A new insight into the understanding of the collapsed form of poly(N-isopropylacrylamide) molecules

Possible collapsed forms of poly(N-isopropylacrylamide) molecules are reviewed on the basis of first principle calculations. Various configurations and associated conformations are detailed. The calculated optimized structures exhibit different possibilities of creating networks of intra-molecular bonds of the hydrogen type. We show that the most remarkable one is able to form a local, self-saturated and well ordered helix. We also indicate in which direction the synthesis of the molecule should be oriented to improve its global behavior in term of hydrophobic/hydrophilic behavior.     

Spray thermometry using thermographic phosphors

In this study a novel technique for 2D spray temperature measurement is presented. For this purpose the thermographic phosphor (TP) Mg₄GeO_5.5F:Mn was dispersed in n-dodecane and atomised using a conventional semi solid-cone nozzle. The thermographic phosphor was excited electronically by a frequency tripled Nd:YAG laser (355 nm). An ICCD-camera in combination with an image doubler detected the subsequently emitted phosphorescence at both peak emission wavelengths located at 633 nm and 659 nm, respectively. Utilising suitable calibration measurements, the local spray temperature was determined by evaluating the intensity ratio of both emission wavelengths. To the knowledge of the authors this is the first approach of spray temperature measurement exploiting the temperature dependent intensity ratio of thermographic phosphors. PACS 07.20.Dt; 32.50.+d     

Problems, Models and Complexity. Part II: Application to the DLSP

In Part I of this study, we suggest to identify an operations research (OR) problem with the equivalence class of models describing the problem and enhance the standard computer-science theory of computational complexity to be applicable to this situation of an often model-based OR context. The Discrete Lot-sizing and Scheduling Problem (DLSP) is analysed here in detail to demonstrate the difficulties which can arise if these aspects are neglected and to illustrate the new theoretical concept. In addition, a new minimal model is introduced for the DLSP which makes this problem eventually amenable to a rigorous analysis of its computational complexity.     

Idempotency of Extensions via the Bicompletion

Let Top ₀ be the category of topological T ₀-spaces, QU ₀ the category of quasi-uniform T ₀-spaces, T : QU ₀ → Top ₀ the usual forgetful functor and K : QU ₀ → QU ₀ the bicompletion reflector with unit k : 1 → K. Any T-section F : Top ₀ → QU ₀ is called K-true if KF = FTKF, and upper (lower) K-true if KF is finer (coarser) than FTKF. The literature considers important T-sections F that enjoy all three, or just one, or none of these properties. It is known that T(K,k)F is well-pointed if and only if F is upper K-true. We prove the surprising fact that T(K,k)F is the reflection to Fix(TkF) whenever it is idempotent. We also prove a new characterization of upper K-trueness. We construct examples to set apart some natural cases. In particular we present an upper K-true F for which T(K,k)F is not idempotent, and a K-true F for which the coarsest associated T-preserving coreflector in QU ₀ is not stable under K. We dedicate this paper to the memory of Sérgio de Ornelas Salbany (1941–2005).     

Formation of β-distonic oxonium ions: Study of ROCH2CH2OR′ radical cations

Radical cations derived from the ethers ROCH₂CH₂OR′ (R, R′ = H, CH₃, C₂₅) were studied, since β-distonic oxonium ions are often prepared from ionized ethers of glycol. The first step in the fragmentation is a 1,5-transfer of an α-hydrogen to oxygen of a terminal alkoxy group leading to a δ-distonic oxonium ion. This step is thermo-neutral and reversible in the ROCH₂CH₂OH radical cations and exothermic and irreversible in the dialkyl ether radical cations. Depending on R and R,′ these δ-distonic oxonium ions fragment by three reactions: the loss of an alcohol or a water molecule, the formation of a β-distonic oxonium ion ˙CH₂CH₂O(H)⁺R and a 1,4-H migration between carbon atoms. Competition between these processes is discussed.     

Overloaded elution band profiles of ionizable compounds in reversed‐phase liquid chromatography: Influence of the competition between the neutral and the ionic species

The parameters that affect the shape of the band profiles of acido‐basic compounds under moderately overloaded conditions (sample size less than 500 nmol for a conventional column) in RPLC are discussed. Only analytes that have a single pK_a are considered. In the buffer mobile phase used for their elution, their dissociation may, under certain conditions, cause a significant pH perturbation during the passage of the band. Two consecutive injections (3.3 and 10 μL) of each one of three sample solutions (0.5, 5, and 50 mM) of ten compounds were injected on five C₁₈‐bonded packing materials, including the 5 μm Xterra‐C₁₈ (121 Å), 5 μm Gemini‐C₁₈ (110 Å), 5 μm Luna‐C₁₈(2) (93 Å), 3.5 μm Extend‐C₁₈ (80 Å), and 2.7 μm Halo‐C₁₈ (90 Å). The mobile phase was an aqueous solution of methanol buffered at a constant _W^WpH of 6, with a phosphate buffer. The total concentration of the phosphate groups was constant at 50 mM. The methanol concentration was adjusted to keep all the retention factors between 1 and 10. The compounds injected were phenol, caffeine, 3‐phenyl 1‐propanol, 2‐phenyl butyric acid, amphetamine, aniline, benzylamine, p‐toluidine, procainamidium chloride, and propranololium chloride. Depending on the relative values of the analyte pK_a and the buffer solution pH, these analytes elute as the neutral, the cationic, or the anionic species. The influence of structural parameters such as the charge, the size, and the hydrophobicity of the analytes on the shape of its overloaded band profile is discussed. Simple but general rules predict these shapes. An original adsorption model is proposed that accounts for the unusual peak shapes observed when the analyte is partially dissociated in the buffer solution during its elution.     

Comportement asymptotique d'une grue

We study the asymptotic behaviour of a structure depending of two small parameters. The ratio of these two parameters plays a part in the limit problems. To cite this article: G. Griso, C. R. Acad. Sci. Paris, Ser. I 338 (2004).     

Investigations of alkali doped Fe2O3--V2O5 catalysts by transmission and conversion electron Mössbauer spectroscopy

Fe₂O₃--V₂O₅ catalysts doped with Cs₂SO₄ (molar ratio: V:Fe:Cs=1:0.74:0.06) were found to be a rather inhomogeneous mixture of various crystalline and amorphous iron vanadate phases. After calcination in air the catalyst was divided into three different parts which were analyzed separately revealing the formation of FeVO₄ in the top and bottom fraction of the crucible and Fe₂V₄O₁₃ in the middle fraction. As compared to the well crystallized FeVO₄ reference sample, the quadrupole splittings of FeVO₄ in the Cs-doped catalysts were larger pointing to more distorted iron sites which were assumed to be responsible for high catalytic selectivities. In contrast, the quadrupole splittings of FeVO₄ in the less selective K- and Rb-doped Fe₂O₃--V₂O₅ catalysts were smaller. Additional components in the bottom fraction were also α-Fe₂O₃ and Fe_1-xS. As indicated by the CEMS spectra the latter is located preferentially on the surface of the catalyst particles. This revised version was published online in August 2006 with corrections to the Cover Date.