Achiral Polyoxometalates Research Articles

Design and synthesis of a novel chiral photoacoustic probe and accurate imaging detection of hydrogen peroxide in vivo.

Nanocatalytic medicine, which aims to accurately target and effectively treat tumors through intratumoral in situ catalytic reactions triggered by tumor-specific environments or markers, is an emerging technology. However, the relative lack of catalytic activity of nanoenzymes in the tumor microenvironment (TME) has hampered their use in biomedical applications. Therefore, it is crucial to develop a highly sensitive probe that specifically responds to the TME or disease markers in the TME for precision diagnosis and treatment of diseases. In this work, a chiral photoacoustic (PA) nanoprobe (D/L-Ce@MoO3) based on the H2O2-catalyzed TME activation reaction was constructed in a one-step method using D-cysteine (D-Cys) or L-cysteine (L-Cys), polymolybdate, and cerium nitrate as raw materials. The designed and synthesized D/L-Ce@MoO3 chiral nanoprobe can perform in situ, non-invasive, and precise imaging of pharmacological acute liver injury. In vivo and in vitro experiments have shown that the D/L-Ce@MoO3 probe had chiral properties, the CD signal decreased upon reaction with H2O2, and the absorption and PA signals increased with increasing H2O2 concentration. This is because of the catalytic reaction between Ce ions doped in the nanoenzyme and the high expression of H2O2 caused by drug-induced liver injury to produce ·OH, which has a strong oxidizing property to kill tumor cells and destroy the Mo-S bond in the probe, thus converting the chiral probe into an achiral polyoxometalate (POM) with PA signal.

Step-by-Step Assembly of 2D Confined Chiral Space Endowing Achiral Clusters with Asymmetric Catalytic Activity for Epoxidation of Allylic Alcohols.

Endowing achiral polyoxometalates (POMs) with asymmetric catalytic properties is always an intriguing but challenging topic because of their high catalytic activities yet highly symmetrical molecular structures. In this work, a novel strategy was proposed to fabricate a series of two-dimensional chiral POM catalysts. Following the steps of exfoliation, covalent modification, and reassembly, the achiral POMs were orderly confined into the chiral interstitial domains of chiral ionic liquid (CIL)-modified layered double hydroxide materials with a decreased molecular symmetry. The chirality of POM molecules was induced by the l- or d-pyrrolidine-type CILs, and their asymmetric catalytic activity was enhanced by the confinement effect. Compared with the reported chiral POM-based catalysts [e.g., 8 turnover frequency (TOF) and 79% enantiomeric excess (ee) for chiral POM-based metal-organic frameworks], the constructed chiral POM catalysts showed a significantly higher TOF and enantioselectivity (up to 240 TOF and 93% ee) for the asymmetric epoxidation of allylic alcohols. The facilitated mass transfer in the IL channels and the increased binding efficiency between the chiral catalytic sites and reactants render this strategy highly promising for constructing efficient chiral catalysts from the catalytically active while achiral building blocks.

Solvent Dielectricity-Modulated Helical Assembly and Morphologic Transformation of Achiral Surfactant-Inorganic Cluster Ionic Complexes.

Ionic complexes comprising single/double chain cationic surfactant and Lindqvist-type polyoxomolybdate anionic cluster were used for controlled self-assembly in organic solutions. In the solvent with low dielectric constant the complexes self-assembled into flat ribbon like lamellar aggregations with an inverse bilayer substructure where the cluster located at the middle. Under the condition of increased dielectric constant, the solvent triggered the formation of helical self-assemblies, which finally transformed from helical ribbons to the flower-like assemblies due to the bilayer becoming excessively twisted. The self-assembled morphology and the substructure were characterized by SEM, TEM, and XRD. The solvent dielectricity-controlled morphologic transformations modulated by the variation of electrostatic interactions between organic cations and inorganic polyanions were demonstrated by 1H NMR and IR spectra. The strategy in this work represents an effective route in targeting the chirality-directed functionalization of inorganic clusters by combining controllable and helical assemblies of achiral polyoxometalate complexes in one system.

Optically Active Liquid Crystalline Polyoxometalates via Electrostatic Encapsulation with Cholesterol-Containing Amphiphile.

A novel cholesterol-containing amphiphile was designed and prepared in the study, which is a room-temperature ionic liquid crystal over a broad temperature range with pronounced chiroptical properties. Four types of inorganic polyoxometalates (PMs) with different numbers of charges were encapsulated by the chiral amphiphile. The incorporation of chiral organic cations triggers achiral PMs in the complexes to show induced chirality through intermolecular interactions, as demonstrated by circular dichroism spectroscopy. The electrostatic encapsulation with mesomorphic promoters provides the inorganic PMs with liquid crystalline behavior, characterized by differential scanning calorimetry, polarized optical microscopy, and X-ray diffraction. The strategy applied herein represents a unique example of liquid crystalline PM complexes with optical activity.

Counterion-dominating chirality transfer between chiral and achiral polyoxometalates.

We show that chirality transfer from chiral polyoxometalates to achiral polyoxometalates can occur in aqueous solution with unexpected selectivity of surrounding counterions. In comparison with sodium ions, protonated dimethylammonium counterions play a critical role in shortening the inter-cluster distance, thus promoting the efficiency of chirality transfer.

Controlled chiral electrochromism of polyoxometalates incorporated in supramolecular complexes.

A three-component supramolecular system was constructed by combining host-guest recognition and electrostatic interaction for realization of induced circular dichroism of achiral polyanionic clusters in aqueous solution, while the induced chiral heteropoly blue was built and switched off by controlling the redox of the inorganic component via electrochemistry.

Chiral Heteropoly Blues and Controllable Switching of Achiral Polyoxometalate Clusters

Redoxschaltung: Chirale Heteropolyblauverbindungen wurden aus achiralen Polyoxometallatclustern durch intermolekulare Wechselwirkung mit einer chiralen organischen Verbindung erzeugt. Die reversible Photochromie der Polyoxometallate wurde genutzt, um ein gezieltes chiroptisches Schalten der Clusterkomplexe zu erreichen (siehe Bild).

Chiral Heteropoly Blues and Controllable Switching of Achiral Polyoxometalate Clusters

Managing the blues: Chiral heteropoly blues of achiral polyoxometalate clusters were created through an intermolecular interaction with a chiral organic compound. Controllable chiroptical switching of the cluster complexes was possible through reversible photochromism of the polyoxometalates (see picture).