Coordination and Supramolecular Assemblies from Alkali+-Cucurbit[5]uril-[CdCl_(4)]^(2-)Systems

Thispaper has investigated the coordination and supramolecular assemblies of alkali metal ions,cucurbit[5]uril(Q[5]),and[CdCl_(4)]^(2-)to confirm whether[CdCl_(4)]^(2-)can produce the“honeycomb effect”,induce coordination of alkali metal ions to Q[5],and form linear coordination polymers.In this work,the effect of alkali metal ions on the construction of Q[5]-Cd^(2+)ion system under acidic conditions was investigated.Five complexes were successfully obtained by solvent evaporation method.Among the five crystal structures obtained,it can be observed that the presence of[CdCl_(4)]^(2-)did not result in the complexation of alkali metal ions by the Q[5]molecule.Instead,a bowl-like Cd^(2+)@Q[5]complex was formed.Indeed,[CdCl_(4)]^(2-)did not produce the honeycomb effect but led to the formation of Q[5]-based honeycomb frameworks with hexagonal cellsoccupied by[CdCl_(4)]^(2-).The experimental results show that cadmium ion showed stronger ability to coordinate to Q[5]in HCl solution.

Dual-responsive supramolecular photodynamic nanomedicine with activatable immunomodulation for enhanced antitumor therapy

A major challenge facing photodynamic therapy(PDT) is that the activity of the immuneinduced infiltrating CD8^(+)T cells is subject to the regulatory T lymphocytes(Tregs), leaving the tumor at risk of recurrence and metastasis after the initial ablation. To augment the antitumor response and reprogram the immunosuppressive tumor microenvironment(TME), a supramolecular photodynamic nanoparticle(DACss) is constructed by the host-guest interaction between demethylcantharidin-conjugated β-cyclodextrin(DMC-CD) and amantadine-terminated disulfide-conjugated FFVLGGGC peptide with chlorin e6 decoration(Ad-ss-pep-Ce6) to achieve intelligent delivery of photosensitizer and immunomodulator for breast cancer treatment. The acid-labile β-carboxamide bond of DMC-CD is hydrolyzed in response to the acidic TME, resulting in the localized release of DMC and subsequent inhibition of Tregs.The guest molecule Ad-ss-pep-Ce6 can be cleaved by a high level of intracellular GSH, reducing photosensitizer toxicity and increasing photosensitizer retention in the tumor. With a significant increase in the CTL/Treg ratio, the combination of Ce6-based PDT and DMC-mediated immunomodulation adequately achieved spatiotemporal regulation and remodeling of the TME, as well as improved primary tumor and in situ lung metastasis suppression with the aid of PD-1 antibody.

Double-cavity nor-seco-cucurbit[10]uril-based supramolecular assembly for selective detection and removal of trinitrophenol

The effective removal and selective detection of explosive and toxic pollutant trinitrophenol (TNP) is an attractive but challenging field.Herein,a double-cavity nor-seco-cucurbit[10]uril (ns-Q[10])-based supramolecular assembly 8-HQ@ns-Q[10]was fabricated and its structure was characterized by X-ray single crystal diffraction.In this assembly,the stoichiometric ratio of ns-Q[10]and 8-hydroxyquinoline (8-HQ) is 1:2,which is also attributed to the special double-cavity structure of ns-Q[10].The luminescence sensing experiments showed that 8-HQ@ns-Q[10]can be used as a good fluorescence-enhanced sensing material (enhanced 27-fold) for the rapid detection of explosives and the aqueous contaminant TNP,with a limit of detection (LOD) of 2.07×10^(-5)mol/L,without interference from other phenolic compounds.Furthermore,TNP can be efficiently removed in the presence of assembly 8-HQ@ns-Q[10],and the removal efficiency is more than 89%.Therefore,the supramolecular assembly 8-HQ@ns-Q[10],as a fluorescenceenhanced luminescence sensor and adsorption material,has rich research value and potential application prospect when applied to the detection and removal of TNP in aqueous environment.