RESUMO
Non-derivatizing, high-efficiency and low-toxicity solvents are important for studying the dissolution behavior and potential applications of starch. In this study, we investigated the starch dissolution mechanism and molecular conformation in KOH/thiourea aqueous solutions and compared these with KOH/urea and KOH aqueous solutions. Solubility analysis revealed that the KOH/thiourea solution demonstrates a better ability to dissolve corn starch than KOH/urea and KOH solutions. Rheological behavior and dynamic and static light scattering indicated that starch is stable in KOH/thiourea solution and exists as a regular star structure. Fourier transform infrared spectroscopy, 13C NMR, and molecular dynamics simulations indicated that hydrated K+ and OH- destroy the strong starch hydrogen bond interactions; thiourea hydrate self-assembles into a shell surrounding the starch-KOH complex through interaction with KOH, whereas there is no direct strong interaction between urea and KOH. Therefore, adding thiourea to a KOH solution can promote dissolution and prevent self-aggregation of the starch chain.
Assuntos
Hidróxidos/química , Compostos de Potássio/química , Solventes/química , Amido/química , Tioureia/química , Configuração de Carboidratos , Espectroscopia de Ressonância Magnética Nuclear de Carbono-13 , Ligação de Hidrogênio , Simulação de Dinâmica Molecular , Reologia , Solubilidade , Espectroscopia de Infravermelho com Transformada de Fourier , Água/químicaRESUMO
Finding an efficient and eco-friendly solution for starch dissolution has attracted considerable attentions in recent years. This study investigated the structural characteristics, and degradation behavior of corn starch in KOH/thiourea aqueous solution by the comparison with DMSO/LiBr and 1-allyl-3-methylimidazolium chloride (AMIMCl). Results showed that KOH/thiourea solution was an effective solvent for corn starch dissolution (30 min with 97.01% solubility). X-ray diffraction (XRD) and 13C CP-MAS NMR spectroscopy revealed that native crystallinity of the corn starch was altered by all tested solvents, especially DMSO/LiBr and AMIMCl. Conversely, this new solvent did not change the primary molecular structure, chain-length distribution, or thermal stability of starch, compared with the native starch. Furthermore, KOH/thiourea solution was more suitable for measuring the molecular weight of corn starch, with a weight-average molecular weight (Mw) of 7.18 × 107 g/mol. Therefore, KOH/thiourea solution is a promising novel solvent for starch dissolution and structural exploration.
