Computational Study of Metathesis Degradation of Rubber, 3. Distribution of Cyclic and Linear Oligomers via Intermolecular Degradation of cis‐Poly(butadiene)

The molecular modeling of the product distributions for the intermolecular metathesis degradation of cis‐poly(butadiene) (cis‐PB) in the presence of ethylene as chain‐transfer agent (CTA) at 298.15 K using the B3LYP/6‐31G (d, p) level of theory reveals that chain–ring and chain‐chain equilibria are shifted toward the formation of 1,5‐hexadiene. The amount of cyclic oligomers at equilibrium with linear molecules is negligible. The α,ω‐vinyl‐terminated butadiene oligomers–1,5‐hexadiene equilibrium constant depends on the cis/trans isomer ratio in linear butadiene molecules. While the concentration of 1,5‐hexadiene at equilibrium with cis‐butadiene oligomers is 86 mol‐%, this value for trans‐butadiene oligomers corresponds to 50 mol‐% of 1,5‐hexadiene. The results of calculations are in reasonable agreement with recent experimental data on the intermolecular metathesis of 1,4‐cis‐PB with ethylene using a well‐defined ruthenium alkylidene catalyst. The calculations predict that cis‐butene as a CTA is more efficient in the metathesis depolymerization of cis‐PB compared with ethylene.     

Structure and rheology of hyperbranched and dendritic polymers. I. Modification and characterization of poly(propyleneimine) dendrimers with acetyl groups

Commercially available fourth and fifth generation poly(propyleneimine) (PPI) dendrimers were functionalized with acetyl chloride and deuterated acetyl chloride. Their solution properties in water and D₂O were measured with dilution viscometry, densitometry, rheology, and small‐angle neutron scattering (SANS) and compared to molecular modeling. Both the acetylated and PPI dendrimers exhibited Newtonian rheology in solution at all concentrations, but the functionalized dendrimers were less viscous than the nonacetylated dendrimers at an equal weight fraction (50 wt %). The acetylated dendrimers exhibited a pronounced structure peak in SANS, however, that was not evident for PPI in solution and a greatly enhanced solubility. This structure peak, evident at concentrations as low as 0.2 wt %, was evidence for long‐range electrostatic interdendrimer forces, which were screened by added salt. A quantitative agreement was obtained between the dilute‐limiting absolute scattering spectra of both the nonacetylated and acetylated dendrimers in solution with model calculations via a homogeneous spherical model and input parameters independently obtained from dilution viscometry or direct calculation. The combined measurements verified significant solvent penetration for both dendrimer types. The form factors measured in this manner were also in good quantitative agreement with the results of molecular dynamics simulations, which pointed to significant backfolding of the terminal groups. SANS and rheology measurements at higher concentrations suggested dendrimer clustering and interpenetration with increasing concentration, leading to less structure and lower viscosity than would be predicted from the dilute‐limiting behavior. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 857–873, 2000     

In Vitro Bioaccessibility of Bioactive Compounds from Rosehip-Enriched Corn Extrudates

The rosehip (Rosa canina L.) fruit has gained researchers′ attention due to its rich chemical composition in vitamin C, phenols, carotenoids, and high antioxidant activity; meanwhile, polymers such as pea protein are generally recognized as exhibiting a protection role against the extrusion process. Corn snacks extrudates obtained by replacing corn flour with 10% R. canina powder (R) and 10% R. canina with pea protein (RPP) were evaluated for the physicochemical, textural, optical, and nutritional characteristics. A sample manufactured without R. canina powder was used as a control. Hardness, crispiness, chewiness, and solubility index (WSI) of the final extrudates were improved by addition of R. canina and pea protein powder (PP); meanwhile, b* (yellow/blue coordinate), C (chroma), and h* (tone) optical parameters were significantly different from the control sample (p < 0.05). Extrusion highlighted a negative impact on total phenols, carotenoids, vitamin C, and antioxidant activity extrudates, while PP exhibited a good protection against the extrusion process. In vitro digestion increased the bioaccessibility of vitamin C, folate, antioxidant activity, total phenols, and total carotenoids mainly on RPP extrudates.     

