Microencapsulation of vitamins: A review and meta-analysis of coating materials, release and food fortification.

Vitamins are responsible for providing biological properties to the human body; however, their instability under certain environmental conditions limits their utilization in the food industry. The objective was to conduct a systematic review on the use of biopolymers and lipid bases in microencapsulation processes, assessing their impact on the stability, controlled release, and viability of fortified foods with microencapsulated vitamins. The literature search was conducted between the years 2013-2023, gathering information from databases such as Scopus, PubMed, Web of Science and publishers including Taylor & Francis, Elsevier, Springer and MDPI; a total of 49 articles were compiled The results were classified according to the microencapsulation method, considering the following information: core, coating material, solvent, formulation, process conditions, particle size, efficiency, yield, bioavailability, bioaccessibility, in vitro release, correlation coefficient and references. It has been evidenced that gums are the most frequently employed coatings in the protection of vitamins (14.04%), followed by alginate (10.53%), modified chitosan (9.65%), whey protein (8.77%), lipid bases (8.77%), chitosan (7.89%), modified starch (7.89%), starch (7.02%), gelatin (6.14%), maltodextrin (5.26%), zein (3.51%), pectin (2.63%) and other materials (7.89%). The factors influencing the release of vitamins include pH, modification of the coating material and crosslinking agents; additionally, it was determined that the most fitting mathematical model for release values is Weibull, followed by Zero Order, Higuchi and Korsmeyer-Peppas; finally, foods commonly fortified with microencapsulated vitamins were described, with yogurt, bakery products and gummy candies being notable examples.

Palladium(II)-catalyzed annulation of N-methoxy amides and arynes: computational mechanistic insights and substituents effects.

CONTEXT: The combined use of transition metal-catalyzed C-H activation with aryne annulation reactions has emerged as an important strategy in organic synthesis. In this study, the mechanisms of the palladium(II)-catalyzed annulation reaction of N-methoxy amides and arynes were computationally investigated by density functional theory. The role of methoxy amide as a directing group was elucidated through the calculation of three different pathways for the C-H activation step, showing that the pathway where amide nitrogen acts as a directing group is preferable. At the reductive elimination transition state, an unstable seven-membered ring is formed preventing the lactam formation. A substituent effect study based on an NBO analysis, Hammet, and using a More O'Ferall-Jenks plot indicates that the C-H activation step proceeds via an electrophilic concerted metalation-deprotonation (eCMD) mechanism. The results show that electron-withdrawing groups increase the activation barrier and contribute to an early Pd-C bond formation and a late C-H bond breaking when compared with electron-donating substituents. Our computational results are in agreement with the experimental data provided in the literature. METHODS: All calculations were performed using Gaussian 16 software. Geometry optimizations, frequency analyses at 393.15 K, and IRC calculations were conducted at the M06L/Def2-SVP level of theory. Corrected electronic energies, NBO charges, and Wiberg bond indexes were computed at the M06L/Def2-TZVP//M06L/Def2-SVP level of theory. Implicit solvent effects were considered in all calculations using the SMD model, with acetonitrile employed as the solvent.

Dissociation Mode of the O-H Bond in Betanidin, pKa-Clusterization Prediction, and Molecular Interactions via Shape Theory and DFT Methods.

Betanidin (Bd) is a nitrogenous metabolite with significant bioactive potential influenced by pH. Its free radical scavenging activity and deprotonation pathway are crucial to studying its physicochemical properties. Motivated by the published discrepancies about the best deprotonation routes in Bd, this work explores all possible pathways for proton extractions on that molecule, by using the direct approach method based on pKa. The complete space of exploration is supported by a linear relation with constant slope, where the pKa is written in terms of the associated deprotonated molecule energy. The deprotonation rounds 1, …, 6 define groups of parallel linear models with constant slope. The intercepts of the models just depend on the protonated energy for each round, and then the pKa can be trivially ordered and explained by the energy. We use the direct approximation method to obtain the value of pKa. We predict all possible outcomes based on a linear model of the energy and some related verified assumptions. We also include a new measure of similarity or dissimilarity between the protonated and deprotonated molecules, via a geometric-chemical descriptor called the Riemann-Mulliken distance (RMD). The RMD considers the cartesian coordinates of the atoms, the atomic mass, and the Mulliken charges. After exploring the complete set of permutations, we show that the successive deprotonation process does not inherit the local energy minimum and that the commutativity of the paths does not hold either. The resulting clusterization of pKa can be explained by the local acid and basic groups of the BD, and the successive deprotonation can be predicted by using the chemical explained linear models, which can avoid unnecessary optimizations. Another part of the research uses our own algorithm based on shape theory to determine the protein's active site automatically, and molecular dynamics confirmed the results of the molecular docking of Bd in protonated and anionic form with the enzyme aldose reductase (AR). Also, we calculate the descriptors associated with the SET and SPLET mechanisms.

