Enrichment of deuterium oxide at hydrophilic interfaces in aqueous solutions

The structure of water at aqueous interfaces is of the utmost importance in biology, chemistry, and geology. We use neutron reflectivity and quartz crystal microbalance to probe an interface between hydrophilic quartz and bulk liquid solutions of H2O/D2O mixtures. We find that near the interface the neutron scattering length density is larger than in the bulk solution and there is an excess adsorbed mass. We interpret this as showing that there is a region adjacent to the quartz that is enriched in D2O and extends 5-10 nm into the solution. This suggests caution when interpreting results where D2O is substituted for H2O in aqueous interfacial chemistry.     

Using freezing and drying techniques of emulsions for the microencapsulation of fish oil to improve oxidation stability

Epidemiological investigations show that n-3-polyunsaturated fatty acids (PUFA) have a protective effect with respect to coronary heart disease. For a long time fish oil has been known as a source of PUFA. The successful incorporation of fish oil into the normal food components offers an opportunity to increase the intake of PUFA, but fish oil has to be protected against oxidation preferably by microencapsulation. The high temperatures during the traditional spray-drying microencapsulation process lead to an increased oxidation of the PUFA. The authors demonstrate the application of a freeze-drying technique with respect to the production of dried microencapsulated fish oil with high quality and oxidation stability. The influence of emulsion parameters, freezing parameters and formulation on the stability of a dried fish oil emulsion is presented and illustrated. The used procedure gave a product with a good oxidation stability which is available as pellets or powder. It was found that the stability was mainly influenced by the freezing rate and the used encapsulation carbohydrate, whereby the powder showed a better shelf life than the pellets. Concluding, it can be summarized that the production of microencapsulated fish oil by freezing and subsequent freeze-drying offers an opportunity to achieve a product with a good oxidation stability.     

Temporal resolution and temporal masking properties of transient stimuli: data and an auditory model.

Temporal resolution is often measured using the detection of temporal gaps or signals in temporal gaps embedded in long-duration stimuli. In this study, psychoacoustical paradigms are developed for measuring the temporal encoding of transient stimuli. The stimuli consisted of very short pips which, in two experiments, contained a steady state portion. The carrier was high-pass filtered, dynamically compressed noise, refreshed for every stimulus presentation. The first experiment shows that, with these very short stimuli, gap detection thresholds are about the same as obtained in previous investigations. Experiments II and III show that, using the same stimuli, temporal-separation thresholds and duration-discrimination thresholds are better than gap-detection thresholds. Experiment IV investigates the significance of residual spectral cues for the listeners' performance. In experiment V, temporal separation thresholds were measured as a function of the signal-pip sensation level (SL) in both forward- and backward-masking conditions. The separation thresholds show a strong temporal asymmetry with good separation thresholds independent of signal-pip SL in backward-masking conditions and increasing separation thresholds with decreasing signal-pip SL in forward-masking conditions. A model of the auditory periphery is used to stimulate the gap-detection and temporal-separation thresholds quantitatively. By varying parameters like auditory-filter width and transduction time constants, the model provides some insight into how the peripheral auditory system may cope with temporal processing tasks and thus represents a more physiology-related complement to current models of temporal processing.     

Cationic Xylan Derivatives with High Degree of Functionalization

Xylan from birch wood was characterized regarding both the supramolecular structure (X-ray, CP/MAS ¹³C-NMR) and the sugar composition. The reaction of the birch wood xylan with 2,3-epoxypropyltrimethylammonium chloride in 1,2-dimethoxyethane as slurry medium yields water-soluble, cationic 2-hydroxypropyltrimethylammonium xylan derivatives with high degree of substitution (DS). The DS values up to 1.6 can be controlled by adjusting the molar ratio in a one step synthesis. The structure of the cationic xylan derivatives was confirmed by means of DEPT(135) NMR spectroscopy. Film forming properties of cationic xylan derivatives were investigated with SEM measurements.     

The Resolved Mutual Information Function as a Structural Fingerprint of Biomolecular Sequences for Interpretable Machine Learning Classifiers

In the present article we propose the application of variants of the mutual information function as characteristic fingerprints of biomolecular sequences for classification analysis. In particular, we consider the resolved mutual information functions based on Shannon-, Rényi-, and Tsallis-entropy. In combination with interpretable machine learning classifier models based on generalized learning vector quantization, a powerful methodology for sequence classification is achieved which allows substantial knowledge extraction in addition to the high classification ability due to the model-inherent robustness. Any potential (slightly) inferior performance of the used classifier is compensated by the additional knowledge provided by interpretable models. This knowledge may assist the user in the analysis and understanding of the used data and considered task. After theoretical justification of the concepts, we demonstrate the approach for various example data sets covering different areas in biomolecular sequence analysis.     

Preparative and 1H NMR Investigation on Regioselective Silylation of Starch Dissolved in Dimethyl Sulfoxide

Reaction of starch 1 dissolved in dimethyl sulfoxide (DMSO) with bulky thexyldimethylchlorosilane (TDSCl) in the presence of pyridine leads to regioselectively functionalized silyl ethers with a degree of substitution (DS) up to 1.8. The control of the DS_Si, of the regioselectivity, and of the reaction pathway is described in detail. The reaction proceeds homogeneously up to DS_Si of 0.6. With ongoing silylation the polymers form a separate phase incorporating the silylating agent to form TDS‐starches with DS_Si values higher than 1.0. After peracetylation of the silyl starches, the substitution pattern has been characterized not only in the anhydroglucose repeating units (AGU) but also in the non‐reducing terminal end groups (TEG) by means of two‐dimensional ¹H NMR techniques. Up to DS_Si 1.0, a very high regioselective functionalization of the primary 6‐OH groups in the AGU as well as in the TEG is detectable. With increasing silylation (DS_Si > 1.0), the subsequent silylation takes place at the 2‐OH groups of the AGU and at the 3‐OH groups of the TEG. These results are compared with our own investigations on the silylation of starch in the reaction system N‐methylpyrrolidone (NMP)/ammonia and on the silylation of cellulose in N,N‐dimethylacetamide (DMA)/LiCl/pyridine solution.