Zinc- and Copper-Loaded Nanosponges from Cellulose Nanofibers Hydrogels: New Heterogeneous Catalysts for the Synthesis of Aromatic Acetals

Herein we report the synthesis of cellulose-based metal-loaded nano-sponges and their application as heterogeneous catalysts in organic synthesis. First, the combination in water solution of TEMPO-oxidized cellulose nanofibers (TOCNF) with branched polyethyleneimine (bPEI) and citric acid (CA), and the thermal treatment of the resulting hydrogel, leads to the synthesis of an eco-safe micro- and nano-porous cellulose nano-sponge (CNS). Subsequently, by exploiting the metal chelation characteristics of CNS, already extensively investigated in the field of environmental decontamination, this material is successfully loaded with Cu (II) or Zn (II) metal ions. Efficiency and homogeneity of metal-loading is confirmed by scanning electron microscopy (SEM) analysis with an energy dispersive X-ray spectroscopy (EDS) detector and by inductively coupled plasma-optical emission spectrometry (ICP-OES) analysis. The resulting materials perform superbly as heterogeneous catalysts for promoting the reaction between aromatic aldehydes and alcohols in the synthesis of aromatic acetals, which play a fundamental role as intermediates in organic synthesis. Optimized conditions allow one to obtain conversions higher than 90% and almost complete selectivity toward acetal products, minimizing, and in some cases eliminating, the formation of carboxylic acid by-products. ICP-OES analysis of the reaction medium allows one to exclude any possible metal-ion release, confirming that catalysis undergoes under heterogeneous conditions. The new metal-loaded CNS can be re-used and recycled five times without losing their catalytic activity.

One-Pot Preparation of Hydrophilic Polylactide Porous Scaffolds by Using Safe Solvent and Choline Taurinate Ionic Liquid

Polylactides (PLAs) are a class of polymers that are very appealing in biomedical applications due to their degradability in nontoxic products, tunable structural, and mechanical properties. However, they have some drawbacks related to their high hydrophobicity, lack of functional groups able to graft bioactive molecules, and solubility in unsafe solvents. To circumvent these shortcomings, porous scaffolds for tissue engineering were prepared by vigorously mixing a solution of isotactic and atactic PLA in nontoxic ethyl acetate at 70 °C with a water solution of choline taurinate. The partial aminolysis of the polymer ester bonds by taurine -NH2 brought about the formation of PLA oligomers with surfactant activity that stabilized the water-in-oil emulsion. Upon drying, a negligible shrinking occurred, and mechanically stable porous scaffolds were obtained. By varying the polymer composition and choline taurinate concentration, it was possible to modulate the pore dimensions (30–50 µm) and mechanical properties (Young’s moduli: 1–6 MPa) of the samples. Furthermore, the grafted choline taurinate made the surface of the PLA films hydrophilic, as observed by contact angle measurements (advancing contact angle: 76°; receding contact angle: 40°–13°). The preparation method was very simple because it was based on a one-pot mild reaction that did not require an additional purification step, as all the employed chemicals were nontoxic.

Prevention of quercetin precipitation in red wines: a promising enzymatic solution

Flavonols are known for causing undesirable deposits in both red and white wines. Among flavonols, quercetin is widely considered the principal factor determining this phenomenon. One of the most accredited hypotheses claims that glycosylated derivatives of quercetin undergo hydrolysis of the glycosylic bond during the fermentation and the wine ageing, releasing quercetin aglycone, which is much less soluble in water solution and causes the precipitation. Our work describes the dynamics of quercetin-derived deposition in Chianti wines and purposes a new method, based on the enzymatic quercetin glycoside hydrolysis of the glycosidic bond, to prevent the unpleasant deposit formation during the wine ageing. In our study, forty-four monovarietal wines obtained from 7 different Italian grape varieties were compared in the content of total quercetin-3-glycosides (rutin, quercetin-3-glucuronide, quercetin-3-glucoside) and quercetin aglycone. The data confirmed the literature revealing Sangiovese as the richest in quercetin. We tested then, in a Sangiovese wine, four fining agents (PVPP, PVPP/PVI, bentonite and a vegetal protein) for quercetin removal, showing that only the PVPP had a modest aglycone removal activity. Then, the kinetics of deposit formation was studied in three Chianti wines which differed in the initial content of quercetin aglycone. This investigation highlighted that the chemical equilibrium of quercetin changes over time as the turbidity slowly increases, as previously documented. The comparison of the three dynamics also permitted us to conclude that different wines show a different ability to keep in solution quercetin. Finally, a new approach for deposit prevention was studied by a precocious Chianti wine treatment with a pectolytic enzyme having secondary glycosidase activity. This enzyme significantly accelerated the hydrolysis of glycosylated quercetins into their aglycone, which could enhance the deposition before bottling, without serious wine colour depletion. Our study represents the first evidence of the promising potential of using the pectolytic enzyme with secondary glycosidase activity to prevent quercetin deposit during Chianti ageing, in a way that is compatible with organic wine production.

