Residual lignin inhibits thermal degradation of cellulosic fiber sheets

The market for cellulosic fiber based food packaging applications is growing together with the importance of improving the thermal durability of these fibers. To shed light on this, we investigated the role of residual lignin in pulp on the thermal stability of refined pulp sheets. The unbleached, oxygen delignified, and fully bleached pulp sheets were studied after four separate refining degrees. Comparison by Gurley air resistance, Bendtsen porosity, and the oxygen transmission rate tests showed that lignin containing sheets had better air and oxygen barrier properties than fully bleached sheets. Sheet density and light scattering coefficient measurements further confirmed that the lignin containing pulps underwent more intense fibrillation upon refining that changed the barrier properties of the sheets. Thermal treatments (at 225 °C, 20 and 60 min, in water vapor atmospheres of 1 and 75 v/v %) were applied to determine the thermal durability of the sheets. The results revealed that the residual lignin in pulps improved the thermal stability of the pulp sheets in the hot humid conditions. This effect was systematically studied by tensile strength, brightness, and light absorption coefficient measurements. The intrinsic viscosity results support the findings and suggest that lignin is able to hinder the thermal degradation of pulp polysaccharides. In spite of the fact that lignin is known to enhance the thermal yellowing of paper, no significant discoloration of the pulp sheets containing residual lignin was observed in the hot humid conditions (75 v/v %). Our results support the idea of lignin strengthening the thermal durability of paper.     

Solvation of calcium ions in methanol-water mixtures: molecular dynamics simulation

Molecular dynamics simulations of CaCl2 solutions in water and methanol-water mixtures, with methanol concentrations of 5, 10, 50, and 90 mol %, at room temperature, have been performed. The methanol and water molecules have been modeled as flexible three-site bodies. Solvation of the calcium ions has been discussed on the basis of the radial and angular distribution functions, the orientation of the solvent molecules, and their geometrical arrangement in the coordination shells. Analysis of the H-bonds of the solvent molecules coordinated by Ca2+ has been done. Residence time of the solvent molecules in the coordination shell has been calculated. The preferential hydration of the calcium ions has been found over the whole range of the mixture composition. The water concentration in the first and second coordination shells of Ca2+ significantly exceeds the water content in the solution, despite the very similar interaction energy of the calcium ion with water and methanol. In aqueous solution and methanol-water mixtures, the first coordination shell of Ca2+ is irregular and long-living. The solvent molecules prefer the anti-dipole arrangement, but, in aqueous solutions and water-rich mixtures, the water molecules in the primary shell have only one H-bonded neighbor.     

Structure and dynamics of the aniline-argon complex as derived from its potential energy surface

The structure and dynamics of the van der Waals (vdW) complex of aniline (An) with argon (Ar) are studied using ab initio methods. The inversion potential of the aniline-argon (AnAr) complex perturbed by the weak vdW interaction is calculated taking into account subtle corrections from the zero-point energy of the vdW modes and from the frequency shifts of the An normal modes modified by the complexation. The intermolecular potential energy surface (PES) of the AnAr complex is determined by performing a large-scale computation of the interaction energy and the fitting of the analytical many-body expansion to the set of single-point interaction energies. The PES determined shows two deep local minima corresponding to the anti and syn AnAr conformers. The difference in the energies of these two minima is only 15 cm-1, but it is sufficient to localize the inversion wave functions and to form the two conformers. In the conformer anti (syn) of lower (higher) energy, Ar is bound to the An ring opposite (adjacent) the amino-hydrogens. In the additional local minima higher in energy, Ar approaches the aniline ring between the C-H bonds near its plane. An additional local minimum is located opposite of nitrogen between the two N-H bonds. The high-energy minima are, however, too flat to form stable conformers. The perturbation of the interaction of Ar with the phenyl ring by the NH2 group is described by the vdW hole, which is responsible for unusually strong intermode mixing in the excited intermolecular vibrational states. The analysis of these states calculated for the ground (S0) as well as the first excited electronic state (S1) resolves difficulties faced earlier with the assignment of the observed vibronic bands of AnAr.     

Hydration of aprotic donor solvents studied by means of FTIR spectroscopy

The paper attempts to explain the mutual influence of nonpolar and electron-donor groups on solute hydration, the problem of big importance for biological aqueous systems. Aprotic organic solvents have been used as model solutes, differing in electron-donating power. Hydration of acetonitrile, acetone, 2-butanone, and triethylamine has been studied by HDO and (partially) H2O spectra. The quantitative version of difference spectra method has been applied to determine solute-affected water spectra. Analysis of the data suggests that solvent-water interaction via the donor center of the solute is averaged between water-water interactions around the solute. Such behavior can be simply explained by the model of solute rotating in a cavity of water structure, which is formed by clathratelike hydrogen-bonded water network. On the basis of the band shape of solute-affected HDO spectra and the corresponding distribution of intermolecular distances, the criterion for hydrophobic type hydration has been proposed. From that point of view, all the studied solutes could be treated as hydrophobic ones. The limiting band position and the corresponding intermolecular distance of affected water, gained with increasing electron-donating power of solutes, has been inferred from the data obtained. These observations are important for interpretation of vibrational spectra of water as well as for volumetric measurements of solutions. The simple model of hydration, proposed to better justify the results, connects the values obtained from the methods providing microscopic and macroscopic characteristics of the system studied.     

