Controlled Synthesis of Large Single Crystals of Metal-Organic Framework CPO-27-Ni Prepared by a Modulation Approach: In situ Single-Crystal X-ray Diffraction Studies

The size of single crystals of the metal-organic framework CPO-27-Ni was incrementally increased through a series of modulated syntheses. A novel linker modulated synthesis using 2,5-dihydroxyterephthalic acid and the isomeric ligand 4,6-dihydroxyisophthalic acid yielded large single crystals of CPO-27-Ni (∼70 μm). All materials were shown to have high crystallinity and phase purity through powder X-ray diffraction, electron microscopy methods, thermogravimetry, and compositional analysis. For the first time single-crystal structure analyses were carried out on CPO-27-Ni. High BET surface areas and nitric oxide (NO) release efficiencies were recorded for all materials. Large single crystals of CPO-27-Ni showed a prolonged NO release and proved suitable for in situ single-crystal diffraction experiments to follow the NO adsorption. An efficient activation protocol was developed, leading to a dehydrated structure after just 4 h, which subsequently was NO-loaded, leading to a first NO loaded single-crystal structural model of CPO-27-Ni.     

Rapid initiation of reactions in Al/Ni multilayers with nanoscale layering

Research into nanoenergetic materials is enabling new capabilities for controlling exothermic reaction rates and energy output, as well as new methods for integrating these materials with conventional electronics fabrication techniques. Many reactions produce primarily heat, and in some cases it is desirable to increase the rate of heat release beyond what is typically observed. Here we investigate the Al-Ni intermetallic reaction, which normally propagates across films or foils at rates lower than 10 m/s. However, models and experiments indicate that local heating rates can be very high (10⁷ K/s), and uniform heating of such a multilayer film can lead to a rapid, thermally explosive type of reaction. With the hopes of using a device to transduce electrical energy to kinetic energy of a flyer plate in the timescale of 100's of nanoseconds, we have incorporated a Ni/Al nanolayer film that locally heats upon application of a large electrical current. We observed flyer plate velocities in the 2-6 km/s range, corresponding to 4-36 kJ/g in terms of specific kinetic energy. Several samples containing Ni/Al films with different bilayer thicknesses were tested, and many produced additional kinetic energy in the 1.1-2.3 kJ/g range, as would be expected from the Ni-Al intermetallic reaction. These results provide evidence that nanoscale Ni/Al layers reacted in the timescale necessary to contribute to device output.     

Selective preparation of (E)-3-oxo-1-alkenylphosphonates by insertion of acyl chlorides and nitriles into zirconacycles

Zirconacycles 1, obtained from diethyl 1-alkynylphosphonates, insert either acyl chlorides or nitriles to provide, after acidic workup, (E)-3-oxo-1-alkenylphosphonates, 2, in isolated yields of 55-83%. Insertion produces only one regio- and stereoisomer. The reaction is quite general and proceeds well with both aliphatic and aromatic acyl chlorides. Acetonitrile and p-methoxybenzonitrile also inserted efficiently. Insertion of isobutyl chloroformate produced the vinylphosphonocarboxylate, 2c, the first representative of this class of compounds.     

Evidence for static magnetism in the vortex cores of ortho-II YBa2Cu3O6.50

Evidence for static alternating magnetic fields in the vortex cores of underdoped YBa2Cu3O6+x is reported. Muon spin rotation measurements of the internal magnetic field distribution of the vortex state of YBa2Cu3O6.50 in applied fields of H = 1 T and H = 4 T reveal a feature in the high-field tail of the field distribution which is not present in optimally doped YBa2Cu3O6.95 and which fits well to a model with static magnetic fields in the vortex cores. The magnitude of the fields is estimated to be 18(2) G and decreases above T = 10 K. We discuss possible origins of the additional vortex core magnetism within the context of existing theories.     

Distributed automated docking of flexible ligands to proteins: Parallel applications of AutoDock 2.4

Summary AutoDock 2.4 predicts the bound conformations of a small, flexible ligand to a nonflexible macromolecular target of known structure. The technique combines simulated annealing for conformation searching with a rapid grid-based method of energy evaluation based on the AMBER force field. AutoDock has been optimized in performance without sacrificing accuracy; it incorporates many enhancements and additions, including an intuitive interface. We have developed a set of tools for launching and analyzing many independent docking jobs in parallel on a heterogeneous network of UNIX-based workstations. This paper describes the current release, and the results of a suite of diverse test systems. We also present the results of a systematic investigation into the effects of varying simulated-annealing parameters on molecular docking. We show that even for ligands with a large number of degrees of freedom, root-mean-square deviations of less than 1 Å from the crystallographic conformation are obtained for the lowest-energy dockings, although fewer dockings find the crystallographic conformation when there are more degrees of freedom.The AutoDock 2.4 suite is written in ANSI C, and is supplied with Makefiles for the following platforms: Convex, DEC Alpha OSF/1, Hewlett-Packard Precision Architecture, Silicon Graphics, and Sun. The AutoDock suite of programs is freely available to the noncommercial scientific community and to educational establishments. Further information, including additional figures and MPEG animations showing all docked conformations for each test system, can be found at the following URL: http://www.scripps.edu/pub/olson-web/doc/autodock.     

Free products of kω-topological groups with normal amalgamation

It is shown in this paper that if A is a closed normal subgroup of k_ω-topological groups G and H, then the free product of G and H with A amalgamated, G1_AH, exists, is Hausdorff and indeed a k_ω-group.