Role of Proteins in the Formation of Melanoidins during Coffee Roasting.

The objective of the study was to investigate structural changes in the protein-rich, high-molecular-weight fraction of coffee during roasting and their contribution to the melanoidin formation in the course of the Maillard reaction. For this purpose, high- and low-molecular-weight fractions of one raw and five coffee beans with an increased roasting degree were analyzed in terms of general (color, molecular weight, functionality, elemental composition) and specific parameters (amino acid composition, Maillard reaction products). It could be demonstrated that the high -molecular-weight fraction undergoes significant changes during roasting, where proteins appear to play an important role in melanoidin formation due to their diverse nucleophilic side chains. Modification of the amino acid side chains with known Maillard reaction products (MRPs) occurs in the early stages of roasting and decreases rapidly as color development progresses. The decrease suggests that MRPs are involved in further reactions and thus extend the functionality of the amino acid side chains, opening further possibilities for protein modification. Overall, the large number of reaction pathways leads to the formation of a well-mixed, continuous melanoidin spectrum covering a wide range of molecular masses. In this process, cross-linking and fragmentation reactions oppose each other, leading to an approximation of the molecular weight.

Recycling of Brewer's Spent Grain as a Biosorbent by Nitro-Oxidation for Uranyl Ion Removal from Wastewater.

Developing biosorbents derived from agro-industrial biomass is considered as an economic and sustainable method for dealing with uranium-contaminated wastewater. The present study explores the feasibility of oxidizing a representative protein-rich biomass, brewer's spent grain (BSG), to an effective and reusable uranyl ion adsorbent to reduce the cost and waste generation during water treatment. The unique composition of BSG favors the oxidation process and yields in a high carboxyl group content (1.3 mmol/g) of the biosorbent. This makes BSG a cheap, sustainable, and suitable raw material independent from pre-treatment. The oxidized brewer's spent grain (OBSG) presents a high adsorption capacity of U(VI) of 297.3 mg/g (c 0(U) = 900 mg/L, pH = 4.7) and fast adsorption kinetics (1 h) compared with other biosorbents reported in the literature. Infrared spectra (Fourier transform infrared), 13C solid-state nuclear magnetic resonance spectra, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and thermogravimetric analysis were employed to characterize the biosorbents and reveal the adsorption mechanisms. The desorption and reusability of OBSG were tested for five cycles, resulting in a remaining adsorption of U(VI) of 100.3 mg/g and a desorption ratio of 89%. This study offers a viable and sustainable approach to convert agro-industrial waste into effective and reusable biosorbents for uranium removal from wastewater.

Acid-Induced Gelation of Enzymatically and Nonenzymatically Cross-Linked Caseins-Texture Properties, and Microstructural Insights.

Casein gels consist of a fractal organized network of aggregated casein particles. The gel texture thereby depends on the structure, the spatial distribution, and the interaction forces of the network's elementary building blocks. The aim of this study was to explore the technofunctional consequences of a possible specificity of Maillard reaction-induced cross-linking reactions on casein with respect to texture and microstructure of acid gels. Therefore, sodium caseinate glycated with lactose in the dry state (60 °C, aw 0.5) was compared with casein samples cross-linked with methylglyoxal, with glutaraldehyde, or via microbial transglutaminase, respectively, at similar levels of protein cross-linking as confirmed by size-exclusion chromatography under denaturing conditions. Casein gels prepared by acidification with glucono-δ-lactone were characterized concerning pH kinetics during gelation, mechanical texture properties under large deformation, and water-holding capacity, while viscometric properties of casein suspensions were obtained prior to gelation. The gel microstructure was captured by confocal laser scanning microscopy and evaluated by means of image texture analysis. All protein cross-linking reactions studied led to an enhanced gel strength which was accompanied by an increased interconnectivity of the gel network and a decrease in apparent pore sizes. Gels with more densely packed strands, as was the case for enzymatically modified casein, exhibited pronounced mechanical stability. The spontaneous destabilization of the gel network upon prolonged glycation reactions, which was not obviously displayed by microstructural features but connected to an increased viscosity and pronounced pseudoplastic flow of the unacidified suspension, suggests a limitation of particle rearrangements and the weakening of interparticle protein-protein interactions by additional structure attributes formed during the early Maillard reaction (glycoconjugation).

Association of Enzymatically and Nonenzymatically Functionalized Caseins Analyzed by Size-Exclusion Chromatography and Light-Scattering Techniques.

The influence of covalent protein modifications resulting from the Maillard reaction (glycation) of casein and lactose on the noncovalent association behavior of the protein was studied. Nonenzymatic cross-linking with methylglyoxal (MGO) and glutaraldehyde (GTA) as well as enzymatic cross-linking with microbial transglutaminase (mTG) was investigated in comparison. Molar mass, particle size, and conformational characteristics of nonmicellar casein associates as well as the extent of intraparticle protein cross-linking were examined utilizing size-exclusion chromatography (SEC) combined with UV detection and static and dynamic light scattering. Cross-linking resulted in the stabilization of a certain fraction of casein associates, with particle sizes of approximately 30 nm in radius of gyration (Rg), and promoted an incorporation of further casein molecules into those particles, yielding molar masses (Mw) of 1.0-1.2 × 106 g/mol. When caseins were additionally conjugated with lactose during the early Maillard reaction, a further growth of the associates up to approximately 50 nm in Rg with a Mw of 2.1 × 106 g/mol was observed. Furthermore, glycation reactions induced a transition from slightly elongated, random-coil structures toward more anisotropic conformations. Associates consisting of caseins cross-linked with GTA appeared to preserve the original particle conformation.

Mild hydrothermally treated brewer's spent grain for efficient removal of uranyl and rare earth metal ions.

The increasing concerns on uranium and rare earth metal ion pollution in the environment require sustainable strategies to remove them from wastewater. The present study reports an eco-friendly approach to convert a kind of protein-rich biomass, brewer's spent grain (BSG), into effective biosorbents for uranyl and rare earth metal ions. The employed method reduces the energy consumption by performing the hydrothermal treatment at a significantly lower temperature (150 °C) than conventional hydrothermal carbonization. In addition, with the aid of the Maillard reaction between carbohydrates and proteins forming melanoidins, further activation processes are not required. Treatment at 150 °C for 16 h results in an altered biosorbent (ABSG) with increased content of carboxyl groups (1.46 mmol g-1) and a maximum adsorption capacity for La3+, Eu3+, Yb3+ (pH = 5.7) and UO2 2+ (pH = 4.7) of 38, 68, 46 and 221 mg g-1, respectively. Various characterization methods such as FT-IR, 13C CP/MAS NMR, SEM-EDX and STA-GC-MS analysis were performed to characterize the obtained material and to disclose the adsorption mechanisms. Aside from oxygen-containing functional groups, nitrogen-containing functional groups also contribute to the adsorption. These results strongly indicate that mild hydrothermal treatment of BSG could be applied as a greener, low-cost method to produce effective adsorbents for uranyl and rare earth metal ion removal.