Chemo‐ and Magnetotaxis of Self‐Propelled Light‐Emitting Chemo‐electronic Swimmers

Miniaturized autonomous chemo‐electronic swimmers, based on the coupling of spontaneous oxidation and reduction reactions at the two poles of light‐emitting diodes (LEDs), are presented as chemotactic and magnetotactic devices. In homogeneous aqueous media, random motion caused by a bubble‐induced propulsion mechanism is observed. However, in an inhomogeneous environment, the self‐propelled devices exhibit positive chemotactic behavior, propelling themselves along a pH or ionic strength gradient (?pH and ?I, respectively) in order to reach a thermodynamically higher active state. In addition, the intrinsic permanent magnetic moment of the LED allows self‐orientation in the terrestrial magnetic field or following other external magnetic perturbations, which enables a directional motion control coupled with light emission. The interplay between chemotaxis and magnetotaxis allows fine‐tuning of the dynamic behavior of these swimmers.     

Remote Actuation of a Light-Emitting Device Based on Magnetic Stirring and Wireless Electrochemistry

We propose a straightforward access to a rotating light-emitting device powered by wireless electrochemistry. A magnetic stirrer is used to rotate a light-emitting diode (LED) due to the intrinsic magnetic properties of the tips that contain iron. At the same time, the LED is submitted to an electric field and acts as a bipolar electrode. The electrochemical processes that are coupled on both extremities of the LED drive an electron flow across the device, resulting in light emission. The variation of the LED alignment in time enables an alternating light emission that is directly controlled by the rotation rate. The stirring also enables a continuous mixing of the electrolyte that improves the stability of the output signal. Finally, the LED brightness can readily reveal a change of chemical composition in the electrolyte solution.     

Comparison of electron spin resonance probe and dielectric relaxation in physically and chemically crosslinked polymers

Dielectric relaxation spectroscopy in the frequency range from 10⁻² Hz to 10⁶ Hz and electron spin resonance (ESR) experiments are employed to study the dynamics in chemically and physically crosslinked networks. As examples for physically crosslinked networks ortho- and para-cresol novolacs were investigated. Dielectrically these materials show low-temperature β- and high-temperature α-relaxation. Both relaxation regions differ for both types of novolacs. This is also reflected by the ESR measurements and is discussed in terms of different hydrogen bonds found to be stronger in para-cresol novolac. For the chemically crosslinked poly(triallyl isocyanurate) only a β-peak is found by the dielectric measurements. Also in the ESR experiment the slow motion regime is characterized up to high temperatures. This means that the segmental motion is strongly suppressed by chemical crosslinking. Nevertheless the obtained change in the formal T_50G value can be used to characterize the glass transition in highly crosslinked systems by the ESR method.     

Influence of the mesophase structure on the β-relaxation in liquid crystalline poly(meth)acrylates

The dependence of the rotation of the mesogenic unit around its long axis (β-relaxation) on the actual mesophase in liqid crystalline polymethacrylates and polyacrylates was studied by dielectric spectroscopy in the frequency range from 10⁻² Hz to 10⁶ Hz and in a temperature range from 170 K to 430 K. As mesogenic units derivatives of (p-alkoxy-phenyl)-benzoate were used where different mesophases were achieved by small variation of the mesogenic structure, the spacer length and the tail group of the mesogenic unit. For all samples the temperature dependence of the relaxation rate of the β-relaxation can be described by an Arrhenius equation where both the pre-exponential factor and the activation energy increase significantly with the order of the mesophase. To characterize the structure X-ray measurements were also carried out. The mean lateral mesogenic distance was correlated directly with relaxational quantities.     

Self-assembled monolayer protection of chiral-imprinted mesoporous platinum electrodes for highly enantioselective synthesis

In modern chemistry, chiral (electro)catalysis is a powerful strategy to produce enantiomerically pure compounds (EPC). However, it still struggles with uncontrollable stereochemistry due to side reactions, eventually producing a racemic mixture. To overcome this important challenge, a well-controlled design of chiral catalyst materials is mandatory to produce enantiomers with acceptable purity. In this context, we propose the synergetic combination of two strategies, namely the elaboration of mesoporous Pt films, imprinted with chiral recognition sites, together with the spatially controlled formation of a self-assembled monolayer. Chiral imprinted metals have been previously suggested as electrode materials for enantioselective recognition, separation and synthesis. However, the outermost surface of such electrodes is lacking chiral information and thus leads to unspecific reactions. Functionalising selectively this part of the electrode with a monolayer of organosulfur ligands allows an almost total suppression of undesired side reactions and thus leads to a boost of enantiomeric excess to values of over 90% when using these surfaces in the frame of enantioselective electrosynthesis. In addition, this strategy also decreases the total reaction time by one order of magnitude. The study therefore opens up promising perspectives for the development of heterogeneous enantioselective electrocatalysis strategies.

Highly enantioselective electrosynthesis with up to 90% ee and short reaction times can be achieved with alkanethiol protected chiral imprinted mesoporous Pt surfaces.     

A novel 3D mammalian cell perfusion-culture system in microfluidic channels

Mammalian cells cultured on 2D surfaces in microfluidic channels are increasingly used in drug development and biological research applications. These systems would have more biological or clinical relevance if the cells exhibit 3D phenotypes similar to the cells in vivo. We have developed a microfluidic channel based system that allows cells to be perfusion-cultured in 3D by supporting them with adequate 3D cell-cell and cell-matrix interactions. The maximal cell-cell interaction was achieved by perfusion-seeding cells through an array of micropillars; and 3D cell-matrix interactions were achieved by a polyelectrolyte complex coacervation process to form a thin layer of matrix conforming to the 3D cell shapes. Carcinoma cell lines (HepG2, MCF7), primary differentiated (hepatocytes) and primary progenitor cells (bone marrow mesenchymal stem cells) were perfusion-cultured for 72 hours to 1 week in the microfluidic channel, which preserved their 3D cyto-architecture and cell-specific functions or differentiation competence. This transparent 3D microfluidic channel-based cell culture system also allows direct optical monitoring of cellular events for a wide range of applications.     

Novel aflatoxin derivatives and protein conjugates

Aflatoxins, a group of structurally related mycotoxins, are well known for their toxic and carcinogenic effects in humans and animals. Aflatoxin derivatives and protein conjugates are needed for diverse analytical applications. This work describes a reliable and fast synthesis of novel aflatoxin derivatives, purification by preparative HPLC and characterisation by ESI-MS and one- and two-dimensional NMR. Novel aflatoxin bovine serum albumin conjugates were prepared and characterised by UV absorption and MALDI-MS. These aflatoxin protein conjugates are potentially interesting as immunogens for the generation of aflatoxin selective antibodies with novel specificities.