Interpolymer radical coupling: A toolbox complementary to controlled radical polymerization

The current review focuses on the relevance and practical benefit of interpolymer radical coupling methods. The latter are developing rapidly and constitute a perfectly complementary macromolecular engineering toolbox to the controlled radical polymerization techniques (CRP). Indeed, all structures formed by CRP are likely to be prone to radical coupling reactions, which multiply the available synthetic possibilities. Basically, the coupling systems can be divided in two main categories. The first one, including the atom transfer radical coupling (ATRC), silane radical atom abstraction (SRAA) and cobalt-mediated radical coupling (CMRC), relies on the recombination of macroradicals produced from a dormant species. The second one, including atom transfer nitroxide radical coupling (ATNRC), single electron transfer nitroxide radical coupling (SETNRC), enhanced spin capturing polymerization (ESCP) and nitrone/nitroso mediated radical coupling (NMRC), makes use of a radical scavenger in order to promote the conjugation of the polymer chains. More than a compilation of macromolecular engineering achievements, the present review additionally aims to emphasize the particularities, synthetic potential and present limitations of each system.     

Synthesis of Ultra-high Weight Average Molecular Mass of Poly-L-lactide

High purity in high yield L-lactide was prepared using a new purification method, and poly-L-lactide (PLLA) with ultra-high weight average molecular mass and narrow polydispersity index was synthesized by ring-opening polymerization. The effects of the purification method on the purity and yield of L-lactide were investigated, and the influences of initiator concentration, polymerization temperature and polymerization time on the weight average molecular mass of PLLA were also studied. A synthetic purification method involving a water bath and two times recrystallization could improve the purity of L-lactide to 100%. The yield of L-lactide reached 40.6% and increased 12.1% compared with the recrystallization method. Poly-L-lactide with a weight average molecular mass of about 102.4 × 10⁴ and a polydispersity index of 1.16 was obtained when polymerization was conducted with molar ratio of monomer to initiator ([M]/[I]) of 12000 for 24 h at 140°C.     

Preparation of low- and medium-molecular weight chitosan nanoparticles and their antimicrobial evaluation against a panel of microorganisms,including cheese-derived cultures

This study employed the technique of ionic gelation in the manufacture of low- and medium-molecular weight chitosan nanoparticles. Nanoparticles were characterised (size, size distribution, surface charge and morphology) and their antimicrobial activity assessed against cheese-derived cultures, as well as a select panel of Gram-positive and Gram-negative microorganisms. Antimicrobial activity was determined by the minimum inhibition concentration via the micro dilution method using 96-well microplates. Synthesised particles were small-sized, with a moderate size distribution and positive zeta potential. Generated nanoparticles exhibited successful solubility in both water and acetic acid. Acidic nanosuspensions demonstrated greater microbial reduction than water-based nanoparticles, with no difference in activity observed between molecular weights. Cheese-derived cultures were effectively controlled, and Gram-negative species were more susceptible than Gram-positive species to the action of nanoparticles in acetic acid. Nanoparticles suspended in an acidic-based medium show promise as antimicrobial agents, particularly for use with cheese products.     

Changes in Molecular Characteristics of Cereal Carbohydrates after Processing and Digestion

Different extraction, purification and digestion methods were used to investigate the molecular properties of carbohydrates in arabinoxylan and β-glucan concentrates, dietary fiber (DF) rich breads and ileum content of bread fed pigs. The breads studied were: a low DF wheat bread (WF), whole meal rye bread (GR), rye bread with kernels (RK), wheat bread supplemented with wheat arabinoxylan concentrate (AX) and wheat bread supplemented with oat β-glucan concentrate (BG). The weight average molecular weight (M_w) of extractable carbohydrates in β-glucan concentrate decreased eight-fold after inclusion in the BG bread when exposed to in vitro digestion, while the M_w of purified extractable carbohydrates in AX bread was reduced two-fold, and remained almost unaffected until reaching the terminal ileum of pigs. Similarly, the M_w of purified extractable carbohydrates in GR and RK bread was not significantly changed in the ileum. The AX bread resulted in the highest concentration of dissolved arabinoxylan in the ileum among all the breads that caused a substantial increased in ileal AX viscosity. Nevertheless, for none of the breads, the M_w of extractable carbohydrates was related neither to the bread extract nor ileal viscosity.     

Gone with the wind? Newspaper discourse of eutrophication and blue‐green algae blooms in Finland

The mass media shape the public and policy agenda by giving prominence to certain ecosystem changes and risks, as well as by framing some policy measures as the preferred ones. Based on longitudinal analysis of the leading Finnish newspaper, this study considers the media coverage of eutrophication. The results show an increase of reporting in the late 1990s as a result of intertwined ecological and social factors – i.e. intense algal occurrences and establishment of a national communication system. The news coverage has highlighted the harmful algal blooms and health risks of algal toxins and has framed short‐term weather conditions as the key factor regulating algal occurrences. This creates a challenge for environmental management aimed at reduction in the nutrient discharges that influence the state of the environment in the long term.     

Dispersity in polymer science (IUPAC Recommendation 2009)

This recommendation defines just three terms, viz., 1. molar‐mass dispersity, relative‐molecular‐mass dispersity, or molecular‐weight dispersity, 2. degree‐of‐polymerization dispersity, and 3. dispersity. “Dispersity” is a new word, coined to replace the misleading, but widely used term “polydispersity index” for M?_w/M?_n and X?_w/X?_n. The document, although brief, also has a broader significance in that it seeks to put the terminology describing dispersions of distributions of properties of polymeric (and non‐polymeric) materials on an unambiguous and justifiable footing. Copyright © 2009 Society of Chemical Industry     

NEURAL NETWORK PREDICTION OF CETANE NUMBERS FOR ISOPARAFFINS AND DIESEL FUEL

A backpropagation neural network was used to correlate and predict the cetane numbers of isoparaffins and diesel fuels. For the isoparaffins, the correlation was made between the chemical structure of the branched paraffins and their cetane number. Thirteen branched paraffins were employed to train the network. The group additivity method was used to express the degree of branching of the isoparaffins. According to their positions in the molecule structure, three carbon groups (methylene [-CH₂-] subdivided into methylene α, β and γ, or further, to a carbon that is not a methylene, methyne [>CH-] and quaternary carbon [>C<]) were regrouped into four categories, and included along with normal boiling points, as the network inputs. For the selected diesel fuels, different combinations of physical properties such as density, viscosity, aniline point, and distillation temperatures were tested as the neural network input. The best model was obtained using density, viscosity, aniline point and ASTM D86 measured distillation temperatures (IBP, 10%, 50%, 90% and FBP) as inputs. The trained network models, when applied to predict the cetane number of other isoparaffins and diesel fuel, were quite accurate.