Source-based nomenclature for single-strand homopolymers and copolymers (IUPAC Recommendations 2016)

IUPAC recommendations on source-based nomenclature for single-strand polymers have so far addressed its application mainly to copolymers, non-linear polymers and polymer assemblies, and within generic source-based nomenclature of polymers. In this document, rules are formulated for devising a satisfactory source-based name for a polymer, whether homopolymer or copolymer, which are as clear and rigorous as possible. Thus, the source-based system for naming polymers is presented in a totality that serves as a user-friendly alternative to the structure-based system of polymer nomenclature. In addition, because of their widespread and established use, recommendations for the use of traditional names of polymers are also elaborated

A brief guide to polymer characterization: structure (IUPAC technical report)

To bolster the series of Brief Guides released by International Union of Pure and Applied Chemistry (IUPAC), here we introduce the first Brief Guide to Polymer Characterization. This article provides a concise overview of characterization methods for teachers, students, non-specialists, and newcomers to polymer science as well as being a useful manual for researchers and technicians. Unlike pure low molar mass chemical substances, polymers are not composed of identical molecules. The macromolecules which comprise a single polymer sample vary from one another, primarily in terms of size and shape, but often also in the arrangement or positioning of atoms within macromolecules (e.g., chain branching, isomerism, etc.). Polymer properties are often drastically different from those of other substances and their characterization relies on specialist equipment and/or common equipment used in a specialized way (e.g., particular sample preparation or data analysis). This Brief Guide focuses uniquely on the structural characterization (i.e., analyzing the molecular and multi-molecular aspects) of polymers. The complex nature of the structural variables possible in macromolecular materials often presents a challenge with regard to the detailed structural characterization of polymers. This Brief Guide provides a useful starting point to direct the reader to the most commonly used and useful techniques to characterize these structural variables

An exercise-based international polymer syllabus

The IUPAC Subcommittee on Polymer Education has been pursuing the development of a compact syllabus covering the essential topics required for a tertiary education in polymer science, with numerical and short answer exercises addressing each topic. The primary goal of the document is to provide a framework for a complete course made freely available worldwide so that any educator can implement a professionally-curated course in polymer science for their students without needing expensive textbooks or reliable internet access. An important secondary goal is to popularize the use of approved IUPAC terminology in polymer science by using it consistently throughout the document and providing references to IUPAC source documents. Professor Melissa Chin Han Chan was an active and enthusiastic participant in the project who played a significant role in its design and implementation. The late Professor Richard ‘Dick’ Jones also had a keen interest in the project and had a great influence on its direction and structure. This brief note is dedicated to these two illustrious polymer scientists

Klasické a nově navržené popisné charakteristiky: porovnání výběrových vlastností na základě Monte Carlo simulace

Na základě Monte Carlo simulace bylo provedeno porovnání estimátorů klasických a některých nově navržených měr variability, relativní variability, šikmosti a kurtozy. Z celkem 40 různých populací bylo pořízeno vždy 16 000 výběrů o rozsahu n = {7; 15; 23; 31; 47; 63; 100; 200; 350; 500; 1000}. Z každého výběru byly vypočteny hodnoty estimátorů měr založených na momentech, kvantilech, L momentech a jejich modifikacích a robustních měr založených na mediánu funkce lineární kombinace pořádkových statistik. Na základě experimentu bylo provedeno porovnání výběrových vlastností jednotlivých estimátorů z hlediska variability, vychýlení a rychlosti konvergence jejich výběrových rozdělení k normalitě. U estimátorů vybraných charakteristik byla dále na základě experimentálně odhadnuté průměrné síly testu posouzena vhodnost jejich použití jako testového kritéria při testu o rozdělení, z něhož výběr pochází. Zároveň byla porovnána síla závislosti estimátorů nově navržených charakteristik s estimátory momentovými s cílem posoudit, zda je možné danou charakteristiku skutečně považovat za vhodnou alternativu charakteristiky momentové. Výsledky ukazují, že estimátory momentových měr jsou vyhovující pro popis souboru pouze při výběrech z populací nepříliš odlišných od normálního rozdělení. S rostoucí odlišností od normality rychle roste relativní variabilita i vychýlení jejich estimátorů a projevují se různé anomálie v jejich chování. Vhodnou alternativou k mírám založeným na klasických momentech i kvantilech by se mohly stát míry založené na L momentech, jejichž estimátory vykazují ve většině případů nejlepší výběrové vlastnosti a zároveň vykazují vysokou míru závislosti s hodnotami estimátorů momentových charakteristik. Modifikace L-momentů, tzv. LQ- a TL-momenty, nepřinášejí oproti mírám založeným na L-momentech žádné zlepšení, v některých ohledech vykazují výrazně horší vlastnosti

