Postsynthetic modification of zirconium metal-organic frameworks

Metal-organic frameworks (MOFs) have been in the spotlight for a number of years due to their chemical and topological versatility. As MOF research has progressed, highly functionalised materials have become desirable for specific applications, and in many cases the limitations of direct synthesis have been realised. This has resulted in the search for alternative synthetic routes, with postsynthetic modification (PSM), a term used to collectively describe the functionalisation of pre-synthesised MOFs whilst maintaining their desired characteristics, becoming a topic of interest. Advances in the scope of reactions performed are reported regularly; however reactions requiring harsh conditions can result in degradation of the framework. Zirconium-based MOFs present high chemical, thermal and mechanical stabilities, offering wider opportunities for the scope of reaction conditions that can be tolerated, which has seen a number of successful examples reported. This microreview discusses pertinent examples of PSM resulting in enhanced properties for specific applications, alongside fundamental transformations, which are categorised broadly into covalent modifications, surface transformations, metalations, linker and metal exchange, and cluster modifications

Crystallographic investigation into the self-assembly, guest binding, and flexibility of urea functionalised metal-organic frameworks

Introduction of hydrogen bond functionality into metal-organic frameworks can enhance guest binding and activation, but a combination of linker flexibility and interligand hydrogen bonding often results in the generation of unwanted structures where the functionality is masked. Herein, we describe the self-assembly of three materials, where Cd2+, Ca2+, and Zn2+ are linked by N,Nʹ-bis(4-carboxyphenyl)urea, and examine the effect of the urea units on structure formation, the generation of unusual secondary building units, structural flexibility, and guest binding. The flexibility of the Zn MOF is probed through single-crystal to single-crystal transformations upon exchange of DMF guests for CS2, showing that the lability of the [Zn4O(RCO2)6] cluster towards solvation enables the urea linkers to adopt distorted conformations as the MOF breathes, even facilitating rotation from the trans/trans to the trans/cis conformation without compromising the overall topology. The results have significant implications in the mechanistic understanding of the hydrolytic stability of MOFs, and in preparing heterogeneous organocatalysts

Violation of Kohler's rule by the magnetoresistance of a quasi-two-dimensional organic metal

The interlayer magnetoresistance of the quasi-two-dimensional metal $\alpha$-(BEDT-TTF)$_2$KHg(SCN)$_4$ is considered. In the temperature range from 0.5 to 10 K and for fields up to 10 tesla the magnetoresistance has a stronger temperature dependence than the zero-field resistance. Consequently Kohler's rule is not obeyed for any range of temperatures or fields. This means that the magnetoresistance cannot be described in terms of semiclassical transport on a single Fermi surface with a single scattering time. Possible explanations for the violations of Kohler's rule are considered, both within the framework of semi-classical transport theory and involving incoherent interlayer transport. The issues considered are similar to those raised by the magnetotransport of the cuprate superconductors.Comment: 5 pages, RevTeX + epsf, 2 figures. Slightly revised version to appear in Physical Review B, May 15, 199

Hydrodynamic Irreversibility in Particle Suspensions with Non-Uniform Strain

A dynamical phase transition from reversible to irreversible behavior occurs when particle suspensions are subjected to uniform oscillatory shear, even in the Stokes flow limit. We consider a more general situation with non-uniform strain (e.g. oscillatory channel flow), which is observed to exhibit markedly different dynamics. Self-organization and shear-induced migration only partially explain the delayed, simultaneous onset of irreversibility across the channel. The onset of irreversibility is accompanied by long-range correlated particle motion. This motion leads to particle activity even at the channel center, where the strain is negligible, and prevents the system from evolving into a reversible state

Fast, high fidelity information transmission through spin chain quantum wires

Spin chains have been proposed as quantum wires for information transfer in solid state quantum architectures. We show that huge gains in both transfer speed and fidelity are possible using a minimalist control approach that relies only a single, local, on-off switch actuator. Effective switching time sequences can be determined using optimization techniques for both ideal and disordered chains. Simulations suggest that effective optimization is possible even in the absence of accurate models.Comment: revtex4, 4 pages, 5 figure

Prediction of the flow-field interference induced by the long-range laser velocimeter in the Ames 40- by 80-foot and the 80- by 120-foot wind tunnels

The predicted flow disturbances induced in the test sections of the Ames 40- by 80-Foot Wind Tunnels by the presence of the Long-Range Laser Velocimeter (LRLV) are presented. The predictions were made using a potential-flow paneling code to model the test section and the LRLV, and a calculation of the resulting flow field was made. The flow velocity and angularity were calculated at numerous locations in the flow field relative to the LRLV, and the results are presented

The selection, appraisal and retention of digital scientific data: dighlights of an ERPANET/CODATA workshop

CODATA and ERPANET collaborated to convene an international archiving workshop on the selection, appraisal, and retention of digital scientific data, which was held on 15-17 December 2003 at the Biblioteca Nacional in Lisbon, Portugal. The workshop brought together more than 65 researchers, data and information managers, archivists, and librarians from 13 countries to discuss the issues involved in making critical decisions regarding the long-term preservation of the scientific record. One of the major aims for this workshop was to provide an international forum to exchange information about data archiving policies and practices across different scientific, institutional, and national contexts. Highlights from the workshop discussions are presented

Location Patterns of Confectionery Manufacturers in a Post NAFTA Environment

Changes in international trade agreements while retaining protectionist sugar policies have led to the opportunity for confectionery manufacturers to relocate to take advantage of favorable international trade policies. Results suggest that NAFTA did not have a significant impact on location decisions of confectionery manufacturers in the U.S.Agribusiness, International Relations/Trade,