Design,Synthesis, and Biological Evaluation of Unconventional Aminopyrimidine,Aminopurine, and Amino‐1,3,5‐triazine Methyloxynucleosides

Herein we describe a class of unconventional nucleosides (methyloxynucleosides) that combine unconventional nucleobases such as substituted aminopyrimidines, aminopurines, or aminotriazines with unusual sugars in their structures. The allitollyl or altritollyl derivatives were pursued as ribonucleoside mimics, whereas the tetrahydrofuran analogues were pursued as their dideoxynucleoside analogues. The compounds showed poor, if any, activity against a broad range of RNA and DNA viruses, including human immunodeficiency virus (HIV). This inactivity may be due to lack of an efficient metabolic conversion into their corresponding 5′‐triphosphates and poor affinity for their target enzymes (DNA/RNA polymerases). Several compounds showed cytostatic activity against proliferating human CD4⁺ T‐lymphocyte CEM cells and against several other tumor cell lines, including murine leukemia L1210 and human prostate PC3, kidney CAKI‐1, and cervical carcinoma HeLa cells. A few compounds were inhibitory to Moloney murine sarcoma virus (MSV) in C3H/3T3 cell cultures, with the 2,6‐diaminotri‐O‐benzyl‐D ‐allitolyl‐ and ‐D ‐altritolyl pyrimidine analogues being the most potent among them. This series of unconventional nucleosides may represent a novel family of potential antiproliferative agents.     

Synergistic effect of organoclay fillers based on fluorinated surfmers for preparation of polystyrene nanocomposites

Novel fluorinated reactive surfactants were used for the organic modification of monmorillonite clays. These organoclays were used for the preparation of polystyrene?clay nanocomposites by in‐situ free radical polymerization. Reference systems based on hydrocarbon homologous surfmer and nonpolymerizable surfactants were also used to deduce the effect of the fluorine moiety and the polymerizable function on the morphology and thermal stability of the prepared nanocomposites. Different structural parameters of the surfactants were investigated and modulated for the clay modification including: the nature of surfactant (surfmer/classical surfactant, fluorinated, or hydrocarbonated), the length of the fluorinated chain as well as the length of the hydrocarbon spacers linking the ammonium head to the fluorine chain or the polymerizable acrylic function. Wide angle‐X‐ray scattering (WAXD), thermogravimetric analysis (TGA), and electronic microcopies (TEM and SEM) were used to establish a structure‐morphology, thermal properties relationships, and to highlight the key parameters governing the exfoliation process. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42347.     

Densification of 8Y‐Tetragonal‐Stabilized Zirconia Optoceramics with Improved Optical Properties by Y Segregation

8% Yttria‐stabilized zironcia (8YSZ) transparent ceramics have a wide technological applications. Segregation of the Y around the grain boundaries is favored by slow heating rate. The optimized sintering parameters helped in obtaining transparent ceramics of 8YSZ with a high percentage of cubic phase in addition to the presence of tetragonal phase. HRTEM was used to verify the grain growth suppression and to observe the presence of the cubic phase. The presence of cubic phase has suppressed the grain growth, which increased the transparency in the visible and infrared region without the addition of dopants or by utilizing high pressure.     

Calculation of the Orientation Relationships of Directionally Solidified Eutectic Ceramics by a Modified Coincidence of Reciprocal Lattice Points Model (CRLP)

The Coincidence of Reciprocal Lattice Points (CRLP) method was used to predict, according to geometric considerations, the most favorable orientation relationships (ORs) between the component phases in a family of directionally solidified eutectic ceramics (DSEC) (NiO–YSZ, CoO–YSZ, NiO–CeO₂, NiO–GDC, CoO–CeO₂, and CoO–GDC) grown by the laser floating zone method. The ORs predicted by the CRLP model are consistent with those experimentally found in a previous work by means of Electron Backscatter Diffraction (EBSD). In this article, we also present a modification to the model with the aim of taking into account that the most stable ceramic–ceramic interfaces are usually formed between atomic planes with low Miller indices, due to their higher atomic density and bigger interplanar spacing. Thus, we introduce in the calculation of the overall coincidence volume a weighting factor which is a function of the interplanar spacing. This modified CRLP method has been applied to the aforementioned eutectic ceramics, and the results are presented and discussed in comparison with the traditional CRLP results and the experimental findings.     

Natural Polyphenols Selectively Inhibit β‐Carbonic Anhydrase from the Dandruff‐Producing Fungus Malassezia globosa: Activity and Modeling Studies

Around 50 % of the worldwide population is affected by dandruff, which is triggered by a variety of factors. The yeast Malassezia globosa has been labeled as the most probable causative agent for the onset of dandruff. The β‐carbonic anhydrase (CA) of MgCA was recently validated as an anti‐dandruff target, with its inhibition being responsible for in vivo growth defects in the fungus. As classical CA inhibitors of the sulfonamide type give rise to permeability problems through biological membranes, finding non‐sulfonamide alternatives for MgCA inhibition is of considerable interest in the cosmetic field. We recently screened a large library of human (h) CA inhibitors for MgCA inhibition, including different chemotypes, such as monothiocarbamates, dithiocarbamates, phenols, and benzoxaboroles. Herein, we expanded the research toward new MgCA inhibitors by considering a set of natural polyphenols (including flavones, flavonols, flavanones, flavanols, isoflavones, and depsides) that exhibited MgCA inhibitory activity in the micromolar range, as well as selectivity for the fungal isozyme over off‐target human isoforms. The binding mode of representative derivatives within the MgCA catalytic cleft was investigated by docking studies using a homology‐built model.     

