Two new zinc-terephthalate MOFs, (H2NEt2)[Zn3(BDC)3(HCO2)]1.5DEF (1) and Zn4(BDC)3(HCO2)2(DEF)4(2), based on trinuclear zinc secondary building units have been solvothermally synthesized from the well-studied MOF-5 system Zn–H2BDC–DEF (H2BDC = 1,4-benzenedicarboxylic acid or terephthalic acid; DEF = N,N-diethylformamide). It is shown that adding small amounts of formic acid to this system has a great influence on the formation of 3D networks based upon trimetallic zinc building units Zn3(O2CR)6. The structures of 1 and 2 comprise stacked 36 tessellated 2D zinc-terephthalate layers which are linked into 3D frameworks either by bridging formate monoanions (1) or by in situ generated neutral bridging units Zn(HCO2)2(DEF)4 (2). Flowing supercritical-CO2 activation of 1 led to a partially (80%) desolvated and probably collapsed structure (1-SC) with a measured BET (Brunauer–Emmett–Teller) surface area of 38 m2 g-1
Cr-MIL-101-NH 2 (MOF1) has been used to encapsulate large amounts of copper sulfate and the resulting loaded material, Cu@MOF1, was successfully used to promote the CuAAC click reaction.
Considering the importance of organic functionalization of MOFs, we here report a simple, tunable and efficient one-step post-modification procedure for introducing amino and carboxylic groups into the mesoporous metal–organic framework Al- and Cr-MIL-101-NH2 based on its reaction with alkyl bromides. This procedure allows also access to polyfunctionalized MIL-101 decorated with both carboxylic and primary amino groups. Other chemical functions, such as alcohols and alkynes, were also successfully introduced by this method.
1 May 2024 in International Journal of Pharmaceutics
Because of the difficult challenges of nanopharmaceutics, the development of a variety of nanovectors is still highly desired. Photodynamic therapy, which uses a photosensitizer to locally produce reactive oxygen species to kill the undesired cells, is a typical example for which encapsulation has been shown to be beneficial. The present work describes the use of coumarin-functionalized polymeric nanovectors based on the self-assembly of amphiphilic poly(2-oxazoline)s. Encapsulation of pheophorbide a, a known PDT photosensitizer, is shown to lead to an increased efficiency compared to the un-encapsulated version. Interestingly, the presence of coumarin both enhances the desired photocytotoxicity and enables the crosslinking of the vectors. Various nanovectors are examined, differing by their size, shape and hydrophilicity. Their behaviour in PDT protocols on HCT-116 cells monolayers is described, the influence of their crosslinking commented. Furthermore, the formation of a protein corona is assessed.
Considering the importance of organic functionalization of MOFs, we here report a simple, tunable and efficient one-step post-modification procedure for introducing amino and carboxylic groups into the mesoporous metal-organic framework Al- and Cr-MIL-101-NH2 based on its reaction with alkyl bromides. This procedure allows also access to polyfunctionnalized MIL-101 decorated with both carboxylic and primary amino groups. Other chemical functions, such as alcohols and alkynes, were also successfully introduced by this method.
4 September 2024 in Organic & Biomolecular Chemistry
Synthesis of natural (2Z)-Lachnophyllum methyl ester and (4Z)-Lachnophyllum lactone is reported. The developed routes enabled the first synthesis of non-natural analogs of these natural compounds. Biological activities of the series were evaluated.