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Environmental contamination with bisphenol A (BPA), produced via degradation of plastic waste, can be disintegrated to monoaryls by its reaction with elemental sulfur.

Oleic acid is used to esterify lignin and the esterified lignin reacts with elemental sulfur and different temperatures to produce composites with compressional and flexural strength that can exceed that of traditional Portland cement.

Successive modification of starch with octenyl succinic anhydride (OSA) and plant-derived geraniol allows for a largely bio-derived starch derivative that can undergo facile reaction with elemental sulfur to generate sustainable composite materials.

Sulfur cements have drawn significant attention as binders because sulfur is a byproduct of fossil fuel refining. Sulfur cements that can be formed by the vulcanization of elemental sulfur and plant-derived olefins such as terpenoids are particularly promising from a sustainability standpoint. A range of terpenoid–sulfur cements have shown compressional and flexural properties exceeding those of some commercial structural mineral cements. Pozzolans such as fly ash (FA), silica fume (SF), and ground granulated blast furnace slag (GGBFS) and abundant clay resources such as metakaolin (MK) are attractive fines for addition to binders. Herein, we report 10 composites prepared by a combination of sulfur, terpenoids (geraniol or citronellol), and these pozzolans. This study reveals the extent to which the addition of the pozzolan fines to the sulfur–terpenoid cements influences their mechanical properties and chemical resistance. The sulfur–terpenoid composites CitS and GerS were prepared by the reaction of 90 wt% sulfur and 10 wt% citronellol or geraniol oil, respectively. The density of the composites fell within the range of 1800–1900 kg/m3 and after 24 h submersion in water at room temperature, none of the materials absorbed more than 0.7 wt% water. The compressional strength of the as-prepared materials ranged from 9.1–23.2 MPa, and the percentage of compressional strength retained after acid challenge (submersion in 0.1 M H2SO4 for 24 h) ranged from 80–100%. Incorporating pozzolan fines into the already strong CitS (18.8 MPa) had negligible effects on its compressional strength within the statistical error of the measurement. CitS-SF and CitS-MK had slightly higher compressive strengths of 20.4 MPa and 23.2 MPa, respectively. CitS-GGBFS and CitS-FA resulted in slightly lower compressive strengths of 17.0 MPa and 15.8 MPa, respectively. In contrast, the compressional strength of initially softer GerS (11.7 MPa) benefited greatly after incorporating hard mineral fines. All GerS derivatives had higher compressive strengths than GerS, with GerS-MK having the highest compressive strength of 19.8 MPa. The compressional strengths of several of the composites compare favorably to those required by traditional mineral cements for residential building foundations (17 MPa), whereas such mineral products disintegrate upon similar acid challenge.

Herein we report a route to sulfur–starch composites by the modification of corn starch with octenyl succinic anhydride (OSA, degree of substitution = 2.6%) and its subsequent reaction with elemental sulfur through an inverse vulcanization process to generate OSSx (where x = wt% sulfur, either 90 or 95). This work represents an expansion into a previously untapped biomass source for the preparation of recyclable thermoplastic materials by this process. Composites OSSx are comprized of 83–89% by mass of extractable sulfur, and have reasonable thermal stability (Td = 214–216 °C) and Tm (DSC) of 118 °C. The starch modification strategy employed herein allowed for lower degree of substitution of the starch than was feasible for other bioploymers, leading to materials with high strength despite relatively low crosslink density relative to that in previous biopolymer–sulfur composites. The low crosslink density resulted in relatively long polysulfur catenates, thus producing materials with impressive flexural strengths (5.3–5.4 MPa) and highlighting the potential for biomass–sulfur materials to exhibit a range of mechanical properties depending on the biopolymer scaffold and modification strategy.

The extent to which lignocellulose biomass particle size influences the properties of biomass–sulfur composites prepared from these particles was evaluated. For this purpose several materials were prepared by the reaction of sulfur with peanut shell particles that had been fractionated into narrow size ranges using ASTM certified sieves. Eight particle size fractions with an upper cutoff range of 710 microns were thus used to prepare a series of eight composites PSS-1 to PSS-8. The use of biomass particles having defined size ranges allowed for a 36-fold faster reaction rate relative to the analogous reactions employing unfractionated biomass, while the resultant composites still maintained excellent strength characteristics. Composites prepared with smaller biomass particles exhibited the most uniform dispersion, yet similar ultimate strength characteristics were observed for most of the composites irrespective of the biomass particle size. The strength characteristics of these materials could be rationalized by the interplay of the dispersion of filler in the network versus the unfavorable interactions between the hydrophilic biomass filler and hydrophobic sulfur network. This work highlights the importance of quantifying filler effect for microscopically non-homogeneous composite materials and provides insight on simple strategies for drastically impacting the time and energy expenditures for biomass composite synthesis and resultant properties.

