Porous metal–organic-framework nanoscale carriers as a potential platform for drug delivery and imaging

Horcajada, Patricia,Chalati, Tamim,Serre, Christian,Gillet, Brigitte,Sebrie, Catherine,Baati, Tarek,Eubank, Jarrod F.,Heurtaux, Daniela,Clayette, Pascal,Kreuz, Christine,Chang, Jong-San,Hwang, Young K Nature Publishing Group 2010 NATURE MATERIALS Vol.9 No.2

In the domain of health, one important challenge is the efficient delivery of drugs in the body using non-toxic nanocarriers. Most of the existing carrier materials show poor drug loading (usually less than 5 wt% of the transported drug versus the carrier material) and/or rapid release of the proportion of the drug that is simply adsorbed (or anchored) at the external surface of the nanocarrier. In this context, porous hybrid solids, with the ability to tune their structures and porosities for better drug interactions and high loadings, are well suited to serve as nanocarriers for delivery and imaging applications. Here we show that specific non-toxic porous iron(III)-based metal–organic frameworks with engineered cores and surfaces, as well as imaging properties, function as superior nanocarriers for efficient controlled delivery of challenging antitumoural and retroviral drugs (that is, busulfan, azidothymidine triphosphate, doxorubicin or cidofovir) against cancer and AIDS. In addition to their high loadings, they also potentially associate therapeutics and diagnostics, thus opening the way for theranostics, or personalized patient treatments.

In Situ Energy-Dispersive X-ray Diffraction for the Synthesis Optimization and Scale-up of the Porous Zirconium Terephthalate UiO-66

Ragon, Florence,Horcajada, Patricia,Chevreau, Hubert,Hwang, Young Kyu,Lee, U-Hwang,Miller, Stuart R.,Devic, Thomas,Chang, Jong-San,Serre, Christian American Chemical Society 2014 Inorganic Chemistry Vol.53 No.5

<P>The synthesis optimization and scale-up of the benchmarked microporous zirconium terephthalate UiO-66(Zr) were investigated by evaluating the impact of several parameters (zirconium precursors, acidic conditions, addition of water, and temperature) over the kinetics of crystallization by time-resolved in situ energy-dispersive X-ray diffraction. Both the addition of hydrochloric acid and water were found to speed up the reaction. The use of the less acidic ZrOCl<SUB>2</SUB>·8H<SUB>2</SUB>O as the precursor seemed to be a suitable alternative to ZrCl<SUB>4</SUB>·<I>x</I>H<SUB>2</SUB>O, avoiding possible reproducibility issues as a consequence of the high hygroscopic character of ZrCl<SUB>4</SUB>. ZrOCl<SUB>2</SUB>·8H<SUB>2</SUB>O allowed the formation of smaller good quality UiO-66(Zr) submicronic particles, paving the way for their use within the nanotechnology domain, in addition to higher reaction yields, which makes this synthesis route suitable for the preparation of UiO-66(Zr) at a larger scale. In a final step, UiO-66(Zr) was prepared using conventional reflux conditions at the 0.5 kg scale, leading to a rather high space-time yield of 490 kg m<SUP>–3</SUP> day<SUP>–1</SUP>, while keeping physicochemical properties similar to those obtained from smaller scale solvothermally prepared batches.</P><P>In situ energy-dispersive X-ray diffraction studies for the understanding and scale-up of the porous zirconium terephthalate UiO-66(Zr). The crystallization of the porous metal−organic framework UiO-66(Z) was studied by in situ energy-dispersive X-ray diffraction experiments to approach its formation and investigate the influence of different synthetic conditions. These experiments allow optimizing and up-scaling the synthesis of this phase at the 0.5 kg scale.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/inocaj/2014/inocaj.2014.53.issue-5/ic402514n/production/images/medium/ic-2013-02514n_0005.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ic402514n'>ACS Electronic Supporting Info</A></P>

N/S-Heterocyclic Contaminant Removal from Fuels by the Mesoporous Metal–Organic Framework MIL-100: The Role of the Metal Ion

Van de Voorde, Ben,Boulhout, Mohammed,Vermoortele, Frederik,Horcajada, Patricia,Cunha, Denise,Lee, Ji Sun,Chang, Jong-San,Gibson, Emma,Daturi, Marco,Lavalley, Jean-Claude,Vimont, Alexandre,Beurroies, American Chemical Society 2013 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.135 No.26

