Here we introduce for the first time a metal-free trianglamine-based supramolecular organic framework, T-SOF-1, with permanent intrinsic porosity and high affinity to CO 2 . The capability of tuning the pore aperture dimensions is also demonstrated by molecular guest encapsulation to afford excellent CO 2 /CH 4 separation for natural gas upgrading.

Engineering membranes for molecular separation in organic solvents is still a big challenge. When the selectivity increases, the permeability tends to drastically decrease, increasing the energy demands for the separation process. Ideally, organic solvent nanofiltration membranes should be thin to enhance the permeant transport, have a well-tailored nanoporosity and high stability in harsh solvents. Here, we introduce a trianglamine macrocycle as a molecular building block for cross-linked membranes, prepared by facile interfacial polymerization, for high-performance selective separations. The membranes were prepared via a two-in-one strategy, enabled by the amine macrocycle, by simultaneously reducing the thickness of the thin-film layers (<10 nm) and introducing permanent intrinsic porosity within the membrane (6.3 Å). This translates into a superior separation performance for nanofiltration operation, both in polar and apolar solvents. The hyper-cross-linked network significantly improved the stability in various organic solvents, while the amine host macrocycle provided specific size and charge molecular recognition for selective guest molecules separation. By employing easily customized molecular hosts in ultrathin membranes, we can significantly tailor the selectivity on-demand without compromising the overall permeability of the system.

Developing the competence of molecular sorbents for energy‐saving applications, such as C8 separations, requires efficient, stable, scalable, and easily recyclable materials that can readily transition to commercial implementation. Herein, we report an azobenzene‐based cage for the selective separation of p‐xylene isomer across a range of C8 isomers in both vapor and liquid states with selectivity that is higher than the reported all‐organic sorbents. The crystal structure shows non‐porous cages that are separated by p‐xylene molecules through selective CH–π interactions between the azo bonds and the methyl hydrogen atoms of the xylene molecules. This cage is stable in solution and can be regenerated directly under vacuum to be used in multiple cycles. We envisage that this work will promote the investigation of the azo bond as well as guest‐induced crystal‐to‐crystal phase transition in non‐porous organic solids for energy‐intensive separations.

Abstract:The delivery of large cargos of diameter above 15 nm for biomedical applications has proved challenging since it requires biocompatible, stably-loaded, and biodegradable nanomaterials. In this study, we describe the design of biodegradable silica-iron oxide hybrid nanovectors with large mesopores for large protein delivery in cancer cells. The mesopores of the nanomaterials spanned from 20 to 60 nm in diameter and post-functionalization allowed the electrostatic immobilization of large proteins (e.g. mTFP-Ferritin, ~534 kDa). Half of the content of the nanovectors was based with iron oxide nanophases which allowed the rapid biodegradation of the carrier in fetal bovine serum and a magnetic responsiveness. The nanovectors released large protein cargos in aqueous solution under acidic pH or magnetic stimuli. The delivery of large proteins was then autonomously achieved in cancer cells via the silica-iron oxide nanovectors, which is thus a promising for biomedical applications.

Plumbagin [5-hydroxy- 2-methyl-1, 4-naphthaquinone] is a well-known plant derived anticancer lead compound. Several efforts have been made to synthesize its analogs and derivatives in order to increase its anticancer potential. In the present study, plumbagin and its five derivatives have been evaluated for their antiproliferative potential in one normal and four human cancer cell lines. Treatment with derivatives resulted in dose- and time-dependent inhibition of growth of various cancer cell lines. Prescreening of compounds led us to focus our further investigations on acetyl plumbagin, which showed remarkably low toxicity towards normal BJ cells and HepG2 cells. The mechanisms of apoptosis induction were determined by APOPercentage staining, caspase-3/7 activation, reactive oxygen species production and cell cycle analysis. The modulation of apoptotic genes (p53, Mdm2, NF-kB, Bad, Bax, Bcl-2 and Casp-7) was also measured using real time PCR. The positive staining using APOPercentage dye, increased caspase-3/7 activity, increased ROS production and enhanced mRNA expression of proapoptotic genes suggested that acetyl plumbagin exhibits anticancer effects on MCF-7 cells through its apoptosis-inducing property. A key highlighting point of the study is low toxicity of acetyl plumbagin towards normal BJ cells and negligible hepatotoxicity (data based on HepG2 cell line). Overall results showed that acetyl plumbagin with reduced toxicity might have the potential to be a new lead molecule for testing against estrogen positive breast cancer.

