Metallo-Supramolecular Helical Fibres from Chiral Phenylacetylene Monomers: Cation Induced Self-Assembly.

Chiral metallo-supramolecular fibres can be easily obtained by mixing a chloroform solution of a phenylacetylene monomer (PA) that bears a chiral sulfoxide group as pendant, with different equivalents of a methanolic solution of AgClO4 . Thus, while the PA is found molecularly dissolved in chloroform, the addition of Ag+ ions induce its aggregation through the formation of an axially chiral metallo-supramolecular aggregate with high thermal stable properties. In this case, the ability of the metal ion to coordinate the PA triple bond, combined with the argentophilicity of the metal ion and the planarity of the phenylacetylene drives to the formation of a helical coordination polymer, whose P or M axial chirality is determined by the chirality of the sulfoxide used as substituent of the PA. Depending on the PA/Ag+ (mol/mol) ratio, it is possible to tune the morphology of the metallo-supramolecular aggregate from chiral fibers to chiral gel.

Osteogenic and Chondrogenic Potential of the Supramolecular Aggregate T-LysYal®.

Hard tissue regeneration represents a challenge for the Regenerative Medicine and Mesenchymal stem cells (MSCs) could be a successful therapeutic strategy. T-LysYal® (T-Lys), a new derivative of Hyaluronic Acid (HA) possessing a superior stability, has already been proved efficient in repairing corneal epithelial cells damaged by dry conditions in vitro. We investigated the regenerative potential of T-Lys in the hard tissues bone and cartilage. We have previously demonstrated that cells isolated from the tooth germ, Dental Bud Stem Cells (DBSCs), differentiate into osteoblast-like cells, representing a promising source of MSCs for bone regeneration. Herewith, we show that T-Lys treatment stimulates the expression of typical osteoblastic markers, such as Runx-2, Collagen I (Col1) and Alkaline Phosphatase (ALP), determining a higher production of mineralized matrix nodules. In addition, we found that T-Lys treatment positively affects αVß3 integrin expression, key integrin in the osteoblastic commitment, leading to the formation of focal adhesions (FAs). The efficacy of T-Lys was also tested on chondrogenic differentiation starting from human articular chondrocytes (HACs) resulting in an increase of differentiation markers and cell number.

A Novel Approach Based on Two-Dimensional Correlation Spectroscopy to Determine the Stoichiometric Ratio of Two Substances Involved in Intermolecular Interactions.

A novel technique called AOSD@Job's, combining asynchronous orthogonal sample design scheme (AOSD) with Job's method, is proposed to estimate the stoichiometric ratio of two substances that form a supramolecular aggregate under intermolecular interactions. First, a mathematical analysis was performed along with the procedure of the AOSD@Job's method. Then, the validity of the AOSD@Job's method was manifested by computer simulation on two model systems. Finally, the AOSD@Job's method was applied on two real chemical systems. The stoichiometric ratio between the coordination complex of Ni2+ and ethylenediaminetetraacetic acid disodium salt (EDTA) was estimated to be 1.0. Benzyl alcohol (BA) and ß-cyclodextrin (ß-CD) were determined to form a 1 : 1 host-guest complex. These values were consistent with the values reported in the literature. Compared with the traditional Job's method, the AOSD@Job's method has an evident advantage since it is still valid even if all the peaks of the supramolecular aggregate severely overlap with the peaks of the substances that form the aggregate.

Supramolecular Aggregate as a High-Efficiency Gene Carrier Mediated with Optimized Assembly Structure.

For cancer gene therapy, a safe and high-efficient gene carrier is a must. To resolve the contradiction between gene transfection efficiency and cytotoxicity, many polymers with complex topological structures have been synthesized, although their synthesis processes and structure control are difficult as well as the high molecular weight also bring high cytotoxicity. We proposed an alternative strategy that uses supramolecular inclusion to construct the aggregate from the small molecules for gene delivery, and to further explore the relationship between the topological assembly structure and their ability to deliver gene. Herein, PEI-1.8k-conjugating ß-CD through 6-hydroxyl (PEI-6-CD) and 2-hydroxyl (PEI-2-CD) have been synthesized respectively and then assembled with diferrocene (Fc)-ended polyethylene glycol (PEG-Fc). The obtained aggregates were then used to deliver MMP-9 shRNA plasmid for MCF-7 cancer therapy. It was found that the higher gene transfection efficiency can be obtained by selecting PEI-2-CD as the host and tuning the host/guest molar ratios. With the rational modulation of supramolecular architectures, the aggregate played the functions similar to macromolecules which exhibit higher transfection efficiency than PEI-25k, but show much lower cytotoxicity because of the nature of small/low molecules. In vitro and in vivo assays confirmed that the aggregate could deliver MMP-9 shRNA plasmid effectively into MCF-7 cells and then downregulate MMP-9 expression, which induced the significant MCF-7 cell apoptosis, as well inhibit MCF-7 tumor growth with low toxicity. The supramolecular aggregates maybe become a promising carrier for cancer gene therapy and also provided an alternative strategy for designing new gene carriers.

Aggregates of a cationic porphyrin as supramolecular probes for biopolymers.

The copper(II) derivative of the dicationic trans-bis(N-methylpyridinium-4-yl)diphenylporphyrin (t-CuPagg) forms large fractal aggregates in aqueous solution under moderate ionic strength conditions. A kinetic investigation of the aggregation process allows for a choice of experimental conditions to quickly obtain stable assemblies in solution. These positively charged aggregates are able to interact efficiently with negatively charged chiral species, (including bacterial spores) leading to induced circular dichroism signals in the Soret region of the porphyrin, now acting as a sensitive chiroptical probe.