Microwave‐assisted synthesis of α‐hydroxy‐benzylphosphonates and ‐benzylphosphine oxides

A series of α‐hydroxy‐benzylphosph‐ onates and ‐benzylphosphine oxides was synthesized by the Na₂CO₃‐catalyzed microwave‐assisted addition of dialkyl phosphites and dipenylphosphine oxide to P‐substituted benzaldehydes. The solventless reaction provided the products in short reaction times and in 71–88% yield. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 22:15–17, 2011; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20649     

D-optimal design of an untargeted HS-SPME-GC-TOF metabolite profiling method

In recent times we have seen the development of many "-omics" technologies. One of the youngest is undoubtedly metabolomics, which aims to define the whole chemical fingerprint unique to each specific organism. The development and optimisation of an untargeted high-throughput method capable of investigating the volatile fraction of a biological system represents a crucial step for the success of such holistic approaches, and specific optimisation criteria must be developed in connection with suitable experimental designs. In this paper experimental designs (D-optimal) were applied for the first time as an automatic optimisation tool to an untargeted HS-SPME-GC-TOF method. In this case, optimal conditions correspond to a maximal number of detected features, in order to provide a fingerprint that is as complete as possible. The system under study is the grape berry. Four variables were considered: the type of fibre, extraction time, equilibration time and temperature. The results show that the D-optimal design methodology provides an easily interpretable assessment of experimental settings. This and other specific properties of the D-optimal design, such as the possibility to explicitly exclude certain experimental conditions, make it an extremely suitable strategy for method optimisation in untargeted metabolomics.     

Metastable 11 K Superconductor Na(1-y)Fe(2-x)As(2)

The topochemical deintercalation of Na(+) ions from solid NaFeAs at room temperature in THF with iodine yields the superconducting phase Na(1-y)Fe(2-x)As(2) (T(c) ≈ 11 K). This metastable iron arsenide decomposes at 120 °C and is not accessible by high-temperature solid-state synthesis. X-ray powder diffraction confirms the ThCr(2)Si(2)-type structure, but reveals very small coherently scattering domains with a mean composition Na(0.9(2))Fe(1.7(1))As(2). HRTEM investigations show crystalline as well as strongly distorted areas with planar defects. The latter are probably due to sodium loss and disorder which is also detected by (23)Na solid state NMR. The (57)Fe-M?ssbauer spectrum of Na(1-y)Fe(2-x)As(2) shows one type of iron atoms in tetrahedral coordination. All results point to one crystallographic phase with very small domains due to fluctuations of the chemical composition. From electronic reasons we suggest the superconducting phase is presumably NaFe(2)As(2) in the ordered fractions of the sample.     

Synthesis, structure and thermal analysis of the gallium complex of 1,4,7,10-tetraazacyclo-dodecane-N,N′,N″,N-tetraacetic acid (DOTA)

As part of our efforts to synthesize gallium bioconjugates based on folic acid and thiamin we have utilized 1,4,7,10-tetraazacyclo-dodecane-N,N′,N″,N-tetraacetic acid (DOTA) as the chelating ligand for gallium(III). The reaction of gallium chloride with DOTA at room temperature in aqueous solution affords the complex [Ga(HDOTA) · 5.5H₂O] (1), which is characterized by single-crystal X-ray spectroscopy, electrospray mass spectrometry and thermal gravimetric analysis. Gallium displays 6-coordinate distorted octahedral geometry within a puckered macrocyclic DOTA framework. The equatorial plane comprises two nitrogens of the DOTA ring and two oxygens from two of the four pendant carboxylic acid groups. The axial positions are comprised of the remaining two transannular nitrogens of the DOTA ring.     

Mechanistic analysis of the oxygen reduction reaction at (La,Sr)MnO3 cathodes in solid oxide fuel cells

The primary aim of this work was to establish the mechanism of the oxygen reduction reaction (ORR) at (La(0.8)Sr(0.2))0.98MnO3 (LSM)-based cathodes in solid oxide fuel cells. Rate equations, based on the Butler-Volmer equation and employing either Langmuir or Temkin adsorption conditions for reactant and intermediate species, were derived, yielding predicted reaction orders and transfer coefficients. Experimental data were collected using half-cell cyclic voltammetry in a variable pO2 atmosphere (0.03 to 1 atm) at 600 to 900 degrees C, using both dense and porous LSM-based cathodes, employed to establish the impact of the accessibility of the active site on cathode activity. The rate of the ORR at dense LSM has been found to be limited by the dissociation of O(2ads)- at low currents and by the first electron-transfer step, reducing O(2ads) to O(2ads)-, at high currents. However, at porous LSM cathodes, the reaction mechanism is more difficult to deduce because the electrode morphology impacts significantly on the measured kinetic and mechanistic parameters, giving anomalous transfer coefficients of <0.5.     

Inside Cover: Giant Pores in a Chromium 2,6‐Naphthalenedicarboxylate Open‐Framework Structure with MIL‐101 Topology (Angew. Chem. Int. Ed. 21/2009)

Highly porous and stable metal–organic frameworks, isoreticular to MIL‐101 and with cage diameters of 39 and 46 Å, are obtained by replacement of the 1,4‐benzenedicarboxylate ligands in that framework with 2,6‐naphthalenedicarboxylate. In their Communication on page 3791 ff. , N. Stock and co‐workers report high‐throughput methods used to optimize reaction conditions and characterization of this MTN zeolite analogue by a combination of structure simulation, electron microscopy, and sorption measurements.

     

One-way multiparty communication lower bound for pointer jumping with applications

In this paper we study the one-way multiparty communication model, in which every party speaks exactly once in its turn. For every k, we prove a tight lower bound of Ω(n ^1/(k?1)}) on the probabilistic communication complexity of pointer jumping in a k-layered tree, where the pointers of the i-th layer reside on the forehead of the i-th party to speak. The lower bound remains nontrivial even for k = (logn)^1/2?? parties, for any constant ? > 0. Previous to our work a lower bound was known only for k =3 (Wigderson, see [7]), and in restricted models for k>3 [2},24,18,4,13]. Our results have the following consequences to other models and problems, extending previous work in several directions. The one-way model is strong enough to capture general (not one-way) multiparty protocols with a bounded number of rounds. Thus we generalize two problem areas previously studied in the 2-party model (cf. [30,21,29]). The first is a rounds hierarchy: we give an exponential separation between the power of r and 2r rounds in general probabilistic k-party protocols, for any k and r. The second is the relative power of determinism and nondeterminism: we prove an exponential separation between nondeterministic and deterministic communication complexity for general k-party protocols with r rounds, for any k,r. The pointer jumping function is weak enough to be a special case of the well-studied disjointness function. Thus we obtain a lower bound of Ω(n ^1/(k?1)) on the probabilistic complexity of k-set disjointness in the one-way model, which was known only for k = 3 parties. Our result also extends a similar lower bound for the weaker simultaneous model, in which parties simultaneously send one message to a referee [12]. Finally, we infer an exponential separation between the power of any two different orders in which parties send messages in the one-way model, for every k. Previous results [29, 7] separated orders based on who speaks first. Our lower bound technique, which handles functions of high discrepancy over cylinder intersections, provides a “party-elimination” induction, based on a restricted form of a direct-product result, specific to the pointer jumping function.