Polysaccharides are one of the most abundant natural polymers and their molecular structure influences many crucial characteristics—inter alia hydrophobicity, mechanical, and physicochemical properties. Vibrational spectroscopic techniques, such as infrared (IR) and Raman spectroscopies are excellent tools to study their arrangement during polymerization and cross-linking processes. This review paper summarizes the application of the above-mentioned analytical methods to track the structure of natural polysaccharides, such as cellulose, hemicellulose, glucan, starch, chitosan, dextran, and their derivatives, which affects their industrial and medical use.

Chitosan/1,3-β-D-glucan matrices have been recently used in various biomedical applications. Within this study, the structural changes in hybrid polysaccharide chitosan/1,3-β-D-glucan matrices cross-linked at 70 °C and 80 °C were detected with Attenuated Total Reflection Fourier Transform Infrared spectroscopy (ATR FT-IR) and Raman spectroscopy enabled thorough insights into molecular structure of studied biomaterials, whereas X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) provided their surface characteristics with confirmation of their effective and non-destructive properties. There are temperature-dependent differences in the chemical interactions between 1,3-β-D-glucan units and N-glucosamine in chitosan, resulting in surface polarity changes. The second order derivatives and deconvolution revealed the alterations in the secondary structure of studied matrices, along with different sized grain-like structures revealed by AFM. Since surface physicochemical properties of biomaterials have great impact on cell behavior, abovementioned techniques may allow to optimize and modify the preparation of polymeric matrices with desired features.

The cross-linking temperature of polymers may affect the surface characteristics and molecular arrangement, which are responsible for their mechanical and physico-chemical properties. The aim of this research was to determine and explain in detail the mechanism of unit interlinkage of two-component chitosan/1,3-β-d-glucan matrices gelled at 90 °C. This required identifying functional groups interacting with each other and assessing surface topography providing material chemical composition. For this purpose, various spectroscopic and microscopic approaches, such as attenuated total reflection Fourier transform infrared spectroscopy (ATR FT-IR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), were applied. The results indicate the involvement mainly of the C-C and C-H groups and C=O⋯HN moieties in the process of biomaterial polymerization. Strong chemical interactions and ionocovalent bonds between the N-glucosamine moieties of chitosan and 1,3-β-d-glucan units were demonstrated, which was also reflected in the uniform surface of the sample without segregation. These unique properties, hybrid character and proper cell response may imply the potential application of studied biomaterial as biocompatible scaffolds used in regenerative medicine, especially in bone restoration and/or wound healing.