Fluorescent core-sheath fibers by electrospinning of a phenyleneethynylene/poly(styrene-co-maleimide) blend

Ultrafine fluorescent fibers were prepared by electrospinning of a phenyleneethynylene oligomer mixed in DMF with a poly(styrene-co-maleimide) (PSM). The microscopic characterization by SEM reveals that the fibers are smooth and entangled one to the others forming a non-woven mat with an average diameter of 490 nm. By TEM, a core-sheath type structure is observed which derives from phase segregation between the PSM interacting with the oligomer and the excess of PSM that acts as matrix, as supported by XRD and DSC analysis. The membranes are fluorescent emitting at 420 nm, in the blue region, a high energy light, opening the possibility of their application in optoelectronic devices such as fluorescent sensors. Preliminary assays have been performed for the detection of sodium ions.     

An improved kinetic model for the peroxide initiated modification of polyethylene

We propose a generalized kinetic model for the peroxide initiated modification of polyethylene. It takes into account not only combination reactions but also transfer to polymer and scission. The model describes the length of the polymer chain and the concentration of vinyl groups simultaneously. Any number of vinyl groups per molecule is allowed. The resulting infinite system of mass balance equations is solved using a double moment technique. The model calculates number, weight and z-average molecular weights and the average concentration of vinyl groups as functions of time. The kinetic constants and the initiation efficiency were estimated through a nonlinear regression using experimental data. The relevance of each one of the reactions included in the mechanism was assessed. By means of the model we studied the influence of temperature and initial peroxide concentration on the modified polymer properties. It follows well the observed experimental trends and gives good estimates of both average molecular weights and average vinyl content, within experimental error.     

Obtaining the consensus and inconsistency among a set of assertions on a qualitative attribute

It is well understood how to compute the average or centroid of a set of numeric values, as well as their variance. In this way we handle inconsistent measurements of the same property. We wish to solve the analogous problem on qualitative data: How to compute the “average” or consensus of a set of affirmations on a non-numeric fact, as reported for instance by different Web sites? What is the most likely truth among a set of inconsistent assertions about the same attribute?Given a set (a bag, in fact) of statements about a qualitative feature, this paper provides a method, based in the theory of confusion, to assess the most plausible value or “consensus” value. It is the most likely value to be true, given the information available. We also compute the inconsistency of the bag, which measures how far apart the testimonies in the bag are. All observers are equally credible, so differences arise from perception errors, due to the limited accuracy of the individual findings (the limited information extracted by the examination method from the observed reality).Our approach differs from classical logic, which considers a set of assertions to be either consistent (True, or 1) or inconsistent (False, or 0), and it does not use Fuzzy Logic.     

A new synthetic route to molecularly imprinted ORMOSIL: Characterization and evaluation

A new strategy for synthesis of molecularly imprinted organically modified silica (MIORMOSIL) has been described. The MIORMOSIL was prepared by reacting vinyl acetate and 3-(trimethoxysilyl) propyl methacrylate, followed by condensation and hydrolysis with tetraethyl orthosilicate in the presence of caffeine. The ORMOSIL was characterized by SEM, FTIR, ²⁹Si MAS NMR, ¹³C MAS NMR, TGA, nitrogen adsorption/desorption and tested to extract analyte from coffee samples. The percentage recovery of caffeine 88 ± 5% (n = 9), limits of detection and quantification, 5.14 × 10^–4 and 1.71 × 10^?3 mmolL^?1 respectively, were achieved. Cross reactivity studies for theophylline and theobromine showed high recovery (77% and 82% respectively).

Abbreviations: HMIP: Molecularly Imprinted ORMOSIL; HNIP: non imprinted ORMOSIL; TMSPM: 3-(Trimethoxysilyl)propylmethacrylate     

A Beckwith–Wiedemann-Associated CDKN1C Mutation Allows the Identification of a Novel Nuclear Localization Signal in Human p57Kip2