Manufacturing and Assessing the New Orally Disintegrating Tablets,Containing Nimodipine-hydroxypropyl-β-cyclodextrin and Nimodipine-methyl-β-cyclodextrin Inclusion Complexes

The aim of the present study was to manufacture new orally disintegrating tablets containing nimodipine–hydroxypropyl-β-cyclodextrin and nimodipine–methyl-β-cyclodextrin inclusion complexes. For obtaining a better quality of the manufactured tablets, three methods of the preparation of inclusion complexes, in a 1:1 molar ratio, were used comparatively; namely, a solid-state kneading method and two liquid state coprecipitation and lyophilization techniques. The physical and chemical properties of the obtained inclusion complexes, as well as their physical mixtures, were investigated using Fourier transformed infrared spectroscopy, scanning electron microscopy, X-ray diffraction analyses, and differential scanning calorimetry. The results showed that the lyophilization method can be successfully used for a better complexation. Finally, the formulation and precompression studies for tablets for oral dispersion, containing Nim–HP-β-CD and Nim–Me-β-CD inclusion complexes, were successfully assessed.     

In Vitro Assessment of the Cytotoxic and Antiproliferative Profile of Natural Preparations Containing Bergamot,Orange and Clove Essential Oils

Medicinal plants and essential oils (EOs), in particular, were intensively studied in recent years as viable alternatives for antiproliferative chemical synthetic agents. In the same lines, the present study focuses on investigating the effects of natural preparations (emulsions) based on EOs obtained from Citrus bergamia Risso (bergamot-BEO), Citrus sinensis Osbeck (orange-OEO), and Syzygium aromaticum Merill et L. M. Perry (clove-CEO) on different healthy (human immortalized keratinocytes—HaCaT and primary human gingival fibroblasts—HGF) and human tumor cell lines (human melanoma—A375 and oral squamous carcinoma—SCC-4) in terms of the cells’ viability and cellular morphology. The obtained results indicate that the CEO emulsion (ECEO) induced a dose-dependent cytotoxic in both healthy (HaCaT and HGF) and tumor (A375 and SCC-4) cells. OEO emulsion (EOEO) increased cell viability percentage both for HaCaT and A375 cells and had an antiproliferative effect at the highest concentration in HGF and SCC-4 cells. BEO emulsion (EBEO) decreased the viability percentage of SCC-4 tumor cells. By associating OEO with CEO as a binary mixture in an emulsified formulation, the inhibition of tumor cell viability increases. The E(BEO/OEO) binary emulsion induced an antiproliferative effect on oral health and tumor cells, with a minimal effect on skin cells. The non-invasive tests performed to verify the safety of the test compound’s emulsions at skin level indicated that these compounds do not significantly modify the physiological skin parameters and can be considered safe for human skin.     

A Lactic Acid Bacteria Consortium Impacted the Content of Casein-Derived Biopeptides in Dried Fresh Cheese

This study aimed to define a consortium of lactic acid bacteria (LAB) that will bring added value to dried fresh cheese through specific probiotic properties and the synthesis of bioactive peptides (biopeptides). The designed LAB consortium consisted of three Lactobacillus strains: S-layer carrying Levilactobacillus brevis D6, exopolysaccharides producing Limosilactobacillus fermentum D12 and plantaricin expressing Lactiplantibacillus plantarum D13, and one Enterococcus strain, Enterococcus faecium ZGZA7-10. Chosen autochthonous LAB strains exhibited efficient adherence to the Caco-2 cell line and impacted faecal microbiota biodiversity. The cheese produced by the LAB consortium showed better physicochemical, textural and sensory properties than the cheese produced by a commercial starter culture. Liquid chromatography coupled with matrix-assisted laser desorption/ionization-time of flight tandem mass spectrometry (LC-MALDI-TOF/TOF) showed the presence of 18 specific biopeptides in dried fresh cheeses. Their identification and relative quantification was confirmed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) using multiple reaction monitoring (MRM). The results also showed that their synthesis resulted mainly from β-casein and also α-S1 casein degradation by proteolytic activities of the LAB consortium. The designed LAB consortium enhanced the functional value of the final product through impact on biopeptide concentrations and specific probiotic properties.     

