Eutectic Media Open a Synthetic Route to Oligocitrazinic Acid Fluorophores of Purple Hue.

Under isochoric and solvent-free conditions, the reaction between ammonium formate and citric acid results in a deeply purple reaction product with fluorescent properties. This brings this reaction in the realm of bio-based fluorophores and bottom-up carbon nanodots from citric acid. The reaction conditions are optimized in terms of UV-vis spectroscopic properties and, subsequently, the main reaction product is separated. While the structural analysis does not give any indication for carbon nanodots in a general sense, it points towards the formation of molecular fluorophores that consist of oligomerized citrazinic acid derivatives. Furthermore, EPR spectroscopy reveals the presence of stable free radicals in the product. We hypothesize that such open-shell structures may play a general role in molecular fluorophores from citric acid and are not yet sufficiently explored. Therefore, we believe that analysis of these newly discovered fluorophores may contribute to a better understanding of the properties of fluorophores and CND from citric acid in general.

Aqueous Modification of Chitosan with Itaconic Acid to Produce Strong Oxygen Barrier Film.

In this study, the chemical modification of chitosan using itaconic acid as a natural-based unsaturated dicarboxylic acid was investigated. In an aqueous environment, the amine group of chitosan reacts with itaconic acid to produce a chitosan derivative with pyrrolidone-4-carboxylic acid group. On the basis of the elemental analysis, 15% of the amine groups of chitosan reacted, thus creating modified chitosan with amine and carboxylic acid functionalities. Due to the presence of amine and carboxylic acid groups, the surface charge properties of the chitosan were notably altered after itaconic acid modification. In an aqueous solution, the modified chitosan exhibited zwitterionic properties, being cationic at low pH and turning anionic when the pH was increased over 6.5, whereas the original chitosan remained cationic until pH 9. Furthermore, it was demostrated that the modified chitosan was suitable for the preparation of a self-standing film with similarly high transparency but notably higher mechanical strength and oxygen barrier properties compared to a film made from the original chitosan. In addition, the thermal stability of the modified chitosan film was higher than that of the original chitosan film, and the modified chitosan exhibited flame-retardant properties.

Reactive Eutectic Media for Lignocellulosic Biomass Fractionation.

This study introduces an alternative approach towards lignocellulosic biomass fractionation. For this purpose, reactive eutectic media (REM) based on ammonium formate and different organic acids are investigated, possible products are identified, and the REM are employed for lignin extraction and terminal isolation of cellulose pulp from beech wood. The method promises a considerable process intensification by simultaneous separation of high purity cellulose pulp, lignin isolation as a cationically modified species, and production of value-added chemicals from reaction products of the REM. This study puts a further focus on the generated cellulose pulp and investigates it with respect to surface charge and fiber length.

Cationic CNC-stabilized Pickering emulsions of linseed oil for hydrophobic coatings.

Coating paper with polymers is an efficient way of awarding it with gas-tightness and moisture protection in food packaging applications, but it impedes the recyclability of the both paper and polymer. Cellulose nanocrystals were found to be excellent gas barrier materials, but their hydrophilicity forbids their straightforward application as protective coatings. To introduce hydrophobicity into a CNC coating, this work exploited the capability of cationic CNCs isolated in a one-step treatment with a eutectic medium to stabilize Pickering emulsions in order to include a natural drying oil in a dense layer of CNCs. This way, a hydrophobic coating with improved water vapor barrier properties was achieved.

Changes in Selected Organic and Inorganic Compounds in the Hydrothermal Carbonization Process Liquid While in Storage.

Although many studies have investigated the hydrothermal transformation of feedstock biomass, little is known about the stability of the compounds present in the process liquid after the carbonization process is completed. The physicochemical characteristics of hydrothermal carbonization (HTC) liquid products may change over storage time, diminishing the amount of desired products or producing unwanted contaminants. These changes may restrict the use of HTC liquid products. Here, we investigate the effect of storage temperature (20, 4, and -18 °C) and time (weeks 1-12) on structural and compositional changes of selected organic compounds and physicochemical characteristics of the process liquid from the HTC of digested cow manure. ANOVA showed that the storage time has a significant effect on the concentrations of almost all of the selected organic compounds, except acetic acid. Considerable changes in the composition of the process liquid took place at all studied temperatures, including deep freezing at -18 °C. Prominent is the polymerization of aromatic compounds with the formation of precipitates, which settle over time. This, in turn, influences the inorganic compounds present in the liquid phase by chelating or selectively adsorbing them. The implications of these results on the further processing of the process liquid for various applications are discussed.

Highly effective fractionation chemistry to overcome the recalcitrance of softwood lignocellulose.