<P>The influence of the metal ion in the mesoporous metal trimesate MIL-100(Al<SUP>3+</SUP>, Cr<SUP>3+</SUP>, Fe<SUP>3+</SUP>, V<SUP>3+</SUP>) on the adsorptive removal of N/S-heterocyclic molecules from fuels has been investigated by combining isotherms for adsorption from a model fuel solution with microcalorimetric and IR spectroscopic characterizations. The results show a clear influence of the different metals (Al, Fe, Cr, V) on the affinity for the heterocyclic compounds, on the integral adsorption enthalpies, and on the uptake capacities. Among several factors, the availability of coordinatively unsaturated sites and the presence of basic sites next to the coordinative vacancies are important factors contributing to the observed affinity differences for N-heterocyclic compounds. These trends were deduced from IR spectroscopic observation of adsorbed indole molecules, which can be chemisorbed coordinatively or by formation of hydrogen bonded species. On the basis of our results we are able to propose an optimized adsorbent for the deep and selective removal of nitrogen contaminants out of fuel feeds, namely MIL-100(V).</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jacsat/2013/jacsat.2013.135.issue-26/ja403571z/production/images/medium/ja-2013-03571z_0007.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ja403571z'>ACS Electronic Supporting Info</A></P>

Stable polyoxometalate insertion within the mesoporous metal organic framework MIL-100(Fe)

Canioni, Romain,Roch-Marchal, Catherine,Sé,cheresse, Francis,Horcajada, Patricia,Serre, Christian,Hardi-Dan, Menaschi,Fé,rey, Gé,rard,Grenè,che, Jean-Marc,Lefebvre, Fré,d Royal Society of Chemistry 2011 Journal of materials chemistry Vol.21 No.4

<P>Successful encapsulation of polyoxometalate (POM) within the framework of a mesoporous iron trimesate MIL-100(Fe) sample has been achieved by direct hydrothermal synthesis in the absence of fluorine. XRPD, <SUP>31</SUP>P MAS NMR, IR, EELS, TEM and <SUP>57</SUP>Fe Mössbauer spectrometry corroborate the insertion of POM within the cavities of the MOF. The experimental Mo/Fe ratio is 0.95, in agreement with the maximum theoretical amount of POM loaded within the pores of MIL-100(Fe), based on steric hindrance considerations. The POM-MIL-100(Fe) sample exhibits a pore volume of 0.373 cm<SUP>3</SUP> g<SUP>−1</SUP> and a BET surface area close to 1000 m<SUP>2</SUP> g<SUP>−1</SUP>, indicating that small gas molecules can easily diffuse inside the cavities despite the presence of heavy phosphomolybdates. These latter contribute to the decrease in the overall surface area, due to the increase in molar weight, by 65%. Moreover, the resulting Keggin containing MIL-100(Fe) solid is stable in aqueous solution with no POM leaching even after more than 2 months. In addition, no exchange of the Keggin anions by tetrabutylammonium perchlorate in organic media has been observed.</P> <P>Graphic Abstract</P><P>Keggin 12-phosphomolybdates were encapsulated into mesoporous iron trimesate MIL-100(Fe) by direct synthesis, maintaining gas accessibility and avoiding POM leaching. <IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c0jm02381g'> </P>

Reverse Shape Selectivityin the Liquid-PhaseAdsorption of Xylene Isomers in Zirconium Terephthalate MOF UiO-66

Moreira, MarianaA.,Santos, Joã,o C.,Ferreira, Alexandre F. P.,Loureiro, José,M.,Ragon, Florence,Horcajada, Patricia,Shim, Kyu-E.,Hwang, Young-K.,Lee, U.-Hwang,Chang, Jong-S.,Serre, Christi American ChemicalSociety 2012 Langmuir Vol.28 No.13

<P>Powder, agglomerates, and tablets of the microporous zirconium(IV)terephthalate metal–organic framework UiO-66 were evaluatedfor the selective adsorption and separation of xylene isomers in theliquid phase using <I>n</I>-heptane as the eluent. Pulseexperiments, performed at 313 K in the presence of <I>n</I>-heptane, revealed the <I>o</I>-xylene preference of thismaterial, which was further confirmed by binary and multicomponentbreakthrough experiments in the presence of <I>m</I>- and <I>p</I>-xylene, resulting in selectivities at 313 K of 1.8 and2.4 with regards to <I>m</I>-xylene and <I>p</I>-xylene, respectively. Additionally, because <I>p</I>-xyleneis the less retained isomer, UiO-66 presents a selectivity patternthat is reverse of that of the xylenes' molecular dimension with respectto shape selectivity. The shaping of the material as tablets did notsignificantly change its selectivity toward the <I>o</I>-xylene isomer or toward <I>p</I>-xylene, which was theless retained isomer, despite a loss in capacity. Finally, the selectivitybehavior of UiO-66 in the liquid <I>n</I>-heptane phasemakes it a suitable material for <I>o</I>-xylene separationin the extract (heavy product) or <I>p</I>-xylene separationin the raffinate (light product) by simulated moving bed technology.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/langd5/2012/langd5.2012.28.issue-13/la3004118/production/images/medium/la-2012-004118_0011.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/la3004118'>ACS Electronic Supporting Info</A></P>