Hydrogels for load-bearing biomedical applications, such as soft tissue replacement, are required to be tough and biocompatible. In this sense, alginate-methacrylate hydrogels (H-ALGMx) are well known to present modulable levels of elasticity depending on the methacrylation degree; however, little is known about the role of additional structural parameters. In this work, we present an experimental-computational approach aimed to evaluate the effect of the molecular conformation and electron density of distinct methacrylate groups on the mechanical properties of photocrosslinked H-ALGMx hydrogels. Three alginate-methacrylate precursor macromers (ALGMx) were synthesized: alginate-glycidyl methacrylate (ALGM1), alginate-2-aminoethyl methacrylate (ALGM2), and alginate-methacrylic anhydride (ALGM3). The macromers were studied by Fourier-transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (1H-NMR), and density functional theory method (DFT) calculations to assess their molecular/electronic configurations. In parallel, they were also employed to produce H-ALGMx hydrogels, which were characterized by compressive tests. The obtained results demonstrated that tougher hydrogels were produced from ALGMx macromers presenting the C=C reactive bond with an outward orientation relative to the polymer chain and showing free rotation, which favored in conjunction the covalent crosslinking. In addition, although playing a secondary role, it was also found that the presence of acid hydrogen atoms in the methacrylate unit enables the formation of supramolecular hydrogen bonds, thereby reinforcing the mechanical properties of the H-ALGMx hydrogels. By contrast, impaired mechanical properties resulted from macromer conditions in which the C=C bond adopted an inward orientation to the polymer chain accompanied by a torsional impediment.
In the present work, we report the library preparation on solid supports of 20 derivatives of 1,4,10,13-tetraoxa-7,15-diaza-cycloctadecane 1(a-e)(w,x,y,z) carrying a fluorescent dansyl group. The sensing fluorescence behavior of these materials toward alkali and alkali earth metal ions was studied by packing the beads into a conventional flow-through cell in a FIA (flow injection analysis) approach. The fluorescence emission of these materials' responses shows a fluorescence increase to Li+, Na+, K+, NH4+, Ca2+, and Mg2+ with maximum sensitivity for Mg2+ over the rest of the ions. The analytical potential of these materials is outlined, and the sensing response mechanism, based on a photoinduced electron-transfer process, is proposed.
The direct monitoring of reaction progress on solid supports by fluorescence spectroscopy is described. An immobilized fluorescent tracer molecule (dansyl chloride) is used to monitor the reaction on OH resins (Argopore Wang, PS Wang, and Argogel Wang), both in batch and in parallel chemistry. Fluorescence measurements were obtained directly on solid phase. The method demonstrated to be a valuable tool for the quantitative determination of resin-bound hydroxyl groups, to study reaction kinetics and for continuously monitoring the progress of the conversion of the hydroxyl resins into the chlorinated ones. The procedure proposed is highly sensitive compared to the traditional ones. The system can be extended to monitor a variety of reactions on solid supports, and in conjunction with a well-established technique such as flow analysis, basic studies on solid-phase become possible.
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