Tetrahedral onsager crosses for solubility improvement and crystallization bypass

Pure organic molecules exhibiting a suitable concave rigid shape are expected to give porous glasses in the solid state. Such a feature opens new opportunities to avoid crystallization and to improve molecular solubility in relation to the high internal energy of these solid phases. To quantitatively explore the latter strategy, a series of rigid tetrahedral conjugated molecules nC and the corresponding models nR have been synthesized. Related to the present purpose, several properties have been investigated using UV absorption, steady-state fluorescence emission, differential scanning calorimetry, (1)H NMR translational self-diffusion, magic angle spinning (13)C NMR, and multiple-beam interferometry experiments. The present tetrahedral crosses are up to 8 orders of magnitude more soluble than the corresponding model compounds after normalization to the same molecular length. In addition, they give concentrated monomeric solutions that can be used to cover surfaces with homogeneous films whose thickness goes down to the nanometer range. Such attractive features make cross-like molecular architectures promising for many applications.     

Zinc(II)-porphyrin Receptors in Multi-point Molecular Recognition: Recent Progress

The tremendous efforts made in order to control the coordination chemistry of hemoprotein models have considerably enhanced the synthesis of functionalized porphyrins, whose carefully designed architectures allowed for selective bindings of exogenic substrates. The common use of zinc(II) in place of pentacoordinated iron(II) has induced the use of zinc(II) porphyrins as building blocks for selective receptors. These receptors offer a convenient combination of multi-point recognition of substrates, and monitoring of the complexation due to the chromophoric nature of the tetrapyrrolic unit. This review is dedicated to recent progress made in the field of molecular recognition involving multi-point selective binding processes, in whichthe establishment of a strong coordination bond is finely tuned by one or more weak interactions adequately introduced in the architecture of a functionalized zinc(II)-porphyrin.     

Simultaneous determination of betamethasone and dexamethasone residues in bovine liver by liquid chromatography/tandem mass spectrometry

In this study a new method for the simultaneous confirmation of betamethasone and dexamethasone residues in bovine liver is presented. A Quattro LCZ triple quadrupole mass spectrometer, equipped with an atmospheric pressure ionization (API) source, was coupled to a high performance liquid chromatograph (HPLC) system. Spiked liver samples were first extracted with acetonitrile, and the extracts were purified on C-18 columns. LC separations were performed on a Hypercarb column, with acetonitrile/water (90:10, v/v, +0.3% formic acid) as the mobile phase. Retention times for dexa- and betamethasone were 6.60 and 8.50 min, respectively. Fluorometholone had a retention time of 6.70 min and was used as the internal standard. The detection of the analytes was performed in the multiple reaction monitoring (MRM) mode. The assay was linear over the range of 0.5 to 8 microg/kg for both analytes. The estimated determination limits were 0.2 microg/kg for both beta- and dexamethasone and the quantification limits were 0.4 microg/kg for dexamethasone and 0.3 microg/kg for betamethasone. Analysis precision at 1, 2 and 4 microg/kg was lower than 6.1% (relative standard deviation, RSD) and accuracy was at least 97.5%. Recoveries at 1, 2 and 4 microg/kg ranged between 56 and 69%.     

Studies on high-temperature amination reactions of aromatic chlorides using discrete Palladium-N-Heterocyclic Carbene (NHC) complexes and in situ palladium/imidazolium salt protocols

The palladium catalysed coupling of aryl chlorides and amines can be readily achieved with short reaction times when carried out at high temperatures under thermal or microwave conditions. These coupling protocols are successful using two co-ordinate palladium-N-heterocyclic carbene complexes, or imidazolium salt protocols.     

Computation of Almost Split Sequences with Applications to Relatively Projective and Prinjective Modules

Let be an Artin algebra, let mod be the category of finitely generated -modules, and let Amod be a contravariantly finite and extension closed subcategory. For an indecomposable and not Ext-projective module CA, we compute the almost split sequence 0ABC0 in A from the almost split sequence 0DTrCEC0 in mod. Since the computation is particularly simple if the minimal right A-approximation of DTrC is indecomposable for all indecomposable and not Ext-projective CA, we manufacture subcategories A with the desired property using orthogonal subcategories. The method of orthogonal subcategories is applied to compute almost split sequences for relatively projective and prinjective modules.     

Numerical Representations of Interval Orders

In the framework of the analysis of orderings whose associated indifference relation is not necessarily transitive, we study the structure of an interval order and its representability through a pair of real-valued functions. We obtain a list of characterizations of the existence of a representation, showing that the three main techniques that have been used in the literature to achieve numerical representations of interval orders are indeed equivalent.     

Local Power Properties of Kernel Based Goodness of Fit Tests

If (X_i, i ) is a strictly stationary process with marginal density function f, we are interested in testing the hypothesis H₀: {f=f₀}, where f₀ is given. We consider different test statistics based on integrated quadratic forms measuring the proximity between f_n, a kernel estimator of f, and f₀, or between f_n and its expected value computed under H₀. We study the asymptotic local power properties of the testing procedures under local alternatives. This study generalizes to the multidimensional case in a context of dependence the corresponding one made by P. J. Bickel and M. Rosenblatt in 1973 (Ann. Statist.1, 1071–1095).     

The elliptic functions and integrals of the “{1 \mathord{\left/ {\vphantom {1 9}} \right. \kern-\nulldelimiterspace} 9}” problem

We describe the functions needed in the determination of the rate of convergence of best $L^\infty $ rational approximation to $\exp ( - x)$ on [0,∞) when the degree n of the approximation tends to ∞ (“1/9” problem).     

Second Order Perturbations of a Schwarzschild Black Hole: Inclusion of Odd Parity Perturbations

We consider perturbations of a Schwarzschild black hole that can be of both even and odd parity, keeping terms up to second order in perturbation theory, for the l = 2 axisymmetric case. We develop explicit formulae for the evolution equations and radiated energies and waveforms using the Regge–Wheeler–Zerilli approach. This formulation is useful, for instance, for the treatment in the "close limit approximation" of the collision of counterrotating black holes.