Metal–Organic Frameworks as Metal Ion Precursors for the Synthesis of Nanocomposites for Lithium‐Ion Batteries

Metal–organic frameworks (MOFs) are promising materials with fascinating properties. Their widespread applications are sometimes hindered by the intrinsic instability of frameworks. However, this instability of MOFs can also be exploited for useful purposes. Herein, we report the use of MOFs as metal ion precursors for constructing functional nanocomposites by utilizing the instability of MOFs. The heterogeneous growth process of nanostructures on substrates involves the release of metal ions, nucleation on substrates, and formation of a covering structure. Specifically, the synthesized CoS with carbon nanotubes as substrates display enhanced performance in a lithium‐ion battery. Such strategy not only presents a new way for exploiting the instability of MOFs but also supplies a prospect for designing versatile functional nanocomposites.     

Functional Nanoparticles with a Reducible Tetrasulfide Motif to Upregulate mRNA Translation and Enhance Transfection in Hard‐to‐Transfect Cells

Effective messenger RNA (mRNA) transfection in hard‐to‐transfect cells delivered by vectors is a long‐standing challenge. Now it is hypothesized that the high intracellular glutathione level is associated with suppressed mRNA translation. This theory leads to a new design principle of next‐generation mRNA vectors: nanoparticles with glutathione depletion chemistry upregulate mRNA translation and enhance transfection, which is beneficial for mRNA delivery in hard‐to‐transfect cells in vitro and in vivo.     

A Phototheranostic Strategy to Continuously Deliver Singlet Oxygen in the Dark and Hypoxic Tumor Microenvironment

Continuous irradiation during photodynamic therapy (PDT) inevitably induces tumor hypoxia, thereby weakening the PDT effect. In PDT‐induced hypoxia, providing singlet oxygen from stored chemical energy may enhance the cell‐killing effect and boost the therapeutic effect. Herein, we present a phototheranostic (DPPTPE@PEG‐Py NPs) prepared by using a 2‐pyridone‐based diblock polymer (PEG‐Py) to encapsulate a semiconducting, heavy‐atom‐free pyrrolopyrrolidone‐tetraphenylethylene (DPPTPE) with high singlet‐oxygen‐generation ability both in dichloromethane and water. The PEG‐Py can trap the ¹O₂ generated from DPPTPE under laser irradiation and form a stable intermediate of endoperoxide, which can then release ¹O₂ in the dark, hypoxic tumor microenvironment. Furthermore, fluorescence‐imaging‐guided phototherapy demonstrates that this phototheranostic could completely inhibit tumor growth with the help of laser irradiation.     

A Molecular Thermochromic Ferroelectric

Molecular ferroelectrics have attracted considerable interests because of their easy and environmentally friendly processing, low acoustical impedance and mechanical flexibility. Herein, a molecular thermochromic ferroelectric, N,N′‐dimethyl‐1,4‐diazoniabicyclo[2.2.2]octonium tetrachlorocuprate(II) ([DMe‐DABCO]CuCl₄) is reported, which shows both excellent ferroelectricity and intriguing thermochromism. [DMe‐DABCO]CuCl₄ undergoes a ferroelectric phase transition from Pca2₁ to Pbcm at a significantly high Curie temperature of 413 K, accompanied by a color change from yellow to red that is due to the remarkable deformation of [CuCl₄]^2? tetrahedron, where the ferroelectric and paraelectric phases correspond to yellow and red, respectively. Combined with multiple bistable physical properties, [DMe‐DABCO]CuCl₄ would be a promising candidate for next‐generation smart devices, and should inspire further exploration of multifunctional molecular ferroelectrics.     

Onion‐like Multifunctional Microtrap Vehicles for Attraction–Trapping–Destruction of Biological Threats

A multifunctional motile microtrap is developed that is capable of autonomously attracting, trapping, and destroying pathogens by controlled chemoattractant and therapeutic agent release. The onion‐inspired multi‐layer structure contains a magnesium engine core and inner chemoattractant and therapeutic layers. Upon chemical propulsion, the magnesium core is depleted, resulting in a hollow structure that exposes the inner layers and serves as structural trap. The sequential dissolution and autonomous release of the chemoattractant and killing agents result in long‐range chemotactic attraction, trapping, and destruction of motile pathogens. The dissolved chemoattractant (l ‐serine) significantly increases the accumulation and capture of motile pathogens (E. coli) within the microtrap structure, while the internal release of silver ions (Ag⁺) leads to lysis of the pathogen accumulated within the microtrap cavity.     

