First-principles calculations with experimental validations enable to radically predict and compare the electron transport, elastic softness, and thermodynamic phase stabilities of black phosphorus (BP) and GeP3 to figure out the crucial factors for desiging the most kinetically favorable P-based compounds toward the alloying with Na ions. In the viewpoint of electron transport, Ge is able to provide P with electrons due to the difference of electronegativity, rendering GeP3 to have significantly reduced band gap and lower electron-hopping barrier compared to BP. Because the structure of GeP3 looks more elastically softened than that of BP, its Na+ migration barriers in the sodiated states must be lower than those of the sodiated BP structure as proven by higher Na+ diffusion coefficients of GeP3. The thermodynamic phase stabilities of BP and GeP3 could be predicted by calculating their mixing enthalpy values and thereby homogeneous bulk free energies were obtained for Na1-x(GeP3) (0.0 ≤ x ≤ 0.5) indicating that any phase separation do not occur in the sodiated GeP3 because of an additional stable single-phase at x = 0.25. By contrast, the sodiated P easily gets separated into NaP and Na0.5P with the same sodiation contents. The suppressed phase separation in GeP3 makes Na+ distribution homogeneous as confirmed by TEM-EDS color mappings and thus contributes to increasing Na+ diffusion coefficients because Na+ migrations can be primarily interrupted by the interfaces or grain boundaries between the separated phases. Taking into account three enhanced physicochemical properties, the GeP3 electrodes may well present superior rate capability to the BP electrode, underscoring that electron transport, elastic softness, and thermodynamic phase stabilities must be the most important design factors for realizing kinetically favorable P-based compounds toward the alloying with Na+. In details, even at an ultrahigh current density of 20 A g−1, the capacity of GeP3 electrode still comes to 0.197 Ah g−1. At 1 A g−1, GeP3 could maintain a discharge capacity of 0.499 Ah g−1 even after 1000 cycles. This study may provide a promising guideline for the design of alloying-based electrode materials for high power and energy SIBs.

Chiral carbazole-based BODIPYs with a binaphthyl unit were synthesized via the Al-mediated reaction. Et2AlCl was found to be a convenient reagent for the reaction to give the chiral BODIPYs in high yields. It has been shown for the first time that these chiral carbazole-based BODIPYs show circularly polarized luminescence (CPL) both in solution and in the solid state.

Industrial specifications require CO2 concentrations in natural gas of below 50 ppm during liquefaction because of corrosion and CO2 freezing. Herein, we report a physisorbent (TIFSIX-3-Ni) that exhibits new benchmark CO2/CH4 selectivity and fast kinetics, thereby enabling one-step LNG processing to CO2 levels of 25 ppm.

A facile fluorescent method was developed to quantitatively monitor the hydrolysis kinetics of nonfluorescent esters by using the fluorecent endo-functionalized molecular tube and its recognition ability to small polar molecules in water. It is possible to determine the apparent rate constants and study structure-activity relationship.

Synthesis of renewable acetic acid from CO2 and lignin was effectively achieved over an ionic liquid (e.g., [BMIm][Cl])-based catalytic system containing Ru-Rh bimetal catalyst (Ru3(CO)12 and RhI3) and LiI. As far as we know, this is the first work to produce acetic acid from lignin and CO2.

Reliable and easy detection of oxygen in food packaging without the aid of sophisticated instruments is highly coveted. A tetraphenylethene probe based on the oxygen mediated polymerization via the formation of disulfides causes restricted intramolecular rotation the TPE phenyls resulting in a >100 fold enhancement of emission and thus detects O2 in food package.

Supramolecular assembly with tumor-targeting property or photodynamic therapy (PDT) ability has recently become a focus of interest in biomaterial fields because of their high therapeutic efficacy against tumor cells. Herein, we reported a new type of targeted supramolecular nanoparticles for photodynamic therapy of tumor cells constructed by adamantane-functionalized transferrin protein (Ad-TRF) and cyclodextrin-functionalized ruthenium complex (Ru-HOP-CD), where Ad-TRFs acted as the targeted sites for tumor cells, the coordinated Ru(II) centers acted as the PDT active sites, and the biocompatible polysaccharide cyclodextrins acted as the non-covalent linkers. Significantly, the resultant Ru/polysaccharide/protein exhibited not only the specific targeting property towards tumor cells but also the high PDT ability under the irradiation of visible light. Furthermore, the assembly showed the selective killing towards tumor cells along with the negligible toxicity towards normal cells.

