Introducing Enantioselective Ultrahigh-Pressure Liquid Chromatography (eUHPLC): Theoretical Inspections and Ultrafast Separations on a New Sub-2-μm Whelk-O1 Stationary Phase

A new chiral stationary phase for ultrahigh-pressure liquid chromatography (UHPLC) applications was prepared by covalent attachment of the Whelk-O1 selector to spherical, high-surface-area 1.7-μm porous silica particles. Columns of varying dimensions (lengths of 50, 75, 100, and 150 mm and internal diameters of 3.0 or 4.6 mm) were packed and characterized in terms of permeability, efficiency, retention, and enantioselectivity, using both organic and water-rich mobile phases. A conventional HPLC Whelk-O1 column based on 5.0-μm porous silica particles and packed in a 250 mm × 4.6 mm column was used as a reference. Van Deemter curves, generated with low-molecular-weight solutes on a 100 mm × 4.6 mm column packed with the 1.7-μm particles, showed H(min) (μm) and μ(opt) (mm/s) values of 4.10 and 5.22 under normal-phase and 3.74 and 4.34 under reversed-phase elution conditions. The flat C term of the van Deemter curves observed with the 1.7-μm particles allowed the use of higher-than-optimal flow rates without significant efficiency loss. Kinetic plots constructed from van Deemter data confirmed the ability of the column packed with the 1.7-μm particles to afford subminute separations with good efficiency and its superior performances in the high-speed regime, compared to the column packed with 5.0-μm particles. Resolutions in the time scale of seconds were obtained using a 50-mm-long column in the normal phase or polar organic mode. The intrinsic kinetic performances of 1.7-μm silica particles are retained in the Whelk-O1 chiral stationary phase, clearly demonstrating the potentials of enantioselective UHPLC in terms of high speed, throughput, and resolution.     

Solvent vapor treatment controls surface wettability in PMMA femtosecond-laser-ablated microchannels

A solvent vapor treatment was applied to femtosecond-laser-ablated microchannels in PMMA to selectively restore the original hydrophilic wetting behavior of the pristine surface. The hydrophobic surface of the microchannels from the submicron porosity induced by ablation becomes smoother and more transparent after the treatment. This simple and low-cost method, together with suitable masking, can produce wettability patterns that may be exploited to develop passive microfluidic elements such as valves and mixers.     

Impact of Debaryomyces hansenii strains inoculation on the quality of slow dry-cured fermented sausages

Debaryomyces hansenii strains, M4 and P2, isolated from natural fermented sausages were inoculated in slow fermented sausages to study their effect on processing parameters, microbial population, volatile compound and sensory characteristics. The inoculation of D. hansenii strains, M4 and P2, did not affect the ripening process as no differences in pH and Aw were detected. The dominance of the inoculated yeast strains along the process was followed by RAPDs of M13 minisatellite. The inoculated yeasts, P2 and M4, were recovered at the end of the ripening process although P2 appeared in higher counts than M4. The sausages inoculated with P2 resulted in a decrease in lipid oxidation values (TBARS) and a reduction of lipid-oxidation derived aldehydes in addition to a highest acid compound abundance. M4 inoculated sausages resulted in highest sulphur containing compound abundance. However, no differences in consumer acceptance were detected. Moreover, both yeast strains were responsible for the generation of ethyl methyl-branched ester compounds in the dry-cured sausages.     

Optical and electrical characterization of carbon nanoparticles produced in laminar premixed flames

Optical and electrical properties of carbonaceous particles produced in laboratory scale, premixed ethylene/air flames are obtained. Light absorption and Raman spectroscopy show that the change in particle nanostructure follows a graphitization trajectory as the flame richness increases. The optical band gap decreases and the size of the aromatic network in the particle increases, while the interlayer spacing between parallel layers decreases. The electrical conductivity of the materials increases by increasing flame richness in agreement to the graphitization trajectory. A non-ohmic behavior has been found and explained in terms of electron tunneling in a percolative network. Our results show that the electrical properties of flame formed carbon nanoparticles are strongly dependent on their nanostructure, and hence they have to be used carefully for the determination of particle concentration with conductometric sensors. Moreover, the dependence of the electrical properties of combustion formed particles might be useful for the development of cheap sensors for the selective detection of different classes of combustion aerosols.     

Membrane-based technologies for meeting the recovery of biologically active compounds from foods and their by-products

ABSTRACT

To date, according to the latest literature inputs, membranes-based technologies (microfiltration, ultrafiltration and nanofiltration) have demonstrated to meet the recovery of biologically active compounds, mainly phenolic compounds and their derivatives, from agro-food products and by-products. The goal of this paper is to provide a critical overview of the on ongoing development works aimed at improving the separation, fractionation and concentration of phenolic compounds and their derivatives from their original sources. The literature data are analyzed and discussed in relation to separation processes, molecule properties, membrane characteristics and key factors affecting the performance of such technologies. Technological advances and improvements over conventional technologies, as well as critical aspects to be further investigated are highlighted and discussed. Finally, a critical outlook about the current status for a large-scale application and the role of these processes from an environmental viewpoint is provided.     

