Polypiperazinamides: new polymers useful for membrane processes

A class of polymers based on piperazinamides is described. The structures and physical properties of main polymers are compared and the osmotic performance is examined. Among these polymers, the trans-2,5-dimethylpiperazinthiofurazan 3,4-amide was developed as a precursor for reverse osmosis. The osmotic properties of asymmetric membranes obtained from TFZ amides are reported. The resistance to temperature, to pH variation (from 1.5 to 11.9 at 25°C) and to chlorine and its derivatives are of great interest. This type of membrane assembled in different modules, is used in the desalination field as well as in other technological processes (fluid treatment, oenological field, material recovery).     

Monitoring food quality by microfluidic electrophoresis, gas chromatography, and mass spectrometry techniques: effects of aquaculture on the sea bass (Dicentrarchus labrax)

Monitoring food quality is a critical task for analytical chemistry and an important way to preserve human health. Fish is a valuable source of highly digestible proteins and contains large amounts of polyunsaturated fatty acids and fat-soluble vitamins. Since the world's wild fish stocks are limited, farmed fish is nowadays proposed as an alternative to consumers. It is now emerging that the fish muscle protein content is assuming great importance from an aquaculture perspective. Many data have been collected on the physiology and biochemistry of fish muscle, but few proteomic studies are available on farmed fish. Application of proteomics to aquaculture may play a key role in the development of new farming strategies. In this paper, a proteomic approach based on SDS-PAGE separation of proteins, in situ protein hydrolysis, de novo sequencing of peptides by MALDI and ESI MS(2), protein identification, and relative quantitation of protein by denaturing capillary electrophoresis was coupled with the determination of fatty acids and metal ions content by GM-MS and ICPMS in farmed and wild sea bass filet. Our results show that aquaculture could induce significant chemical and biochemical differences in fish muscle that may have an impact on food quality.     

Properties of piperazine homopolyamide films

Properties of films prepared from the following poly(piperazine amides) were examined: poly(2-methylpiperazine fumaramide); poly(trans-2,5-dimethylpiperazine fumaramide); poly(trans-2,5-dimethylpiperazine mesaconamide); poly(trans-2,5-dimethylpiperazine terephthalamide); poly(trans-2,5-dimethylpiperazine isophthalamide); poly(trans-2,5-dimethylpiperazine adipamide). Mechanical properties of these films are good; they have in fact a high tensile strength and in accordance with the rigidity of the polymer chain, low elongations and a high modulus of elasticity. Optical properties are very good. Since the films have a high water absorption, permeability to water vapour is very high while treatment of the films in water causes lowering of mechanical properties. Resistance to thermal ageing in an atmosphere of nitrogen is good. Among the various films considered those obtained from polymers with an unsaturated acid (fumaric and mesaconic) seem to show the best properties.     

Interferential lithography of 1D thin metallic sinusoidal gratings: Accurate control of the profile for azimuthal angular dependent plasmonic effects and applications

Nonlinear processes involved in the manufacture of nominally sinusoidal surface relief diffraction gratings generated by interference lithography can introduce distortions into the profile of these surfaces. Such distortions may dramatically affect both the specular reflectivity and diffracted efficiencies from such a surface [H. Raether, Phys. Thin Film 9 (1977) 145–261]. We shall consider in particular the case of metallic gratings used to investigate plasmonic effects that can be engineered for bio-sensing applications. To investigate these effects, interference lithography (IL) has been used for the generation of profile controlled sinusoidal plasmonic crystals. IL exposure contrast study has been performed to control the amplitude oscillation and the surface roughness quality. Bi-metallic layer of silver and gold have been systematically deposited with different film thicknesses. A comprehensive numerical model that studies the optical coupling to surface plasmon polaritons on Ag/Au gratings has been undertaken for the simulation of the reflectivity and azimuthal angle dependence [Z. Chen, I.R. Hooper, J.R. Sambles, J. Opt. A: Pure Appl. Opt. 10 (1) (2008) 015007]. This computation illustrates the sensitivity of individual features to specific harmonic components of the surface, for surface plasmon resonances recorded in both the zeroth and higher diffracted orders. The roughness surface control after development and after bi-metallic evaporation strongly contributes to tighten the width of the reflectivity peak. Optimization process has shown that for an Ag (37 nm) and Au (7 nm) metallic bilayer, a semi-amplitude of 20 nm provides the best reflectivity.     

Design and Discovery of Plasmepsin II Inhibitors Using an Automated Workflow on Large‐Scale Grids

Novel and potent inhibitors of Plasmodium falciparum plasmepsin II were identified by post‐processing the results of a docking screening with BEAR, a recently reported procedure for the refinement and rescoring of docked ligands in virtual screening. FRET substrate degradation assays performed on the 30 most promising compounds resulted in 26 inhibitors with IC₅₀ values ranging from 4.3 nM to 1.8 μM .

