Novel approach for fritless capillary electrochromatography

At present, the main limitation for the further adoption of capillary electrochromatography (CEC) in the (routine) laboratory is caused by the lack of reproducible and stable columns. The main source of column instability is concentrated in the frits needed to retain the packed bed inside the CEC capillary. The sintering process used to prepare the frits can be rather problematic and irreproducible, particularly for small stationary phase particles and wide column diameters. Since the (surface) composition of the frits is different from the bulk stationary phase packing, different electroosmotic flow (EOF) velocities are generated. This effect is assumed to be primarily responsible for rapid column destruction. In this contribution, a novel approach for the preparation of fritless CEC capillaries is presented and evaluated. Using 5 microm Hypersil ODS particles, separation efficiencies in the range of 130,000-200,000 plates/m were obtained. In a 100 microm inner diameter packed column, electrical currents up to 50 microA could be tolerated without negative effects such as bubble formation. The prepared CEC columns were found to be stable and could easily be operated continuously for several days without column damage. An additional advantage of the proposed tapering approach is that application of pressure on the in- and outlet vial during separation was not required to prevent bubble formation.     

Extending solid-phase methods in inorganic synthesis: the first dinuclear platinum complex synthesised via the solid phase

A method for obtaining potentially anti-tumour active dinuclear platinum coordination compounds via solid-phase inorganic synthesis is described for the first time.     

Internal modification of poly(dimethylsiloxane) microchannels with a borosilicate glass coating

We report on an original technique for the in situ coating of poly(dimethylsiloxane) (PDMS) microchannels with borosilicate glass, starting from an active nonaqueous and alkali-free precursor solution. By chemical reaction of this active solution inside the microchannel and subsequent thermal annealing, a protective and chemically inert glass borosilicate coating is bonded to the PDMS. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and nuclear magnetic resonance spectroscopy of the active solution show that it is composed of a silicon oxide network with boron connectivity. Thermal gravimetric analysis demonstrates the absence of organic content when curing is done above 150 degrees C. The borosilicate nature of the glass coating covalently bonded to the PDMS is demonstrated using ATR-FTIR spectroscopy and X-ray photoelectron spectroscopy. Atomic force microscopy and scanning electron microscopy show a smooth and crack-free coating. The latter is used as an efficient protective barrier against diffusion in PDMS of fluorescent rhodamine B dye that is dissolved either in water or in toluene. Moreover, the coating prevents swelling and consequent structural damage of the PDMS when the latter is exposed to harsh chemicals such as toluene.     

Rate dependence and role of disorder in linearly sheared two-dimensional foams

The shear flow of two-dimensional foams is probed as a function of shear rate and disorder. Disordered, bidisperse foams exhibit strongly shear rate dependent velocity profiles. This behavior is captured quantitatively in a simple model based on the balance of the time-averaged drag forces in the system, which are found to exhibit power-law scaling with the foam velocity and strain rate. Disorder makes the scaling of the bulk drag forces different from that of the local interbubble drag forces, which we evidence by rheometrical measurements. In monodisperse, ordered foams, rate independent velocity profiles are found, which lends further credibility to this picture.     

Visualization by PIV of dynamic stall on a vertical axis wind turbine

The aerodynamic behavior of a vertical axis wind turbine (VAWT) is analyzed by means of 2D particle image velocimetry (PIV), focusing on the development of dynamic stall at different tip speed ratios. The VAWT has an unsteady aerodynamic behavior due to the variation with the azimuth angle θ of the blade’s sections’ angle of attack, perceived velocity and Reynolds number. The phenomenon of dynamic stall is then an inherent effect of the operation of a VAWT at low tip speed ratios, impacting both loads and power. The present work is driven by the need to understand this phenomenon, by visualizing and quantifying it, and to create a database for model validation. The experimental method uses PIV to visualize the development of the flow over the suction side of the airfoil for two different reference Reynolds numbers and three tip speed ratios in the operational regime of a small urban wind turbine. The field-of-view of the experiment covers the entire rotation of the blade and almost the entire rotor area. The analysis describes the evolution of the flow around the airfoil and in the rotor area, with special focus on the leading edge separation vortex and trailing edge shed vorticity development. The method also allows the quantification of the flow, both the velocity field and the vorticity/circulation (only the results of the vorticity/circulation distribution are presented), in terms of the phase locked average and the random component.     

(Automated) Synthesis of Well-defined Staphylococcus Aureus Wall Teichoic Acid Fragments

Wall teichoic acids (WTAs) are important components of the cell wall of the opportunistic Gram-positive bacterium Staphylococcus aureus. WTAs are composed of repeating ribitol phosphate (RboP) residues that are decorated with d -alanine and N-acetyl-d -glucosamine (GlcNAc) modifications, in a seemingly random manner. These WTA-modifications play an important role in shaping the interactions of WTA with the host immune system. Due to the structural heterogeneity of WTAs, it is impossible to isolate pure and well-defined WTA molecules from bacterial sources. Therefore, here synthetic chemistry to assemble a broad library of WTA-fragments, incorporating all possible glycosylation modifications (α-GlcNAc at the RboP C4; β-GlcNAc at the RboP C4; β-GlcNAc at the RboP C3) described for S. aureus WTAs, is reported. DNA-type chemistry, employing ribitol phosphoramidite building blocks, protected with a dimethoxy trityl group, was used to efficiently generate a library of WTA-hexamers. Automated solid phase syntheses were used to assemble a WTA-dodecamer and glycosylated WTA-hexamer. The synthetic fragments have been fully characterized and diagnostic signals were identified to discriminate the different glycosylation patterns. The different glycosylated WTA-fragments were used to probe binding of monoclonal antibodies using WTA-functionalized magnetic beads, revealing the binding specificity of these WTA-specific antibodies and the importance of the specific location of the GlcNAc modifications on the WTA-chains.     

A density-based segmentation for 3D images,an application for X-ray micro-tomography

Density-based spatial clustering of applications with noise (DBSCAN) is an unsupervised classification algorithm which has been widely used in many areas with its simplicity and its ability to deal with hidden clusters of different sizes and shapes and with noise. However, the computational issue of the distance table and the non-stability in detecting the boundaries of adjacent clusters limit the application of the original algorithm to large datasets such as images. In this paper, the DBSCAN algorithm was revised and improved for image clustering and segmentation. The proposed clustering algorithm presents two major advantages over the original one. Firstly, the revised DBSCAN algorithm made it applicable for large 3D image dataset (often with millions of pixels) by using the coordinate system of the image data. Secondly, the revised algorithm solved the non-stability issue of boundary detection in the original DBSCAN. For broader applications, the image dataset can be ordinary 3D images or in general, it can also be a classification result of other type of image data e.g. a multivariate image.