Hydrolysis effects on the water uptake of starch-g-glycidyl methacrylate (GMASt)/dimethylacrylamide (DMAAm)-based hydrogels for potential agricultural purposes.

This work assessed the effect of different hydrolysis periods on the properties of hydrogels based on 75 % w w-1 of N,N'-dimethyl acrylamide (DMAAm) and 25 % w w-1 of starch-g-(glycidyl methacrylate) (GMASt). FTIR results confirmed the conversion of ester groups into carboxylic acids and carboxylates, besides forming a keto-enol tautomer due to the peeling reaction of starch. For DMAAm, the hydrolysis mostly converted amide into carboxylate groups. The morphology, thermal stability, and the mechanical properties of the predominantly amorphous matrices (as confirmed by XRD results) did not drastically change even after 10 days of hydrolysis in alkali media. However, the thermogravimetric analysis results suggested that DMAAm partially protected GMASt from the hydrolysis. The swelling degree of the matrix increased from (10.1 ± 2.1) g g-1 to (61.9 ± 2.6) g g-1 after 1 day of hydrolysis, but no statistical differences (at 95 % of significance) were observed for the matrices hydrolyzed for longer periods, confirming that the maximum hydrolysis occurred within 24 h. The results confirmed that the hydrolysis increased the water uptake of the GMASt/DMAAm-based matrices, making appealing for uses as a water retentor for agricultural purposes.

A conventional and chemometric analytical approach to solving urea determination with accuracy and precision.

Urea is an essential molecule usually detected using spectroscopy, particularly ultraviolet and visible spectroscopy (UV-vis). However, its detection represents a not always fully acknowledged issue. Its concentration dependency has raised questions about the reliability of the UV-vis results. Derivatization reactions, common alternatives to achieve accuracy and precision with UV-vis measurements, still represent an additional step in the measurement process. Besides the problems mentioned earlier, urea forms complex mixtures in aqueous mediums. Therefore, this work proposes to investigate the accuracy and precision of urea determination by UV-vis spectroscopy in the pure form and derivatized with para-dimethylaminobenzaldehyde. The results show that UV-vis spectroscopy could not quantify urea in both forms with precision and accuracy. On the other hand, when applying multivariate curve resolution with alternating least squares (MCR-ALS) to the UV-vis data, the pure urea analytical signal is mathematically separated. Then, those parameters of merit were successfully achieved.

A comparative study of starch-g-(glycidyl methacrylate)/synthetic polymer-based hydrogels.

Chemical modification reactions and blending formation are two alternatives used to improve the properties of starch-based materials. This work used both approaches to evaluate how they would affect the properties of hydrogels. The hydrogels were based on corn starch (St), modified with glycidyl methacrylate (GMA; starch-g-GMA; GMASt), and blended with N,N'-dimethylacrylamide (DMAAm; GMAStxDMAAmy) or sodium acrylate (SA; GMAStxSAy). The results confirmed that the pure GMASt matrix had a low swelling degree (≈3 g g-1), but when blended with the synthetic polymers, this value reached ≈10 g g-1 (sample GMASt25DMAAm75). All matrices showed responsiveness towards pH variations. In general, they swelled more at pH 5 than at pH 7. While DMAAm had more influence on the swelling degree, SA was more efficient as a mechanical enhancer. Increasing 25 % of the amount of SA in the blend increased Young's Modulus by a factor of ≈10 times. It confirmed that both polymers effectively change the properties of GMASt, but in different ways.

Chitosan hybrid microgels for oral drug delivery.

In the present work, hybrid microgels based on chitosan and SiO2 nanoparticles (NPs) were synthesized. Both chitosan and the SiO2 NPs were submitted to chemical modification reactions to having vinyl groups incorporated into their structures. The microgels were synthesized by emulsion polymerization. SEM analysis indicated a high dispersity of diameter for the microgels, ranging between (18.7 ±â€¯12.3) µm for the samples without SiO2-VTS and (11.3 ±â€¯8.07) µm for the microgels with SiO2-VTS. The material showed pH-responsiveness, especially in acidic pHs. The longest release lasted 45 min and large amounts of drugs were released as soon as the material was added to the release medium. It is interesting for oral drug delivery systems, especially for gastric wound treatment. The fast release of high amounts of drugs promotes an immediate relief of the pain and the following controlled release allows the gradual recovery of the damaged area.

Drug polarity effect over the controlled release in casein and chondroitin sulfate-based hydrogels.

This study compared the controlled release of two drugs: vitamin-B12, and l-dopa from hydrogels based on 50% of casein (CAS, a protein), 50% of chondroitin sulfate (CS, a polysaccharide) and different amounts of SiO2. The results indicated that the incorporation of 5% of SiO2 to the materials, allowed the best organization, distribution, and diameter of the pores, which are responsible for ensuring a more controlled release. Also, the matrices were not efficient in releasing vitamin-B12, but it successfully released l-dopa. It happened because vitamin-B12 is highly hydrophilic, interacting more with the medium than with the CAS/CS matrix, while l-dopa is less polar than vitamin-B12, interacting more with the CAS/CS matrix. It is worth mentioning that all synthesized hydrogels were non-toxic to the cells as showed by the in vitro assay. This work also demonstrated the importance of evaluating drug delivery devices using drugs of different polarities before stating if they are efficient or not.

pH-responsive hybrid hydrogels: Chondroitin sulfate/casein trapped silica nanospheres for controlled drug release.

In this study, the materials were synthesized by chemically crosslinking chondroitin sulfate (CS), casein (CAS), and silica nanospheres (SiO2), creating a highly crosslinked network. The hydrogel release profile was adaptable (that is, it could be faster or slower as needed) simply by changing the polymeric proportion. The incorporation of 5% of silica nanospheres, in mass, for all CAS/CS matrices promoted a better-controlled and sustained release of l-dopa, focusing on the matrix based on 70% of CAS, 30% of CS and 5% of silica, whose l-dopa release lasted for 87 h. Besides, hydrogels are cytocompatible. These new hydrogels can be considered highly attractive materials to be used for controlled and sustained drug release purposes, as well as scaffolds and wound dressing systems.