No abstract

New imidazolyl‐functionalized ordered mesoporous cross‐linked polymers were prepared by the copolymerization of the ionic liquid 3‐benzyl‐1‐vinyl‐1H‐imidazolium bromide with divinylbenzene as the cross‐linker and azobisisobutyronitrile as the radical initiator in the presence of O‐silylated SBA‐15 as the hard template. The materials were characterized by N2 adsorption–desorption analysis, TEM, thermogravimetric analysis, elemental analysis, and FTIR spectroscopy. The material, which benefits from the use of entrapped ionic liquid in the prepared polymer matrix in combination with its ordered mesoporous structure, is an excellent environment for the stabilization of highly dispersed Pd nanoparticles to result in a recyclable catalyst system with a significant activity in the Heck coupling reaction of aryl halides. The presence of well‐distributed imidazolium functionalities in the polymeric framework might be responsible for the relatively uniform and nearly atomic scale distribution of Pd nanoparticles throughout the mesoporous structure and the prevention of Pd agglomeration during the reaction, which results in high durability, high stability, and good recycling characteristics of the catalyst. Although our catalyst system operates in a homogeneous pathway, it is also very stable and recyclable.

An imidazolium based ionic liquid bearing triethylene glycol (TEG) tag was employed as a functional monomer together with divinylbenzene to prepare a novel hydrophilic mesoporous polymer containing ionic liquid functionalities via nanocasting method using SBA‐15 as a hard template. The material was characterized using transmission electron microscopy (TEM), N2 sorption analysis, thermo‐gravimetric analysis (TGA), Fourier‐transform infrared spectroscopy (FT‐IR), elemental analysis (CHN), solid‐state NMR spectroscopy and contact angle measurement. It was found that the hydrophobic/hydrophilic properties of initial template, stepwise addition of monomers and initiator as well as amount of carrier solvent are of the important parameters in preparation of the polymer with uniform pore structure. Benefited from the combined properties such as incorporation of ionic liquid within the pore system of a flexible organic matrix together with its hydrophilic character, the material was found as an appropriate support to generate highly dispersed and very small size of Pd nanoparticles inside the pores. The prepared catalyst in this way, demonstrated outstanding activity, recyclability and high durability in the Suzuki cross‐coupling reaction of varied aryl halides with boronic acids in water as a green reaction medium. The beneficial role of imidazolium ionic liquid in the formation of small and highly active Pd nanoparticles was confirmed with comparative experiments.

Background Cancer nanomedicines based on synthetic polypeptides have attracted much attention due to their superior biocompatibility and biodegradability, stimuli responsive capability through secondary conformation change, adjustable functionalities for various cargos such as peptides, proteins, nucleic acids and small therapeutic molecules. Recently, a few nanoformulations based on polypeptides comprising NK105, NC6004, NK911, CT2103, have entered phase I-III clinical trials for advanced solid tumors therapy. In the current study, we prepared polypeptide-based vesicles called peptosome via self-assembly of amphiphilic polypeptide-based PEG-PBLG diblock copolymer. Results In this regard, poly(γ-benzyl L-glutamate (PBLG) was synthesized via ring opening polymerization (ROP) of γ-benzyl L-glutamate-N-carboxyanhydride (BLG-NCA) using N-hexylamine as initiator. Then amine-terminated PBLG was covalently conjugated to heterofuctional maleimide PEG-carboxylic acid or methyl-PEG-carboxylic acid. The PEG-PBLG peptosomes were prepared through double emulsion method for the co-delivery of doxorubicin.HCl and gold nanorods as hydrophilic and hydrophobic agents in interior compartment and membrane of peptosomes, respectively (Pep@MUA.GNR-DOX) that DOX encapsulation efficiency and loading capacity were determined 42 ± 3.6 and 1.68 ± 3.6. Then, theranostic peptosomes were decorated with thiol-functionalized EpCAM aptamer throught thiol-maleimide reaction producing Apt-Pep@MUA.GNR-DOX for targeted delivery. The non-targeted and targeted peptosomes showed 165.5 ± 1.1 and 185 ± 4.7 nm diameters, respectively while providing sustained, controlled release of DOX. Furthermore, non-targeted and targeted peptosomes showed considerable serum stability. In vitro study on MCF-7 and 4T1 cells showed significantly higher cytotoxicity for Apt-Pep@MUA.GNR-DOX in comparison with Pep@MUA.GNR-DOX while both system did not show any difference in cytotoxicity against CHO cell line. Furthermore, Apt-Pep@MUA.GNR-DOX illustrated higher cellular uptake toward EpCAM-overexpressing 4T1 cells compared to Pep@MUA.GNR-DOX. In preclinical stage, therapeutic and diagnostic capability of the prepared Pep@MUA.GNR-DOX and Apt-Pep@MUA.GNR-DOX were investigated implementing subcutaneous 4T1 tumor model in BALB/c mice. The obtained data indicated highest therapeutic index for Apt-Pep@MUA.GNR-DOX compared to Pep@MUA.GNR-DOX and free DOX. Moreover, the prepared system showed capability of CT imaging of tumor tissue in 4T1 tumorized mice through tumor accumulation even 24 h post-administration. Conclusion In this regard, the synthesized theranostic peptosomes offer innovative hybrid multipurpose platform for fighting against breast cancer. Graphical Abstract

The formation of polymeric micelles in aqueous environments through the self-assembly of amphiphilic polymers can provide a versatile platform to increase the solubility and permeability of hydrophobic drugs and pave...