Synthesis of novel aminophosphonic acids with hydantoin structure

The novel α‐aminophosphonic acids with hydantoin structure have been synthesized reacting 5,5‐dimetylhydantoin with formaldehyde and phosphorus trichloride, or via Kabachnik–Fields reaction. Their structures were proved by means of IR, ¹H, ¹³C{¹H}, and ³¹P NMR spectroscopy. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:87–90, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20515     

TrainMiC®: a programme for life-long learning in metrology in chemistry

This article gives an overview of the programme TrainMiC^®, a European programme for Life-Long Learning in metrology in chemistry. It explains its raison d’être and puts it into perspective to other European and EU member states initiatives. The TrainMiC^® system (http://www.trainmic.org) is described in detail. It is explained how it has developed into a truly unique system which is operational across many parts of Europe (19 countries) via national teams. These teams use shareware pedagogic tools. The learning content has been harmonised at the European level by a joint effort of many experts across Europe working via an Editorial Board. The material has been translated in ten different languages. Possible future evolution of this Life Long Learning programme is discussed.     

Preparation of a new lightly cross-linked liquid crystalline polyamide by interfacial polymerization. Application to the obtainment of microcapsules with photo-triggered release

Microcapsules based on a new liquid crystalline lightly cross-linked polyamide, in which the state of order can be triggered by means of external stimuli, such as temperature and light, were prepared by interfacial polymerization. This polyamide exhibited a nematic phase up to 166 °C and it started to decompose at 340 °C; morphological variations of the film were observed by Scanning Electron Microscopy in correspondence to the clearing temperature; moreover, by continuous irradiation with UV light at room temperature, the polymer underwent E–Z photoisomerization. The prepared microcapsules contained either toluene, or concentrated solutions of naphthalene or β-carotene, as the core; in all cases, their outer surface appeared smooth and dense, while heterogeneities could be seen on the inner face. Capsule diameter lay in the range 30–120 μm, depending on the encapsulated material, with quite narrow size distributions. To the authors’ knowledge, this is the first example of microcapsules whose shell is completely constituted by a liquid crystalline lightly cross-linked polymer. Release experiments of β-carotene were performed in water and in tetrahydrofuran. β-Carotene release in water at 20 °C was strongly influenced by UV irradiation: in the absence of irradiation, it was practically negligible while, when microcapsules were submitted to continuous irradiation with UV light, β-carotene was quickly released and reached 100% release after 5 min. Preliminary experiments concerning the effect of temperature and of a swelling solvent, such as THF, on release, were also performed.     

Poly(ε-caprolactone) modified by functional groups: Preparation and chemical–physical investigation

Functionalization of polymers is a particular relevant approach in the field of biodegradable polymers, where modifications are often required to allow these materials to replace more conventional, not biodegradable polymers in a wider range of applications. This article will report on functionalization of poly(ε-caprolactone) with unsaturated monomers bearing either anhydride groups (PCL-g-(MA-GMA)) or tertiary amines (PCL-g-DMAEA), obtained through radical grafting in a Brabender mixer. Crystallization kinetics parameters have been determined with several techniques (rheology, optical microscopy and differential scanning calorimetry) and the results obtained are in good agreement. It was observed that the crystallization rate significantly increases in the case of the modified polymers.     

Determination and characterization of phytochelatins by liquid chromatography coupled with on line chemical vapour generation and atomic fluorescence spectrometric detection

Liquid chromatography (LC) coupled on line with UV/visible diode array detector (DAD) and cold vapour generation atomic fluorescence spectrometry (CVGAFS) has been developed for the speciation, determination and characterization of phytochelatins (PCs). The method is based on a bidimensional approach, e.g. on the analysis of synthetic PC solutions (apo-PCs and Cd(2+)-complexed PCs) (i) by size exclusion chromatography coupled to UV diode array detector (SEC-DAD); (ii) by the derivatization of PC -SH groups in SEC fractions by p-hydroxymercurybenzoate (PHMB) and the indirect detection of PC-PHMB complexes by reversed phase liquid chromatography coupled to atomic fluorescence detector (RPLC-CVGAFS). MALDI-TOF/MS (matrix assisted laser desorption ionization time of flight mass spectrometry) analysis of underivatized synthetic PC samples was performed in order have a qualitative information of their composition. Quantitative analysis of synthetic PC solutions has been performed on the basis of peak area of PC-PHMB complexes of the mercury specific chromatogram and calibration curve of standard solution of glutathione (GSH) complexed to PHMB (GS-PHMB). The limit of quantitation (LOQ) in terms of GS-PHMB complex was 90 nM (CV 5%) with an injection volume of 35 microL, corresponding to 3.2 pmol (0.97 ng) of GSH. The method has been applied to analysis of extracts of cell cultures from Phaeodactylum tricornutum grown in Cd-containing nutrient solutions, analysed by SEC-DAD-CVGAFS and RPLC-DAD-CVGAFS.     

Changes in the vascular tissue of fresh Hass avocados treated with cobalt 60

This research was based on fresh avocado fruit treated with gamma rays at quarantine doses and stored at room temperature. The effects of irradiation were analyzed and measured by three different types of studies: histological, biochemical and physiological. Histological studies were focused on the effect of Cobalt 60 gamma rays in the mesocarp of avocado irradiated at three different doses; 150, 250, and 350 Gy. Damage was observed principally in the parenchyma tissue where the cell membrane was plazmolized and a red color was observed due to the development of phenol compounds. Another important effect was an increase in the size of xylem and phloem cells in the vascular tissue even at the minimum dose of 150 Gy. The biochemical and the physiological studies were done on avocado fruit irradiated at 100 and 150 Gy. An increase in L-phenilalanine ammonialyase activity was observed and therefore, an increase in the concentration of phenol compounds. These changes were not perceived by panelists in a sensorial test. Irradiated fruits were accepted by panelists as well as control fruit as regards parameters of taste, internal color and external color. These results demonstrate the feasibility of using irradiation to disinfest avocado fruit using a minimum dose of 100 Gy.