Pyrazinyl and pyridinyl bis-azomethines formation: an experimental and computational study

Abstract Formation of bis-azomethines from hydrazine and heterocyclic aromatic carbaldehydes, namely pyridine-2-carbaldehyde and pyrazine-2-carbaldehyde, is studied using density functional theory. The theoretical investigation is correlated with experimental results obtained by means of NMR spectroscopy. The presence of bis-hemiaminal intermediates is evidenced by NMR spectra while surprisingly stable hemiaminal intermediate was isolated experimentally. Water, methanol and acetic acid were outlined to play a crucial role as active catalysts of elementary steps of the reaction mechanisms. The possible reaction sequences, i.e. addition-dehydration-addition-dehydration or addition-addition-dehydration-dehydration are investigated and discussed. Also, alternative mechanistic path via ionic mechanism was proposed for the formation of hemiaminals

Iron (II) Metallo-Supramolecular Polymers Based on Thieno[3,2-<i>b</i>]thiophene for Electrochromic Applications

Four new bis(tpy) unimers with different linkers between the thieno[3,2-b]thiophene-2,5-diyl central unit and terpyridine-4′-yl (tpy) end-groups: no linker (Tt), ethynediyl (TtE), 1,4-phenylene (TtPh) and 2,2′-bithophene-5,5′-diyl (TtB) are prepared, characterized, and assembled with Fe2+ ions to metallo-supramolecular polymers (Fe-MSPs). The Fe-MSP films prepared by spin-casting on Indium Tin Oxide (ITO) glass are characterized by atomic force microscope (AFM) microscopy, cyclic voltammetry, and UV/vis spectroscopy and studied for their electrochromism and effect of the unimer structure on their electrochromic performance. Of the studied MSPs, Fe-Tt shows the highest optical contrast as well as coloration efficiency (CE = 641 cm2 C−1) and the fastest optical response. This makes it an excellent candidate for possible use in electrochromic devices

Conjugated Metallo-Supramolecular Polymers Containing a Phosphole Unit

International audienceA new building block, TPT, composed of the substituted phosphole ring surrounded by two thiophene rings with 2,2':6',2''-terpyridine-4'-yl (tpy) end-groups, is prepared and assembled with metal ions (Co2+, Cu2+, Fe2+, Ni2+ and Zn2+) into metallo-supramolecular polymers (MSPs) and properties of both TPT and the MSPs are compared with those of their counterparts with terthiophene central blocks. A distinct red shift of the UV/vis band about 60 to 100 nm proves the decrease in the bandgap energy due to replacing the thiophene-2,5-diyl with a phosphole-2,5-diyl central unit, which is due to the lowered aromaticity of phosphole ring compared to the aromaticity of thiophene ring. Assembling of TPT with metal ions gives oligomeric chains comprising up to ten unimeric units in dilute solutions. MSPs with Fe2+ and Ni2+ ion couplers exhibit very slow constitutional dynamics, while those with Cu2+ and Zn2+ ion couplers quite fast constitutional dynamics. A metal to ligand charge transfer is observed only for Fe2+-MSPs, while luminescence only for Zn2+-MSPs, mainly at an excess of Zn2+ ions, which indicates a positive effect of the end-capping of MSP chains with these ion

Stability of MEH-PPV: Poly{[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene]vinylene} in solutions exposed to air in the dark and at daylight at laboratory temperature