Lignosulfonate/silica hybrid nanoparticles as a novel biobased filler in polybenzoxazine matrix

Lignin is an abundant and sustainable resource that exhibits numerous attractive functional properties as a reinforcing agent for benzoxazine-based composites, due to its stiffness, thermal stability, and high carbon content. However, the low quality of lignin particles dispersions associated with the weak particles-matrix interactions reduces the reinforcement capability. In this work, hybrid lignin/silica (NaLS/SiO₂) nanoparticles were obtained from sodium lignosulfonate (NaLS) and tetraethylorthosilicate (TEOS) under basic conditions. The particles were characterized by transmission electron microscopy (TEM) confirming their spherical morphology and narrow nanometric-size distributions. The hybrid particles were incorporated into conventional benzoxazine (BA-a) and a difuran biobased benzoxazine (SA-dfda) to prepare nanocomposites with different mass compositions (3, 5, and 10 wt%). Morphological, mechanical, dynamo-mechanical, and thermal properties of the obtained composites were assessed. All the materials exhibited a homogenous filler dispersion that contributed to improve the reinforcement properties. Hybrid nanoparticles proved to be an interesting alternative as a filler in the benzoxazine matrix to prepare high-performance thermosetting composites.     

HPLC/DAD,Antibacterial and Antioxidant Activities of Plectranthus Species (Lamiaceae) Combined with the Chemometric Calculations

The increase in antibiotic resistance and the emergence of new bacterial infections have intensified the research for natural products from plants with associated therapy. This study aimed to verify the antibacterial and antioxidant activity of crude extracts of the genus Plectranthus species, being the first report on the modulation of aminoglycosides antibiotic activity by Plectranthus amboinicus extracts. The chemical composition was obtained by chemical prospecting and High-Performance Liquid Chromatography with diode arrangement detector (HPLC/DAD). The antibacterial activities of the extracts alone or in association with aminoglycosides were analyzed using the microdilution test. The antioxidant activity was evaluated by 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging. The phytochemical prospection allowed the flavonoids, saponins, tannins and triterpenoids to be identified. Quercetin, rutin, gallic acid, chlorogenic acid, caffeic acid, catechin, kaempferol, glycosylated kaempferol, quercitrin, and isoquercitrin were identified and quantified. The principal component analysis (PCA) observed the influence of flavonoids and phenolic acids from Plectranthus species on studied activities. Phytochemical tests with the extracts indicated, especially, the presence of flavonoids, confirmed by quantitative analysis by HPLC. The results revealed antibacterial activities, and synergistic effects combined with aminoglycosides, as well as antioxidant potential, especially for P. ornatus species, with IC₅₀ of 32.21 µg/mL. Multivariate analyzes show that the inclusion of data from the antioxidant and antibacterial activity suggests that the antioxidant effect of these species presents a significant contribution to the synergistic effect of phytoconstituents, especially based on the flavonoid contents. The results of this study suggest the antibacterial activity of Plectranthus extracts, as well as their potential in modifying the resistance of the analyzed aminoglycosides.     

A new cyclopeptide alkaloid from the bark of waltheria douradinha

Waltherine-C (5), a novel 14-membered cyclopeptide alkaloid has been isolated, together with four known cyclopeptide alkaloids, waltherine-A (1) and -B (2), scutianine-B (3) and adouetine-Y' (4), from the bark of Waltheria douradinha (Sterculiaceae) from Rio Grande do Sul, Brazil. The structure and NMR assignments of this new alkaloid were determined by 1D and 2D NMR techniques. The stereochemistry of the ring amino acid residue and the N,N-dimethyl amino acid side-chain has been assigned by gas chromatography employing modified cyclodextrins as chiral stationary phases.     

O(3P)+1，2-丁二烯反应的交叉分子束和理论研究：丙烯+CO和亚乙基+乙烯酮反应的主要分子通道

详细了解O(~3P)与不饱和烃的多通道燃烧反应机理需要鉴定所有主要反应产物、确定分支比、评估三重态与单重态势能面之间的系间窜跃.将交叉分子束实验、软电离、质谱、飞行时间分析,以及高级从头算计算三重态/单线态势能面,RRKM/Master方程计算支化比包括系间窜跃,均可以获得最佳效果.最近已经证明这些方法对于含有两个或三个碳原子的最简单的不饱和烃(炔烃,烯烃,二烯)和O(~3P)反应是成功的.本文通过交叉分子束与理论相结合的方法研究O(~3P)和含有四个C原子的二烯类化合物,1,2-丁二烯(甲基芳烃)的反应,探索产物分布、分支比和系间窜跃如何随着分子复杂性的增加而变化,即从O(~3P)和丙二烯反应到O(~3P)1,2-丁二烯的反应变化.尤其关注了最重要的导致链终止的主导分子通道(即形成丙烯+CO(分支≥0.5)和亚乙基+乙烯酮(分支比≥0.15))与导致链传递的自由基形成通道进行对比(分支比≥0.35).