Inclusion networks of a calix[5]arene-based exoditopic receptor and long-chain alkyldiammonium ions

[structure: see text]. Tail-to-tail connection of two cone calix[5]arene moieties by a rigid p-xylyl spacer affords the new exoditopic receptor 3 featuring two pi-rich cavities (assembling cores) in a centrosymmetric divergent arrangement, as established by a single-crystal X-ray analysis. 1H NMR complexation studies of 3 with alkyldiammonium ions support the formation of discrete bis-endo-cavity complexes and/or capsular assemblies along a polymer chain (polycaps), according to the length of the connector.     

Reducing Properties of Superalkalis on Pyridinic Graphene Surfaces: a Computational Study

The hyperlithiated species (k=1, 2, 3, and 4) have been studied by quantum mechanical (QM) methods. Different structures have been localized for each molecule by the CBS-QB3 composite method: all the isomers show superalkali properties and strong tendency to donate an electron to carbon dioxide forming stable complexes. With the aim to find molecular systems able to stabilize superalkalis, geometries of complexes between superalkalis and pyridine and superalkalis and graphene surfaces doped with a pyridinic vacancy were calculated. The pyridinic graphene sheets were modeled with two finite molecular systems C₆₉H₂₁N₃ and C₁₁₇H₂₇N₃. The interaction with one pyridine molecule is quite weak and the superalkali maintains its structure and electron properties. The affinity for graphene sheets is instead stronger and the superalkalis tend to deform their geometry to better interact with the graphene surface. However, the superalkalis continue to show the tendency to transfer electrons to carbon dioxide reducing CO₂, as found in graphene absence.     

Two-dimensional mapping of three phenotype-associated isoforms of the prion protein in sporadic Creutzfeldt-Jakob disease

Transmissible spongiform encephalopathies (TSE), or prion diseases, are mammalian neurodegenerative disorders characterized by a conformational modification of the host-encoded prion protein (PrP(C)) into an isoform which is detergent-insoluble and partially resistant to protease treatment (PrP(Sc)). Distinct types of PrP(Sc), differing in conformation and variation in the relative amount of their glycoforms, have been associated with different phenotypes of TSE. In sporadic Creutzfeldt-Jakob disease (sCJD), two major types of PrP(Sc), with proteinase K (PK)-resistant fragments of 21 and 19 kDa, have been described. No consensus exists, however, on the molecular classification of PrP(Sc) in sCJD, since further heterogeneity within PrPSc conformers has been reported. We studied 19 subjects with dementia or dementia/ataxia at onset and 12 subjects with ataxia at onset. Following two-dimensional gel electrophoresis, we characterized PrP(C) and PrP(Sc) species in normal and sCJD brains by immunoblotting with antibodies recognizing N-terminal and C-terminal PrP regions. Three types of PrP(Sc) were detected in detergent-insoluble fractions from sCJD brains, mainly consisting of full-length PrP(Sc) in subjects with rapidly progressive dementia, and two different sets of amino-truncated PrP(Sc) glycoforms in subjects with dementia/ataxia and ataxia at onset. Examination of the PrP(Sc) core fragment, following PK treatment and deglycosylation, confirmed the existence of three distinctive patterns. These findings have immediate implications for the molecular classification of sCJD.     

Expanding the Scope of Atropisomeric Monodentate P‐Donor Ligands in Asymmetric Catalysis: Hydrogen‐Transfer Reduction of α,β‐Unsaturated Acid Derivatives by Rhodium/Ph‐binepine Catalysts

A range of α,β‐unsaturated acids and esters have been selectively reduced to the corresponding saturated acid derivatives by hydrogen transfer. As the reducing agent, formic acid was used in the presence of Rh^I complexes formed with the powerful chiral ligand Ph‐binepine ( 1 ), an axially chiral binaphthalene‐type monodentate P‐donor ligand. Very high stereoselectivities (up to 97% ee) were obtained in the case of itaconic acid ( 2a ).     

