporation altering the distribution of the key frontier orbitals across the helical backbone relative to carbo-helicenes.The hydrofluoroolefin Z-1,3,3,3-tetrafluoropropene has been activated via an initial C-F bond activation and subsequent C-H bond activation using [Rh(H)(PEt3)3] (1) or via C-H bond activation at [Rh(CH3)(PEt3)3] (8). In both cases the formation of [Rh(E)-CF[double bond, length as m-dash]CHCF3(PEt3)3] (3) was observed. Importantly, the C-F activation product [Rh(E)-CH[double bond, length as m-dash]CHCF3(PEt3)3] (2) reacts in the presence of Z-1,3,3,3-tetrafluoropropene into 3. The latter converted into [Rh(C[triple bond, length as m-dash]CCF3)(PEt3)3] (6) by an unprecedented dehydrofluorination reaction, presumably via a vinylidene complex as intermediate. When the carbonyl complex [Rh(C[triple bond, length as m-dash]CCF3)(CO)(PEt3)3] (12) was treated with an excess of NEt3·3HF or HBF4 at low temperature, the formation of the phosphonioalkenyl compounds [Rh(Z)-C(PEt3)[double bond, length as m-dash]CHCF3(CO)(PEt3)2]X (X = F(HF) x , BF4) (13) was observed. The formation of 13 can be explained by an attack of PEt3 at the electrophilic α-carbon atom of an intermediate vinylidene complex. The employment of PiPr3 derivatives as model compounds allowed for the isolation of the unique fluorido vinylidene complex trans-[Rh(F)([double bond, length as m-dash]C[double bond, length as m-dash]CHCF3)(PiPr3)2] (16), which in the presence of PEt3 transforms into [Rh(C[triple bond, length as m-dash]CCF3)(PEt3)3] (6).Bimolecular fluorescence complementation (BiFC) and its derivative molecular biosensor systems provide effective tools for visualizing biomolecular interactions. The introduction of red and near-infrared fluorescence emission proteins has expanded the spectrum of signal generating modules, enabling BiFC for in vivo imaging. However, the large size of the signal module of BiFC can hinder the interaction between proteins under investigation. In this study, we constructed the near-infrared BiFC and TriFC systems by splitting miRFP670nano, the smallest cyanobacteriochrome-evolved phytochrome available. The miRFP670nano-BiFC sensor system identified and enabled visualization of protein-protein interactions in living cells and live mice, and afforded a faster maturation rate and higher photostability and cellular stability when compared with those of reported near-infrared BiFC systems. We used the miRFP670nano-BiFC sensor system to identify interactions between the nucleocapsid (N) protein of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and cellular stress granule proteins in living cells and found that the N protein downregulated the expression level of granule protein G3BP1. With the advantages of small size and long wavelength emission of the signal module, the proposed molecular biosensor system should be suitable for various applications in cell imaging studies.Porous materials have recently attracted much attention owing to their fascinating structures and broad applications. Moreover, exploring novel porous polymers affording the efficient capture of iodine is of significant interest. In contrast to the reported porous polymers fabricated with small molecular blocks, we herein report the preparation of porous polymer frameworks using rigid polyisocyanides as building blocks. First, tetrahedral four-arm star polyisocyanides with predictable molecular weight and low dispersity were synthesized; the chain-ends of the rigid polyisocyanide blocks were then crosslinked, yielding well-defined porous organic frameworks with a designed pore size and narrow distribution. Polymers of appropriate pore size were observed to efficiently capture radioactive iodine in both aqueous and vapor phases. More than 98% of iodine could be captured within 1 minute from a saturated aqueous solution (capacity of up to 3.2 g g-1), and an adsorption capacity of up to 574 wt% of iodine in vapor was measured within 4 hours. Moreover, the polymers could be recovered and recycled for iodine capture for at least six times, while maintaining high performance.Compartmentalization is an attractive approach to enhance catalytic activity by retaining reactive intermediates and mitigating deactivating pathways. Such a concept has been well explored in biochemical and more recently, organometallic catalysis to ensure high reaction turnovers with minimal side reactions. However, the scarcity of theoretical frameworks towards confined organometallic chemistry impedes broader utility for the implementation of compartmentalization. Herein, we report a general kinetic model and offer design guidance for a compartmentalized organometallic catalytic cycle. In comparison to a non-compartmentalized catalysis, compartmentalization is quantitatively shown to prevent the unwanted intermediate deactivation, boost the corresponding reaction efficiency (γ), and subsequently increase catalytic turnover frequency (TOF). The key parameter in the model is the volumetric diffusive conductance (F V) that describes catalysts' diffusion propensity across a compartment's boundary. Optimal values of F V for a specific organometallic chemistry are needed to achieve maximal values of γ and TOF. As illustrated in specific reaction examples, our model suggests that a tailored compartment design, including the use of nanomaterials, is needed to suit a specific organometallic catalytic cycle. This work provides justification and design principles for further exploration into compartmentalizing organometallics to enhance catalytic performance. The conclusions from this work are generally applicable to other catalytic systems that need proper design guidance in confinement and compartmentalization.