CuPc molecules adsorbed on Au(1 1 0)-(1 × 2): growth morphology and evolution of valence band states

We present the growth morphology, the long-range ordering, and the evolution of the valence band electronic states of ultrathin films of copper phthalocyanine (CuPc) deposited on the Au(1 1 0)-(1 × 2) reconstructed surface, as a function of the organic molecule coverage. The low energy electron diffraction patterns present a (5 × 3) reconstruction from the early adsorption stages. High-resolution UV photoelectron spectroscopy data show the disappearance of the Au surface states related to the (1 × 2) reconstruction, and the presence of new electronic features related to the molecule-substrate interaction and to the CuPc molecular states. The CuPc highest occupied molecular orbital gradually emerges in the valence band, while the interface electronic states are quenched, upon increasing the coverage.     

High-performance anion-exchange chromatography of carbohydrates using a new resin and pulsed amperometric detection

Summary This paper reports the results of a study on the use of a new polymer-based, strong anion-exchange, stationary phase for rapid and selective separation of carbohydrates and related compounds by high-pH, anion-exchange chromatography with pulsed amperometric detection. The new adsorbent has been obtained by direct nitration of 2.8 μm, spherical non-porous highly cross-linked, styrene-divinylbenzene copolymer beads, followed by reduction of superficially introduced nitro groups with nascent hydrogen and quaternization of the resultant amino groups with iodomethane. It is reported that by optimizing the ionic strength of the mobile phase, columns packed with the new anion-exchanger can be successfully employed to separate, either in isocratic or gradient elution mode, oligosaccharides, positional isomers of gluco-disaccharides, as well as uronic acids and sugar monophosphates.     

A Combined Approach Employing Soxhlet Extraction and Linear Gradient Elution Reversed-Phase HPLC for the Fingerprinting of Soil Organic Matter According to Hydrophobicity

This paper reports the results of a study carried out to evaluate the potentiality of combining selective solvent extraction and linear gradient elution reversed-phase high performance liquid chromatography (RP-HPLC) for characterizing soil organic matter on the basis of polarity of its constituting organic compounds. Such approach comprises the sequential extraction of soil organic matter with organic solvents of increasing polarity in a Soxhlet extractor and the subsequent separation of each extract by RP-HPLC. Accordingly, each soil sample has been subjected to cycles of sequential extraction with n-hexane, dichloromethane, ethyl acetate, and methanol. Each sample extracted by one of the four solvents have been dried in a rotary evaporator device at 40°C and then dissolved again in the proper volume of extraction solvent to obtaining sample solutions of concentration ranging from 5.0 to 15 mg ml⁻¹. These sample solutions have been subjected to RP-HPLC separation using a Supelcosil LC-ABZ column that has been eluted by a linear acetonitrile gradient in water, having the same profile for all samples. The study has evidenced the possibility of producing highly repeatable chromatographic profiles, which are correlated to the polarity of organic solvents employed for extracting the organic matter in the Soxhlet extractor.

     

Mechanical,thermal and morphological properties of poly(ε‐caprolactone)/zein blends

Blends of poly(ε‐caprolactone) (PCL) with zein (PCL/zein) in different proportions (100/0, 75/25, 50/50, 25/75 and 0/100 wt% containing 5 wt% glycerol) were compared based on their mechanical properties (tensile strength, elongation at break, and Young's modulus), and on their thermal properties, the latter determined by thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA). The morphology of the materials was studied by scanning electron microscopy (SEM). Blends of PCL/zein showed reduced tensile strength and elongation at break, but increased Young's modulus compared to the pure polymers, in agreement with the DMTA and SEM results. These findings indicated that PCL and zein were incompatible. TGA showed that the thermal stability was enhanced by the addition of zein to PCL, whereas SEM showed a poor interfacial interaction between the polymers. Copyright © 2004 John Wiley & Sons, Ltd.     

