Copper(I) and silver(I) complexes of 1,5-methylene- and diethylmethylene-bridged bis(oxazoline) ligands. In situ Cu(II)-catalyzed oxidation of methylene bridge

Silver(I) and copper(I) complexes of C₂-symmetric bis(oxazoline) ligands were studied by UV, NMR, IR, EPR and ES-MS spectroscopies. The stability constants of the Ag-1a and Ag-1b complexes with 1:1 and 1:2 stoichiometries in acetonitrile were determined by NMR spectrometric titrations. The evidence of tetrahedral coordination for complex (Ag(1a)₂(⁺ was obtained from the complexation induced shifts (CIS) and NOEs. Mass spectra revealed the Cu(II) mediated oxidation of methylene bridge in copper complexes of 1a and 1b, which was in accordance with the UV, NMR, IR and EPR findings. The efficiency of Cu(I) complexes of methylene-bridged 1,5-bis(oxazoline)s 1 as chiral catalysts in stereoselective cyclopropanation of styrene with ethyl diazoacetate, was compared to that of the dialkylmethylene-bridged 1,5-bis(oxazoline)s 2.     

Quantum and Classical Implication Algebras with Primitive Implications

Join in an orthomodular lattice is obtained inthe same form for all five quantum implications. Theform holds for the classical implication in adistributive lattice as well. Even more, the definition added to an ortholattice makes it orthomodularfor quantum implications and distributive for theclassical one. Based on this result a quantumimplication algebra with a single primitive — andin this sense unique — implication is formulated. Acorresponding classical implication algebra is alsoformulated. The algebras are shown to be special casesof a universal implication algebra.     

Magnetic nanostructures as amplifiers of transverse fields in magnetic resonance

We introduce the concept of amplifying the transverse magnetic fields produced and/or detected with inductive coils in magnetic resonance settings by using the reversible transverse susceptibility properties of magnetic nanostructures. First, we describe the theoretical formalism of magnetic flux amplification through the coil in the presence of a large perpendicular DC magnetic field (typical of magnetic resonance systems) achieved through the singularity in the reversible transverse susceptibility in anisotropic single domain magnetic nanoparticles. We experimentally demonstrate the concept of transverse magnetic flux amplification in an inductive coil system using oriented nanoparticles with uni-axial magnetic anisotropy. We also propose a composite ferromagnetic/anti-ferromagnetic core/shell nanostructure system with uni-directional magnetic anisotropy that, in principle, provides maximal transverse magnetic flux amplification.     

Electron slip influence on quasimolecular X-rays in heavy ion collisions

The rotation of the quasimolecular axis in the heavy ion collision is treated dynamically by taking into account the 2pπ-2pσ electron slip. This is done by the correct quantum mechanical method in the perturbation approximation for low ion velocities. The various radiative processes resulting from initial alignments are discussed. The spectra and anisotropies are calculated. Their dependence on the electron slip is investigated.     

A new formulation of immiscible compressible two-phase flow in porous media

A new formulation is proposed to describe immiscible compressible two-phase flow in porous media. The main feature of this formulation is the introduction of a global pressure. The resulting equations are written in a fractional flow formulation and lead to a coupled system which consists of a nonlinear parabolic (the global pressure equation) and a nonlinear diffusion–convection one (the saturation equation) which can be efficiently solved numerically. To cite this article: B. Amaziane, M. Jurak, C. R. Mecanique 336 (2008).     

Integration of third order ordinary differential equations possessing two-parameter symmetry group by Lie’s method

The solution of a class of third order ordinary differential equations possessing two parameter Lie symmetry group is obtained by group theoretic means. It is shown that reduction to quadratures is possible according to two scenarios: (1) if upon first reduction of order the obtained second order ordinary differential equation besides the inherited point symmetry acquires at least one more new point symmetry (possibly a hidden symmetry of Type II). (2) First, reduction paths of the fourth order differential equations with four parameter symmetry group leading to the first order equation possessing one known (inherited) symmetry are constructed. Then, reduction paths along which a third order equation possessing two-parameter symmetry group appears are singled out and followed until a first order equation possessing one known (inherited) symmetry are obtained. The method uses conditions for preservation, disappearance and reappearance of point symmetries.     

