In this study, electrospinning of nanofibers from alpha-lipoic acid/cyclodextrin inclusion complex systems was successfully performed without having any polymeric matrix. Alpha-lipoic acid (α-LA) is a natural antioxidant compound which is widely used as a food supplement. However, it has limited water solubility and poor thermal and oxidative stability. Nevertheless, it is possible to enhance its water solubility and thermal stability by inclusion complexation with cyclodextrins. Here, hydroxypropyl-beta-cyclodextrin (HP-β-CyD) and hydroxypropyl-gamma-cyclodextrin (HP-γ-CyD) were chosen as host molecules for forming inclusion complexation with α-LA. Accordingly, α-LA was inclusion complexed with HP-β-CyD and HP-γ-CyD by using very high concentrated aqueous solutions of CyD (200%, w/v) having 1/1 and 2/1 molar ratio of α-LA/CyD. Except α-LA/HP-β-CyD (1/1) solution, other α-LA/CyD solutions were turbid indicating the presence of some noncomplexed α-LA whereas α-LA/HP-β-CyD (1/1) solution was very homogeneous signifying that α-LA was fully complexed with HP-β-CyD. Even so, electrospinning was performed for all of the α-LA/HP-β-CyD (1/1 and 2/1) and α-LA/HP-γ-CyD (1/1 and 2/1) aqueous solutions, and defect-free bead-less and uniform nanofibers were successfully obtained for all of the α-LA/CyD solutions. However, the electrospinning process for α-LA/CyD (1/1) systems was much more efficient than the α-LA/CyD (2/1) systems, and we were able to produce self-standing and flexible nanofibrous webs from α-LA/CyD (1/1) systems. α-LA was efficiently preserved during the electrospinning process of α-LA/CyD (1/1) systems and the resulting electrospun α-LA/HP-β-CyD and α-LA/HP-γ-CyD nanofibers were produced with the molar ratios of ∼1/1 and ∼0.85/1 (α-LA/CyD), respectively. The better encapsulation efficiency of α-LA in α-LA/HP-β-CyD nanofibers was due to higher solubility increase and higher binding strength between α-LA and HP-β-CyD as revealed by the phase solubility test. α-LA was in the amorphous state in α-LA/CyD nanofibers and both α-LA/HP-β-CyD and α-LA/HP-γ-CyD nanofibers were dissolved very quickly in water and also when they wetted with artificial saliva. Additionally, the antioxidant activity of pure α-LA and α-LA/CyD nanofibers was comparatively evaluated using ABTS radical cation assay. α-LA/CyD nanofibers have shown significantly higher antioxidant performance compared to pure α-LA owing to improved water solubility by CyD inclusion complexation. The thermal stability enhancement of α-LA in α-LA/CyD nanofibers was achieved compared to pure α-LA under heat treatment (100 °C for 24 h). These promising results support that antioxidant α-LA/CyD nanofibers may have potential applications as orally fast-dissolving food supplements.
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