Kinetic Control of Aggregation Shape in Micellar Self‐Assembly

The first steps towards top‐down morphology control in micellar self‐assembly are introduced. Kinetically stable micelles are formed from block copolymers (BCPs) using continuous flow techniques by turbulent mixing of water with a THF solution of polymers. In this way, particle shape and size can be altered from spheres to ellipsoids solely via tuning of mixing parameters from a single BCP.     

Formation of mixed aryl–, alkyl–lithium aggregates in the heteroatom assisted lithiation of α,α′-dialkyl substituted 1,3-bis[(dimethylamino)methyl]benzene

The heteroatom assisted lithiation of 1,3-bis[1-(dimethylamino)ethyl]benzene with n-BuLi afforded 2,6-bis[1-(dimethylamino)ethyl]phenyllithium. An X-ray crystal structure determination revealed a dimeric aggregate in which the four benzylic chiral centers are identical, pointing to stereoselective crystallization. In contrast, reaction of 1,3-bis[1-(dimethylamino)propyl]benzene with n-BuLi afforded a dimeric aggregate comprising the parent lithiated compound and n-BuLi in a 1:1 molar ratio. The four Li atoms and the four bridging carbon atoms are arranged in a unique ladder-type C–Li₂–C₂′–Li₂–C framework.     

Development of an on-line high performance liquid chromatography detection system for human cytochrome P450 1A2 inhibitors in extracts of natural products

An on-line HPLC screening method for detection of inhibitors of human cytochrome P450 1A2 in extracts was developed. HPLC separation of extracts is connected to a continuous methoxyresorufin-O-demethylation (MROD) assay in which recombinant human P450 1A2 converts methoxyresorufin to its fluorescent metabolite resorufin. The system was tested with three P450 1A2 inhibitors, for which minimum detectable amounts (MDA) ranging from 0.7 to 9.5 ng were obtained. Analysis of a kava kava and a basil extract showed that the on-line system is applicable to complex mixtures, since in both extracts, peaks with P450 1A2 inhibiting activity were observed.     

Enzymatic Crosslinking of Polymer Conjugates is Superior over Ionic or UV Crosslinking for the On‐Chip Production of Cell‐Laden Microgels

Cell‐laden micrometer‐sized hydrogels (microgels) hold great promise for improving high throughput ex‐vivo drug screening and engineering biomimetic tissues. Microfluidics is a powerful tool to produce microgels. However, only a limited amount of biomaterials have been reported to be compatible with on‐chip microgel formation. Moreover, these biomaterials are often associated with mechanical instability, cytotoxicity, and cellular senescence. To resolve this challenge, dextran‐tyramine has been explored as a novel biomaterial for on‐chip microgel formation. In particular, dextran‐tyramine is compared with two commonly used biomaterials, namely, polyethylene‐glycol diacrylate (PEGDA) and alginate, which crosslink through enzymatic reaction, UV polymerization, and ionic interaction, respectively. Human mesenchymal stem cells (hMSCs) encapsulated in dextran‐tyramine microgels demonstrate significantly higher (95%) survival as compared to alginate (81%) and PEGDA (69%). Long‐term cell cultures demonstrate that hMSCs in PEGDA microgels become senescent after 7 d. Alginate microgels dissolve within 7 d due to Ca²⁺ loss. In contrast, dextran‐tyramine based microgels remain stable, sustain hMSCs metabolic activity, and permit for single‐cell level analysis for at least 28 d of culture. In conclusion, enzymatically crosslinking dextran‐tyramine conjugates represent a novel biomaterial class for the on‐chip production of cell‐laden microgels, which possesses unique advantages as compared to the commonly used UV and ionic crosslinking biomaterials.

     

Is politics power or policy oriented? A comparative analysis of dynamic access models in policy networks*

We will show that these base models and some intermediate ones result in fundamentally different network structures and predicted outcomes. Moreover, we will show that the policy driven models do fundamentally better than the power driven models.

In policy networks actors use access relations to influence preferences of other actors. Establishment and shifts of access relations and their consequences for outcomes of decisions are the main focal points in this paper. Unlike most policy network studies, we therefore do not take the network and its relations as given and constant. Instead we device computer simulation models to account for the dynamics in policy networks. We compare different models and investigate the resulting network structures and predicted outcomes of decisions. The choice among the alternative models is made by their correspondence with empirical network structures and actual outcomes of decisions.

In our models, we assume that all relevant actors aim at policy outcomes as close as possible to their own preferences. Policy outcomes are determined by the preferences of the final decision makers at the moment of the vote. In general, only a small fraction of the actors takes part in the final vote. Most actors have therefore to rely on access relations for directly or indirectly shaping the preferences of the final decision makers. For this purpose actors make access requests to other actors. An access relation is assumed to be established if such a request is accepted by the other actor.

Access relations require time and resources. Actors are therefore assumed to be restricted in the number of access requests they can make and the number of requests they can accept Moreover, due to incomplete information and simultaneous actions by other actors, actors have to make simplifying assumptions in the selection of their “best” requests and learn by experience.

We device two base models that correspond to two basic views on the nature of political processes. In the first view politics is seen as power driven. Corresponding to this view, actors aim at access relations with the most powerful actors in the field. They estimate their likelihood of success by comparing their own resources with those of the target actors. Power also determines the order in which actors accept requests. In the second view, policy matters and actors roughly estimate the effects access relations might have on the outcome of decisions. Actors select requests to “bolster” their own preference as much as possible.     

Enantiopure Isoindolinones through Viedma Ripening

Here we demonstrate that deracemization of isoindolinones using Viedma ripening is possible starting from a racemic mixture of conglomerate crystals. Crystals of the enantiopure isoindolinones lose their chiral identity upon dissolution even without the need for a catalyst. This enabled complete deracemization of the reported isoindolinones without a catalyst.     

High-yield cell ordering and deterministic cell-in-droplet encapsulation using Dean flow in a curved microchannel

In this article high-yield (77%) and high-speed (2700 cells s(-1)) single cell droplet encapsulation is described using a Dean-coupled inertial ordering of cells in a simple curved continuous microchannel. By introducing the Dean force, the particles will order to one equilibrium position after travelling less than 1 cm. We use a planar curved microchannel structure in PDMS to spatially order two types of myeloid leukemic cells (HL60 and K562 cells), enabling deterministic single cell encapsulation in picolitre drops. An efficiency of up to 77% was reached, overcoming the limitations imposed by Poisson statistics for random cell loading, which yields only 37% of drops containing a single cell. Furthermore, we confirm that > 90% of the cells remain viable. The simple planar structure and high throughput provided by this passive microfluidic approach makes it attractive for implementation in lab on a chip (LOC) devices for single cell applications using droplet-based platforms.     

An integrated AFM-Raman instrument for studying heterogeneous catalytic systems: a first showcase

The integration of Atomic Force Microscopy and Raman spectroscopy is tested for use in heterogeneous catalysis research by a preliminary investigation, the photo-oxidation of rhodamine-6G. Temperature and atmosphere were varied in an in situ cell to show compatibility with realistic reaction conditions.