Changes in the Local Conformational States Caused by Simple Na+ and K+ Ions in Polyelectrolyte Simulations: Comparison of Seven Force Fields with and without NBFIX and ECC Corrections

Electrostatic interactions have a determining role in the conformational and dynamic behavior of polyelectrolyte molecules. In this study, anionic polyelectrolyte molecules, poly(glutamic acid) (PGA) and poly(aspartic acid) (PASA), in a water solution with the most commonly used K+ or Na+ counterions, were investigated using atomistic molecular dynamics (MD) simulations. We performed a comparison of seven popular force fields, namely AMBER99SB-ILDN, AMBER14SB, AMBER-FB15, CHARMM22*, CHARMM27, CHARMM36m and OPLS-AA/L, both with their native parameters and using two common corrections for overbinding of ions, the non-bonded fix (NBFIX), and electronic continuum corrections (ECC). These corrections were originally introduced to correct for the often-reported problem concerning the overbinding of ions to the charged groups of polyelectrolytes. In this work, a comparison of the simulation results with existing experimental data revealed several differences between the investigated force fields. The data from these simulations and comparisons with previous experimental data were then used to determine the limitations and strengths of these force fields in the context of the structural and dynamic properties of anionic polyamino acids. Physical properties, such as molecular sizes, local structure, and dynamics, were studied using two types of common counterions, namely potassium and sodium. The results show that, in some cases, both the macroion size and dynamics depend strongly on the models (parameters) for the counterions due to strong overbinding of the ions and charged side chain groups. The local structures and dynamics are more sensitive to dihedral angle parameterization, resulting in a preference for defined monomer conformations and the type of correction used. We also provide recommendations based on the results.

The interphase distribution of light REE Ce(III) and La(III) in system based on PEG-1500 – NaNO3 – H2O with the quaternary ammonium base addition

The problem of e-waste processing and recovery of valuable metals from such waste for the second use is attracting more and more scientists’ attention. Liquid extraction as one of hydrometallurgy steps is a traditional method for the metal recovery. However, application of solvent extraction is not meet the green chemistry principles due to organic solvents. Aqueous two-phase systems based on water-soluble polymers are promising alternative for hazardous organic solvents. In this work the dependencies of Ce(III) and La(III) distribution coefficients from process time and the initial quaternary ammonium base concentration have been achieved. Also, based on the Ce(III) and La(III) extraction isotherms it has been shown that the metals initial concentrations are highly affects the distribution coefficients of studied metals. The possibility of aqueous two-phase system application as a solvent for quaternary ammonium salt for light REE (Ce(III) and La(III)) extraction from water solution has been shown.

Preparation, characterization and cell labelling of strong pH-controlled bicolor fluorescence carbonized polymer dots

Multicolor fluorescence N-doped CPDs from dextrin water solution in strong acidic and alkaline environments were synthesized and characterized, which revealed that pH value plays a vital role in the process of CPD growth.

The Art of Positronics in Contemporary Nanomaterials Science: A Case Study of Sub-Nanometer Scaled Glassy Arsenoselenides

The possibilities surrounding positronics, a versatile noninvasive tool employing annihilating positrons to probe atomic-deficient sub-nanometric imperfections in a condensed matter, are analyzed in application to glassy arsenoselenides g-AsxSe100−x (0 < x < 65), subjected to dry and wet (in 0.5% PVP water solution) nanomilling. A preliminary analysis was performed within a modified two-state simple trapping model (STM), assuming slight contributions from bound positron–electron (Ps, positronium) states. Positron trapping in g-AsxSe100−x/PVP nanocomposites was modified by an enriched population of Ps-decay sites in PVP. This was proven within a three-state STM, assuming two additive inputs in an overall trapping arising from distinct positron and Ps-related states. Formalism of x3-x2-CDA (coupling decomposition algorithm), describing the conversion of Ps-decay sites into positron traps, was applied to identify volumetric nanostructurization in wet-milled g-As-Se, with respect to dry-milled ones. Under wet nanomilling, the Ps-decay sites stabilized in inter-particle triple junctions filled with PVP replaced positron traps in dry-milled substances, the latter corresponding to multi-atomic vacancies in mostly negative environments of Se atoms. With increased Se content, these traps were agglomerated due to an abundant amount of Se-Se bonds. Three-component lifetime spectra with nanostructurally- and compositionally-tuned Ps-decay inputs and average lifetimes serve as a basis to correctly understand the specific “rainbow” effects observed in the row from pelletized PVP to wet-milled, dry-milled, and unmilled samples.