In contrast to the catalytic asymmetric dearomative reactions of indole substrates, the analogous benzofuran derivatives have been less explored. Here we report that the stereoselective domino Rauhut-Currier/Michael addition process of 3-benzofuranyl vinyl ketones and 3-olefinic (7-aza)oxindoles can be realised under the catalysis of a chiral bifunctional phosphine, furnishing the previously unreported direct asymmetric dearomative reaction of benzofuran substrates tethered to a carbonyl group in a formal [4 + 2] cycloaddition manner. An array of hydrodibenzofuran derivatives with dense substitutions is generally constructed with excellent diastereoselectivity and enantioselectivity (up to >19:1 dr, >99% ee).

In this work, we propose a pH-regulated and target-activated fluorescent nanoprobe for high selective monitoring lysosomal azoreductase under hypoxia in living cells. We expect it will offer a potentially rich opportunity to understand the physiological processes of lysosome under hypoxia conditions.

Amphiphilic molecules linked by an aromatic nucleus were developed that showed high selectivity toward bacteria over mammalian cells, and low drug resistance. Promising compound 4g exhibited strong bactericidal activity against a panel of sensitive and resistant bacteria, low toxicity, the ability to reduce cell viability in biofilms, stability in mammalian fluids, rapid killing of pathogens, and high in vivo efficacy against methicillin-resistant Staphylococcus aureus (MRSA).

Trivalent metal hypophosphites with the general formula M(H2PO2)3 (M = V, Al, Ga) adopt the ReO3 structure, with each compound displaying two structural polymorphs. High-pressure synchrotron X-ray studies reveal a pressure-driven phase transition in Ga(H2PO2)3 that can be understood on the basis of ab initio thermodynamics.

Due to their high theoretical energy density and low cost, lithium-sulphur (Li–S) batteries are promising next-generation energy storage devices. The electrochemical performance of Li-S batteries largely depends on the efficient reversible conversion of Li polysulphides to Li2S in discharge, and to elemental S during charging. Here, we report on our discovery that monodisperse cobalt atoms embedded in nitrogen-doped graphene (Co-N/G) can trigger the surface-mediated reaction of Li polysulphides. Using a combination of operando X-ray absorption spectroscopy and first-principles calculation, we reveal that the Co-N-C coordination centre serves as a bifunctional electrocatalyst to facilitate both the formation and the decomposition of Li2S in discharge and charge processes, respectively. The S@Co-N/G composite, with a high S mass ratio of 90 wt.%, can deliver a gravimetric capacity of 1210 mAh g-1, and exhibits an areal capacity of 5.1 mAh cm-2 with capacity fading rate of 0.029% per cycle over 100 cycles at 0.2 C at S loading of 6.0 mg cm-2 on the electrode disk.

Reacting (NHC)(cyclopropenyl)gold(I) complexes with cationic gold complexes [(IPr)AuX] afforded extremely reactive allylium-1,1-diido-bridged digold intermediates. We prove the existence and constitution of this structure with FT-ICR-MS/MS, NMR, and UV-Vis-NIR experiments and isolated the nucleophilic addi-tion product [(Me)(Ph)(CCHC){Au(IPr)}2(SOMe2)]NTf2 with DMSO. Our computational investigation unveiled that the bond-ing situation of this -allylium-1,1-diido digold domain was best described as a three-center four electron bond with -backbond. The valence orbitals showed extreme delocalization and strong -interactions between the three centers Au1–C1–Au2. The bridging carbon atom C1 was best described as trigonal planar sp-hybridized carbon in this structure. Excitation succeeded in UV-Vis-NIR measurements with energies as low as near IR radiation.

1,1,1,3,3,3‐hexafluoro‐propan‐2‐ol aggregates preferentially into an achiral dimer of achiral monomers, but the trimer is found to prefer three metastable chiral monomer units arranged into a strained OH‐O hydrogen‐bonded ring which is reinforced by secondary CH‐FC interactions. This is shown by a combination of infrared, microwave and Raman spectroscopy in supersonic jet expansions and supported by high level quantum chemical calculations. It involves an activation of the monomers by >15 kJ mol‐1, clearly driven by the much stronger hydrogen bond interaction available to the gauche and even more to the cis monomer units.

