Some recent advances in polyolefin functionalization

Polyolefin‐based materials are increasingly being used in many industrial applications for packaging, automotive and construction materials. The recent developments of research have been aimed at making these materials, often complex, being mixtures, block copolymers, micro‐ and nanocomposites with inorganic and organic fillers, more efficient and environmentally friendly (through recycling processes, and the use of bio‐polyolefins). In this context, functionalized polyolefins, on the one hand, play a fundamental role in improving the morphology and thus the thermal and mechanical properties of heterophase systems, and, on the other hand, provide new materials difficult to obtain by conventional synthesis in connection with the type of inserted functionality. Therefore it appears to be of interest to report and discuss here the recent results concerning the radical grafting in the melt of different functionalities onto polyolefins as well as the capability reached of modulating ad hoc the degree of grafting and the final structure/architecture of functionalized polyolefins. © 2013 Society of Chemical Industry     

Core Cross-Linked Amphiphilic Star-Block Copolymers with (Meth)acrylic Acid Shells Prepared by Atom Transfer Radical Polymerization

Core cross-linked amphiphilic star-block copolymers were prepared by hydrolysis of the outer shell of star-block copolymers prepared using copper mediated atom transfer radical polymerization (ATRP). In an arm-first approach, linear poly(tert-butyl methacrylate) macroinitiators (PtBMA-Cl) were extended with styrene to yield PtBMA-b-PS-Cl and then cross-linked with divinylbenzene (DVB) in order to yield (PtBMA-b-PS)_arms-PDVB_core star-block copolymers. Then, PMAA-b-PS block and (PMAA-PS)_arms-PDVB_core star-block copolymers were obtained by hydrolysis of the PtBMA blocks in both linear and cross-linked copolymers, as confirmed by ¹H NMR analyses. The amphiphilic character of these copolymers was confirmed by solubilisation in water. Several factors affecting the polymer aggregation and solubility such as the length, the composition of the arms and the catalyst used were studied. An acrylate analogue, that is, (PAA-b-PS)_arms-PDVB_core, was also prepared for comparison purposes. Atomic force microscopy (AFM) and differential scanning calorimetry (DSC) were used to elucidate the morphology and the thermal behaviour of the star-block copolymers.     

Computational intelligence modelling of pharmaceutical tabletting processes using bio-inspired optimization algorithms

In pharmaceutical development, it is very useful to exploit the knowledge of the causal relationship between product quality and critical material attributes (CMA) in developing new formulations and products, and optimizing manufacturing processes. With the big data captured in the pharmaceutical industry, computational intelligence (CI) models could potentially be used to identify critical quality attributes (CQA), CMA and critical process parameters (CPP). The objective of this study was to develop computational intelligence models for pharmaceutical tabletting processes, for which bio-inspired feature selection algorithms were developed and implemented for optimisation while artificial neural network (ANN) was employed to predict the tablet characteristics such as porosity and tensile strength. Various pharmaceutical excipients (MCC PH 101, MCC PH 102, MCC DG, Mannitol Pearlitol 200SD, Lactose, and binary mixtures) were considered. Granules were also produced with dry granulation using roll compaction. The feed powders and granules were then compressed at various compression pressures to produce tablets with different porosities, and the corresponding tensile strengths were measured. For the CI modelling, the efficiency of seven bio-inspired optimization algorithms were explored: grey wolf optimization (GWO), bat optimization (BAT), cuckoo search (CS), flower pollination algorithm (FPA), genetic algorithm (GA), particle swarm optimization (PSO), and social spider optimization (SSO). Two-thirds of the experimental dataset was randomly chosen as the training set, and the remaining was used to validate the model prediction. The model efficiency was evaluated in terms of the average reduction (representing the fraction of selected input variables) and the mean square error (MSE). It was found that the CI models can well predict the tablet characteristics (i.e. porosity and tensile strength). It was also shown that the GWO algorithm was the most accurate in predicting porosity. While the most accurate prediction for the tensile strength was achieved using the SSO algorithm. In terms of the average reduction, the GA algorithm resulted in the highest reduction of inputs (i.e. 60%) for predicting both the porosity and the tensile strength.     

Beyond Cognitive Framing Processes: Anger Mediates the Effects of Responsibility Framing on the Preference for Punitive Measures

A new stream of research indicates that framing effects are based on emotional as well as cognitive processes. However, it is not entirely clear whether emotions mediate framing effects and what the moderators of emotional mediation processes are. To address these questions, we conducted an experiment in which the framing of responsibility for a social problem was manipulated (ambivalent vs. high‐responsibility frame). We find that the high‐responsibility frame increased the preference for punitive measures by increasing responsibility beliefs and eliciting anger. Furthermore, we find that trait anger moderates the framing effect on anger and that responsibility beliefs are positively associated with anger intensity. The significance of these findings for framing research and suggestions for future studies are discussed.     

Evaluation of in vitro antioxidant properties of some traditional Sardinian medicinal plants: Investigation of the high antioxidant capacity of Rubus ulmifolius

The antioxidant capacities of 11 botanical species used in the tradition of Sardinia as teas beverages or as decoction for medicinal purposes were evaluated using different in vitro methods (BR, TEAC, DPPH and FC). Among the various species, Rubus ulmifolius, resulted the more active with all the used methods. Phytochemical investigation on the extract yields in the isolation of several phenolic compounds namely caffeic acid, ferulic acid, quercetin-3-O-glucuronide, kaempferol-3-O-glucuronide, kaempferol-3-O-(6″-p-coumaroyl)-β-d-glucopyranoside, kaempferol-3-O-(6″-caffeoyl)-β-d-glucopyranoside, chlorogenic acid, 4-caffeoylquinic acid and 5-caffeoylquinic acid. The antioxidant activity of isolated compounds was also evaluated.     