Energetic calculations of the chain conformation of isotactic polymers of olefins in the crystalline state

Energetic calculations have been carried out on a correlated series of isotactic aliphatic polymers (polypropylene (PP), poly-α-butene (PB), poly-3-methylbutene (P3MB), poly-(S)-3-methylpentene-1 (P(S)3MP) and isotactic polystyrene (PS). The possible variation of the CCC bond angles and of all the internal rotation angles (no group of atoms being taken as a unit) was considered.The possibility to predict the experimental helical parameters without any previous assumption is discussed. The differences in the shape of the minima for polymers with aliphatic and aromatic branched chains have been critically evaluated.For the P(S)3MP the results have shown how the asymmetric configuration of the side group influences the chain conformation of the polymer.     

Study of process parameters for starch,gluten, and glycerol mixtures

This work involved a study of the effect of processing variables (temperature, water content, rotor speed, and time) on the mechanical properties of starch:gluten:glycerol mixtures in the weight ratio of 40:40:20. The properties of the materials were affected by the processing variables. The torque decreased with water content, indicating that water facilitates the plasticization of mixtures, whereas the increase in temperature accelerated the evaporation of water, thus increasing the torque. Ultimate tensile strength was achieved at the lowest temperature (110°C) and the highest water content (20%), whereas maximum elongation was achieved for the material processed at the highest temperature, 150°C, and the fastest rotor speed, 70 rpm. Copyright © 2007 John Wiley & Sons, Ltd.     

Densities and excess molar volumes for binary mixtures of N,N-dimethylformamide+ 1,2-dimethoxyethane

Densities are reported for N,N-dimethylformamide and 1,2-dimethoxyethane binary mixtures at different mole fractions covering the whole miscibility range and at 19 temperatures ranging from –10 to 80°C. The experimental density data have been fitted by empirical relations and the excess volumes by a Redlich-Kister equation. The 11 N,N-dimethylformamide and 1,2-dimethoxyethane adduct appears to be stable throughout the temperature range. A comparison with other DMF containing mixtures is made.     

Complex formation equilibria of L-Amino-Acid amides with copper(II) in aqueous solution

Protonation and Cu(II) complexation equilibria of L -phenyhilaninamide, N²-methyl-L-phenylalaninamide, N², N²-dimethyl-L-phenylalaninamide, L -valinamide, and L -prolinamide have been studied by potentiometry in aqueous solution. The formation constants of the species observed, CuL²⁺, CuL, CuLH, CuL₂H and CuL₂H_?2, are discussed in relation to the structures of the ligands. Possible structures of bisamidato complexes are proposed on the ground of VIS and CD spectra. Since Cu(II) complexes of the present ligands (pH range 6–8) perform chiral resolution of dansyl- and unmodified amino acids in HPLC (reversed phase), it is relevant for the investigation of the resolution mechanism to know which are the species potentially involved in the recognition process.     

Enantiomeric separation of chiral peptide nucleic acid monomers by capillary electrophoresis with charged cyclodextrins

Direct chiral separation of chiral peptide nucleic acid (PNA) monomers has been achieved for the first time by capillary electrophoresis (CE) with charged cyclodextrins as chiral selectors added to the electrophoretic buffer. Selectively modified 6-deoxy-6-N-histamino-beta-cyclodextrin and sulfobutyl ether-beta-CD were successfully used as chiral selectors for the enantiomeric separation of chiral monomers based on different aminoethylamino acids bearing thymine or adenine as nucleobases. Chiral separations were obtained at low selector concentrations (1-3 mM) with good enantioselectivity and resolution factors. Separations were optimized as a function of pH in order to exploit the effect of the electrostatic interactions between the oppositely charged selector and selectand. The method has been applied to the analysis of the enantiomeric excess of chiral monomers used for the solid phase synthesis of chiral PNA oligomers. CE chiral analysis showed that a very high enantiomeric purity was generally achieved in the synthesis of all monomers, except for histidine and aspartic acid based monomers in which ca. 10% of the "wrong" enantiomer was always present.