Metal Organic Frameworks in Biomedicine Patricia Horcajada,* Ruxandra Gref, Tarek Baati, Phoebe K. Allan, Guillaume Maurin, Patrick Couvreur, G erard F erey, Russell E. Morris, and Christian Serre* Institut Lavoisier, UMR CNRS 8180, Universit e de Versailles St-Quentin en Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles Cedex, France Facult e de Pharmacie, UMR CNRS 8612, Universit e Paris-Sud, 92296 Châtenay-Malabry Cedex, France Institut Charles Gerhardt Montpellier, UMR CNRS 5253, Universit e Montpellier 2, 34095 Montpellier cedex 05, France EaStChem School of Chemistry, University of St. Andrews Purdie Building, St Andrews, KY16 9ST U.K.

Metal-organic frameworks in biomedicine.

A highly stable pillared and double-walled zinc(II) metal-organic framework with regular nanochannels displays single-crystal to single-crystal transformation upon desolvation and a large quantity of iodine uptake, controlled release, and electrical conductivity elevation due to synergy between the iodine guests and the host framework.

Rigid Pillars and Double Walls in a Porous Metal-Organic Framework: Single-Crystal to Single-Crystal, Controlled Uptake and Release of Iodine and Electrical Conductivity

Cyclodextrins as Supramolecular Hosts for Organometallic Complexes

Selective fatty acid hydrophobization of the inner surface of tubule halloysite clay is demonstrated. Aqueous phosphonic acid was found to bind to alumina sites at the tube lumen and did not bind t...

Selective modification of halloysite lumen with octadecylphosphonic acid: new inorganic tubular micelle.

Layered double hydroxides and human health: An overview

Three representative nonsteroidal anti-inflammatory drug molecules, Ibuprofen, Diclofenac, and Indomethacin, have been intercalated within the galleries of an anionic clay, Mg−Al layered double hydroxide (LDH). X-ray diffraction, IR and Raman vibrational spectroscopy and 13C cross-polarization magic-angle spinning NMR have been used to characterize the confined drug molecules, while molecular dynamics (MD) simulations were used to probe the interlayer structure, arrangement, orientation, and geometry of the intercalated species. All three drug molecules are arranged as bilayers in the interlamellar space of the anionic clay. But while the structure of the intercalated Ibuprofen is identical to that of the molecule outside the layers, spectroscopy as well as MD simulation shows that there is a change in the geometry of Diclofenac and Indomethacin upon confinement within the galleries of the LDH. The change in geometry of Diclofenac and Indomethacin upon intercalation is shown to originate from the electros...

Anionic Clays Containing Anti-Inflammatory Drug Molecules: Comparison of Molecular Dynamics Simulation and Measurements

The galleries of a Mg-Al layered double hydroxide have been functionalized by intercalation of (carboxymethyl)-\beta-cyclodextrin cavities. The functionalized inorganic solid can adsorb iodine molecules from vapor as well as nonaqueous and aqueous solutions. The adsorbed iodine complexes with the grafted cyclodextrin cavities, disassociating heterolytically to form polyiodide species. Electronic and Raman spectra provide conclusive evidence for the existence of linear symmetric triodide, $I_3-$, and pentaiodide, $I_5-$, species within the cyclodextrin cavities confined in the layered double hydroxide.

Insertion of iodine in a functionalized inorganic layered solid.

The galleries of an anionic clay, Mg-Al Layered Double Hydroxide (Mg-Al LDH) have been functionalized by intercalating the anionic surfactant do-decyl sulfate. Within the galleries, the alkyl chains of the surfactant adopt a bilayer structure with the sulfate headgroup anchored to the inorganic sheet. Pyrene molecules have been solubilized in the anchored bilayer by partitioning from polar solvents. The presence of pyrene molecules induces conformational disorder in the alkyl chains of the bilayer and more importantly inhibits the rotational disordering motion of the sulfate headgroup. Pyrene fluorescence indicates formation of excimers whose intensity increases with concentration of solubilized pyrene indicating that they are mobile. Pyrene solubilized in the anchored bilayer exhibits unusual phenomena; on evacuation the excimer band disappear but reappears on releasing vacuum. It is shown that this behavior arises due to the loss of water of hydration of the headgroup on evacuation and as a consequence the pyrene moves into the less polar interior of the bilayer where it is immobile and can no longer diffuse and form excimers. The motion of pyrene into the interior of the bilayer creates free space near the surfactant chain termini, which manifests in the disappearance of the methyl-rocking mode of the ordered (-tt) end-chain conformer in the Raman spectra.

/pdf/aromatic-molecules-in-restricted-geometries-pyrene-excimer-2mrnswsywi.pdf

Aromatic Molecules in Restricted Geometries: Pyrene Excimer Formation in an Anchored Bilayer

Carboxy-methyl β-cyclodextrin (CMCD) cavities have been intercalated within the galleries of anionic clay, Mg−Al layered double hydroxide (LDH). The cyclodextrin functionalized LDH has been reported to adsorb neutral and nonpolar guest molecules. X-ray diffraction, IR, and Raman vibrational spectroscopy and 13C CPMAS NMR have been used to characterize the confined CMCD molecules, whereas molecular dynamics simulations have been used to probe the interlayer arrangement and orientation of the intercalated species. Spectroscopic measurements as well as MD simulations show that there is no significant change in the geometry of the CMCD cavity on intercalation. Within the galleries of the anionic clay, the CMCD anions are arranged as bilayers with the carboxy methyl substituents, located at the narrower opening of the bucket-like cyclodextrin toroid, anchored to the LDH sheet. This arrangement leaves the wider opening of the CMCD anion facing away from the layers allowing the interior of the cyclodextrin cavit...

Structure of a cyclodextrin functionalized anionic clay: XRD analysis, spectroscopy, and computer simulations.

Cyclodextrin cavities have been grafted into a layered metal hydroxide to create hydrophobic nanopockets within the galleries of the inorganic solid. Neutral ferrocene molecules can be included within the grafted cavities by partitioning from a polar solvent to generate a new organometallic-organic-inorganic hybrid. The included ferrocene has been characterized by electronic and Raman spectroscopy. The capability of the cyclodextrin-functionalized solid to separate hydrophobic and hydrophilic derivatives of ferrocene is demonstrated.

L Mohanambe

Papers

Anionic Clays Containing Anti-Inflammatory Drug Molecules: Comparison of Molecular Dynamics Simulation and Measurements

Insertion of iodine in a functionalized inorganic layered solid.

Aromatic Molecules in Restricted Geometries: Pyrene Excimer Formation in an Anchored Bilayer

Structure of a cyclodextrin functionalized anionic clay: XRD analysis, spectroscopy, and computer simulations.

Inclusion of ferrocene in a cyclodextrin-functionalized layered metal hydroxide: a new organometallic--organic-LDH nanohybrid.