CO2/CH4 and CH4/N2 separation on isomeric metal organic frameworks☆

Two isomeric metal-organic frameworks(MOFs) with 2-dimensional(2D) and 3-dimensional(3D) topologies both comprised of Cu(Ⅱ) and OTf(OTf = trifluoromethanesulfonate) ions were synthesized and characterized.The CO_2,CH_4 and N_2 adsorption properties of the two isomeric MOFs were investigated from 263 K to 298 K at0.1 MPa.The results showed that the 2D MOF exhibited a higher selectivity for CO_2 from CO_2/CH_4 and CH_4from CH_4/N_2 compared to the 3D MOF,even though it possessed a lower surface area and pore volume.The higher adsorption heats of gases on the 2D MOF inferred the strong adsorption potential energy in the layered MOFs.Dynamic separation experiments using CO_2/CH_4 and CH_4/N_2 mixtures on the two MOFs proved that the2 D MOF had a longer elution time than the 3D MOF as well as better separation abilities.     

Quantifying spectral changes experienced by plasmonic nanoparticles in a cellular environment to inform biomedical nanoparticle design

Metal nanoparticles (NPs) scatter and absorb light in precise, designable ways, making them agile candidates for a variety of biomedical applications. When NPs are introduced to a physiological environment and interact with cells, their physicochemical properties can change as proteins adsorb on their surface and they agglomerate within intracellular endosomal vesicles. Since the plasmonic properties of metal NPs are dependent on their geometry and local environment, these physicochemical changes may alter the NPs'' plasmonic properties, on which applications such as plasmonic photothermal therapy and photonic gene circuits are based. Here we systematically study and quantify how metal NPs'' optical spectra change upon introduction to a cellular environment in which NPs agglomerate within endosomal vesicles. Using darkfield hyperspectral imaging, we measure changes in the peak wavelength, broadening, and distribution of 100-nm spherical gold NPs'' optical spectra following introduction to human breast adenocarcinoma Sk-Br-3 cells as a function of NP exposure dose and time. On a cellular level, spectra shift up to 78.6 ± 23.5 nm after 24 h of NP exposure. Importantly, spectra broaden with time, achieving a spectral width of 105.9 ± 11.7 nm at 95% of the spectrum''s maximum intensity after 24 h. On an individual intracellular NP cluster (NPC) level, spectra also show significant shifting, broadening, and heterogeneity after 24 h. Cellular transmission electron microscopy (TEM) and electromagnetic simulations of NPCs support the trends in spectral changes we measured. These quantitative data can help guide the design of metal NPs introduced to cellular environments in plasmonic NP-mediated biomedical technologies.     

Effectiveness of metal-organic frameworks for removal of refractory organo-sulfur compound present in liquid fuels

Adsorption of organo-sulfur compounds present in liquid fuels on metal-organic framework (MOF) compounds is an efficient alternative to the conventional hydrodesulfurization process. It has been demonstrated that the extent of dibenzothiophene (DBT) adsorption at temperatures close to ambient (304 K) is much higher on MOFs systems than on the benchmarked Y-type zeolite. In addition, the DBT adsorption capacity depends strongly on the MOF type as illustrated by the much higher extent of adsorption observed on the copper- (C300) and Al-containing (A100) MOF systems than on the Fe-containing (F300) MOF counterpart. With the aim to investigate the operation in consecutive cycles, the MOFs used in adsorption experiments were regenerated. In addition, the remaining S-containing compounds were identified and quantified by photoelectron spectroscopy (XPS). Examination of S2p core-level spectrum of the adsorbed S-compounds of regenerated MOFs pointed out that a fraction of these molecules become oxidized into S(VI) species.     

Intracellular ZnO Nanorods Conjugated with Protoporphyrin for Local Mediated Photochemistry and Efficient Treatment of Single Cancer Cell

ZnO nanorods (NRs) with high surface area to volume ratio and biocompatibility is used as an efficient photosensitizer carrier system and at the same time providing intrinsic white light needed to achieve cancer cell necrosis. In this letter, ZnO nanorods used for the treatment of breast cancer cell (T47D) are presented. To adjust the sample for intracellular experiments, we have grown the ZnO nanorods on the tip of borosilicate glass capillaries (0.5 μm diameter) by aqueous chemical growth technique. The grown ZnO nanorods were conjugated using protoporphyrin dimethyl ester (PPDME), which absorbs the light emitted by the ZnO nanorods. Mechanism of cytotoxicity appears to involve the generation of singlet oxygen inside the cell. The novel findings of cell-localized toxicity indicate a potential application of PPDME-conjugated ZnO NRs in the necrosis of breast cancer cell within few minutes.     