The long-term stability of poly{[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene]vinylene} (MEH-PPV) in solutions exposed to air at daylight and in the dark at room temperature has been studied using the size exclusion chromatography (SEC), UV/vis, fluorescence and IR spectra of aged samples, and comparison of UV/vis spectra of SEC fractions. Solvents currently used in the preparation, analysis and processing of MEH-PPV were used: tetrahydrofuran (THF), chloroform (CHCl3) and chlorobenzene (PhCl). The SEC-DAD data revealed a serious decrease in the delocalization of electrons in MEH-PPV chains, even in the large ones, which proves a deep damage to the structure of the chains prior to their cleavage. The IR spectra of aged samples show that the saturation of main-chain double bonds and the changes in the substitution of phenylene rings are the main chemical structure defects present in chains of aged MEH-PPV. The rate as well as the extent of the overall degradation process is ca ten to fifty times enhanced by the ordinary daylight. The rate of cleavage and the damage to the structure of MEH-PPV molecules are significantly influenced by the choice of the solvent; they increase in the order: PhCl &lt; CHCl3&lt; THF. PhCl can be recommended as one of the best solvents for MEH-PPV processing from solutions

Novel conjugated polyelectrolytes based on polythiophene bearing phosphonium side groups

The synthesis and photophysical properties of poly{3-[6-(triethylphosphonium)hexyl]-thiophene-2,5-diyl bromide} and poly{3-[6-(triphenylphosphonium)hexyl]-thiophene-2,5-diyl bromide} are reported in the present contribution. Three various polymer precursors (poly[3-(6-bromohexyl)thiophene-2,5-diyl]s) with molecular weights 7.2, 11.8 and 13.2 kg mol−1 respectively and head to tail regioregularity from 62% to 94% were prepared and consecutively transformed into the corresponding polyelectrolytes by a simple quaternization reaction with appropriate phosphines. Synthesized polyelectrolytes exhibited solvatochromism. Detailed aggregation experiments via changing water/DMSO ratio have been performed. Photoluminiscence spectra of the polyelectrolyte solutions indicate that the emission maxima are red-shifted gradually with the increasing solvent polarity. Fluorescence quenching has been studied by interaction with model quenchers: K4[Fe(CN)6] and K3[Fe(CN)6] in water using Stern-Volmer methodology. © 2016 Elsevier LtdP108/12/1143, GACR, Czech Science FoundationCzech Science Foundation [P108/12/1143]; Science Foundation of Charles University [876213]; COST Action (SIPS) European Network on Smart Inorganic Polymers [CM1302

Novel Metallo-Supramolecular Polymers with 1-Thioxophosphole Main-Chain Units and Remarkable Photoinduced Changes in Their Resonance Raman Spectra

New low-bandgap unimers, with the central thiophene-(1-thioxophosphole)-thiophene (TPT) ring sequence and 2,2′:6′,2″-terpyridin-4′-yl (tpy) end groups connected to the central unit via conjugated linkers of different size, are prepared and assembled with Zn(II) and Fe(II) ions to metallo-supramolecular polymers (MSPs) that are studied regarding their properties. The most interesting feature of Zn-MSPs is the luminescence extended deep into the NIR region. Fe-MSPs not only show the metal-to-ligand charge transfer (MLCT) manifested by the MLCT band (an expected feature) but also an as-yet-undescribed remarkable phenomenon: specific damping of the bands of the TPT sequence in the resonance Raman spectra taken from solid Fe-MSPs using the excitation to the MLCT band (532 nm). The damping is highly reversible at the low laser power of 0.1 mW but gradually becomes irreversible as the power reaches ca. 5 mW. The revealed phenomenon is not shown by the same Fe-MSPs in solutions, nor by Fe-MSPs containing no phosphole units. A hypothesis is proposed that explains this phenomenon and its dependence on the irradiation intensity as a result of the interplay of three factors: (i) enhancement of the MLCT process by excitation radiation, (ii) the electron-acceptor character of the 1-thioxophosphole ring, and (iii) morphological changes of the lattice and their dependence on the population of new structures in the lattice