Thermal lens spectrometry under excitation of a divergent pump beam

Thermal lens spectrometry (TLS) under excitation of a divergent pump beam is discussed in both conventional and microscopic TLS instruments. A refined thermal lens (TL) model was proposed for calculating the TL signal of a “finite TL element.” Experiments as well as comparison with numerical simulations demonstrated that the effective sample length for a certain pump beam profile was about six times the confocal distance of the pump beam for laser-excited case and 1.5 mm for incoherent light source-excited case. For laser-excited conventional TLS instrument or thermal lens microscope (TLM), an empirical formula of the optimum pump beam waist radius for maximum detection sensitivity was obtained at a given sample length. At larger pump beam waist radius of 7 μm, the TL signal was found 2.5 times lower compared to the diffraction limit; however, the resulting two orders of magnitude lower power density in the sample could be quite desirable for the detection of photolabile analytes. By investigating the influence of a finite TL element on the TL signal, we found that an optimal distance between the probe beam waist and the sample was needed to assure the maximum detection sensitivity and good response linearity. Under the optimal detection scheme, limit of detection of the laser-excited TLM at 4 mW power was evaluated to be 8.6 × 10^?9 M for 100-μm-thick ferroin solution, corresponding to an absorbance of 9.5 × 10^?7 absorbance units.     

Chiral Hexa‐ and Nonamethylene‐Bridged Bis(L‐Leu‐oxalamide) Gelators: The First Oxalamide Gels Containing Aggregates with a Chiral Morphology

Chiral amino acid‐ and amino alcohol‐oxalamides are well‐known as versatile and efficient gelators of various lipophilic and polar organic solvents and water. To further explore the capacity of the amino acid/oxalamide structural fragment as a gelation‐generating motif, the dioxalamide dimethyl esters 1₆Me and 1₉Me , and dicarboxylic acid 2₆OH / 2₉OH derivatives containing flexible methylene bridges with odd ( 9 ; n=7) and even ( 6 ; n=4) numbers of methylene groups were prepared. Their self‐assembly motifs and gelation properties were studied by using a number of methods (FTIR, ¹H NMR spectroscopy, CD, TEM, DSC, XRPD, molecular modeling, MMFF94, and DFT). In contrast to the previously studied chiral bis(amino acid or amino alcohol) oxalamide gelators, in which no chiral morphology was ever observed in the gels, the conformationally more flexible 1₆Me , 1₉Me , 2₆OH , and 2₉OH provide gelators that are capable of forming diverse aggregates of achiral and chiral morphologies, such as helical fibers, twisted tapes, nanotubules, straight fibers, and tapes, in some cases coexisting in the same gel sample. It is shown that the differential scanning calorimetry (DSC)‐determined gelation enthalpies could not be correlated with gelator and solvent clogP values. Spectroscopic results show that intermolecular hydrogen‐bonding between the oxalamide units provides the major and self‐assembly directing intermolecular interaction in the aggregates. Molecular modeling studies reveal that molecular flexibility of gelators due to the presence of the polymethylene bridges gives three conformations ( zz , p1 , and p2 ) close in energy, which could form oxalamide hydrogen‐bonded layers. The aggregates of the p1 and p2 conformations tend to twist due to steric repulsion between neighboring iBu groups at chiral centers. The X‐ray powder diffraction (XRPD) results of 1₆Me and 1₉Me xerogels prove the formation of p1 and p2 gel aggregates, respectively. The latter results explain the formation of gel aggregates with chiral morphology and also the simultaneous presence of aggregates of diverse morphology in the same gel system.     

Direct determination of free bilirubin in serum at sub-nanomolar levels

Direct analysis of free bilirubin in human and animal blood serum samples is reported for the first time. A state-of-the-art system comprised of newly developed high-performance liquid chromatography (HPLC) on reverse-phase (RP) C18 support coupled with thermal lens spectrometric detection (TLS), based on excitation at λ = 457.9 nm by an argon laser was used for this purpose. This HPLC-TLS method enabled a baseline separation of all three structural isomers of bilirubin (XIII-α, IX-α and III-α) and the respective degradation products in isocratic mode in fewer than 7 min. The method excels in ultra-high sensitivity with limit of detection (LOD) and limit of quantitation (LOQ) of 90 pM and 250 pM, respectively. Moreover, this method also affords high precision and accuracy, with correlation coefficients R² > 0.997 over a broad linear range (0.250–150 nM) and R² = 0.9998 in a concentration range of clinical interest (0.500–25 nM). The method's boosted sensitivity enabled to streamline sample preparation to just one serum ultrafiltration step, which made qualitative evaluation of sample preparation possible for the first time. The performance of the HPLC-TLS method was assessed to have 20-fold enhanced sensitivity when compared to a comparable method incorporating HPLC coupled with diode array detector (DAD), which is also a novel method by itself, and could be applied for free bilirubin determination in patients with elevated bilirubin levels.     

Kochen�CSpecker Sets and Generalized Orthoarguesian Equations

We prove that the 7oa class (equational variety) of generalized orthoarguesian lattices is properly included in all noa classes for n?<?7. This result strengthens the conjecture that any generalized orthoarguesian equation is strictly stronger than those of lower orders. The result emerged from our recent analysis of whether three-dimensional Kochen?CSpecker sets can be represented by Greechie lattices, which are a kind of orthomodular lattice.