Shear induced relaxation of polymer micelles at the solid-liquid interface

A 20% aqueous solution of (ethylene oxide) 99-(propylene oxide) 65-(ethylene oxide) 99, F127, was investigated by combining rheology in a cone/plate-geometry and surface-sensitive grazing incident neutron scattering. The crystalline structure formed by the polymer micelles becomes less pronounced for low shear rates, but correlations increase for higher shear rates. After stopping shear a slow relaxation of the micelles is found in the vicinity (50 mum thick layer) of a hydrophilic silicon wall (strong micelle-wall interaction), while a fast relaxation is observed in the boundary layer against the hydrophobic silicon wall (weak micelle-wall interaction). The results show that in the vicinity of the interface wall-particle interactions compete heavily with the shear force acting on the liquid.     

Microstructure of thermoelectric (Bi0.15Sb0.85)2Te3 film

The film of thermoelectric ternary p-type (Bi_0.15Sb_0.85)₂Te₃ was deposited on polyimide foil substrate at 168 °C using direct-current magnetron sputtering. Microstructural investigations of the film were performed by electron microscopy techniques. SEM observations showed that the film surface consisted of large-sized particulates with small-sized particles and also mound-like crystal agglomerates in some areas. Chemical composition of the film was analyzed using energy-dispersive X-ray spectrometer (EDS). It has been observed that the EDS results were in an agreement with nominal composition for the film. Detailed microstructural investigations were carried out using transmission electron microscopy (TEM). TEM images and selected area electron diffraction patterns showed that the film has randomly oriented polycrystalline grain structure. High-resolution TEM images indicated that the microstructure of film also contained nano-crystal structure, smaller than 10 nm.     

Studying lateral diffusion in lipid bilayers by combining a magic angle spinning NMR probe with a microimaging gradient system

An alternative technique for studying the lateral diffusion in lipid membranes using pulsed field gradients in combination with magic angle spinning is presented. It is shown that MAS probes inserted in a microimaging device that produce high field gradients can be used to monitor also slow diffusion processes. As an example, measurements of the lateral diffusion of lipids embedded in the bilayer of a cubic phase are presented.     

Novel Hyperbranched Poly([1,2,3]‐triazole)s Derived from AB2 Monomers by a 1,3‐Dipolar Cycloaddition

Summary: Novel hyperbranched poly([1,2,3]‐triazole)s were synthesized from several AB₂ monomers by a 1,3‐dipolar cycloaddition reaction. The compound 3,5‐bis(propargyloxy)benzyl azide was polymerized thermally at room temperature leading to 1,4‐ and 1,5‐disubstituted poly([1,2,3]‐triazole) and catalytically leading only to the 1,4‐disubstituted poly([1,2,3]‐triazole). Only the thermal reaction led to fully soluble products. The AB₂ monomers containing an internal alkyne A unit could be autopolymerized thermally under mild reaction conditions leading to soluble, high‐molecular‐weight hyperbranched poly([1,2,3] triazole)s. All products were characterized by detailed NMR investigations.

Synthesis route for polymers 8a and 8b .     

Hyperbranched thermolabile polycarbonates derived from a A2+B3 monomer system

Hyperbranched polycarbonates were synthesized successfully via the A₂ + B₃ route by the reaction of a bis(carbonylimidazolide) with triethanolamine. These polymers containing the carbonate group as thermolabile moiety are decomposing into volatile products at around 200°C. The polymers were characterized with ¹H/¹³C NMR spectroscopy, SEC, DSC and TGA techniques.     

Matrix‐Free Formation of Gas‐Phase Biomolecular Ions by Soft Cluster‐Induced Desorption

All in a ball : Neutral molecular clusters consisting of a few thousand molecules can be seen as tiny snow balls; if they are thrown fast enough onto a surface, they are able to pick up biomolecules such as insulin from that surface. Since they break down and evaporate during and after the collision, bare biomolecular ions are available for mass spectrometry after such an energetic throw.

     

1H detection in MAS solid-state NMR spectroscopy of biomacromolecules employing pulsed field gradients for residual solvent suppression

In this communication, we demonstrate the feasibility of 1H detection in MAS solid-state NMR for a microcrystalline, uniformly 2H,15N-labeled sample of a SH3 domain of chicken alpha-spectrin, using pulsed field gradients for suppression of water magnetization. Today, B0 gradients are employed routinely in solution-state NMR for coherence order selection and solvent suppression. We suggest to use gradients to purge water magnetization which cannot be suppressed using conventional water suppression schemes. The achievable gain in sensitivity for 1H detection is in the order of 5 compared to the 15N detected version of the experiment (at a MAS rotation frequency of 13.5 kHz). We expect that this labeling concept which achieves high sensitivity due to 1H detection, in combination with the possibility to measure long range 1H-1H distances as we have shown previously, to be a useful tool for the determination of protein structures in the solid state.     

Application of displacement chromatography for the proteome analysis of a human plasma protein fraction

It was the aim of this study to compare the performance of displacement chromatography with gradient elution chromatography both applied as the cation-exchange separation step for a proteome analysis in a bottom-up approach using multidimensional chromatography for the separation of tryptic peptides prior to their mass spectrometric analysis. The tryptic digest of the human Cohn fraction IV-4 served as a sample. For both chromatography modes commonly used operating parameters were chosen thus ensuring optimal separation results of equal sample amounts for each mode. All resulting fractions were analyzed with an HPLC-chip–LC–MS system. The eluate of the HPLC-chip column was ionized by electrospray ionization (ESI) and analyzed with an ion-trap mass spectrometer. For guaranteeing high confidence concerning the identity of the peptides, the mass spectrometric data were processed by different bioinformatic tools applying stringent criteria. By the displacement approach the total amount of identified proteins (78) was significantly higher than in the gradient mode (58). The results showed that displacement chromatography is a well suited alternative in comparison to gradient elution separation for analysis of proteomes via the bottom-up approach applying multidimensional chromatography, especially in those cases when larger quantities of proteins are available.