Cyclohexanone is an important intermediate in the manufacture of polyamides in chemical industry, but direct selective hydrogenation of phenol to cyclohexanone under mild conditions is a challenge. ...We report here a catalyst made of Pd nanoparticles supported on a mesoporous graphitic carbon nitride, Pd@mpg-C3N4, which was shown to be highly active and promoted the selective formation of cyclohexanone under atmospheric pressure of hydrogen in aqueous media without additives. Conversion of 99% and a selectivity higher than 99% were achieved within 2 h at 65 °C. The reaction can be accelerated at higher temperature, but even at room temperature, 99% conversion and 96% selectivity could still be obtained. The generality of the Pd@mpg-C3N4 catalyst for this reaction was demonstrated by selective hydrogenation of other hydroxylated aromatic compounds with similar performance.
Classification systems for all-ceramic materials are useful for communication and educational purposes and warrant continuous revisions and updates to incorporate new materials. This article proposes ...a classification system for ceramic and ceramic-like restorative materials in an attempt to systematize and include a new class of materials. This new classification system categorizes ceramic restorative materials into three families: (1) glass-matrix ceramics, (2) polycrystalline ceramics, and (3) resin-matrix ceramics. Subfamilies are described in each group along with their composition, allowing for newly developed materials to be placed into the already existing main families. The criteria used to differentiate ceramic materials are based on the phase or phases present in their chemical composition. Thus, an all-ceramic material is classified according to whether a glass-matrix phase is present (glass-matrix ceramics) or absent (polycrystalline ceramics) or whether the material contains an organic matrix highly filled with ceramic particles (resin-matrix ceramics). Also presented are the manufacturers' clinical indications for the different materials and an overview of the different fabrication methods and whether they are used as framework materials or monolithic solutions. Current developments in ceramic materials not yet available to the dental market are discussed.
We report the design, synthesis, and evaluation of a new type of non-precious-metal catalyst made from network polymers. 2,6-Diaminopyridine was selected as a building-block monomer for the formation ...of a nitrogen-rich network polymer that forms self-supporting spherical backbone structures and contains a high density of metal-coordination sites. A Co-/Fe-coordinating pyrolyzed polymer exhibited a high specific oxygen reduction activity with onset and half-wave potentials of 0.87 and 0.76 V vs RHE, respectively, in neutral media. There was no crossover effect of organics on its activity. The power output of a microbial fuel cell equipped with this catalyst on its cathode was more than double the output with a commercial 20 wt % Pt/C catalyst.
This review summarizes the multifaceted aspects of antioxidants and the basic kinetic models of inhibited autoxidation and analyzes the chemical principles of antioxidant capacity assays. Depending ...upon the reactions involved, these assays can roughly be classified into two types: assays based on hydrogen atom transfer (HAT) reactions and assays based on electron transfer (ET). The majority of HAT-based assays apply a competitive reaction scheme, in which antioxidant and substrate compete for thermally generated peroxyl radicals through the decomposition of azo compounds. These assays include inhibition of induced low-density lipoprotein autoxidation, oxygen radical absorbance capacity (ORAC), total radical trapping antioxidant parameter (TRAP), and crocin bleaching assays. ET-based assays measure the capacity of an antioxidant in the reduction of an oxidant, which changes color when reduced. The degree of color change is correlated with the sample's antioxidant concentrations. ET-based assays include the total phenols assay by Folin−Ciocalteu reagent (FCR), Trolox equivalence antioxidant capacity (TEAC), ferric ion reducing antioxidant power (FRAP), “total antioxidant potential” assay using a Cu(II) complex as an oxidant, and DPPH. In addition, other assays intended to measure a sample's scavenging capacity of biologically relevant oxidants such as singlet oxygen, superoxide anion, peroxynitrite, and hydroxyl radical are also summarized. On the basis of this analysis, it is suggested that the total phenols assay by FCR be used to quantify an antioxidant's reducing capacity and the ORAC assay to quantify peroxyl radical scavenging capacity. To comprehensively study different aspects of antioxidants, validated and specific assays are needed in addition to these two commonly accepted assays. Keywords: Antioxidants; assay; hydrogen atom transfer reaction; electron-transfer reaction; free radicals; oxidants
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•Low viscosity chitosan solution (5% w/w) was associated with a microemulsion.•The vehicle with chitosan undergoes a phase transition after water absorption in situ.•The vehicle with ...chitosan showed improved mechanical properties, as adhesiveness.•The topical formulation incorporated herbal medicines with antifungal activity.•Molecular networking studies indicated expressive amounts of proanthocyanidins.