The synthesis and photodynamic properties of meso-substituted, cationic porphyrin derivatives in HeLa cells

A series of asymmetric porphyrins with varying substituents, such as 4-hydrophenyl and N-methyl-4-pyridyl, were synthesized and characterized and their cell uptake, intracellular localization, cytotoxicities and phototoxicities were evaluated in vitro. The most phototoxic of the porphyrins synthesized, 5,10-di-(N-methyl-4-pyridyl)-15,20-(4-hydroxyphenyl)-21,23H-porphyrin, which was mainly localized in the mitochondria and displayed low levels of dark toxicity toward human cancer HeLa cells, offers potential application in photodynamic therapy.     

Understanding the mechanism of hydrogen adsorption into metal organic frameworks

Hydrogen adsorption mechanism into MOF-5, a porous metal-organic framework (MOF) has been studied by density functional theory calculation. The selected functionals for the prediction of interaction energies between hydrogen and potential adsorption sites of MOF-5 were utilized after the evaluation with the various functionals for interaction energy of H₂C₆H₆ model system. The adsorption energy of hydrogen molecule into MOF-5 was investigated with the consideration of the favorable adsorption sites and the orientations. We also calculated the second favorable adsorption sites by geometry optimization using every combination of two first adsorbed hydrogen molecules. Based on the calculation of the first and the second adsorption sites and energies, it has been suggested that the hydrogen adsorption into MOF-5 follows a cooperative mechanism in which the metal sites initiate the propagation of the hydrogen adsorption on the whole frameworks. In addition, the interaction mode between the simple benzene ring with hydrogen is significantly changed when the benzene ring has been incorporated into the framework of MOF-5.     

Biomedical Applications of Magnetically Functionalized Organic/Inorganic Hybrid Nanofibers

Nanofibers are one-dimensional nanomaterial in fiber form with diameter less than 1 µm and an aspect ratio (length/diameter) larger than 100:1. Among the different types of nanoparticle-loaded nanofiber systems, nanofibers loaded with magnetic nanoparticles have gained much attention from biomedical scientists due to a synergistic effect obtained from the unique properties of both the nanofibers and magnetic nanoparticles. These magnetic nanoparticle-encapsulated or -embedded nanofiber systems can be used not only for imaging purposes but also for therapy. In this review, we focused on recent advances in nanofibers loaded with magnetic nanoparticles, their biomedical applications, and future trends in the application of these nanofibers.     

Barium Titanate Nanoparticles: Highly Cytocompatible Dispersions in Glycol-chitosan and Doxorubicin Complexes for Cancer Therapy

In the latest years, innovative nanomaterials have attracted a dramatic and exponentially increasing interest, in particular for their potential applications in the biomedical field. In this paper, we reported our findings on the cytocompatibility of barium titanate nanoparticles (BTNPs), an extremely interesting ceramic material. A rational and systematic study of BTNP cytocompatibility was performed, using a dispersion method based on a non-covalent binding to glycol-chitosan, which demonstrated the optimal cytocompatibility of this nanomaterial even at high concentration (100 μg/ml). Moreover, we showed that the efficiency of doxorubicin, a widely used chemotherapy drug, is highly enhanced following the complexation with BTNPs. Our results suggest that innovative ceramic nanomaterials such as BTNPs can be realistically exploited as alternative cellular nanovectors.     

Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

Since the discovery of Metal Organic Frameworks (MOFs) in the early 1990s, the amount of new structures has grown exponentially. A MOF typically consists of inorganic nodes that are connected by organic linkers to form crystalline, highly porous structures. MOFs have attracted a lot of attention lately, as the versatile design of such materials holds promises of interesting applications in various fields. In this review, we will focus on the use of MOFs as heterogeneous oxidation catalysts. MOFs are very promising candidates to replace homogeneous catalysts by sustainable and stable heterogeneous catalysts.

The catalytic active function can be either the active metal sites of the MOF itself or can be introduced as an extra functionality in the linker, a dopant or a “ship-in-a-bottle” complex. As the pore size, pore shape, and functionality of MOFs can be designed in numerous ways, shape selectivity, and even chiral selectivity can be created. In this article, we will present an overview on the state of the art of the use of MOFs as a heterogeneous catalyst in liquid phase oxidation reactions.