Russell E. Morris

Metal–Organic Frameworks in Biomedicine

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.

Gas Storage in Nanoporous Materials

Gas storage in solids is becoming an ever more important technology, with applications and potential applications ranging from energy and the environment all the way to biology and medicine. Very highly porous materials, such as zeolites, carbon materials, polymers, and metal-organic frameworks, offer a wide variety of chemical composition and structural architectures that are suitable for the adsorption and storage of many different gases, including hydrogen, methane, nitric oxide, and carbon dioxide. However, the challenges associated with designing materials to have sufficient adsorption capacity, controllable delivery rates, suitable lifetimes, and recharging characteristics are not trivial in many instances. The different chemistry associated with the various gases of interest makes it necessary to carefully match the properties of the porous material to the required application.

Ionic liquids and eutectic mixtures as solvent and template in synthesis of zeolite analogues

The challenges associated with synthesizing porous materials mean that new classes of zeolites (zeotypes)—such as aluminosilicate zeolites and zeolite analogues—together with new methods of preparing known zeotypes, continue to be of great importance. Normally these materials are prepared hydrothermally with water as the solvent in a sealed autoclave under autogenous pressure. The reaction mixture usually includes an organic template or ‘structure-directing agent’ that guides the synthesis pathway towards particular structures. Here we report the preparation of aluminophosphate zeolite analogues by using ionic liquids and eutectic mixtures. An imidazolium-based ionic liquid acts as both solvent and template, leading to four zeotype frameworks under different experimental conditions. The structural characteristics of the materials can be traced back to the solvent chemistry used. Because of the vanishingly low vapour pressure of ionic liquids, synthesis takes place at ambient pressure, eliminating safety concerns associated with high hydrothermal pressures. The ionic liquid can also be recycled for further use. A choline chloride/urea eutectic mixture is also used in the preparation of a new zeotype framework.

BioMOFs: Metal–Organic Frameworks for Biological and Medical Applications

The class of highly porous materials called metal-organic frameworks offer many opportunities for applications across biology and medicine. Their wide range of chemical composition makes toxicologically acceptable formulation possible, and their high level of functionality enables possible applications as imaging agents and as delivery vehicles for therapeutic agents. The challenges in the area encompass not only the development of new solids but also improvements in the formulation and processing of the materials, including tailoring the morphology and surface chemistry of the frameworks to fit the proposed applications.

Induction of chiral porous solids containing only achiral building blocks.

In many areas of chemistry the synthesis of chiral compounds is a target of increasing importance. They play a vital role in biological function and in many areas of society and science, including biology, medicine, biotechnology, chemistry and agriculture. Many pharmaceutical molecules, like their biological targets, are chiral and it is therefore easy to understand the growing demand for efficient methods of producing enantiomerically pure compounds. This is equally true for the preparation of chiral solids, which have potential applications in asymmetric catalysis, chiral separations and the like. In this Review we will consider recent progress and future potential in the development of methods for the preparation of chirally pure solids, in particular where the building blocks of the structure are achiral themselves. We will discuss strategies for the synthesis of both inorganic (for example, zeolites) and inorganic-organic hybrid (for example, metal organic framework) chiral porous solids.

Two-Dimensional Zeolites: Current Status and Perspectives

Wieslaw J. Roth,†,∥ Petr Nachtigall,‡ Russell E. Morris, and Jirí̌ Čejka*,† †J. Heyrovsky ́ Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, v.v.i., Dolejsǩova 3, CZ-182 23 Prague 8, Czech Republic ‡Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, Prague 2, 128 00, Czech Republic EaStCHEM School of Chemistry, University of St. Andrews, St. Andrews KY16 9ST, Scotland Faculty of Chemistry, Jagiellonian University in Krakoẃ, ul. Ingardena 3,30-060 Krakoẃ, Poland

Exceptional Behavior over the Whole Adsorption−Storage−Delivery Cycle for NO in Porous Metal Organic Frameworks

Two porous metal organic frameworks (MOFs), [M2(C8H2O6)(H2O)2] x 8 H2O (M = Co, Ni), perform exceptionally well for the adsorption, storage, and water-triggered delivery of the biologically important gas nitric oxide. Adsorption and powder X-ray diffraction studies indicate that each coordinatively unsaturated metal atom in the structure coordinates to one NO molecule. All of the stored gas is available for delivery even after the material has been stored for several months. The combination of extremely high adsorption capacity (approximately 7 mmol of NO/g of MOF) and good storage stability is ideal for the preparation of NO storage solids. However, most important is that the entire reservoir of stored gas is recoverable on contact with a simple trigger (moisture). The activity of the NO storage materials is proved in myography experiments showing that the NO-releasing MOFs cause relaxation of porcine arterial tissue.

A family of zeolites with controlled pore size prepared using a top-down method

The properties of zeolites, and thus their suitability for different applications, are intimately connected with their structures. Synthesizing specific architectures is therefore important, but has remained challenging. Here we report a top-down strategy that involves the disassembly of a parent zeolite, UTL, and its reassembly into two zeolites with targeted topologies, IPC-2 and IPC-4. The three zeolites are closely related as they adopt the same layered structure, and they differ only in how the layers are connected. Choosing different linkers gives rise to different pore sizes, enabling the synthesis of materials with predetermined pore architectures. The structures of the resulting zeolites were characterized by interpreting the X-ray powder-diffraction patterns through models using computational methods; IPC-2 exhibits orthogonal 12- and ten-ring channels, and IPC-4 is a more complex zeolite that comprises orthogonal ten- and eight-ring channels. We describe how this method enables the preparation of functional materials and discuss its potential for targeting other new zeolites.

Microwave-assisted synthesis of anionic metal–organic frameworks under ionothermal conditions

Two new isostructural coordination polymers with novel anionic metal-organic frameworks are synthesized under microwave conditions using an ionic liquid EMIm-Br as solvent and template.

The synthesis of molecular sieves from non-aqueous solvents

Molecular sieves are important in many industrial processes and their synthesis has been the focus of much research. In addition to the traditional synthetic methods based on aqueous media there is a growing body of work describing preparations using non-aqueous solvents. This review will summarise some of the results of this work in the areas of zeolite, aluminophosphate and gallophosphate synthesis.