Polymer brush coatings for combating marine biofouling

A variety of functional polymer brushes and coatings have been developed for combating marine biofouling and biocorrosion with much less environmental impact than traditional biocides. This review summarizes recent developments in marine antifouling polymer brushes and coatings that are tethered to material surfaces and do not actively release biocides. Polymer brush coatings have been designed to inhibit molecular fouling, microfouling and macrofouling through incorporation or inclusion of multiple functionalities. Hydrophilic polymers, such as poly(ethylene glycol), hydrogels, zwitterionic polymers and polysaccharides, resist attachment of marine organisms effectively due to extensive hydration. Fouling release polymer coatings, based on fluoropolymers and poly(dimethylsiloxane) elastomers, minimize adhesion between marine organisms and material surfaces, leading to easy removal of biofoulants. Polycationic coatings are effective in reducing marine biofouling partly because of their good bactericidal properties. Recent advances in controlled radical polymerization and click chemistry have also allowed better molecular design and engineering of multifunctional brush coatings for improved antifouling efficacies.     

Synthesis,Pharmacological Evaluation,and Docking Studies of Novel Pyridazinone‐Based Cannabinoid Receptor Type 2 Ligands

In recent years, cannabinoid type 2 receptors (CB₂R) have emerged as promising therapeutic targets in a wide variety of diseases. Selective ligands of CB₂R are devoid of the psychoactive effects typically observed for CB₁R ligands. Based on our recent studies on a class of pyridazinone 4‐carboxamides, further structural modifications of the pyridazinone core were made to better investigate the structure–activity relationships for this promising scaffold with the aim to develop potent CB₂R ligands. In binding assays, two of the new synthesized compounds [6‐(3,4‐dichlorophenyl)‐2‐(4‐fluorobenzyl)‐cis‐N‐(4‐methylcyclohexyl)‐3‐oxo‐2,3‐dihydropyridazine‐4‐carboxamide ( 2 ) and 6‐(4‐chloro‐3‐methylphenyl)‐cis‐N‐(4‐methylcyclohexyl)‐3‐oxo‐2‐pentyl‐2,3‐dihydropyridazine‐4‐carboxamide ( 22 )] showed high CB₂R affinity, with K_i values of 2.1 and 1.6 nm , respectively. In addition, functional assays of these compounds and other new active related derivatives revealed their pharmacological profiles as CB₂R inverse agonists. Compound 22 displayed the highest CB₂R selectivity and potency, presenting a favorable in silico pharmacokinetic profile. Furthermore, a molecular modeling study revealed how 22 produces inverse agonism through blocking the movement of the toggle‐switch residue, W6.48.     

Molecular Mechanisms and Physiological Changes behind Benign Tracheal and Subglottic Stenosis in Adults

Laryngotracheal stenosis (LTS) is a complex and heterogeneous disease whose pathogenesis remains unclear. LTS is considered to be the result of aberrant wound-healing process that leads to fibrotic scarring, originating from different aetiology. Although iatrogenic aetiology is the main cause of subglottic or tracheal stenosis, also autoimmune and infectious diseases may be involved in causing LTS. Furthermore, fibrotic obstruction in the anatomic region under the glottis can also be diagnosed without apparent aetiology after a comprehensive workup; in this case, the pathological process is called idiopathic subglottic stenosis (iSGS). So far, the laryngotracheal scar resulting from airway injury due to different diseases was considered as inert tissue requiring surgical removal to restore airway patency. However, this assumption has recently been revised by regarding the tracheal scarring process as a fibroinflammatory event due to immunological alteration, similar to other fibrotic diseases. Recent acquisitions suggest that different factors, such as growth factors, cytokines, altered fibroblast function and genetic susceptibility, can all interact in a complex way leading to aberrant and fibrotic wound healing after an insult that acts as a trigger. However, also physiological derangement due to LTS could play a role in promoting dysregulated response to laryngo-tracheal mucosal injury, through biomechanical stress and mechanotransduction activation. The aim of this narrative review is to present the state-of-the-art knowledge regarding molecular mechanisms, as well as mechanical and physio-pathological features behind LTS.     

Significant others and contingencies of self-worth: Activation and consequences of relationship-specific contingencies of self-worth.

Three studies tested the activation and consequences of contingencies of self-worth associated with specific significant others, that is, relationship-specific contingencies of self-worth. The results showed that activating the mental representation of a significant other with whom one strongly desires closeness led participants to stake their self-esteem in domains in which the significant other wanted them to excel. This was shown in terms of self-reported contingencies of self-worth (Study 1), in terms of self-worth after receiving feedback on a successful or unsatisfactory performance in a relationship-specific contingency domain (Study 2), and in terms of feelings of reduced self-worth after thinking about a failure in a relationship-specific contingency domain (Study 3). Across studies, a variety of contingency domains were examined. Furthermore, Study 3 showed that failing in an activated relationship-specific contingency domain had negative implications for current feelings of closeness and acceptance in the significant-other relationship. Overall, the findings suggest that people’s contingencies of self-worth depend on the social situation and that performance in relationship-specific contingency domains can influence people’s perceptions of their relationships. (PsycINFO Database Record (c) 2010 APA, all rights reserved)