Pathway from N‐Alkylglycine to Alkylisonitrile Catalyzed by Iron(II) and 2‐Oxoglutarate‐Dependent Oxygenases

N‐alkylisonitrile, a precursor to isonitrile‐containing lipopeptides, is biosynthesized by decarboxylation‐assisted ‐N≡C group (isonitrile) formation by using N‐alkylglycine as the substrate. This reaction is catalyzed by iron(II) and 2‐oxoglutarate (Fe/2OG) dependent enzymes. Distinct from typical oxygenation or halogenation reactions catalyzed by this class of enzymes, installation of the isonitrile group represents a novel reaction type for Fe/2OG enzymes that involves a four‐electron oxidative process. Reported here is a plausible mechanism of three Fe/2OG enzymes, Sav607, ScoE and SfaA, which catalyze isonitrile formation. The X‐ray structures of iron‐loaded ScoE in complex with its substrate and the intermediate, along with biochemical and biophysical data reveal that ‐N≡C bond formation involves two cycles of Fe/2OG enzyme catalysis. The reaction starts with an Fe^IV‐oxo‐catalyzed hydroxylation. It is likely followed by decarboxylation‐assisted desaturation to complete isonitrile installation.     

Adjusting the chromatographic properties of poly(ionic liquid)‐modified stationary phases by substitution on the imidazolium cation

Poly(ionic liquid)‐modified stationary phases can have multiple interactions with solutes. However, in most stationary phases, separation selectivity is adjusted by changing the poly(ionic liquid) anions. In this work, two poly(ionic liquid)‐modified silica stationary phases were prepared by introducing the cyano or tetrazolyl group on the pendant imidazolium cation on the polymer chains. Various analytes were selected to investigate their mechanism of retention in the stationary phases using different mobile phases. Two poly(ionic liquid)‐modified stationary phases can provide various interactions toward solutes. Compared to the cyano‐functionalized poly(ionic liquid) stationary phase, the tetrazolyl‐functionalized poly(ionic liquid) stationary phase provides additional cation‐exchange and π‐π interactions, resulting in different separation selectivity toward analytes. Finally, applicability of the developed stationary phases was demonstrated by the efficient separation of nonsteroidal anti‐inflammatory drugs.     

Inhibition of resveratrol glucosides (REs) on advanced glycation endproducts (AGEs) formation: inhibitory mechanism and structure-activity relationship

Abstract

The study on inhibitory effects of resveratrol glucosides (REs) on advanced glycation endproducts (AGEs) formation is still unmet. Herein, for the first time, the antiglycation activities of five REs in the fetal bovine serum proteins (FBS)/fructose system were evaluated, and its structure-activity relationship and antiglycation mechanism were further explored. These REs showed remarkable inhibition toward AGEs formation. Among them, Piceatannol-3'-O-glucoside (PG) exhibited highest antiglycation activity as reflected in approximately 80% inhibition of fluorescent AGEs at the concentration of 1.0?mM. The structure-activity relationship analysis indicated that glucoside attached to the B ring of resveratrol displays a superior antiglycation activity. Moreover, the results of antiglycation mechanism showed that the antiglycation activity of REs was proportional to their antioxidant capacity and methylglyoxal (MGO) trapping capacity. Therefore, the REs are promising candidates worthy of further exploration for preventing AGEs accumulation in vivo, thereby treating AGEs-associated diseases.     

Self‐assembly of poly(ionic liquid) functionalized mesoporous magnetic microspheres for the solid‐phase extraction of preservatives from milk samples

In this work, a novel, rapid, and simple analytical method was proposed for the detection of parabens in milk sample by gas chromatography coupled with mass spectrometry. At the same time, milk sample was pretreated by magnetic solid phase extraction, which detected up to five parabens. A series of important parameters of magnetic solid phase extraction were investigated and optimized, such as pH value of loading buffer, amount of material, adsorption time, ionic strength, eluting solvents, and eluting time. Under the optimized conditions, the corresponding values were more than 0.9991, limits of detection and the limit of quantification were 0.1 and 0.5 ng/mL, respectively. In addition, the recoveries were achieved in range of 95–105%, the liner range were within 0.1–600 ng/mL, and the relative standard deviations were even lower than 5%.     

A synchronous nucleation and passivation strategy for controllable synthesis of Au36(PA)24: unveiling the formation process and the role of Au22(PA)18 intermediate

Science China Chemistry - Despite the recent progress on controllable synthesis of alkynyl-protected Au nanoclusters, the effective synthetic means are very limited and the cluster formation...