The efficient fractionation and thus production of individual biomass components are pivotal processes in the biorefinery concept. However, the recalcitrant nature of lignocellulose biomass, especially in the case of softwood, is one of the main obstacles to the wider application of biomass-based chemicals and materials. In this study, the use of aqueous acidic systems in the presence of thiourea was studied for the fractionation of softwood in mild conditions. Despite relatively low temperature (100 °C) and treatment times (30-90 min), notable high lignin removal efficiency (approximately 90 %) was obtained. Chemical characterization and the isolation of minor fraction of cationic, water-soluble lignin indicated that the fractionation proceed via nucleophilic addition of thiourea to lignin, resulting in dissolution of lignin in acidic water in relatively mild conditions. Besides high fractionation efficiency, both fiber and lignin fractions were obtained with bright color, significantly elevating their usability in material applications.

Pickering emulgels reinforced with host-guest supramolecular inclusion complexes for high fidelity direct ink writing.

Direct ink writing (DIW) of Pickering emulsions offers great potential for constructing on-demand objects. However, the rheological properties of fluid emulsions greatly undermines the shape fidelity and structural integrity of 3D-printed structures. We solve here these challenges and realize a new route towards complex constructs for actual deployment. A dynamic, supramolecular host-guest hydrogel based on poly(ethylene glycol) and α-cyclodextrin was synthesized in the continuous phase of cellulose nanocrystal-stabilized Pickering emulsions. The storage modulus of the obtained emulgels could reach up to ∼113 kPa, while being shear thinning and yielding precise printability. Diverse complex architectures were possible with high shape fidelity and structural integrity. The printed objects, for example a double-wall cylinder with 75 layers, demonstrated excellent dimensional stability (shrinkage of 7 ± 2% after freeze-drying). With the merits of a simple fabrication process and the high biocompatibility of all the components, the concept of dynamic supramolecular hydrogel-reinforced emulgels represent a potentially versatile route to construct new materials and structures VIA DIW for use in bioproducts and biomedical devices.

Intelligent modeling and experimental study on methylene blue adsorption by sodium alginate-kaolin beads.

As tighter regulations on color in discharges to water bodies are more widely implemented worldwide, the demand for reliable inexpensive technologies for dye removal grows. In this study, the removal of the basic dye, methylene blue, by adsorption onto low-cost sodium alginate-kaolin beads was investigated to determine the effect of operating parameters (initial dye concentration, contact time, pH, adsorbent dosage, temperature, agitation speed) on dye removal efficiency. The composite beads and individual components were characterized by a number of analytical techniques. Three models were developed to describe the adsorption as a function of the operating parameters using regression analysis, and two powerful intelligent modeling techniques, genetic programming and artificial neural network (ANN). The ANN model is best in predicting dye removal efficiency with R2 = 0.97 and RMSE = 3.59. The developed model can be used as a useful tool to optimize treatment processes using the promising adsorbent, to eliminate basic dyes from aqueous solutions. Adsorption followed a pseudo-second order kinetics and was best described by the Freundlich isotherm. Encapsulating the kaolin powder in sodium alginate resulted in removal efficiency of 99.56% and a maximum adsorption capacity of 188.7 mg.g-1, a more than fourfold increase over kaolin alone.

Gold Nanoparticle Self-Aggregation on Surface with 1,6-Hexanedithiol Functionalization.

Here we study the morphology and the optical properties of assemblies made of small (17 nm) gold nanoparticles (AuNPs) directly on silicon wafers coated with (3-aminopropyl)trimethoxysilane (APTES). We employed aliphatic 1,6-hexanedithiol (HDT) molecules to cross-link AuNPs during a two-stage precipitation procedure. The first immersion of the wafer in AuNP colloidal solution led mainly to the attachment of single particles with few inclusions of dimers and small aggregates. After the functionalization of precipitated NPs with HDT and after the second immersion in the colloidal solution of AuNP, we detected a sharp rise in the number of aggregates compared to single AuNPs and their dimers. The lateral size of the aggregates was about 100 nm, while some of them were larger than 1µm. We propose that the uncompensated dipole moment of the small aggregates appeared after the first precipitation and acts further as the driving force accelerating their further growth on the surface during the second precipitation. By having such inhomogeneous surface coating, the X-ray reciprocal space maps and modulation polarimetry showed well-distinguished signals from the single AuNPs and their dimers. From these observations, we concluded that the contribution from aggregated AuNPs does not hamper the detection and investigation of plasmonic effects for AuNP dimers. Meantime, using unpolarized and polarized light spectroscopy, the difference in the optical signals between the dimers, being formed because of self-aggregation and the one being cross-linked by means of HDT, was not detected.

Synthesis and Properties of Water-Soluble Blue-Emitting Mn-Alloyed CdTe Quantum Dots.

In this work, we prepared CdTe quantum dots, and series of Cd1-xMnxTe-alloyed quantum dots with narrow size distribution by an ion-exchange reaction in water solution. We found that the photoluminescence peaks are shifted to higher energies with the increasing Mn2+ content. So far, this is the first report of blue-emitting CdTe-based quantum dots. By means of cyclic voltammetry, we detected features of electrochemical activity of manganese energy levels formed inside the Cd1-xMnxTe-alloyed quantum dot band gap. This allowed us to estimate their energy position. We also demonstrate paramagnetic behavior for Cd1-xMnxTe-alloyed quantum dots which confirmed the successful ion-exchange reaction.