Luminescence properties of Eu2+, Sn2+, and Pb2+ in SrB6O10 and Sr1 − xMnxB6O10

The luminescence properties of Eu²⁺, Sn²⁺, and Pb²⁺ in SrB₆O₁₀ have been studied both at room-temperature and liquid-helium temperature and the decay times of Sn²⁺ and Pb²⁺ in this matrix have been measured and analyzed. According to the emission spectrum of Eu²⁺ there seems to be three different cation sites in SrB₆O₁₀. Europium, tin, and lead were also used as sensitizers for Mn²⁺ and the energy transfer processes were characterized. Eu²⁺-Mn²⁺ energy transfer was inefficient due to the transfer within different Eu²⁺ centers. The sensitization action of Sn²⁺ and Pb²⁺ on Mn²⁺ was different because lead-lead energy transfer occurs (even at 4.2 K) but tin-tin transfer can be neglected. A fast diffusion model for the Pb²⁺ system is suggested.     

Determination of the carboxylic acids in acidic and basic process samples by capillary zone electrophoresis

Capillary zone electrophoresis (CZE) with indirect UV detection was used in developing a method for the simultaneous determination of inorganic anions, aliphatic and heterocyclic organic acids in various processed samples. The analytes were determined simultaneously in 10 min using an electrolyte containing 20 mM 2,3-pyrazine dicarboxylic acid, 65 mM tricine, 2 mM BaCl₂, 0.5 mM cetyltrimethylammonium bromide, and 2 M urea at pH 8.06. Linear plots for the analytes were obtained in the concentration range of 2–150 mg L⁻¹. Relative standard deviations (RSDs) of peak areas during a 3-day analysis period varied from 5.5% for glycolate to 9.5% for oxalate. RSDs of migration times varied between 0.4% and 1.1%. The detection limit (at S/N 3) was 1 mg L⁻¹ for all the analytes studied. The proposed method was successfully demonstrated for the determination of carboxylic acids in eight oxygen treated samples of commercial softwood and hardwood kraft lignin and two red wine samples of Pinot Noir grapes. In the kraft lignin samples the concentrations of carboxylic acids correspond to the oxidation time. The acid concentrations of wine varied considerable.     

New PP/PLA/cellulose composites: effect of cellulose functionalization on accelerated weathering behavior (accelerated weathering behavior of new PP/PLA/cellulose composites)

Polylactic acid (PLA) was used as partial replacement for conventional thermoplastic matrix, new composites comprising cellulose, polypropylene (PP), and PLA being realized. In order to obtain a compatible interface between cellulosic pulp and polymeric matrix, two chemical modifications of cellulose with stearoyl chloride and toluene di‐isocyanate (TDI) were performed, structural changes being evidenced by X‐ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The composite materials were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, dynamic scanning calorimetry, impact, tensile and melt rheological tests, surface tension, and dynamic vapor sorption. Because promising results for impact strength and Young modulus were recorded when replacing 15% of PP with PLA in blends of PP with the same cellulosic pulp load, the aim of our study was to assess the behavior to accelerate weathering of composites comprising PP, cellulosic pulp, and PLA. Although the slight decrease in the mechanical properties was recorded after accelerated weathering, the use of functionalized cellulose successfully prevented the deterioration of surface materials, especially for composite comprising stearoyl chloride treated cellulose pulp. Copyright © 2015 John Wiley & Sons, Ltd.     

Radioactivity in the Baltic Sea: inventories and temporal trends of <Superscript>137</Superscript>Cs and <Superscript>90</Superscript>Sr in water and sediments

The Baltic Sea is ecologically unique as one of the world’s largest brackish water basins. It was significantly contaminated by radioactivity following the Chernobyl accident in 1986, the major contaminant being long-lived ¹³⁷Cs. Due to the slow exchange of water between the Baltic Sea and the North Sea and the relatively rapid sedimentation rates, radionuclides have prolonged residence times in the Baltic Sea. ¹³⁷Cs levels are consequently still clearly higher than in other water bodies around the world. In addition to the Chernobyl accident, artificial radionuclides in the Baltic Sea originate from the global fallout following nuclear weapons testing in the 1950s and 1960s, while discharges into the Baltic Sea from nuclear power plants and other facilities are of minor importance. Here, inventories and the temporal evolution of radionuclides both in seawater and sediments of the Baltic Sea are presented and discussed.     

Novel applications of the modified polonovski reaction - VII preparation of isoquinuclidines

The first successful preparations of the biochemically important isoquinuclidine ring system by the modified Polonovski reaction are described.     

