Measurements of the Refractive Index Increment on Hydroxyethyl Starch as a Basis for Absolute Molecular Weight Determinations

Solutions of hydroxyethyl starch are used as a blood plasma substitute. If their physiological efficiency is to be optimized, they need to be accurately characterized in terms of their molecular weight and its distribution. The absolute determination of molecular weight and molecular weight distribution by means of light scattering require a knowledge of the refractive index increment. Although numerous investigations of the refractive index increment of hydroxyethyl starch have already been published, the results vary significantly due to the use of different samples and the choice of different measuring parameters. There was therefore an urgent need to examine the extent to which the refractive index increment depends on molecular parameters, the experimental method used and the type of processing. Here it was found that different sample preparations result in different contents of solid matter, so that an exact determination of the quantity is required. Hydroxyethyl starches in the molecular weight range of about Mw = 200.000 g/mol and varying degrees of substitution between DS 0.38 and 0.50 which are regarded as optimal for clinical use give a refractive index increment of dn/dc^633nm = 0.146 = 0.005 cm³/g (solvent: H₂O/0.02% NaN₃; T = 25°C).     

119Sn-NMR spektroskopische Untersuchungen an Tributylzinnderivaten aromatischer Sulfonsäuren

¹¹⁹Sn-NMR Spectroscopic Investigations of Tributyltin Derivatives of Aromatic Sulfonic Acids . Tributyltin derivatives of nine aromatic sulfonic acids were synthesized and investigated by means of ¹¹⁹Sn-n.m.r. spectroscopy. ¹¹⁹Sn-chemical shifts and ¹J (Sn, C) coupling constants in dependence on temperature and concentration were applied to study the association processes of the substances in solution. In CDCl₃ as a solvent a monomeric/polymeric equilibrium of the substances was demonstrated, while CD₃OD as a donor solvent forms five-coordinated complexes with the tin compounds.     

Molecular Cross-Talk between Gravity- and Light-Sensing Mechanisms in Euglena gracilis

Euglena gracilis is a photosynthetic flagellate. To acquire a suitable position in its surrounding aquatic environment, it exploits light and gravity primarily as environmental cues. Several physiological studies have indicated a fine-tuned relationship between gravity sensing (gravitaxis) and light sensing in E. gracilis. However, the underlying molecular mechanism is largely unknown. The photoreceptor photoactivated adenylyl cyclase (PAC) has been studied for over a decade. Nevertheless, no direct/indirect interaction partner (upstream/downstream) has been reported for PAC. It has been shown that a specific protein, kinase A (PKA), showed to be involved in phototaxis and gravitaxis. The current study reports the localization of the specific PKA and its relationship with PAC.     

A Unified Analysis of Structured Sonar-Terrain Data Using Bayesian Functional Mixed Models

Sonar emits pulses of sound and uses the reflected echoes to gain information about target objects. It offers a low cost, complementary sensing modality for small robotic platforms. Although existing analytical approaches often assume independence across echoes, real sonar data can have more complicated structures due to device setup or experimental design. In this article, we consider sonar echo data collected from multiple terrain substrates with a dual-channel sonar head. Our goals are to identify the differential sonar responses to terrains and study the effectiveness of this dual-channel design in discriminating targets. We describe a unified analytical framework that achieves these goals rigorously, simultaneously, and automatically. The analysis was done by treating the echo envelope signals as functional responses and the terrain/channel information as covariates in a functional regression setting. We adopt functional mixed models that facilitate the estimation of terrain and channel effects while capturing the complex hierarchical structure in data. This unified analytical framework incorporates both Gaussian models and robust models. We fit the models using a full Bayesian approach, which enables us to perform multiple inferential tasks under the same modeling framework, including selecting models, estimating the effects of interest, identifying significant local regions, discriminating terrain types, and describing the discriminatory power of local regions. Our analysis of the sonar-terrain data identifies time regions that reflect differential sonar responses to terrains. The discriminant analysis suggests that a multi- or dual-channel design achieves target identification performance comparable with or better than a single-channel design. Supplementary materials for this article are available online.     

Repurposing the Pummerer Rearrangement: Determination of Methionine Sulfoxides in Peptides

The reversible oxidation of methionine residues in proteins has emerged as a biologically important post-translational modification. However, detection and quantitation of methionine sulfoxide in proteins is difficult. Our aim is to develop a method for specifically derivatizing methionine sulfoxide residues. We report a Pummerer rearrangement of methionine sulfoxide treated sequentially with trimethylsilyl chloride and then 2-mercaptoimidazole or pyridine-2-thiol to produce a dithioacetal product. This derivative is stable to standard mass spectrometry conditions, and its formation identified oxidized methionine residues. The scope and requirements of dithioacetal formation are reported for methionine sulfoxide and model substrates. The reaction intermediates have been investigated by computational techniques and by ¹³C NMR spectroscopy. These provide evidence for an α-chlorinated intermediate. The derivatization allows for detection and quantitation of methionine sulfoxide in proteins by mass spectrometry and potentially by immunochemical methods.     

The Kinetics of the Thermal Decomposition of Thermoplastic Polyurethane Elastomers under Thermoplastic Processing Conditions

A theoretical approach to the kinetics of the thermal decomposition of molten thermoplastic polyurethane elastomers, under conditions of thermoplastic processing, is described. On the basis of these considerations, the thermal decomposition in different instruments (melt index analyser and measuring extruder) can be described quantitatively and the various results can be compared. As a result, identical conditions of decomposition of the melt can be defined accurately, thus opening up the possibility of combining experimental values from different instruments. The fundamental kinetic equation obtained for the kinetics of the thermal decomposition of thermoplastic polyurethanes describes the decomposition reaction and the reverse reaction (formation reaction) – which is dependent on the system of measurement and processing – as a function of the molar mass (end‐group concentration) of the original product, determined from the velocity constants for the decomposition reaction and back reaction. The consideration of the limiting value for t → ∞ is in agreement with the equilibrium constant. Consequently, the development of physical characteristic functions of thermoplastic polyurethane elastomers – independent of the system of measurement – is possible.

Experimental values and calculated curves for the thermal decomposition of PUR‐Et in a melt index analyser.     

A Photographic Study of Flash-Boiling Atomization

To gain an insight into the mechanisms of flash-boiling atomization, heated water was injected from a single-hole orifice into heated air (steady injections, liquid pressure 697 kPa, air pressure ambient, test temperatures from 300 to 426 K, orifice diameter 0.34 mm, length 1.37 mm). The breakup regime of interest in the study was that where the spray divergence starts at the nozzle exit. Short-duration backlit photographs and laser diffraction dropsize measurements showed that these flashing jets comprise an inner intact core which is surrounded by the diverging fine spray. These details about the spray structure are not visible in conventional photographs of flashing sprays that use scattered light illumination. The present results cast doubt on a previously proposed theory of flash-boiling atomization that attributes the divergence of the spray cone to the expansion processes that occur in an underex-panded compressible flow, since that theory implies that the liquid is already atomized upon leaving the nozzle. Instead, the photographs show that drops are expelled from the unbroken liquid jet starting at the nozzle exit (presumably by rapid vapor bubble growth within the jet). The core region remains intact for some distance downstream of the nozzle exit, and its breakup eventually produces relatively large drops. As the liquid temperature approaches boiling, the intact length and the core drop size decrease. Thus operation close to boiling is desirable for effective atomization. However, the nozzle mass flow rate decreases and practical difficulties are found (owing to “vapor-lock”) as the liquid is heated near boiling.