Iva Žuvić

Novel colourimetric sensors are readily devised by combining multifunctional (nano)materials with miniature optoelectronic components. The demand to detect and monitor metal ions has resulted in the invention of new colourimetric sensing schemes, especially for use at the Point-of-Need (PoN). Nonetheless, the design of fully reversible optical materials for continuous real-time ion monitoring remains a bottleneck in the practical realisation of sensors. Magnesium ion is vital to physiological and environmental processes, but monitoring can be challenging, particularly in the presence of Ca²⁺ as a cross-sensitive interferent in real samples. In this work, a chromophore molecule Hyphan I (1-(2-hydroxy-5-ß-hydroxyethylsulfonyl-phenyl-azo)-2-naphthol) has been grafted onto a cellulose matrix with a simple one-pot vinylsulfonyl process, to form a transparent, biocompatible and highly flexible thin-film colourimetric magnesium ion sensing material (Cellulose Film with Hyphan-CFH). The CFH film has a pH response time of K_a1 = 5.8. The LOD and LOQ for Mg²⁺ at pH 8 are 0.089 mM and 0.318 mM, respectively, with an RSD = 0.93%. The CFH film exhibits negligible interference from alkaline and alkaline earth metals, but irreversibly binds certain transition metals (Fe³⁺, Cu²⁺ and Zn²⁺). The CFH material has a fast and fully reversible colourimetric response to pH and Mg²⁺ over physiologically relevant ranges without interference by Ca²⁺, demonstrating good potential for integration into microfluidic systems and wearable sensors for biofluid monitoring.

Novel colourimetric sensors are readily devised by combining multifunctional (nano)materials with miniature optoelectronic components. The demand to detect and monitor metal ions has resulted in the invention of new colourimetric sensing schemes, especially for use at the Point-of-Need (PoN). Nonetheless, the design of fully reversible optical materials for continuous real-time ion monitoring remains a bottleneck in the practical realisation of sensors. Magnesium ion is vital to physiological and environmental processes, but monitoring can be challenging, particularly in the presence of Ca2+ as a cross-sensitive interferent in real samples. In this work, a chromophore molecule Hyphan I (1-(2-hydroxy-5-ß-hydroxyethylsulfonyl-phenyl-azo)-2-naphthol) has been grafted onto a cellulose matrix with a simple one-pot vinylsulfonyl process, to form a transparent, biocompatible and highly flexible thin-film colourimetric magnesium ion sensing material (Cellulose Film with Hyphan - CFH). The CFH film has a pH response time of < 60s over the pH range 4 to 9, with a pKa = 5.8. The LOD and LOQ for Mg2+ at pH 8 are 0.089 mM and 0.318 mM, respectively, with an RSD = 0.93%. The CFH film exhibits negligible interference from alkaline and alkaline earth metals, but irreversibly binds certain transition metals (Fe3+, Cu2+ and Zn2+). The CFH material has a fast and fully reversible colourimetric response to pH and Mg2+ over physiologically relevant ranges without interference by Ca2+, demonstrating good potential for integration into microfluidic systems and wearable sensors for biofluid monitoring.

Starch-based pH-sensing films with bacterial nanocellulose (BNC) and red cabbage anthocyanins (RCA) as active components were investigated in this research. Their structural, physical, surface and colorimetric properties were analyzed, mainly as a function of BNC concentration. The aim of the research was to relate the changes in the intermolecular interactions between the components of the films (starch, anthocyanins and BNC) to the physical, surface and colorimetric properties that are important for the primary intended application of the produced films as pH indicators in smart packaging. The results showed that maize starch (MS) was more suitable as a matrix for the stabilization of anthocyanins compared to potato starch (PS). PS-based films showed a lower value of water contact angle than MS-based films, indicating stronger hydrophilicity. The swelling behavior results indicate that the concentrations of BNC in MS-based films (cca 10%) and the concentration of about 50% BNC in PS-based films are required if satisfactory properties of the indicator in terms of stability in a wet environment are to be achieved. The surface free energy results of PS-based films with BNC were between 62 and 68 mJ/m² and with BNC and RCA between 64 and 68 mJ/m²; for MS-based films, the value was about 65 mJ/m² for all samples with BNC and about 68 mJ/m² for all samples with BNC and RCA. The visual color changes after immersion in different buffer solutions (pH 2.0–10.5) showed a gradual transition from red/pink to purple, blue and green for the observed samples. Films immersed in different buffers showed lower values of 2 to 10 lightness points (CIE L*) for PS-based films and 10 to 30 lightness points for MS-based films after the addition of BNC. The results of this research can make an important contribution to defining the influence of intermolecular interactions and structural changes on the physical, surface and colorimetric properties of bio-based pH indicators used in smart packaging applications.