Selective Self-Assembly of Supramolecular Helices and Macrocycles Directed by Halogen Bonding.

In this study, several hydrogen-bonded arylamide foldamers (compounds 1-5) with the same degree of polymerization were designed and synthesized. The polyfluoroiodobenzene or iodoethynyl polyfluoroiodobenzene segment was modified as a halogen donor at the end of the monomer, and pyridine or pyridine oxynitride served as the corresponding halogen acceptor segment. The crystal structure of compound 1 indicates that the supramolecular double helices were constructed by stacking a P helix and an M helix in an antiparallel manner in the direction of intermolecular I⋅⋅⋅O-N halogen bonding.

Supramolecular Organic Framework that Enables Multifunctional Doxorubicin Delivery, Photofrin Post-treatment Phototoxicity Inhibition, and Heparin Neutralization.

Although porous frameworks are structurally ideal for the development of biomaterials through drug adsorption, sequestration, and delivery, integration of multiple biofunctions into a biocompatible porous framework would greatly improve its potential for preclinical investigations by increasing both therapeutic value and research and development efficiency. Herein, we report the preparation of a highly biocompatible supramolecular organic framework from an imidazolium-derived tetrahedral monomer and cucurbit[8]uril. The supramolecular organic framework has been revealed to have regular intrinsic porosity and adsorb doxorubicin, photofrin, and heparins driven by hydrophobicity and/or ion-pairing electrostatic interactions.

Accurate construction of monolayer, bilayer, sandwich bilayer, four-layer, multi-layer and chiral bilayer 2D pillararene-type supramolecular networks.

The accurate construction of mono-, bi- and multi-layer networks has been an important challenge, especially for bi- and multi-layer networks. Monolayer, bilayer, sandwich bilayer, four-layer, and multi-layer two-dimensional pillararene-type metal-organic coordination networks have been constructed from functionalized pillar[5]arene and pillar[6]arene by utilizing the coordination interaction of cobalt and copper ions and combining with temperature control and guest induction. These two-dimensional coordination networks exhibit the excellent plasticity of pillararenes and structural variety, which are characterized by X-ray single crystal diffraction and PXRD, confirming that pillararenes units can function as excellent tunable scaffolds for structural regulation.

Six-Cyclic Crown Ether-Type Pillar[5]Arene: Enhanced Binding Ability to Bispyridinium Derivatives.

A six-cyclic crown ether-type pillar[5]arene was synthesized, and the five ethylene oxide loops were located outside the cavity and not affected by temperature changes which was confirmed by variable-temperature NMR experiment in DMSO-d6 and CDCl and 2D H-H NOESY experiment in CDCl. The six-cyclic pillar[5]-crown also showed greater binding ability of host-guest with bis(pyridinium) derivatives than conventional alkoxy pillar[5]arenes that illustrated through H NMR titration spectroscopic experiment in acetone-d6/CDCl (1 : 1) and UV-vis titration experiments in CHCl at room temperature. The five benzocrown ethers at the periphery were able to bind metal cations by H NMR titration spectroscopic experiment in CDCl/methanol-d4(9 : 1).

Constructing artificial gap junctions to mediate intercellular signal and mass transport.

Natural gap junctions are a type of channel protein responsible for intercellular signalling and mass communication. However, the scope of applications for these proteins is limited as they cannot be prepared at a large scale and are unable to spontaneously insert into cell membranes in vitro. The construction of artificial gap junctions may provide an alternative strategy for preparing analogues of the natural proteins and bottom-up building blocks necessary for the synthesis of artificial cells.

Benzoselenadiazole-Functionalized H-Bonded Arylamide Foldamers: Solvent-Responsive Properties and Helix Self-Assembly Directed by Chalcogen Bonding in Solid State.

In this study, a series of H-bonded arylamide foldamers bearing benzoselenadiazole ends with solvent-responsive properties have been synthesized. In dichloromethane or dimethyl sulfoxide solvents, the molecules exhibit meniscus or linear structures, respectively, which can be attributed to the unique intramolecular hydrogen bonding behavior evidenced by 1D H NMR and 2D NOESY spectra. UV-vis spectroscopy experiments show that the absorption wavelength of H-bonded arylamide foldamers are significantly red-shifted due to the presence of benzoselenadiazole group.

Bioinspired Self-Assembly of Metalloporphyrins and Polyelectrolytes into Hierarchical Supramolecular Nanostructures for Enhanced Photocatalytic H Production in Water.

Polypeptides, as natural polyelectrolytes, are assembled into tailored proteins to integrate chromophores and catalytic sites for photosynthesis. Mimicking nature to create the water-soluble nanoassemblies from synthetic polyelectrolytes and photocatalytic molecular species for artificial photosynthesis is still rare. Here, we report the enhancement of the full-spectrum solar-light-driven H production within a supramolecular system built by the co-assembly of anionic metalloporphyrins with cationic polyelectrolytes in water.

Multiple hydrogen bonding driven supramolecular architectures and their biomedical applications.

Supramolecular chemistry combines the strength of molecular assembly various molecular interactions. Hydrogen bonding facilitated self-assembly with the advantages of directionality, specificity, reversibility, and strength is a promising approach for constructing advanced supramolecules. There are still some challenges in hydrogen bonding based supramolecular polymers, such as complexity originating from tautomerism of the molecular building modules, the assembly process, and structure versatility of building blocks.

Two and three-dimensional halogen-bonded frameworks: self-assembly influenced by crystallization solvents.

In this paper, two types of solid phase 2D and 3D XBOFs were selectively constructed from identical building blocks of tetraphenylmethane tetrapyridine derivative and 1,4-diiodotetrafluorobenzene by changing the crystallization solvent. This 3D XBOF is a novel hybrid supramolecular organic framework with the synergistic control of hydrogen and halogen bonds.

pH-sensing supramolecular fluorescent probes discovered by library screening.

A new design concept for pH-sensing supramolecular fluorescent probes is reported. Supramolecular fluorescent pH probes based on pro-guest are designed and prepared. Pro-guests are designed to degrade under acidic condition and convert to competitive guests to displace encapsulated dyes, which leads to a significant enhancement in fluorescence intensity.