Density Functional Theory (DFT) Investigation of The Oxidative Degradation of NaAsO2 Via Hydroxyl Radical

Arsenic is an environmentally ubiquitous health hazard due to its toxicity combined with its natural abundance and heavy industrial applications. Due to its role in cardiovascular disease, neurotoxicity, and various cancers, it is important to understand environmental fate of arsenic-containing compounds to take steps towards remediation. Sodium arsenite (NaAsO2) is one such compound that has been used worldwide as an herbicide, rodenticide, and insecticide. It is also toxic by ingestion, inhalation, and skin absorption. In aqueous environments arsenite (As(III))-containing compounds can be oxidized to the less-toxic arsenate (As(V)) form. We have investigated the oxidation of sodium arsenite in water solution at the density functional theory level using the Minnesota 06 hybrid (M06-2X) functional and Pople basis sets (6-31G(d,p) and 6-311G(d,p)) with polarizable continuum model (PCM) solvation approach. Our computational results indicate that the oxidation mechanism of NaAsO2 by hydroxyl radical proceeds via sequential addition reactions where sodium arsenite (III) converts to sodium arsenate (V) via an arsenic (IV) intermediate.

TECHNOLOGICAL ASPECTS OF APPLICATION OF THE PHYTOSORBENT WITH NANOTUBES IN THE PROCESS OF ADSORPTIVE OIL PURIFICATION

In the present article importance of adsorptive purification of vegetable oils is shown as the most responsible technological stage. Insufficiency of scientific developments in the scope of domestic sorbents in Ukraine is pointed out. The phytosorbent with nanotubes from sunflower peel improving some quality parameters of non-refined sunflower and soybean oils to standard values for refined oils has been offered. Some literature data on the main characteristics of a number of sorption materials (carbonaceous, natural, fibrous, and sorbents obtained from agricultural waste - Corylus avellana Lambert nuts) as a result of heat treatment are analyzed. The main sorption properties are considered; dignity; limitations. The effect of temperature on the productivity of pyrolysis of plant raw materials and the properties of the resulting carbonizates in the temperature range 150-600 °C was investigated. The duration of exposure of materials at the final temperature of the process in all experiments was the same and amounted to 1 h. Analysis of the experimental data allows us to conclude that temperature is the main factor affecting the process of carbonization of the initial plant material. Regardless of the pyrolysis atmosphere, the yield of the product from plant raw materials decreases with a significant increase in temperature. At present, the main raw material for the industrial production of adsorbents is in many studies organic substances - wood, fossil coal, peat, remnants of the processing of agricultural raw materials due to their low cost and large amount. Solving the problem of creating sorbents based on plant raw materials with the inclusion of hydrated fullerenes in their composition solved the problem of creating sorbents and environmental problems, since the waste did not always find a useful application. Concentration of water solution of hydrated C60, fast C60FWS, є molecular-coloidal systems and spherical fractal clusters, structural unit of which is micro-hydrophilic, high-hydrophilic supramolecular complex, molecules can be folded to fit into ) 24-hydration of fullerene C60 (C60HyFn). The hydrated cultivation is set in its own well-ordered, structurally heterogeneous watery middle, in which the directness and kinetics of chemical processes are seen in such, that it is necessary to be washed in order to clean.

Combination of Capped Gold Nanoslit Array and Electrochemistry for Sensitive Aqueous Mercuric Ions Detection

Label-free surface plasmon resonance (SPR) detection of mercuric ions in various aqueous solutions, using capped gold nanoslit arrays combined with electrochemical (EC) sensing technique, is demonstrated. The nanoslit arrays are fabricated on flexible cyclo-olefin polymer substrates by a nanoimprinting lithography method. The EC and SPR signals for the investigation of current responses and transmission SPR spectra are simultaneously measured during metal ions electrodeposition. Glycerol–water solution is studied to evaluate the resonant peak wavelength sensitivity (480.3 nm RIU−1) with a FOM of 40.0 RIU−1 and the obtained intensity sensitivity is 1819.9%. The ferrocyanide/ferricyanide redox couple performs the diffusion controlled electrochemical processes (R2 = 0.99). By investigating the SPR intensity changes and wavelength shifts of various mercuric ion concentrations, the optical properties are evaluated under chronoamperometric conditions. The sensors are evaluated in the detection range between 100 μM and 10 nM with a detection limit of 1 μM. The time dependence of SPR signals and the selectivity of 10 μM Hg2+ in the presence of 10 μM interfering metal ion species from Ca2+, Co2+, Ni2+, Na+, Cu2+, Pb2 + and Mn2+ are determined. The capped gold nanoslit arrays show the selectivity of Hg2+ and the EC sensing method is effectively utilized to aqueous Hg2+ detection. This study provides a label-free detection technique of mercuric ions and this developed system is potentially applicable to detecting chemicals and biomolecules.