Reaction Mechanisms of Crotonaldehyde Hydrogenation on Pt(111): Density Functional Theory and Microkinetic Modeling

The microkinetics based on density function theory (DFT) calculations is utilized to investigate the reaction mechanism of crotonaldehyde hydrogenation on Pt(111) in the free energy landscape. The dominant reaction channel of each hydrogenation product is identified. Each of them begins with the first surface hydrogenation of the carbonyl oxygen of crotonaldehyde on the surface. A new mechanism, 1,4-addition mechanism generating enols (butenol), which readily tautomerize to saturated aldehydes (butanal), is identified as a primary mechanism to yield saturated aldehydes instead of the 3,4-addition via direct hydrogenation of the ethylenic bond. The calculation results also show that the full hydrogenation product, butylalcohol, mainly stems from the deep hydrogenation of surface open-shell dihydrogenation intermediates. It is found that the apparent barriers of the dominant pathways to yield three final products are similar on P(111), which makes it difficult to achieve a high selectivity to the desired crotyl alcohol (COL).

Frequency selective surface using nested split ring slot elements as a lens with mechanically reconfigurable beam steering capability

The design is described of a double layer frequency selective surface which can produce a differential phase shift of 180 ° as the wave propagates through it at normal incidence. The hand of an applied circularly polarized signal is reversed due to the 180° phase shift, and it is demonstrated that the exit circularly polarized output signal can be phase advanced or phase retarded by 180 ° upon rotation of the elements comprising the structure. This feature allows the surface to act as a spatial phase shifter. In this paper the beam steering capabilities of a 10 × 10 array of such elements are demonstrated. Here the individual elements comprising the array are rotated relative to each other in order to generate a progressive phase shift. At normal incidence the 3 dB Axial Ratio Bandwidth for LHCP to RHCP conversion is 5.3% and the insertion loss was found to be -2.3 dB, with minimum axial ratio of 0.05 dB. This array is shown to be able to steer a beam from -40 ° to +40 ° while holding axial ratio at the pointing angle to below 4 dB. The measured radiation patterns match the theoretical calculation and full-wave simulation results. © 2010 IEEE.

Selectivity control in hydrogenation reactions by nanoconfinement of polymetallic nanoparticles in mesoporous thin films

A one-pot sol-gel synthesis method has been developed for the incorporation of metal nanoparticles into mesoporous oxide thin films deposited on various plane substrates by spin-coating and on the inner surface of fused silica capillaries by dip-coating. The size, the metal loading and the stoichiometry of the metal nanoparticles could be precisely controlled by following this methodology. In the first step, polymer stabilized Pt50Sn50 and Pt90Sn10 nanoparticles were obtained by a solvent-reduction method. Then, the nanoparticles were added to a metal oxide precursor sol, which was destabilized by solvent evaporation. After calcination, the obtained materials were tested in the hydrogenation of citral in both batch and continuous modes. The highest selectivity of 30% towards the unsaturated alcohols was obtained over supported Pt90Sn10 nanoparticles with a preferential formation of the cis-isomer (nerol) due to a unique confinement of the bimetallic nanoparticles in the mesoporous framework. The selectivity towards the unsaturated alcohols was further improved to 56% over the PtRu5Sn nanoparticles supported by impregnation onto mesoporous silica films. (C) 2009 Elsevier B.V. All rights reserved.

Dinitrogen formation over low-exchanged Cu-ZSM-5 in the selective reduction of NO by propane

The role of gaseous NO and C3H8 has been studied over low-exchanged Cu-ZSM-5 zeolite employing TPD, FTIR and pulse technique with the alternate introduction of NO or C3H8 onto the catalyst surface. The rate of the N-2 formation is directly proportional to the content of gaseous NO and the surface coverage with 2-nitrosopropane. There was no formation of N-2 during interaction of gaseous C3H8 with NO adsorbates. However, 2-nitrosopropane and its isomer acetone oxime were also formed in this reaction.

Selective homogeneous snythesis of dimethyl ether from methanol

Selected Bronsted acidic ionic liquids were tested as homogeneous catalysts for the dehydration of methanol to dimethyl ether. Ionic liquids incorporating an alkanesulfonic acid as a part of the cation, a complex acidic anion, [A(2)H](-), or both, proved to be good catalysts for this process, providing high conversions and selectivities. Homogeneous catalysis in the liquid state represents a novel approach to dimethyl ether synthesis.

Path-selective photoinduced electron transfer (PET) in a membrane-associated system studied by pH-dependent fluorescence

The pH-dependent fluorescence behavior of two regioisomeric 'receptor(1)-spacer(1)-fluorophore-spacer(2)-receptor(2)' systems 1 and 2 in micellar solutions of sodium dodecyl sulfate show that photoinduced electron transfer (PET) only occurs from the amine group connected to the 4-amino position of the aminonaphthalimide fluorophore in both cases. This demonstrates the directing influence of the photogenerated electric field within the aminonaphthalimide excited state on the electron transfer process. Since path-selectivity of PET is also known within the membrane-bound photosynthetic reaction center in bacteria, its origins may be illuminated by the simple experiments described here. (C) 2011 Elsevier B. V. All rights reserved.