Tart Cherry Juice and Seeds Affect Pro-Inflammatory Markers in Visceral Adipose Tissue of High-Fat Diet Obese Rats

Background: Tart cherries (Prunus cerasus L.) are a rich source of anthocyanins. They are phytochemical flavonoids found in red and blue fruits, and vegetables that can reduce hyperlipidemia. Visceral Adipose Tissue (VAT) has emerged as a major player in driving obesity-related inflammatory response. Methods: This study has investigated the potential positive effects of tart cherries on rats with Diet-Induced Obesity (DIO). In particular, the inflammatory status in retroperitoneal (RPW) and perigonadal (PGW) adipose tissue were studied. Rats were fed ad libitum for 17 weeks with a hypercaloric diet with the supplementation of tart cherries seeds powder (DS) and seeds powder plus tart cherries juice containing 1mg of anthocyanins (DJS). In RPW and PGW, expression of CRP, IL-1 β, TNF-α, CCL2 and CD36, were measured by qRT-PCR, Western blot and immunohistochemistry techniques. Results: No differences in the weight of RPW and PGW animals were found between DS and DJS groups compared to DIO rats. However, an increase of inflammatory markers was observed in DIO group in comparison with control lean rats. A modulation of these markers was evident upon tart cherry supplementation. Conclusion: Study results suggest that tart cherry enriched-diet did not modify the accumulation of visceral fat, but it decreased inflammatory markers in both tissues. Therefore, this supplementation could be useful, in combination with healthy lifestyles, to modify adipose tissue cell metabolism limiting-obesity related organ damage.     

Influence of chemistry and topology effects on superhydrophobic CF(4)-plasma-treated poly(dimethylsiloxane) (PDMS)

Superhydrophobic surfaces are gaining considerable interest in a lot of different applications, and nonetheless, precise control over the wettability properties of such surfaces is still a challenge due to difficulties when controlling the effects independently induced on superhydrophobicity by the chemical and topological surface characteristics. We have fabricated engineered superhydrophobic surfaces onto poly(dimethylsiloxane) (PDMS) substrates by means of suitable CF4-plasma treatments. These treatments allowed the modification of both the morphological properties of the PDMS surface, due to a preferential etching of certain components of its macromolecules, and the chemical ones, by the deposition of a fluorinated layer. Chemical effects were separated from topological ones by performing a double replica molding process of the CF4-plasma-treated surfaces. This allowed us to obtain positive copies of the structured surfaces without the overlaying fluorinated coating affecting the surface chemistry. Such replicated surfaces showed a decrease of the contact angle if compared to the treated ones and therefore evidenced chemistry's weight in superhydrophobicity effects. In particular, we found that, for highly dense columnar-like PDMS microstructures, the effect of the plasma-deposited fluorinated layer covering surfaces produces an enhancement of the contact angle of about 20 degrees .     

Long-Range Chiral Induction by a Fully Noncovalent Approach in Supramolecular Porphyrin–Calixarene Assemblies

The hierarchical assembly, in aqueous solution, of a new multi-metalloporphyrin/calixarene aggregate has been accomplished. In this supramolecular system transfer of chirality, from the outermost components to the central porphyrin reporter, takes place as a result of favorable and fully noncovalent long-range electronic communication.     

Muscari comosum L. Bulb Extracts Modulate Oxidative Stress and Redox Signaling in HepG2 Cells

Muscari comosum L. bulbs are commonly used as food in South Italy and also in folk medicine. By evaluating in vitro antioxidant activity and biological activities of their aqueous and methanol extracts, we shed light on the potential role, including both the nutraceutical and health benefits, of this plant. Total polyphenol content (TPC) and total flavonoid content (TFC) were evaluated by the Folin–Ciocalteu method and by the aluminum chloride method, respectively. Antioxidant activity was investigated by three in vitro assays and relative antioxidant capacity index (RACI) was calculated to compare results obtained by different tests. The extracts were tested to evaluate their possible involvement in redox homeostasis, using the human hepatoma (HepG2) cell line used as model. The extracts exhibited concentration/solvent dependent radical scavenging activity, as well as dysregulation of some genes involved in redox pathways by promoting Nrf2, SOD-2, GPX1, ABCC6 and ABCG2 expression. NMR metabolomics analysis suggests that HepG2 cells treated with Muscari comosum extracts experience changes in some metabolites involved in various metabolic pathways.     

Synthesis,Dynamic Combinatorial Chemistry,and PCR Amplification of 3′–5′ and 3′–6′ Disulfide‐linked Oligonucleotides

Disulfide dithymidines linked 3′–5′ or 3′–6′ were synthesized and incorporated into oligonucleotides through a combined phosphotriester and phosphoramidite solid‐phase oligonucleotide synthesis approach. The disulfide links are cleaved and formed reversibly in the presence of thiols and oligonucleotides. This link was shown to be sequence‐adaptive in response to given templates in the presence of mercaptoethanol. The artificial 3′–5′ and 3′–6′ disulfide link was tolerated by polymerases in the polymerase chain reaction (PCR). By using sequencing analysis, we show that single mutations frequently occurred randomly in the amplification products of the PCR.