The modification of the biobased polymer chitosan is a broad and widely studied field. Herein, an insight into the hydrophobization of low-molecular-weight chitosan by substitution of amino functionalities with hexanoyl chloride is reported. Thereby, the influence of the pH of the reaction media was investigated. Further, methods for the determination of the degree of substitution based on ¹H-NMR, FTIR, and potentiometric titration were compared and discussed regarding their accuracy and precision. ¹H-NMR was the most accurate method, while FTIR and the potentiometric titration, though precise and reproducible, underlie the influence of complete protonation and solubility issues. Additionally, the impact of the pH variation during the synthesis on the properties of the samples was investigated by Cd²⁺ sorption experiments. The adjusted pH values during the synthesis and, therefore, the obtained degrees of substitution possessed a strong impact on the adsorption properties of the final material.

The human-made pollution of surface and ground waters is becoming an inevitable and persistently urgent problem for humankind and life in general, as these pollutants are also distributed by their natural circulation. For example, from mining activities and metallurgy, toxic heavy metals pollute the environment and present material risk for human health and the environment. Bioadsorbers are an intriguing way to efficiently capture and eliminate these hazards, as they are environmentally friendly, cheap, abundant, and efficient. In this study, we present brewers’ spent grain (BSG) as an efficient adsorber for toxic heavy metal ions, based on the examples of iron, manganese, cadmium, and nickel ions. We uncover the adsorption properties of two different BSGs and investigate thoroughly their chemical and physical properties as well as their efficiency as adsorbers for simulated and real surface waters. As a result, we found that the adsorption behavior of BSG types differs despite almost identical chemistry. Elemental mapping reveals that all components of BSG contribute to the adsorption. Further, both types are not only able to purify water to reach acceptable levels of cleanness, but also yield outstanding adsorption performance for iron ions of 0.2 mmol/g and for manganese, cadmium, and nickel ions of 0.1 mmol/g.

The purity and safety of water as a finite resource is highly important in order to meet current and future human needs. To address this issue, the usage of environmentally friendly and biodegradable adsorbers and flocculants is essential. Chitosan, as a biopolymer, features tremendous properties as an adsorber and flocculant for water treatment. For the application of chitosan as an adsorber under acidic aqueous conditions, such as acid mine drainage, chitosan has been modified with hydrophobic hexanoyl chloride (H-chitosan) to reduce the solubility at a lower pH. In order to investigate the influence of the substitution of the hexanoyl chloride on the adsorption properties of chitosan, two chitosans of different molecular weights and of three different functionalization degrees were analyzed for the adsorption of CdSO_4(aq) and Al₂(SO₄)_3(aq). Among biobased adsorbents, H-chitosan derived from the shorter Chitosan exhibited extraordinarily high maximum adsorption capacities of 1.74 mmol/g and 2.06 mmol/g for Cd²⁺ and sulfate, and 1.76 mmol/g and 2.60 mmol/g for Al³⁺ and sulfate, respectively.