Diastereoselective Cyclobutenol Synthesis: A Heterogeneous Palladium-Catalyzed Oxidative Carbocyclization-Borylation of Enallenols

A highly selective and efficient oxidative carbocyclization/borylation of enallenols catalyzed by palladium immobilized on amino-functionalized siliceous mesocellular foam (Pd-AmP-MCF) was developed for diastereoselective cyclobutenol synthesis. The heterogeneous palladium catalyst can be recovered and recycled without any observed loss of activity or selectivity. The high diastereoselectivity of the reaction is proposed to originate from a directing effect of the enallenol hydroxyl group. Optically pure cyclobutenol synthesis was achieved by the heterogeneous strategy by using chiral enallenol obtained from kinetic resolution.     

Study of the peak effect phenomenon in single crystals of 2H-NbSe2

The weakly pinned single crystals of the hexagonal 2H-NbSe₂ compound have emerged as prototypes for determining and characterizing the phase boundaries of the possible order-disorder transformations in the vortex matter. We present here a status report based on the ac and dc magnetization measurements of the peak effect phenomenon in three crystals of 2H-NbSe₂, in which the critical current densities vary over two orders of magnitude. We sketch the generic vortex phase diagram of a weakly pinned superconductor, which also utilizes theoretical proposals. We also establish the connection between the metastability effects and pinning.     

Label-Free Impedance Biosensors: Opportunities and Challenges

Impedance biosensors are a class of electrical biosensors that show promise for point-of-care and other applications due to low cost, ease of miniaturization, and label-free operation. Unlabeled DNA and protein targets can be detected by monitoring changes in surface impedance when a target molecule binds to an immobilized probe. The affinity capture step leads to challenges shared by all label-free affinity biosensors; these challenges are discussed along with others unique to impedance readout. Various possible mechanisms for impedance change upon target binding are discussed. We critically summarize accomplishments of past label-free impedance biosensors and identify areas for future research.     

Shaping Solid-State Supramolecular Cavities: Chemically Induced Accordionlike Movement of gamma-Zirconium Phosphate Containing Polyethylenoxide Pillars

The hydrophilic oxygen atoms of polyethylenoxide chains inserted as pillars in gamma-zirconium phosphate form hydrogen bonds with the acid groups of the host. As a result the pillars are almost perpendicular to the gamma layers. Upon changing the pH level of the supernatant solution the hydrogen bonds are broken and the pillars become almost perpendicular to the layers (shown schematically). Thus there is a reversible enlargement-shortening of the interlayer space.     

The extraordinary ability of guanidinate derivatives to stabilize higher oxidation numbers in dimetal units by modification of redox potentials: structures of Mo(2)(5+) and Mo(2)(6+) compounds

Full characterization of the first homologous series of dimolybdenum paddlewheel compounds having electronic configurations of the types sigma(2)pi(4)delta(x), x = 2, 1, 0, and Mo-Mo bond orders of 4, 3.5, and 3, respectively, has been accomplished with the guanidinate-type ligand hpp (hpp = the anion of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine). Essentially quantitative oxidation of Mo(2)(hpp)(4), 1, by CH(2)Cl(2) gives Mo(2)(hpp)(4)Cl, 2. The halide in 2 can be replaced by reaction with TlBF(4) to produce Mo(2)(hpp)(4)(BF(4)), 3. Further oxidation of 2 by AgBF(4) produces Mo(2)(hpp)(4)ClBF(4), 4. The change from bond order 4 (in 1) to 3.5 in Mo(2)(hpp)(4)Cl is accompanied by an increase in the Mo-Mo bond length of 0.061 to 2.1280(4) A. A further increase of 0.044 A in the Mo-Mo distance to 2.172(1) A is observed as the bond order decreases to 3 in 4. At the same time, the Mo-N distances decrease smoothly as the oxidation state of the Mo atoms increases. Electrochemical studies have shown two chemically reversible processes at very negative potentials, E(1)(1/2)= -0.444 V and E(2)(1/2)= -1.271 V versus Ag/AgCl. These correspond to the processes Mo(2)(6+/5+) and Mo(2)(5+/4+), respectively. The latter potential is displaced by over 1.5 V relative to those of the Mo(2)(formamidinate)(4) compounds and the first one has never been observed in such complexes. Thus, in surprising contrast to previously observed behavior of the dimolybdenum unit, when it is surrounded by the very basic guanidinate ligand hpp, there is an extraordinary stabilization of the higher oxidation numbers of the molybdenum atoms.