Phosphorylating Tannin in Urea System: A Simple Approach for Enhanced Methylene Blue Removal from Aqueous Media.

Tannin, after lignin, is one of the most abundant sources of natural aromatic biomolecules. It has been used and chemically modified during the past few decades to create novel biobased materials. This work intended to functionalize for the first time quebracho Tannin (T) through a simple phosphorylation process in a urea system. The phosphorylation of tannin was studied by Fourier transform infrared spectroscopy (FTIR), NMR, inductively coupled plasma optical emission spectroscopy (ICP-OES), and X-ray fluorescence spectrometry (XRF), while further characterization was performed by scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX) and thermogravimetric analysis (TGA) to investigate the morphology, composition, structure, and thermal degradation of the phosphorylated material. Results indicated the occurrence of phosphorylation, suggesting the insertion of phosphate-containing groups into the tannin structure, revealing a high content of phosphate for modified tannin (PT). This elevated phosphorus content serves as evidence for the successful incorporation of phosphate groups through the functionalization process. The corresponding PT and T were employed as adsorbents for methylene blue (MB) removal from aqueous solutions. The results revealed that the Langmuir isotherm model effectively represents the adsorption isotherms. Additionally, the pseudo-second-order model indicates that chemisorption predominantly controls the adsorption mechanism. This finding also supports the fact that the introduced phosphate groups via the phosphorylation process significantly contributed to the improved adsorption capacity. Under neutral pH conditions and at room temperature, the material achieved an impressive adsorption capacity of 339.26 mg·g-1 in about 2 h.

Nanocellulose-Bovine Serum Albumin Interactions in an Aqueous Medium: Investigations Using In Situ Nanocolloidal Probe Microscopy and Reactive Molecular Dynamics Simulations.

As a versatile nanomaterial derived from renewable sources, nanocellulose has attracted considerable attention for its potential applications in various sectors, especially those focused on water treatment and remediation. Here, we have combined atomic force microscopy (AFM) and reactive molecular dynamics (RMD) simulations to characterize the interactions between cellulose nanofibers modified with carboxylate or phosphate groups and the protein foulant model bovine serum albumin (BSA) at pH 3.92, which is close to the isoelectric point of BSA. Colloidal probes were prepared by modification of the AFM probes with the nanofibers, and the nanofiber coating on the AFM tip was for the first time confirmed through fluorescence labeling and confocal optical sectioning. We have found that the wet-state normalized adhesion force is approximately 17.87 ± 8.58 pN/nm for the carboxylated cellulose nanofibers (TOCNF) and about 11.70 ± 2.97 pN/nm for the phosphorylated ones (PCNF) at the studied pH. Moreover, the adsorbed protein partially unfolded at the cellulose interface due to the secondary structure's loss of intramolecular hydrogen bonds. We demonstrate that nanocellulose colloidal probes can be used as a sensitive tool to reveal interactions with BSA at nano and molecular scales and under in situ conditions. RMD simulations helped to gain a molecular- and atomistic-level understanding of the differences between these findings. In the case of PCNF, partially solvated metal ions, preferentially bound to the phosphates, reduced the direct protein-cellulose connections. This understanding can lead to significant advancements in the development of cellulose-based antifouling surfaces and provide crucial insights for expanding the pH range of use and suggesting appropriate recalibrations.

Starch biocomposites based on cellulose microfibers and nanocrystals extracted from alfa fibers (Stipa tenacissima).

Cellulose-based biopolymers have emerged as one of the most promising components to produce sustainable composites as a potential substitutes to fossil-based materials. Herein, the aim of this study is to investigate the reinforcing effect of cellulose microfibers (CMFs) and cellulose nanocrystals (CNCs), extracted from alfa fibers (Stipa tenacissima), on the properties of starch biopolymer extracted from potato. The as-extracted CMFs (D = 5.94 ± 0.96 µm), CNCs (D = 14.29 ± 2.53 nm) and starch were firstly characterized in terms of their physicochemical properties. Afterwards, CMFs and CNCs were separately dispersed in starch at different concentrations, and their reinforcing effects as well as the chemical, thermal, transparency and mechanical properties of the resulted starch-based films were evaluated. Thus, CMFs and CNCs incorporation into starch resulted in a minor impact on the films thermal stability, while a considerable impact on the transparency property was observed. In terms of mechanical properties, the addition of up to 20 wt% CMFs reduced the film's elongation but drastically increased its stiffness by 300 %. On the other hand, in the case of CNCs, a loading of 10 wt% was found to be the most effective in increasing film stiffness (by 57 %), while increasing the loading up to 20 wt% CNCs enhanced the film's ductility (strain-to-failure) by 52 %. This study showed that introduction of cellulosic fibers having different sizes into starch can produce biocomposite materials with a wide range of properties for food packaging application.