X‐tended target projection (XTP)—comparison with orthogonal partial least squares (OPLS) and PLS post‐processing by similarity transformation (PLS + ST)

Target projection (TP) also called target rotation (TR) was introduced to facilitate interpretation of latent‐variable regression models. Orthogonal partial least squares (OPLS) regression and PLS post‐processing by similarity transform (PLS + ST) represent two alternative algorithms for the same purpose. In addition, OPLS and PLS + ST provide components to explain systematic variation in X orthogonal to the response. We show, that for the same number of components, OPLS and PLS + ST provide score and loading vectors for the predictive latent variable that are the same as for TP except for a scaling factor. Furthermore, we show how the TP approach can be extended to become a hybrid of latent‐variable (LV) regression and exploratory LV analysis and thus embrace systematic variation in X unrelated to the response. Principal component analysis (PCA) of the residual variation after removal of the target component is here used to extract the orthogonal components, but X‐tended TP (XTP) permits other criteria for decomposition of the residual variation. If PCA is used for decomposing the orthogonal variation in XTP, the variance of the major orthogonal components obtained for OPLS and XTP is observed to be almost the same, showing the close relationship between the methods. The XTP approach is tested and compared with OPLS for a three‐component mixture analyzed by infrared spectroscopy and a multicomponent mixture measured by near infrared spectroscopy in a reactor. Copyright © 2008 John Wiley & Sons, Ltd.     

Cellulose crystallinity and ordering of hemicelluloses in pine and birch pulps as revealed by solid-state NMR spectroscopic methods

Solid-state ¹³C NMR spectroscopy was used to determine the degree of cellulose crystallinity (CrI) in kraft, flow-through kraft and polysulphide–anthraquinone (PS–AQ) pulps of pine and birch containing various amounts of hemicelluloses. The applicability of acid hydrolysis and the purely spectroscopic proton spin-relaxation based spectral edition (PSRE) method to remove the interfering hemicellulose signals prior to the determination of CrI were also compared. For softwood pulps, the spectroscopic removal of hemicelluloses by PSRE was found to be more efficient than the removal of hemicelluloses by acid hydrolysis. In addition to that, the PSRE method also provides information on the associations between cellulose and hemicelluloses. On the basis of the incomplete removal of xylan from the cellulose subspectra by PSRE, the deposition of xylan on cellulose fibrils and therefore an ordered ultrastructure of xylan in birch pulps was suggested. The ordered structure of xylan in birch pulps was also supported by the observed change of xylan conformation after regeneration. Similarly, glucomannan in pine pulps may have an ordered structure. According to the ¹³C CPMAS measurements conducted after acid hydrolysis, the degree of cellulose crystallinity was found to be slightly lower in birch pulps than in the pine pulps. Any significant differences in cellulose crystallinity were not found between the pulps obtained by the various pulping methods. Only in pine PS–AQ pulp, the degree of cellulose crystallinity may be slightly lower than in the kraft pulps containing less hemicelluloses.     

On the interaction of HBT with pulp lignin during mediated laccase delignification—a study using fractionated pyrolysis-GC/MS

An analytical method using fractionated pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) was developed and applied for characterizing the type of interaction between 1-hydroxybenzotriazole (HBT)-mediator and pulp lignin in laccase delignification of pulp. In fractionated pyrolysis, the sample is pyrolyzed at progressively increasing temperatures in order to study particular fractions of the sample and to minimize secondary pyrolysis effects. This makes it possible to determine whether a certain pyrolysis product originates from one chemical moiety or different chemical moieties in one molecule. In the present method, samples were fractionated by thermal desorption at 200 °C followed by pyrolysis at progressively increasing temperatures from 320 to 800 °C. The products formed in each fraction were separated in a capillary GC column and detected and identified using MS. The type of interaction between HBT and pulp lignin was studied by following the formation of nitrogen-containing products during fractionated pyrolysis of a residual lignin isolated from laccase/HBT-treated oxygen-delignified softwood kraft pulp. This residual lignin was found to contain approximately 2% HBT residue. Most (87%) of this residue was covalently linked to the residual lignin. The results also strongly suggest that the HBT residue is present in two chemically different forms.     

Disposable roll-to-roll hot embossed electrophoresis chip for detection of antibiotic resistance gene mecA in bacteria

We present a high-throughput roll-to-roll (R2R) manufacturing process for foil-based polymethyl methacrylate (PMMA) chips of excellent optical quality. These disposable, R2R hot embossed microfluidic chips are used for the identification of the antibiotic resistance gene mecA in Staphylococcus epidermidis. R2R hot embossing is an emerging manufacturing technology for polymer microfluidic devices. It is based on continuous feeding of a thermoplastic foil through a pressurized area between a heated embossing cylinder and a blank counter cylinder. Although mass fabrication of foil-based microfluidic chips and their use for biological applications were foreseen already some years ago, no such studies have been published previously.