No abstract

The exact knowledge of hydrogel microstructure, mainly its pore topology, is a key issue in hydrogel engineering. For visualization of the swollen hydrogels, the cryogenic or high vacuum scanning electron microscopies (cryo-SEM or HVSEM) are frequently used while the possibility of artifact-biased images is frequently underestimated. The major cause of artifacts is the formation of ice crystals upon freezing of the hydrated gel. Some porous hydrogels can be visualized with SEM without the danger of artifacts because the growing crystals are accommodated within already existing primary pores of the gel. In some non-porous hydrogels the secondary pores will also not be formed due to rigid network structure of gels that counteracts the crystal nucleation and growth. We have tested the limits of true reproduction of the hydrogel morphology imposed by the swelling degree and mechanical strength of gels by investigating a series of methacrylate hydrogels made by crosslinking polymerization of glycerol monomethacrylate and 2-hydroxyethyl methacrylate including their interpenetrating networks. The hydrogel morphology was studied using cryo-SEM, HVSEM, environmental scanning electron microscopy (ESEM), laser scanning confocal microscopy (LSCM) and classical wide-field light microscopy (LM). The cryo-SEM and HVSEM yielded artifact-free micrographs for limited range of non-porous hydrogels and for macroporous gels. A true non-porous structure was observed free of artifacts only for hydrogels exhibiting relatively low swelling and high elastic modulus above 0.5 MPa, whereas for highly swollen and/or mechanically weak hydrogels the cryo-SEM/HVSEM experiments resulted in secondary porosity. In this contribution we present several cases of severe artifact formation in PHEMA and PGMA hydrogels during their visualization by cryo-SEM and HVSEM. We also put forward empirical correlation between hydrogel morphological and mechanical parameters and the occurrence and intensity of artifacts.

The behavior of alternating poly(styrene−maleic anhydride) (SMA) in aqueous solution and at the air−water interface was studied by static and dynamic light scattering, by surface tension measurements, and by transmission electron microscopy (TEM). The variables of interest were the polymer concentration, the molecular weight, and the degree of ionization varied with pH. SMA polymers can associate in aqueous solution. The critical size of SMA in solution ranges from the predicted Gaussian radius of gyration (r g) up to 150 nm. The size of the associates increases with decreasing molecular weight. A maximum in associate size was measured at pH = 6.5, which corresponds to the polymer salt under its monosodium form. A mechanism by which SMA molecules zip together forming a macrocoil made of two molecules in cross section was proposed. SMA molecules also adsorb at the air−water interface, very likely as 2D-coils. An equilibrium links the concentration of SMA in solution and at the air−water interface.

In this article, we report on the rheological properties of agarose aqueous solutions and gels. Viscosity curves were determined for homogeneous agarose aqueous solutions at different temperatures (from 68 to 38 8C) to study the viscosity behavior as the systems undergo gelation. The gelation phenomenon of agarose solutions was also investigated by shear oscillation experiments and differential scanning calorimetry. The gelation and melting temperature as a function of agarose concentration were determined together with the gelation and melting enthalpies. The results obtained were interpreted using the two-step model describing the gelation of agarose in water.

No abstract

A growing group of polyfunctional precursors of polymer networks contains more than one branch point (cross-link). The bonds they extend lead either to another branch point or to a functional group. When such precursors are cross-linked, these branch points are gradually activated to reach the status of elastically active cross-links (EAC), i.e., such cross-links from which three or more bonds extend that have infinite continuation. The contribution of EAC's to the concentration of elastically active network chains (EANC) increases gradually with conversion of functional groups and depends on precursor architecture. Cross-linking of specially assembled precursors, functional dendrimers, and hyperbranched polymers is treated theoretically using the stochastic theory of branching processes based on generation of structures from units in different reaction states. Each bond extending from a branch point is considered as to whether the issuing subtree is finite or whether an infinite continuation exists. Several examples of development of concentration of EANC's and other structural parameters of the network demonstrate the importance of the activation process. It is shown that the branch points of dendritic precursors closer to its center are activated sooner than those at the precursor periphery.

Degradable poly(2-hydroxyethyl methacrylate) hydrogels were prepared from a linear copolymer (M = 49 kDa) of 2-hydroxyethyl methacrylate (HEMA), 2-(acethylthio)ethyl methacrylate (ATEMA), and zwitterionic 2-methacryloyloxyethyl phosphorylcholine (MPC). The deprotection of ATEMA thiol groups by triethylamine followed by their gentle oxidation with 2,2'-dithiodipyridine resulted in the formation of reductively degradable polymers with disulfide bridges. Finally, a hydrogel 3D structure with an oriented porosity was obtained by gelation of the polymer in the presence of needle-like sodium acetate crystals. The pore diameter and porosity of resulting poly(2-hydroxyethyl methacrylate-co-2-(acethylthio)ethyl methacrylate-co-2-methacryloyloxyethyl phosphorylcholine) [P(HEMA-ATEMA-MPC)] hydrogels varied between 59 and 65 μm and between 70 and 79.6 vol % according to Hg porosimetry, and complete degradation of these materials was reached in 86 days in 0.33 mmol solution of l-cysteine/L in phosphate buffer. The cross-linked P(HEMA-ATEMA-MPC) hydrogels were evaluated as a possible support for human mesenchymal stem cells (MSCs). No cytotoxicity was found for the un-cross-linked thiol-containing and protected P(HEMA-ATEMA-MPC) chains up to a concentration of 5 and 1 wt % in α-minimum essential medium, respectively.

We present an investigation of the preparation of highly porous hydrogels based on biodegradable synthetic poly(α-amino acid) as potential tissue engineering scaffolds. Covalently cross-linked gels with permanent pores were formed under cryogenic conditions by free-radical copolymerization of poly[N(5)-(2-hydroxyethyl)-L-glutamine-stat-N(5)-(2-methacryloyl-oxy-ethyl)-L-glutamine] (PHEG-MA) with 2-hydrohyethyl methacrylate (HEMA) and, optionally, N-propargyl acrylamide (PrAAm) as minor comonomers. The morphology of the cryogels showed interconnected polyhedral or laminar pores. The volume content of communicating water-filled pores was >90%. The storage moduli of the swollen cryogels were in the range of 1-6 kPa, even when the water content was >95%. The enzymatic degradation of a cryogel corresponded to the decrease in its storage modulus during incubation with papain, a model enzyme with specificity analogous to wound-healing enzymes. It was shown that cryogels with incorporated alkyne groups can easily be modified with short synthetic peptides using azide-alkyne cycloaddition "click" chemistry, thus providing porous hydrogel scaffolds with biomimetic features.