Role of the base Cs2CO3 on the palladium-catalyzed intramolecular cyclization of two bromoindole derivatives to yield paullone-type products.

Reactions for the palladium-catalyzed intramolecular cyclization of the o-bromoindole and the o-bromo-N-methyl-indole derivatives in the presence and absence of base (Cs2CO3) were explored through DFT calculations. For the base-free reactions, the palladium atom firstly interacts with the aromatic rings of the indole molecule to yield a stable adduct. Once this adduct has been formed, reaction proceeds readily to the oxidative addition intermediate that arises from the insertion of the metal atom into the C-Br bond of the organic fragment. Further steps leading to the paullone (or dimethyl paullone) product, mainly those involving the metalation and deprotonation of the inserted intermediate, are not energetically viable for these reactions. When the effect of the base on the metalation-deprotonation steps is modeled by replacing the bromide ion with CO32- in the metal-inserted structure, a feasible pathway connecting the oxidative addition intermediate with the paullone-type product was located for each of the investigated reactions. The results emerging from this study suggest that palladium can insert into the C-Br bond of the indole derivatives to yield the oxidative addition intermediate (without participation of the base). However, the metalation and deprotonation steps that evolve to the paullone-type product take place via a concerted action involving both the metal and the base. Metalation and deprotonation steps that evolve to the paullone-type product take place via a concerted action involving both the metal and the base.

NaOH treatment of chitosan films: Impact on macromolecular structure and film properties.

In this paper, we examine the significance of treatment with NaOH on chitosan (CH) film structure to obtain biodegradable materials for several applications. In order to determine the structure of the films, an analysis based on SEM, FTIR spectroscopy and X-ray diffraction data was performed. In addition, the consequences of this treatment were evaluated by swelling index measurements and mechanical testing. As result of FTIR and X-ray analysis, three effects were identified: the deprotonation and phosphate extraction, which allowed new hydrogen bonds to form, and a higher CH deacetylation. These studies also revealed that two hydrated and anhydrous polymorphs were present in the CH-NaOH films. Moreover, the new hydrogen bond and the reduction of N-acetyl groups produced films with a more compact and disordered structure, reducing their swelling characteristics and increasing their brittleness. The introduction of a mild NaOH treatment is a versatile tool to obtain chitosan films with interesting and tunable properties.

Effects of charging on the chromophores of dissolved organic matter from the Rio Negro basin.

This study demonstrates that the deprotonation of dissolved organic matter (DOM) originating from a small creek characteristic for DOM-rich waters located in the Rio Negro basin can be quantified based on measurements of pH effects on its absorbance spectra. The method was ascertained by the data of Near-Edge X-Ray Absorbance Spectroscopy (NEXAFS), potentiometric titration to quantify the structural and compositional differences between the colloidal and hydrophobic fractions that contribute 91% of black-water creek DOM. Changes in the absorbance spectra of the DOM fractions caused by deprotonation quantified via numeric deconvolution which indicated the presence of six well-resolved Gaussian bands in the differential spectra. The emergence of these bands was determined to be associated with the engagement of carboxylic and phenolic functionalities and changes of inter-chromophore interactions in DOM molecules. Interpretation of the data based on the NICA-Donnan approach showed that behavior of DOM chromophores was consistent with results of potentiometric titrations. Similar trends were observed for changes of the spectral slope of the DOM absorbance spectra in the range of wavelengths 325-375 nm (DSlope325-375). The behavior of DSlope325-375 values was modeled based on the NICA-Donnan approach and correlated with potentiometrically-estimated charges attributed to the carboxylic and phenolic groups. The correlations between DSlope325-375 and charges of low- and high-affinity protonation-active groups in DOM were monotonic but not linear and had important differences between the colloidal and hydrophobic fractions.