p57^Kip2 protein is a member of the CIP/Kip family, mainly localized in the nucleus where it exerts its Cyclin/CDKs inhibitory function. In addition, the protein plays key roles in embryogenesis, differentiation, and carcinogenesis depending on its cellular localization and interactors. Mutations of CDKN1C, the gene encoding human p57^Kip2, result in the development of different genetic diseases, including Beckwith–Wiedemann, IMAGe and Silver–Russell syndromes. We investigated a specific Beckwith–Wiedemann associated CDKN1C change (c.946 C>T) that results in the substitution of the C-terminal amino acid (arginine 316) with a tryptophan (R316W-p57^Kip2). We found a clear redistribution of R316W-p57^Kip2, in that while the wild-type p57^Kip2 mostly occurs in the nucleus, the mutant form is also distributed in the cytoplasm. Transfection of two expression constructs encoding the p57^Kip2 N- and C-terminal domain, respectively, allows the mapping of the nuclear localization signal(s) (NLSs) between residues 220–316. Moreover, by removing the basic RKRLR sequence at the protein C-terminus (from 312 to 316 residue), p57^Kip2 was confined in the cytosol, implying that this sequence is absolutely required for nuclear entry. In conclusion, we identified an unreported p57^Kip2 NLS and suggest that its absence or mutation might be of relevance in CDKN1C-associated human diseases determining significant changes of p57^Kip2 localization/regulatory roles.     

G-Quadruplex in Gene Encoding Large Subunit of Plant RNA Polymerase II: A Billion-Year-Old Story

G-quadruplexes have long been perceived as rare and physiologically unimportant nucleic acid structures. However, several studies have revealed their importance in molecular processes, suggesting their possible role in replication and gene expression regulation. Pathways involving G-quadruplexes are intensively studied, especially in the context of human diseases, while their involvement in gene expression regulation in plants remains largely unexplored. Here, we conducted a bioinformatic study and performed a complex circular dichroism measurement to identify a stable G-quadruplex in the gene RPB1, coding for the RNA polymerase II large subunit. We found that this G-quadruplex-forming locus is highly evolutionarily conserved amongst plants sensu lato (Archaeplastida) that share a common ancestor more than one billion years old. Finally, we discussed a new hypothesis regarding G-quadruplexes interacting with UV light in plants to potentially form an additional layer of the regulatory network.     

Effects of Lipidation on a Proline-Rich Antibacterial Peptide

The emergence of multidrug-resistant bacteria is a worldwide health problem. Antimicrobial peptides have been recognized as potential alternatives to conventional antibiotics, but still require optimization. The proline-rich antimicrobial peptide Bac7(1-16) is active against only a limited number of Gram-negative bacteria. It kills bacteria by inhibiting protein synthesis after its internalization, which is mainly supported by the bacterial transporter SbmA. In this study, we tested two different lipidated forms of Bac7(1-16) with the aim of extending its activity against those bacterial species that lack SbmA. We linked a C12-alkyl chain or an ultrashort cationic lipopeptide Lp-I to the C-terminus of Bac7(1-16). Both the lipidated Bac-C12 and Bac-Lp-I forms acquired activity at low micromolar MIC values against several Gram-positive and Gram-negative bacteria. Moreover, unlike Bac7(1-16), Bac-C12, and Bac-Lp-I did not select resistant mutants in E. coli after 14 times of exposure to sub-MIC concentrations of the respective peptide. We demonstrated that the extended spectrum of activity and absence of de novo resistance are likely related to the acquired capability of the peptides to permeabilize cell membranes. These results indicate that C-terminal lipidation of a short proline-rich peptide profoundly alters its function and mode of action and provides useful insights into the design of novel broad-spectrum antibacterial agents.     

Poly(hexylacrylate)Core‐poly(ethyleneglycol methacrylate)Shell nanogels as fillers for poly(2‐hydroxyethyl methacrylate) nanocomposite hydrogels

The preparation of poly(hexylacrylate)_core‐poly(ethyleneglycol methacrylate)_shell (PHA‐co‐PEGMA) nanogels, to be used as fillers in nanocomposite hydrogels, is reported. Stable nanogels with particle sizes between 90–300 nm were obtained varying the conditions of synthesis. The synthesis recipe of the nanogels could be easily scaled up. Purified and dispersed nanogels in aqueous solution were used as soft fillers for poly(2‐hydroxyethyl methacrylate) (PHEMA) hydrogels, crosslinked with ethylene glycol dimethacrylate (EGDMA). The obtained nanocomposite hydrogels exhibit a larger swelling capacity and a higher thermal stability in comparison with the non‐filled PHEMA hydrogels. Young, storage, and lost moduli, increase largely, in the better case up to 72.5% in the swollen state; while in the dry state the storage modulus increase up to 4.7 fold with a very low load on nanogels (0.64 wt%); resulting in biomaterials with improved properties with potential applications in medical devices. POLYM. ENG. SCI., 59:170–181, 2019. © 2018 Society of Plastics Engineers