Sac7d is a small thermostable protein that induces large helical deformations in DNA upon association. Starting from multiple initial placements of the unbound Sac7d structure relative to a B‐DNA oligonucleotide molecular dynamics (MD) simulations were employed to directly follow several successful binding events at atomic resolution that resulted in structures in close agreement with the native complex geometry. The final native complex formation occurred rapidly within tenth of nanoseconds and included simultaneous large scale kinking, groove opening, twisting and intercalation in the target DNA. The simulations indicate that the complex formation process involved initial non‐native contacts that helped to reach the final bound state with residues intercalated as the center of the kinked DNA. It was also possible to identify several long‐lived trapped intermediate states of the binding process and to follow sliding processes of Sac7d along the DNA minor groove.

Heterostructured nanomaterials, generally possessing unique physicochemical properties different from the individual components, have great potential in a wide range of applications. New platinum (Pt)/nickel bicarbonate (Ni(HCO3)2) heterostructures herein are designed towards efficient alkaline hydrogen evolution reaction (HER). Notably, the specific and mass activity of Pt in Pt/Ni(HCO3)2 are substantially improved as compared with bare Pt NPs. The Ni(HCO3)2 provides abundant water adsorption/dissociation sites and modulate the electronic structure of Pt, both of which determine the elementary reaction kinetics of alkaline HER. Besides, Ni(HCO3)2 nanoplates offer an ideal platform for the uniform dispersion of Pt NPs, ensuring the maximum exposure of active sites. The results demonstrate that, Ni(HCO3)2 is an effective catalyst promoter for alkaline HER, and engineering heterostructures with triggered synergistic effect is a promising strategy towards innovative electrocatalysts development.

Engineering functional amyloids through a modular genetic strategy represents new opportunities for creating multifunctional molecular materials with tailored structures and performance. Despite important advances, how fusion modules affect the self-assembly and functional properties of amyloids remains elusive. Here, using Escherichia coli curli as a model system, we systematically studied the effect of flanking domains on the structures, assembly kinetics and functions of amyloids. The designed amyloids were composed of E. coli biofilm protein CsgA (as amyloidogenic cores) and one or two flanking domains, consisting of chitin-binding domains (CBDs) from Bacillus circulans chitinase, and/or mussel foot proteins (Mfps). Incorporation of fusion domains did not disrupt the typical -sheet structures, but indeed affected assembly rate, morphology, and stiffness of resultant fibrils. Consequently, the CsgA-fusion fibrils, particularly those containing three domains, were much shorter than the CsgA-only fibrils. Furthermore, the stiffness of the resultant fibrils was heavily affected by the structural feature of fusion domains, with β-sheet-containing domains tending to increase the Young’s modulus while random coil domains decreasing the Young’s modulus. In addition, fibrils containing CBD domains showed higher chitin-binding activity compared to their CBD-free counterparts. The CBD-CsgA-Mfp3 construct exhibited significantly lower binding activity than Mfp5-CsgA-CBD due to inappropriate folding of the CBD domain in the former construct, in agreement with results based upon molecular dynamics modeling. Our study provides new insights into the assembly and functional properties of designer amyloid proteins with increasing complex domain structures and lays the foundation for the future design of functional amyloid-based structures and molecular materials.

Phenotypically distinct cellular (sub)populations are clinically relevant for virulence and antibiotic resistance of a bacterial pathogen, but functionally different cells are usually indistinguishable from each other. Here, we introduce fluorescent activity‐based probes as chemical tools for single‐cell phenotypic characterization of enzyme activity levels in Staphylococcus aureus. We screened a 1,2,3‐triazole urea library to identify selective inhibitors of fluorophosphonate‐binding serine hydrolases and lipases in S. aureus and synthesized target‐selective activity‐based probes. Molecular imaging and activity‐based protein profiling studies with these probes revealed a dynamic network within this enzyme family involving compensatory regulation of specific family members and exposed single‐cell phenotypic heterogeneity. We propose chemical probe labeling of enzymatic activities as a generalizable method for phenotyping of bacterial cells at the population and single‐cell level.