Microgel particles containing methacrylic acid: pH-triggered swelling behaviour and potential for biomaterial application

pH-responsive microgels are crosslinked polymer particles that swell when the pH approaches the pK(a) of the ionic monomer incorporated within the particles. In recent work from our group it was demonstrated that the mechanical properties of degenerated intervertebral discs (IVDs) could be restored to normal values by injection of poly(EA/MAA/BDDA) (ethylacrylate, methacrylic acid and butanediol diacrylate) microgel dispersions [J.M. Saunders, T. Tong, C.L. Le Maitre, T.J. Freemont, B.R. Saunders, Soft Matter 3 (2007) 486]. In this work we report the pH dependent swelling and rheological properties of poly(MMA/MAA/EGDMA) (methylmethacrylate and ethyleneglycol dimethacrylate) microgel dispersions. This system was investigated because it contains monomers that are already used as biomaterials. The poly(MMA/MAA/EGDMA) particles exhibit pH-triggered volume swelling ratios of up to ca. 250. The swelling onset for these particles occurs at pH values greater than ca. 6.0. A pK(a) for these particles of ca. 6.7 is consistent with titration and swelling data. Fluid-to-gel phase diagrams for concentrated poly(MMA/MAA/EGDMA) dispersions were determined as a function of polymer volume fraction and pH using tube-inversion measurements. The rheological properties for the gelled microgel dispersions were investigated using dynamic rheology measurements. The elastic modulus data for the poly(MMA/MAA/EGDMA) gelled dispersions were compared to data for poly(EA/MAA/BDDA) microgels. A similar pH-dependence for the elastic modulus was apparent. The maximum elastic modulus was achieved at a pH of about 7.0. The elastic modulus is an exponentially increasing function of polymer volume fraction at pH 7.0. Preliminary cell challenge experimental data are reported that indicate that gelled poly(MMA/MAA/EGDMA) microgel dispersions are biocompatible with cells from human intervertebral discs. However, the duration over which these experiments could be performed was limited by gradual redispersion of the gelled microgel dispersions. Based on the results presented it is suggested that poly(MMA/MAA/EGDMA) microgel would be a good candidate as a biomaterial for structural support of soft connective tissues.     

Developmental aspects of amperometric ATP biosensors based on entrapped enzymes

A novel concept for a dual-enzyme-based microbiosensor for the detection of adenosine-5′-triphosphate (ATP) was developed. The employed enzymes pyrroloquinoline quinone-dependent glucose dehydrogenase (PQQ-GDH) and hexokinase were entrapped, using pH-shift-induced precipitation of electrodeposition paint (EDP) at platinum microelectrodes (diameter of 25 µm). PQQ-GDH is known showing a superior activity for glucose conversion at the relevant conditions (low oxygen concentration) for ATP detection in targeted biomedical studies. For immobilizing the two enzymes PQQ-GDH and hexokinase, the deposition conditions of EDP Resydrol AY498w/35WA were adapted to ensure high immobilization rates. Prior to ATP sensing, the conversion of glucose, which is the co-substrate for both enzymatic reactions, was optimized. Optimization was targeted towards ATP measurements in biomedical environments by optimizing the PQQ-GDH sensor for glucose. Therefore, different mediators were tested regarding their electron transfer rate and their compatibility with the enzyme: free-diffusing N-methylphenazonium methyl sulfate (PMS) and ferrocenemethanol, and an immobilized chromium hexacyanoferrate layer at platinum electrode. Free-diffusing ferrocenemethanol reveals high sensitivity towards glucose of 1.5?±?0.4 nA/mM. In a next step, hexokinase was co-entrapped in the polymer film resulting in a sensitivity of up to 290 pA/µM.     

A Tris(triazolate) Ligand for a Highly Active and Magnetically Recoverable Palladium Catalyst of Selective Alcohol Oxidation Using Air at Atmospheric Pressure

High efficiency and selectivity, easy magnetic recovery and recycling, and use of air as the oxidant at atmospheric pressure are major objectives for oxidation catalysis in terms of sustainable and green processes. A tris(triazolyl) ligand, so far only used in copper‐catalyzed alkyne azide cycloadditions, was found to be extremely efficient in SiO₂/γ‐Fe₂O₃‐immobilized palladium complexes. It was characterized by inductively coupled plasma (ICP) analysis, transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), energy‐dispersive X‐ray spectroscopy (EDX), and X‐ray photoelectron spectra (XPS) and found to fulfill the combined conditions for the selective oxidation of alcohols to aldehydes and ketones.     

Ovoids with a pencil of translation ovals

We show that if an ovoid of PG(3, q), where q>2 is even, has a pencil of translation ovals and if the carrier of the pencil is not an axis of at least one of the ovals in the pencil, then the ovoid is a Tits ovoid. It follows, as a corollary of this and a result of Penttila and Praeger, that if an ovoid of PG(3, q), where q>2 is even, has a pencil of translation ovals then the ovoid is either an elliptic quadric or a Tits ovoid.     

Effect of Er:YAG laser energy on the morphology of enamel/adhesive system interface

The aim of this study was to evaluate in vitro the influence of Er:YAG laser energy variation to cavity preparation on the morphology of enamel/adhesive system interface, using SEM. Eighteen molars were used and the buccal surfaces were flattened without dentine exposure. The specimens were randomly assigned to two groups, according to the adhesive system (conventional total-etching or self-etching), and each group was divided into three subgroups (bur carbide in turbine of high rotation, Er:YAG laser 250 mJ/4 Hz and Er:YAG laser 300 mJ/4 Hz) containing six teeth each. The enamel/adhesive system interface was serially sectioned and prepared for SEM. The Er:YAG laser, in general, produced a more irregular adhesive interface than the control group. For Er:YAG laser 250 mJ there was formation of a more regular hybrid layer with good tag formation, mainly in the total-etching system. However, Er:YAG laser 300 mJ showed a more irregular interface with amorphous enamel and fused areas, for both adhesive systems. It was concluded that cavity preparation with Er:YAG laser influenced on the morphology of enamel/adhesive system interface and the tissual alterations were more evident when the energy was increased.