Photovoltaic field emulation including dynamic and partial shadow conditions

In this paper the development of a new laboratory prototype for the emulation of a photovoltaic (PV) field is presented. The proposed system is based on a DC/DC step-down converter topology and allows to obtain the solar array I–V curves, taking into account the environmental changes in solar irradiance and cell temperature. The DC/DC converter control strategy is deduced by using a comprehensive mathematical model of the PV field whose parameters are obtained from the knowledge of: (a) maximum power point data, measured when the PV plant power converter is running, (b) open circuit voltage and short-circuit current, measured off-line. This approach allows the most accurate representation of the PV source. Computer simulations and experimental results demonstrate that the proposed circuit acts as a highly accurate and efficient laboratory simulator of the photovoltaic array electrical characteristics both in steady state and transient conditions. Partial shading and fluctuating conditions can be reproduced too. Moreover the dynamic behaviour of the proposed laboratory emulator is suitable to its effective connection to power electronic interface to the utility or to load through a DC/DC boost converter.     

A GC-EI-MS/MS Method for the Determination of 15 Polybrominated Diphenyl Ethers (PBDEs) in Fish and Shellfish Tissues

This paper describes the development and validation of an analytical method to determine 15 polybrominated diphenyl ethers (PBDEs) in fish and shellfish tissues with gas chromatography coupled to triple quadrupole mass spectrometry using electron impact source (GC-EI-MS/MS). A QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe)-like procedure was applied; the extract was cleaned up on an acidic Extrelut-NT3 column connected on top of a silica cartridge and further purified with gel permeation chromatography (GPC). The SIM acquisition proved to yield better results than traditional MRM approach for octa-, nona-, and deca-brominated congeners. The validation study was carried out in inter-laboratory conditions. The average recoveries were in the range 66–118%, with relative standard deviations generally lower than or equal to 22%. Quality assurance and quality control practices were thoroughly described and highlighted. These long and tedious practices are fundamental to obtain reliable quantitative data during food monitoring programs and, therefore, to support daily intake assessments. Finally, the procedure was applied to the analysis of marine fish samples collected in local markets. Mackerel and mullet were the most contaminated species.     

α–ω Alkenyl-bis-S-Guanidine Thiourea Dihydrobromide Affects HeLa Cell Growth Hampering Tubulin Polymerization

Cancer is going to be the first cause of mortality worldwide in the 21th century. It is considered a multifactorial disease that results from the combined influence of many genetic aberrations, leading to abnormal cell proliferation. As microtubules are strongly implicated in cellular growth, they represent an important target for cancer treatment. The well-known microtubule-targeting agents (MTAs) including paclitaxel, colchicine and vinca alkaloids are commonly used in the treatment of various cancers. However, adverse effects and drug resistance are major limitations in their clinical use. To find new candidates able to induce microtubule alteration with reduced toxic effects or drug resistance, we studied a small new series of derivatives that present imidazolinic, guanidinic, thioureidic and hydrazinic groups ( 1 – 9 ). All the compounds were tested for their antitumor activity against a panel of six tumoral cell models. In particular, compound 8 (nonane-1,9-diyl-bis-S-amidinothiourea dihydrobromide) showed the lowest IC₅₀ value against HeLa cells, together with a low cytotoxicity for normal cells. This compound was able to induce the apoptotic mitochondrial pathway and inhibited tubulin polymerization with a similar efficacy to vinblastine and nocodazole. Taken together, these promising biological properties make compound 8 useful for the development of novel therapeutic approaches in cancer treatment.     

Polychlorinated biphenyls and organochlorine pesticides in seafood from the Gulf of Naples (Italy)

Seven target polychlorinated biphenyls (PCBs; IUPAC nos. 28, 52, 101, 118, 138, 153, and 180) and the organochlorine pesticides (OCPs) hexachlorobenzene (HCB) and dichlorodiphenyltrichloroethane (DDT) and its related metabolites (p,p'-DDT, p,p'-DDE, and p,p'-DDD) were quantified in edible tissues from seven marine species (European hake, red mullet, blue whiting, Atlantic mackerel, blue and red shrimp, European flying squid, and Mediterranean mussel) from the Gulf of Naples in the southern Tyrrhenian Sea (Italy). PCBs 118, 138, and 153 were the dominant congeners in all the species examined. The concentrations of all PCBs (from not detectable to 15,427 ng g(-1) fat weight) exceeded those of all the DDTs (from not detectable to 1,769 ng g(-1) fat weight) and HCB (not detectable to 150.60 ng g(-1) fat weight) in the samples analyzed. The OCP concentrations were below the maximum residue limits established for fish and aquatic products by the Decreto Ministerale 13 May 2005 in all the samples analyzed; therefore the OCPs in the southern Tyrrhenian Sea species are unlikely to be a significant health hazard. Conversely, the mean concentrations of PCBs exceeded (greatly in some cases) the current limits (200 ng(-1) fat weight) set by the European Union for terrestrial foods. Although the manufacture and use of PCBs are banned or highly restricted, these compounds still are important persistent chemical contaminants in the Gulf of Naples.