     

Synthesis and Optoelectronic Properties of Nonpolar Polyrotaxane Insulated Molecular Wires with High Solubility in Organic Solvents

Hydrophilic polyanionic conjugated polyrotaxanes are readily synthesized in water by Suzuki coupling, but their high polarity and ionic nature limit the potential applications of these materials. Here, we demonstrate three methods for transforming these polar polyelectrolytes into nonpolar lipophilic insulated molecular wires. A water‐soluble polyfluorene‐alt‐biphenylene β‐cyclodextrin (CD) polyrotaxane was converted into nonpolar derivatives by methylation of the carboxylic acid groups with diazomethane and conversion of the hydroxyl groups of the CDs to benzyl ethers, trihexylsilyl ethers, benzoyl esters, and butanoate esters to yield polyrotaxanes that are soluble in organic solvents such as chloroform and cyclohexane. Elemental analysis, NMR spectroscopy, and gel permeation chromatography (GPC) data support the proposed structures of the organic‐soluble polyrotaxanes. The extents of reaction of the polyrotaxane CD hydroxyl groups were 55% for trihexylsilyl chloride/imidazole; 81% for benzyl chloride/sodium hydride; 72% for benzoyl chloride/pyridine/4‐dimethylaminopyridine; and 98% butanoic anhydride/pyridine/4‐dimethylaminopyridine. Alkylation, silylation, and esterification increase the bulk of the encapsulating sheath, preventing interstrand aggregation, increasing the photoluminescence efficiency in the solid state and simplifying the time‐resolved fluorescence decay. The organic‐soluble polyrotaxanes were processed into polymer light‐emitting diodes (PLEDs) from solution in nonpolar organic solvents, thereby excluding ionic impurities from the active layer.     

Short communication: Space allocation in intensive Mediterranean buffalo production influences the profile of functional biomolecules in milk and dairy products

The aim of the present study was to determine if space allocation influenced the concentration of biomolecules in buffalo milk and dairy products. Intensively housed buffaloes (n = 96) were randomly assigned to 2 groups according to days in milk, parity, and milk yield: group S10 had a space allocation of 10 m² per buffalo and group S15 had a space allocation of 15 m² per buffalo. Individual milk yield was recorded daily. Twice a month, a bulk milk sample was collected for each group, as well as whey, ricotta, and mozzarella cheese, to assess cheese yield and to conduct HPLC-electrospray ionization-tandem mass spectrometry, milk antioxidant activity, and cell viability analyses. We tested milk extracts from the 2 groups in vitro to evaluate their efficacy in counteracting endothelial oxidative damage induced by high glucose. We evaluated reproductive function in 28 buffaloes from each group using the Ovsynch-timed artificial insemination program. We observed no differences in milk quantity or quality in terms of fat, protein, or lactose, and reproductive function did not differ between the 2 groups. Compared with group S10, group S15 had higher concentrations of carnitine (56.7 ± 1.1 vs. 39.8 ± 0.7 mg/L in milk and 40.9 ± 0.8 vs. 31.7 ± 0.7 mg/L in whey), acetyl-l-carnitine (51.9 ± 0.3 vs. 39.7 ± 0.7 mg/L in milk and 41.1 ± 1.7 vs. 28.7 ± 2.6 mg/L in whey), propionyl-l-carnitine (34.8 ± 1.0 vs. 21.0 ± 0.9 mg/L in milk and 26.9 ± 0.8 vs. 17.6 ± 1.2 mg/L in whey), glycine betaine (23.1 ± 1.9 vs. 13.5 ± 1.6 mg/L in milk and 10.7 ± 0.4 vs. 7.9 ± 0.5 mg/L in whey), and δ-valerobetaine (24.2 ± 0.5 vs. 16.7 ± 0.5 mg/L in milk and 22.0 ± 0.9 vs. 15.5 ± 0.7 mg/L in whey). Group S15 also had higher total antioxidant activity than group S10 (56.7 ± 1.9 vs. 46.4 ± 1.13 mM Trolox equivalents). Co-incubation of high-glucose-treated endothelial cells with milk extracts from group S15 improved cell viability compared with cells treated with high glucose only; it also reduced intracellular lipid peroxidation (144.3 ± 0.4 vs. 177.5 ± 1.9%), reactive oxygen species (141.3 ± 0.9 vs. 189.3 ± 4.7 optical density units), and cytokine release (tumor necrosis factor-α, IL-1β, IL-6). Greater space allocation was associated with higher levels of biomolecules in buffalo milk. This could have been the result of improved welfare in buffaloes that were allocated more space.     

Peptides from water buffalo cheese whey induced senescence cell death via ceramide secretion in human colon adenocarcinoma cell line

Scope: Milk proteins are a source of bioactive peptides. Recent studies have indicated that protein‐derived peptides released in buffalo cheese acid whey exert a cytomodulatory effect in human epithelial colon cancer (CaCo2) cells. The aim of the present study was to explain the molecular mechanism involved in the response of CaCo2 cells to oxidative stress in the presence of peptide fractions of buffalo cheese whey, purified and characterized by mass spectrometry. Methods and results: We demonstrated that treatment of CaCo2 treated with H₂O₂ (H‐CaCo2) cells with a partially purified peptide sub‐fraction (f3) from buffalo cheese acid whey induced a reduction of mitochondrial superoxide anion with subsequent decrease in heat shock protein 70 and 90 expression. Moreover, we observed a 5‐fold decrease in cyclin A expression and cell cycle arrest in G1/G0 phases. These responses were associated with increased activity of alkaline phosphatase and beta‐galactosidase, markers of differentiation and senescence respectively. Conclusions: The structural characterization of the active peptide fraction and the elucidation of the effects induced by its treatment on H‐CaCo2 cells in vitro demonstrated an activity of this peptide sub‐fraction in the modulation of cell cycle, thus suggesting potential application for the development of nutraceuticals as well as health‐promoting functional foods.     

Stochastic and recursive estimation of the hygro-thermo-chemical-mechanical parameters of concrete through Monte Carlo analysis and extended Kalman filter

Structural and Multidisciplinary Optimization - Hygro-thermo-chemical-mechanical models, used to determine the variations over time of temperature, relative humidity and shrinkage induced...