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Covalent bridges play a crucial role in the folding process of sequence-defined biopolymers. This feature, however, has not been recreated in synthetic polymers because, apart from some simple regular arrangements (such as block co-polymers), these macromolecules generally do not exhibit a controlled primary structure—that is, it is difficult to predetermine precisely the sequence of their monomers. Herein, we introduce a versatile strategy for preparing foldable linear polymer chains. Well-defined polymers were synthesized by the atom transfer radical polymerization of styrene. The controlled addition of discrete amounts of protected maleimide at precise times during the synthesis enabled the formation of polystyrene chains that contained positionable reactive alkyne functions. Intramolecular reactions between these functions subsequently led to the formation of different types of covalently folded polymer chains. For example, tadpole (P-shaped), pseudocyclic (Q-shaped), bicyclic (8-shaped) and knotted (α-shaped) macromolecular origamis were prepared in a relatively straightforward manner.
The aim of this work was to investigate the effects of long-term application of different organic fertilizers (sewage sludge, farmyard manure, compost) as compared to mineral fertilizer on the structure of the soil organic matter. Capillary electrophoresis was employed for the quantification of monosaccharides and phenolic compounds, whereas NMR and FT-IR were used for the overall characterization of the soils organic matter. Application of farmyard manure results in a higher content of organic matter derived from angiosperms, suggested by the higher levels of syringic and vanillic phenols. Spectroscopic studies show an increase of lignin and lignin-like products in the organic matter of the soil, which may be derived from the cereal straw supplied with farmyard manure. According to spectroscopic analysis, 13C CPMAS-NMR and FT-IR spectra, higher contents of methylene groups ( CH2) from proteins and protein-like compounds, as well as higher levels of carbohydrates, were found in the soil supplied with compost. The monosaccharide (rhamnose, xylose, glucose, mannose, arabinose, fucose and galactose) content was not significantly influenced by the different organic fertilizers, suggesting that the type of amendment used does not affect any of these six studied monomers. Comparing the three organic amendments the most significant differences were observed after long-term application of farmyard manure, with an increase in lignin and lignin-like products in the soil organic matter, and compost, which appears to contribute to an increase of protein and protein-like, as well as carbohydrates content on soil organic matter. The knowledge of such changes can be essential to understand the sorption and bioavailability of pollutants, as well as establish/unestablish ways to recycling organic residues as organic fertilizers.
The present work describes the combination of electrochemical investigations by using a gel‐type electrolyte with Fourier‐transformed infrared spectroscopy to investigate partially extremely thin corrosion product films on titanium‐zinc. The gel pad method enables the determination of corrosion relevant parameters such as the potential and the linear polarization resistance without altering the corrosion product layers, which are extremely prone to re‐dissolution when freshly formed. Complementary infrared spectroscopy enables the determination of main compounds of even very thin surface layers of few tenth of nanometers with a certain lateral resolution. It was found that zinc forms mostly zinc carboxy‐hydroxides such as hydrozincite, under various exposure conditions. The protective properties of these hydrozincite layers depend on the structure of the corrosion product film rather than on its thickness. In mid‐term exposure tests, shallow corrosion pits were found even in the absence of corrosive agents such as chloride.
Zinc materials are of high importance in the field of corrosion protection. For example, almost half of the annual production of zinc is used as anti-corrosive layer for steel components, particularly under atmospheric conditions. The corrosion protection is frequently ascribed to zinc carbonate species with low solubility which form on the metal surface under atmospheric conditions. Due to the technological importance and wide use of zinc materials, its corrosion behavior and the formation of reaction products has been intensively investigated over decades.
Assuming atmospheric corrosion conditions, an initial native passive film of few nanometers thickness forms spontaneously. It consists of zinc oxide and hydroxide, transforming into various species in dependence of the surrounding atmospheric conditions.
This study focusses on the investigation of corrosion product layers on massive titanium-zinc sheets, formed during short- and mid-term exposure experiments by Fourier-transformed infrared spectroscopy. This method enables the investigation of extremely thin native passive films which form during the initial hours of exposure. Furthermore, aged surface layers are analyzed which were formed by transformation of initial passive layers over the time of several weeks. The spectroscopic investigations are complemented by scanning electron microscopy (SEM/EDX) in order to obtain information on the chemical composition and morphology of the corrosion products. The combination of both methods offers a comprehensive view on the processes occurring in the early stages of zinc corrosion.
The characterization of technical lignins is a key step for the efficient use and processing of this material into valuable chemicals and for quality control. In this study 31 lignin samples were prepared from different biomass sources (hardwood, softwood, straw, grass) and different pulping processes (sulfite, Kraft, organosolv). Each lignin was analysed by attenuated total reflectance Fourier transform infrared (ATR-FT-IR) spectroscopy. Statistical analysis of the ATR-FT-IR spectra by means of principal component analysis (PCA) showed significant differences between the lignins. Hence, the samples can be separated by PCA according to the original biomass. The differences observed in the ATR-FT-IR spectra result primarily from the relative ratios of the p-hydroxyphenyl, guaiacyl and syringyl units. Only limited influence of the pulping process is reflected by the spectral data. The spectra do not differ between samples processed by Kraft or organosolv processes. Lignosulfonates are clearly distinguishable by ATR-FT-IR from the other samples. For the classification a model was created using the k-nearest neighbor (k NN) algorithm. Different data pretreatment steps were compared for k=1…20. For validation purposes, a 5-fold cross-validation was chosen and the different quality criteria Accuracy (Acc), Error Rate (Err), Sensitivity (TPR) and specificity (TNR) were introduced. The optimized model for k=4 gives values for Acc = 98.9 %, Err = 1.1 %, TPR = 99.2 % and TNR = 99.6 %.