Discovery and Development of a Potent and Highly Selective Small Molecule Muscarinic Acetylcholine Receptor Subtype I (mAChR 1 or M-1) Antagonist In Vitro and In Vivo Probe

This article describes the discovery and development of the first highly selective, small molecule antagonist of the muscarinic acetylcholine receptor subtype I (mAChR1 or M-1). An M-1 functional, cell-based, calcium-mobilization assay identified three distinct chemical series with initial selectivity for M-1 versus M-4. An iterative parallel synthesis approach was employed to optimize all three series in parallel, which led to the development of novel microwave-assisted chemistry and provided important take home lessons for probe development projects. Ultimately, this effort produced VU0255035, a potent (IC50 = 130 nM) and selective (>75-fold vs. M-2-M-5 and >10 mu M vs. a panel of 75 GPCRs, ion channels and transporters) small molecule M-1 antagonist. Further profiling demonstrated that VU0255035 was centrally penetrant (Brain(AUC)/Plasma(AUC) of 0.48) and active in vivo, rendering it acceptable as both an in vitro and in vivo MLSCN/MLPCN probe molecule for studying and dissecting M-1 function.

A Novel Selective Muscarinic Acetylcholine Receptor Subtype 1 Antagonist Reduces Seizures without Impairing Hippocampus-Dependent Learning

Previous studies suggest that selective antagonists of specific subtypes of muscarinic acetylcholine receptors (mAChRs) may provide a novel approach for the treatment of certain central nervous system (CNS) disorders, including epileptic disorders, Parkinson's disease, and dystonia. Unfortunately, previously reported antagonists are not highly selective for specific mAChR subtypes, making it difficult to definitively establish the functional roles and therapeutic potential for individual subtypes of this receptor subfamily. The M 1 mAChR is of particular interest as a potential target for treatment of CNS disorders. We now report the discovery of a novel selective antagonist of M-1 mAChRs, termed VU0255035 [N-(3-oxo-3-(4-(pyridine-4-yl)piperazin-1-yl)propyl)benzo[c][1,2,5]thiadiazole-4-sulfonamide]. Equilibrium radioligand binding and functional studies demonstrate a greater than 75-fold selectivity of VU0255035 for M-1 mAChRs relative to M-2-M-5. Molecular pharmacology and mutagenesis studies indicate that VU0255035 is a competitive orthosteric antagonist of M-1 mAChRs, a surprising finding given the high level of M-1 mAChR selectivity relative to other orthosteric antagonists. Whole-cell patch-clamp recordings demonstrate that VU0255035 inhibits potentiation of N-methyl-D-aspartate receptor currents by the muscarinic agonist carbachol in hippocampal pyramidal cells. VU0255035 has excellent brain penetration in vivo and is efficacious in reducing pilocarpine-induced seizures in mice. We were surprised to find that doses of VU0255035 that reduce pilo-carpine-induced seizures do not induce deficits in contextual freezing, a measure of hippocampus-dependent learning that is disrupted by nonselective mAChR antagonists. Taken together, these data suggest that selective antagonists of M-1 mAChRs do not induce the severe cognitive deficits seen with nonselective mAChR antagonists and could provide a novel approach for the treatment certain of CNS disorders.

Solid-state sodium-selective sensors based on screen-printed Ag/AgCl reference electrodes

The potentiometric and AC impedance characteristics of all solid-state sodium-selective electrodes based on planar screen-printed Ag/AgCl electrodes are described. Two solid-state designs have been investigated. The first was based on the deposition of a sodium-selective PVC membrane directly on top of a screen-printed Ag/AgCl electrode, The second design included a NaCl doped hydrogel layer, between the PVC and Ag\AgCl layers. The hydrogel provides a mechanism to relieve any blockage to charge transfer occurring when PVC membranes are used directly on top of Ag/AgCl and also improves adhesion between the two layers. Results suggest the electrodes display Fast ion exchange kinetics, low noise and drift. The performance compares favorably to that of a conventional ion-selective electrode with internal filling solution.

Femtosecond lasers for mass spectrometry: Proposed application to catalytic hydrogenation of butadiene

Mass spectra from the interaction of intense, femtosecond laser pulses with 1,3-butadiene, 1-butene, and n-butane have been obtained. The proportion of the fragment ions produced as a function of intensity, pulse length, and wavelength was investigated. Potential mass spectrometry applications, for example in the analysis of catalytic reaction products, are discussed.