Preliminary study of the anticancer applications of mesoporous materials functionalized with the natural product betulinic acid

Dehydrated MCM-41 (S1) was functionalized under nitrogen with 3-chloropropyltriethoxysilane (CPTS) and 3-aminopropyltriethoxysilane (APTS) by grafting in toluene at 80 °C over 48 h to give the corresponding materials S2 and S3, respectively. Subsequently, S2 and S3 were suspended in methanol and reacted in a nitrogen atmosphere with betulinic acid (BA) for 48 h at 65 °C (in the presence of the triethylamine of S2) to give the BA-functionalized materials S4 and S5. All materials studied were characterized by powder X-ray diffraction, X-ray fluorescence, nitrogen gas sorption, multinuclear MAS NMR spectroscopy, thermogravimetry, UV spectroscopy, IR, SEM, and TEM. To study the release of BA, S4 and S5 were suspended in solutions simulating various body pH conditions (pH 7.4, 5.5, and 3.0). Results of the quantification of BA release by HPLC for S4 show a pH-dependent and very slow BA release following a logarithmic tendency, while S5 behaves differently, also pH-dependent but, in this case, fast release of BA which requires only days for total release of the therapeutic compound. In addition, the cytotoxic activity of all synthesized materials against various cancer cell lines was studied. The results show the absence of an antiproliferative effect on the surfaces without BA S1-S3, while an antiproliferative effect was observed with S4 and S5 and was attributed to the release of BA in the medium.     

The effect of synthesis conditions on the physicochemical properties of magnesium aluminate materials

Magnesium aluminate-based materials were prepared by applying different methods: (i) mechanochemical milling of the initial mixture of magnesium and aluminium nitrate powders (in appropriate stoichiometric amounts) followed by heat treatment at temperatures of 650 °C and 850 °C and (ii) melting of the mixture of nitrate precursors at 240 °C followed by thermal treatment at 650 °C, 750 °C and 850 °C. The effect of synthesis method on the structure and morphology of the obtained solids was studied by using various techniques such as: nitrogen adsorption-desorption isotherms, powder XRD, IR spectroscopy and SEM. It was shown that the mechanochemical milling performed before calcination procedure leads to obtaining of nanocrystalline magnesium aluminate spinel phase at lower temperature of 650 °C in comparison with the method using thermal treatment only (at 750 °C). The obtained nanomaterials exhibit mesoporous structure.     

Bisorbicillinoids Produced by the Fungus <Emphasis Type="Italic">Trichoderma citrinoviride</Emphasis> Affect Feeding Preference of the Aphid <Emphasis Type="Italic">Schizaphis graminum</Emphasis>

We report the effects of some bisorbicillinoids isolated from biomass of the fungus Trichoderma citrinoviride on settling and feeding preference of the aphid Schizaphis graminum. Purification of the fungal metabolites was carried out by a combination of column chromatography and thin-layer chromatography using direct and reverse phases. Chemical identification was performed by spectroscopic methods including nuclear magnetic resonance and mass spectrometry. The identified bisorbicillinoids appeared to be bislongiquinolide, its 16,17-dihydro derivative, trichodimerol, and dihydrotrichodimerol. A feeding preference test with alate morphs of S. graminum was used to identify the active fractions. Among the four bisorbicillinoids, dihydrotrichodimerol and bislongiquinolide influenced aphid feeding preference, restraining specimens from settling on leaves treated with metabolites. Taste neurons sensitive to these compounds, particularly to bislongiquinolide, were located on tarsi of the S. graminum alate morphs.     

Design,Synthesis, and Biological Evaluation of Levoglucosenone‐Derived Ras Activation Inhibitors

A panel of new potential Ras ligands was generated by decorating a tricyclic levoglucosenone‐derived scaffold with aromatic moieties. Some members of the panel show in vitro inhibitory activity toward the nucleotide exchange process on Ras and are toxic to some human cancer cell lines.

     

Hibiscus sabdariffa L: source of antioxidant dietary fiber

Dietary fiber and antioxidants are food constituents and functional ingredients that are generally addressed separately. Nowadays there is scientific evidence that primary characteristics of DF assigned to non starch polysaccharides and lignin (resistance to digestion and absorption in the small intestine and fermentation in the large intestine) can be extended to other indigestible food constituents that are resistant to digestion and absorption in the human small intestine with complete or partial fermentation in the large intestine. The antioxidant dietary fiber concept was defined as a dietary fiber concentrate containing significant amounts of natural antioxidants associated with non digestible compounds. Hibiscus sabdariffa L flower shows in its composition an important percentage of dietary fiber and high antioxidant capacity. The infusion obtained by decoction of flowers, had been extensibility studied due to the healthy properties. In this work the principal nutritional aspects from Hibiscus sabdariffa L and its use as a possible antioxidant dietary fiber source had been considered.