8 research outputs found
Mindestmengen und Krankenhaussterblichkeit - Analyse der deutschlandweiten Krankenhausabrechnungsdaten von 2006 bis 2012
Redox-performance correlations in Ag-Cu-Mg-Al, Ce-Cu-Mg-Al, and Ga-Cu-Mg-Al hydrotalcite derived mixed metal oxides
Microgel organocatalysts: modulation of reaction rates at liquid–liquid interfaces
Controlling the catalytic activity via the use of smart and responsive carriers is a major challenge in research concerning supported catalysis. In homogeneous reactions, responsive polymeric carriers are often used to switch on/off reagent supply by controlled shielding of embedded catalysts. However, reactions on liquid interfaces are rare subjects of these kinds of studies. As an example of colloidal microgel-catalysts based on poly(N-isopropylacrylamide) (PNIPAM) containing covalently bound l-proline, we herein present how temperature and the effect of cononsolvency can be used as triggers to modulate reaction rates in a homogenous phase and on liquid-liquid interfaces. In particular, the aldol reaction of cyclohexanone with 4-nitrobenzaldehyde in water, methanol and water-methanol mixtures was the focus of our study. The swelling degree of the microgels evaluated by dynamic and static light scattering (DLS and SLS) was adjusted to demonstrate the effect of swelling on the rate of the aldol reaction. Combining our experimental results with computer simulations, based on dissipative particle dynamics (DPD), we could relate significant differences in reaction rates to the temperature-responsive swelling of the microgels. The simulations show that in aqueous reaction mixtures, the microgel-catalysts are adsorbed at the liquid-liquid interface between water and the hydrophobic reagents. Increasing the temperature causes the microgel-catalysts to immerse more into the reagent phase due to the temperature-responsiveness of PNIPAM. As a result, the average number of contacts between the l-proline catalyst and the reagents increases drastically resulting in a more than 5-fold increase of the catalytic rate observed in the experiments. On the contrary, the simulations of the reaction in methanol confirm that reagents form a homogeneous mixture in which the defined average number of contacts changes negligibly with the increasing temperature as PNIPAM does not possess a temperature-responsive behaviour in this solvent
Temperature-Responsive Nanofibrillar Hydrogels for Cell Encapsulation
Natural extracellular
matrices often have a filamentous nature,
however, only a limited number of artificial extracellular matrices
have been designed from nanofibrillar building blocks. Here we report
the preparation of temperature-responsive nanofibrillar hydrogels
from rod-shaped cellulose nanocrystals (CNCs) functionalized with
a copolymer of <i>N</i>-isopropylacrylamide and <i>N</i>,<i>N</i>′-dimethylaminoethyl methacrylate.
The composition of the copolymer was tuned to achieve gelation of
the suspension of copolymer-functionalized CNCs at 37 °C in cell
culture medium and gel dissociation upon cooling it to room temperature.
The mechanical properties and the structure of the hydrogel were controlled
by changing copolymer composition and the CNC-to-copolymer mass ratio.
The thermoreversible gels were used for the encapsulation and culture
of fibroblasts and T cells and showed low cytotoxicity. Following
cell culture, the cells were released from the gel by reducing the
temperature, thus, enabling further cell characterization. These results
pave the way for the generation of injectable temperature-responsive
nanofibrillar hydrogels. The release of cells following their culture
in the hydrogels would enable enhanced cell characterization and potential
transfer in a different cell culture medium