A shapedinduced liquid−liquid extraction strategy by using the highly stable (chemical, moisture, and thermal) macrocyclic host cucurbit[7]uril (CB7) was reported and showed high selectivity for the separation of disubstituted benzene isomers under ambient temperature and pressure.

Bridged silsesquioxane nanocomposites with tunable morphologies incorporating o-nitrophenylene−ammonium bridges are described. The systematic screening of the sol−gel parameters allowed the material to reach the nanoscale with controlled dense and hollow structures of 100−200 nm. The hybrid composition of silsesquioxanes with 50% organic content homogeneously distributed in the nanomaterials endowed them with photoresponsive properties. Light irradiation was performed to reverse the surface charge of nanoparticles from +46 to −39 mV via a photoreaction of the organic fragments within the particles, as confirmed by spectroscopic monitorings. Furthermore, such nanoparticles were applied for the first time for the on-demand delivery of plasmid DNA in HeLa cancer cells via light actuation.

Colloidosome capsules possess the potential for the encapsulation and release of molecular and macromolecular cargos.H owever,t he stabilization of the colloidosome shell usually requires an additional covalent crosslinking which irreversibly seals the capsules,and greatly limits their applications in large-cargos release.H erein we report nanoscaled colloidosomes designed by the electrostatic assembly of organosilica nanoparticles (NPs) with oppositely charged surfaces (rather than covalent bonds), arising from different contents of ab ridged nitrophenylene-alkoxysilane [NB;3nitro-N-(3-(triethoxysilyl)propyl)-4-(((3-(triethoxysilyl)propyl)-amino)methyl)benzamid] derivative in the silica. The surface charge of the positively charged NPs was reversed by light irradiation because of aphotoreaction in the NB moieties, which impacted the electrostatic interactions between NPs and disassembled the colloidosome nanosystems.T his design was successfully applied for the encapsulation and light-triggered release of cargos.Colloidosomes can be formed by the assembly of colloidal particles on emulsion droplets leading to capsule morphologies. [1][2][3][4][5] Va rious colloidal nanobuilding blocks have been used to design colloidosomes such as iron oxide NPs, [6] nanodiamonds, [7] polymeric rod-shaped microparticles, [8] silica NPs, [9,10] cubic metal-organic frameworks NPs, [11] and mixtures of these NPs. [9,10] Thek ey interest of such structures is their important internal volume combined with the properties of the nanobuilding blocks in the shell, which promise many applications as witnessed by few pioneering studies involving enzyme encapsulation, [12,13] bacteria encapsulation, [14] biocatalysis, [3] and passive release or delivery by interparticle pores. [15][16][17] Colloidal NPs assemble at the interface of emulsion droplets during the colloidosome formation in order to decrease interfacial energy of the system. [18] Thea ssembly at the liquid-liquid interface requires that particles should be neither completely wetted by the oil phase nor by the aqueous phase. [19] To adjust the wettability of NPs,t he hydrophobization of the surface of colloids is usually carried out. This can be achieved by physical interactions with additives (e.g. surfactants), [7,9,20] or chemical functionalization. [21,22] Ty pically,c olloidal particles with partially hydrophobic surfaces, such as silica NPs functionalized with organosilane, [23,24] are chosen as nanobuilding blocks of colloidosomes.T hese colloidal NPs assemble at the oil/water (o/w) or water/oil (w/o) interfaces of emulsion droplets, [17] which is much analogous to the behavior of surfactants.Many applications of colloidosomes are nonetheless compromised by several challenges such as the stability of the hollow structure and the accessibility of the internal volume.Controlled release and delivery applications require that the colloidosome carriers be:( 1) stabilized after the emulsion stage, [17] (2) non-permeable to ensure the transportation of the loaded active entities ...