Random fluorinated copolymers of tetrafluoroethylene: a study of the inclusion/exclusion of defects from the crystal by conformational and packing energy calculations

A conformational analysis has been performed on the isolated chains of copolymers of tetrafluoroethylene with hexafluoropropene, chlorotrifluoroethylene or perfluoromethyl vinyl ether, in comparison with polytetrafluoroethylene. The lowest energy conformations in accordance with the chain repeating distance of polytetrafluoroethylene in the low temperature crystal phase have been used in packing energy calculations. The results of both conformational and packing energy calculations suggest that the  Cl group is easily tolerated in the crystal phase. The —CF₃ group could also be tolerated in the crystal phase but at the cost of conformational and crystal lattice deformations. On the contrary, it can be concluded that the —OCF₃ group is excluded from the crystal phase because its presence should require high energy values and wide deformations in the unit cell parameters.     

Use of phase diagrams in the analysis of polymer network formation

A conversion - temperature - transformation (CTT) diagram was used to analyze several non-isothermal processes of polymer network formation: a) range of heating rates where reliable kinetic information can be obtained; b) a novel process involving part of the cure in the glassy state; c) phase separation in rubber-modified epoxies cured in heated molds.     

Structure and properties of polystyrene-polyethylene interpenetrating polymer network (ipn)-like systems

A series of samples of polystyrene (PS) –polyethylene (PE) interpenetrating polymer network (IPN)–like system was prepared by synthesis in situ. The measurement of uniaxial compression modulus of the IPN samples was used for the determination of mean molar mass of the polymer chain between two junction points of the polymer network – M̌_C. The electron microscopic records gave an evidence about two phase structure of the IPN samples. Generally, the crystalline part of PE network in all IPN investigated samples is relatively low. The influence of the concentration of crosslinking agent on mechanical behaviour of the IPN samples was studied.     

A Continuous-Time Random Walk Extension of the Gillis Model

We consider a continuous-time random walk which is the generalization, by means of the introduction of waiting periods on sites, of the one-dimensional non-homogeneous random walk with a position-dependent drift known in the mathematical literature as Gillis random walk. This modified stochastic process allows to significantly change local, non-local and transport properties in the presence of heavy-tailed waiting-time distributions lacking the first moment: we provide here exact results concerning hitting times, first-time events, survival probabilities, occupation times, the moments spectrum and the statistics of records. Specifically, normal diffusion gives way to subdiffusion and we are witnessing the breaking of ergodicity. Furthermore we also test our theoretical predictions with numerical simulations.     

The Sound of Silence: Minorities,Abstention and Democracy

Despite the existence of an extensive literature, no definitive conclusion seems to emerge on the extent to which minorities are guaranteed by democratic rules in political systems. This paper contributes to this debate by proposing a modified Heigselmann and Krauss two-dimensional model of preferences in order to capture the role of abstention on minority representativeness. Regardless of the typology of abstention, simulation results show that voter abstention always benefits minorities.     

NMR Characterization of Lignans

Lignans are particularly interesting secondary metabolites belonging to the phenyl-propanoid biosynthetic pathway. From the structural point of view, these molecules could belong to the aryltetralin, arylnaphtalene, or dibenzylbutyrolactone molecular skeleton. Lignans are present in different tissues of plants but are mainly accumulated in seeds. Extracts from plant tissues could be characterized by using the NMR-based approach, which provides a profile of aromatic molecules and detailed structural information for their elucidation. In order to improve the production of these secondary metabolites, elicitors could effectively stimulate lignan production. Several plant species are considered in this review with a particular focus on Linum species, well recognized as the main producer of lignans.     

Effect of Natural Deep Eutectic Solvents on trans-Resveratrol Photo-Chemical Induced Isomerization and 2,4,6-Trihydroxyphenanthrene Electro-Cyclic Formation