A viscous solution of low molecular weight chitosan (CH) at 5% w/v (10.2 kDa, 75 % deacetylated, 1451 cP at 25 °C) was associated with a microemulsion (ME) that undergoes a phase transition after water absorption in situ (≈28 % w/w), forming a more viscous liquid crystal, which was potentially evaluated as a topical vehicle. The ME was selected from a phase diagram, selecting a composition based on Tween® 80 (52 %), myristate isopropyl (28 %), and the aqueous phase (water and polyethylene glycol 400, 60:40 w/w) (20 %), which was after replaced by CH and herbal medicines (HM). HM are alternatives to treat candidiasis, and Stryphnodendron adstringens shell extract, characterized by molecular networking, and Melaleuca alternifolia Chell essential oil (46 % of terpinen-4-ol), showed in vitro activity against Candida albicans. Associating CH in ME improved the mechanical properties of the topical formulation, as adhesiveness, which is an advantageous feature for the topical treatment of vulvovaginal candidiasis.
One and two scandium ions (Sc3+) are bound strongly to nonheme manganese(IV)–oxo complexes, (N4Py)MnIV(O)2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) and (Bn-TPEN)MnIV(O)2+ ...(Bn-TPEN = N-benzyl-N,N′,N′-tris(2-pyridylmethyl)-1,2-diaminoethane), to form MnIV(O)–(Sc3+)1 and MnIV(O)–(Sc3+)2 complexes, respectively. The binding of Sc3+ ions to the MnIV(O) complexes was examined by spectroscopic methods as well as by DFT calculations. The one-electron reduction potentials of the MnIV(O) complexes were markedly shifted to a positive direction by binding of Sc3+ ions. Accordingly, rates of the electron transfer reactions of the MnIV(O) complexes were enhanced as much as 107–fold by binding of two Sc3+ ions. The driving force dependence of electron transfer from various electron donors to the MnIV(O) and MnIV(O)–(Sc3+)2 complexes was examined and analyzed in light of the Marcus theory of electron transfer to determine the reorganization energies of electron transfer. The smaller reorganization energies and much more positive reduction potentials of the MnIV(O)–(Sc3+)2 complexes resulted in remarkable enhancement of the electron-transfer reactivity of the MnIV(O) complexes. Such a dramatic enhancement of the electron-transfer reactivity of the MnIV(O) complexes by binding of Sc3+ ions resulted in the change of mechanism in the sulfoxidation of thioanisoles by MnIV(O) complexes from a direct oxygen atom transfer pathway without metal ion binding to an electron-transfer pathway with binding of Sc3+ ions.
The absence of detergent and curvature makes nanodiscs excellent membrane mimetics. The lack of structural and mechanistic model of polymer-encapsulated lipid nanodiscs limits their use in the study ...of the structure, dynamics, and functions of membrane proteins. In this study, we parameterized and optimized the coarse-graining (CG) bead mapping for two differently charged and functionalized copolymers, containing styrene–maleic acid (SMAEA) and polymethacrylate (PMAQA), for the Martini force-field framework and showed nanodisc formation (<8 nm diameter) on a time scale of tens of microseconds using molecular dynamics (MD) simulations. Structural models of ∼2.0 or 4.8 kDa PMAQA and ∼2.2 kDa SMAEA polymer-based lipid nanodiscs highlight the importance of the polymer chemical structure, size, and polymer–lipid ratio in the optimization of the nanodisc structure. The ideal spatial arrangement of polymers in nanodiscs, nanodisc size, and thermal stability obtained from our MD simulation correlates well with the experimental observations. The polymer–nanodiscs were tested for the reconstitution of single-pass or multipass transmembrane proteins. We expect this study to be useful in the development of novel polymer-based lipid nanodiscs and for the structural studies of membrane proteins.
The antioxidant capacity and antimicrobial activity of the essential oil of Moringa oleifera (Moringaceae) grown in Mozambique was investigated. The chemical composition was studied by means of GC ...and GC-MS analysis. Hexacosane (13.9%), pentacosane (13.3%) and heptacosane (11.4%) were the main components. Ultra High Performance Chromatography-DAD analysis detected the flavonoids quercetin (126 μg/g) and luteolin (6.2 μg/g). The essential oil exhibited a relatively low free radical scavenging capacity. The antimicrobial activity of the essential oil was assayed against two Gram-positive strains (Bacillus cereus, Staphylococcus aureus), two Gram-negative strains (Escherichia coli, Pseudomonas aeruginosa), and five fungal strains of agro-food interest (Penicillium aurantiogriseum, Penicillium expansum, Penicillium citrinum, Penicillium digitatum, and Aspergillus niger spp.). B. cereus and P. aeruginosa, as well as the fungal strains were sensitive to the essential oil.
Ginseng is a group of cosmopolitan plants with more than a dozen species belonging to the genus
in the family
that has a long history of use in traditional Chinese medicine (TCM). Among the bioactive ...constituents extracted from ginseng, ginseng saponins are a group of natural steroid glycosides and triterpene saponins found exclusively throughout the plant. Studies have shown that these ginseng saponins play a significant role in exerting multiple therapeutic effects. This review covers their chemical structure and classification, as well as their pharmacological activities, including their regulatory effects on immunomodulation, their anticancer effects, and their functions in the central nervous and cardiovascular systems. The general benefits of ginseng saponins for boosting physical vitality and improving quality of life are also discussed. The review concludes with fruitful directions for future research in the use of ginseng saponins as effective therapeutic agents.
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