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.

Thermoresponsive coatings of poly(N-isopropylacrylamide-co-DMAEMA)/cellulose sulfate (PNIPAM-DMAEMA/CS) complexes are reported eluting bone-morphogenetic-protein-2 (BMP-2) on demand relevant for implant assisted local bone healing. PNIPAM-DMAEMA/CS dispersions contained colloid particles with hydrodynamic radii R_H = 170–288 nm at T = 25 °C shrinking to R_H = 74–103 nm at T = 60 °C. Obviously, PNIPAM-DMAEMA/CS undergoes volume phase transition (VPT) analogously to pure PNIPAM, when critical VPT temperature (VPTT) is exceeded. Temperature dependent turbidity measurements revealed broad VPT and VPTT 47 °C for PNIPAM-DMAEMA/CS colloid dispersions at pH = 7.0. FTIR spectroscopy on thermoresponsive PNIPAM-DMAEMA/CS particle coatings at germanium model substrates under HEPES buffer indicated both wet-adhesiveness and VPT behavior based on diagnostic band intensity increases with temperature. From respective temperature courses empirical VPTT ≈ 42 °C for PNIPAM-DMAEMA/CS coatings at pH = 7.0 were found, which were comparable to VPTT found for respective dispersions. Finally, the PNIPAM-DMAEMA/CS coatings were loaded with BMP-2 and model protein papain (PAP). Time dependent FTIR spectroscopic measurements showed, that for T = 37 °C there was a relative protein release of ≈30% for PAP and ≈10% for BMP-2 after 24 h, which did not increase further. Heating to T = 42 °C for PAP and to 47 °C for BMP-2 further secondary protein release of ≈20% after 24 h was found, respectively, interesting for clinical applications. BMP-2 eluted even at 47 °C was found to be still biologically active.

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 separation of toxic pollutants such as Pb²⁺, Cd²⁺, and Al³⁺ from water is a constant challenge as contamination of natural water bodies is increasing. Al³⁺ and especially Pb²⁺ and Cd²⁺ are ecotoxic and highly toxic for humans, even in ppb concentrations, and therefore removal below a dangerous level is demanding. Herein, the potential adsorber material starch, being ecofriendly, cheap, and abundantly available, was investigated. Thus, four different native starch samples (potato, corn, waxy corn, and wheat starch) and two oxidized starches (oxidized potato and corn starch) were comprehensively analyzed with streaming potential and charge density measurements, SEM-EDX, ATR-FTIR, ¹H-NMR, and TGA. Subsequently, the starch samples were tested for the adsorption of Pb²⁺, Cd²⁺, and Al³⁺ from the respective sulfate salt solution. The adsorption process was analyzed by ICP-OES and SEM-EDX, and the adsorption isotherms were fitted comparing Langmuir, Sips, and Dubinin-Radushkevich models. Oxidized starch, for which chemical modification is one of the simplest, and also native potato starch were excellent natural adsorber materials for Al³⁺, Cd²⁺, and especially Pb²⁺ in the low concentration range, exhibiting maximum adsorption capacities of 84, 71, and 104 µmol/g for oxidized potato starch, respectively.