trans-Resveratrol is a natural bioactive compound with well-recognized health promoting effects. When exposed to UV light, this compound can undergo a photochemically induced trans/cis isomerization and a 6π electrochemical cyclization with the subsequent formation of 2,4,6-trihydroxyphenanthrene (THP). THP is a potentially harmful compound which can exert genotoxic effects. In this work we improved the chromatographic separation and determination of the two resveratrol isomers and of THP by using a non-commercial pentafluorophenyl stationary phase. We assessed the effect of natural deep eutectic solvents (NaDES) as possible photo-protective agents by evaluating cis-resveratrol isomer and THP formation under different UV-light exposure conditions with the aim of enhancing resveratrol photostability and inhibiting THP production. Our results demonstrate a marked photoprotective effect exerted by glycerol-containing NaDES, and in particular by proline/glycerol NaDES, which exerts a strong inhibitory effect on the photochemical isomerization of resveratrol and significantly limits the formation of the toxic derivative THP. Considering the presence of resveratrol in various commercial products, these results are of note in view of the potential genotoxic risk associated with its photochemical degradation products and in view of the need for the development of green, eco-sustainable and biocompatible resveratrol photo-stable formulations.     

Crosslinked penicillin acylase aggregates for synthesis of β-lactam antibiotics in organic medium

Crosslinked enzyme aggregates (CLEAs) of a partially purified penicillin acylase from a recombinant Escherichia coli strain have been produced as a novel type of biocatalysts well endowed to perform in organic media. Different protein precipitants were studied and glutaraldehyde was used as the crosslinking agent. Precipitation curves were obtained for all precipitants to determine the concentrations at which all the protein precipitated out of the solution. The effect of the glutaraldehyde-to-protein ratio was studied with respect to process recovery and the specific activity and stability of the biocatalyst. Recovery of penicillin acylase activity was moderately high, about 50%; major losses of enzyme activity were produced at the precipitation step. Specific activities of all CLEAs were very high, which is one of the advantages of using nonsupported biocatalysts. Ammonium sulfate and tert-butyl alcohol were the best precipitants at a glutaraldehyde-protein mass ratio of 2 and were selected to perform the kinetically controlled synthesis of ampicillin in 60% (v/v) ethylene glycol medium. At comparable conversion yields, volumetric and specific antibiotic productivity were much higher for CLEAs than for carrier-bound penicillin acylases.     

Open access atmospheric pressure chemical ionization Mass spectrometry for routine sample analysis

We report the introduction and use of an atmospheric pressure chemical ionization liquid chromatography-mass spectrometry instrument that has been designed specifically for use by the synthetic chemist on an open access, walk-in basis. This instrument has been configured with an easy-to-use sample log-in terminal that requires the user to provide only a sample identification number and a user name. Sample analysis takes approximately 4 min and provides the synthetic and medicinal chemist with rapid and reliable mass spectrometry analysis. Since installation of the system, it has analyzed an average of about 80 samples per day and has the capacity to run over 100 samples per day without the intervention of a specialist operator. This capability has eliminated the need for an operator to analyze routine samples and allows the mass spectroscopist more time to deal with problem solving.     

Treatment of Human Glioblastoma U251 Cells with Sulforaphane and a Peptide Nucleic Acid (PNA) Targeting miR-15b-5p: Synergistic Effects on Induction of Apoptosis

Glioblastoma multiforme (GBM) is a lethal malignant tumor accounting for 42% of the tumors of the central nervous system, the median survival being 15 months. At present, no curative treatment is available for GBM and new drugs and therapeutic protocols are urgently needed. In this context, combined therapy appears to be a very interesting approach. The isothiocyanate sulforaphane (SFN) has been previously shown to induce apoptosis and inhibit the growth and invasion of GBM cells. On the other hand, the microRNA miR-15b is involved in invasiveness and proliferation in GBM and its inhibition is associated with the induction of apoptosis. On the basis of these observations, the objective of the present study was to determine whether a combined treatment using SFN and a peptide nucleic acid interfering with miR-15b-5p (PNA-a15b) might be proposed for increasing the pro-apoptotic effects of the single agents. To verify this hypothesis, we have treated GMB U251 cells with SFN alone, PNA-a15b alone or their combination. The cell viability, apoptosis and combination index were, respectively, analyzed by calcein staining, annexin-V and caspase-3/7 assays, and RT-qPCR for genes involved in apoptosis. The efficacy of the PNA-a15b determined the miR-15b-5p content analyzed by RT-qPCR. The results obtained indicate that SFN and PNA-a15b synergistically act in inducing the apoptosis of U251 cells. Therefore, the PNA-a15b might be proposed in a “combo-therapy” associated with SFN. Overall, this study suggests the feasibility of using combined treatments based on PNAs targeting miRNA involved in GBM and nutraceuticals able to stimulate apoptosis.