This paper is review with 119 references. Approaches to supplant currently used plastics with materials made from more sustainably-sourced monomers is one of the great contemporary challenges in sustainable chemistry. Fatty acids are attractive candidates as polymer precursors because they can be affordably produced on all inhabited continents, and they are also abundant as underutilized by-products of other industries. In surveying the array of synthetic approaches to convert fatty acids into polymers, those routes that produce organosulfur polymers stand out as being especially attractive from a sustainability standpoint. The first well-explored synthetic approach to fatty acid-derived organosulfur polymers employs the thiol-ene click reaction or the closely-related thiol-yne variation. This approach is high-yielding under mild conditions with up to 100% atom economy and high functional group tolerance. More recently, inverse vulcanization has been employed to access high sulfur-content polymers by the reaction of fatty acid-derived olefins with elemental sulfur. This approach is attractive not only because it is theoretically 100% atom economical but also because elemental sulfur is itself an underutilized by-product of fossil fuel refining. The thiol-ene, inverse vulcanization, and mechanistically-related thiol-yne and classic vulcanization are therefore discussed as promising routes to access polymers and composites from fatty acid-derived precursors.

Interest in starch-based films has increased precipitously in response to a growing demand for more sustainable and environmentally sourced food packaging materials. Starch is an optimal candidate for these applications given its ability to form thermoplastic materials and films with affordable and often sustainably sourced plasticizers like those produced as waste byproducts by biodiesel and agricultural industries. Starch is also globally ubiquitous, affordable, and environmentally benign. Although the process of producing starch films is relatively straightforward, numerous factors, including starch source, extraction method, film formulation, processing methods, and curing procedures, drastically impact the ultimate material properties. The significant strides made from 2015 to early 2020 toward elucidating how these variables can be leveraged to improve mechanical and barrier properties as well as the implementation of various additives or procedural modifications are cataloged in this review. Advances toward the development of functional films containing antioxidant, antibacterial, or spoilage indicating components to prevent or signal the degradation of food products are also discussed.

Fossil fuel refining produces over 70 Mt of excess sulfur annually from for which there is currently no practical use. Recently, methods to convert waste sulfur to recyclable and biodegradable polymers have been delineated. In this report, a commercial bisphenol A (BPA) derivative, 2,2&prime, 5,5&prime, tetrabromo(bisphenol A) (Br4BPA), is explored as a potential organic monomer for copolymerization with elemental sulfur by RASP (radical-induced aryl halide-sulfur polymerization). Resultant copolymers, BASx (x = wt% sulfur in the monomer feed, screened for values of 80, 85, 90, and 95) were characterized by thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. Analysis of early stage reaction products and depolymerization products support proposed S&ndash, Caryl bond formation and regiochemistry, while fractionation of BASx reveals a sulfur rank of 3&ndash, 6. Copolymers having less organic cross-linker (5 or 10 wt%) in the monomer feed were thermoplastics, whereas thermosets were accomplished when 15 or 20 wt% of organic cross-linker was used. The flexural strengths of the thermally processable samples (&gt, 3.4 MPa and &gt, 4.7 for BAS95 and BAS90, respectively) were quite high compared to those of familiar building materials such as portland cement (3.7 MPa). Furthermore, copolymer BAS90 proved quite resistant to degradation by oxidizing organic acid, maintaining its full flexural strength after soaking in 0.5 M H2SO4 for 24 h. BAS90 could also be remelted and recast into shapes over many cycles without any loss of mechanical strength. This study on the effect of monomer ratio on properties of materials prepared by RASP of small molecular aryl halides confirms that highly cross-linked materials with varying physical and mechanical properties can be accessed by this protocol. This work is also an important step towards potentially upcycling BPA from plastic degradation and sulfur from fossil fuel refining.

Herein we report a green route to thermoplastics from cellulose, the terpenoid geraniol, and fossil fuel byproduct sulfur with an overall atom economy of 90% over three steps. The only stoichiometr...

A review with 132 references. Societal and regulatory pressures are pushing industry towards more sustainable energy sources, such as solar and wind power, while the growing popularity of portable cordless electronic devices continues. These trends necessitate the ability to store large amounts of power efficiently in rechargeable batteries that should also be affordable and long-lasting. Lithium-sulfur (Li-S) batteries have recently gained renewed interest for their potential low cost and high energy density, potentially over 2600 Wh kg−1. The current review will detail the most recent advances in early 2020. The focus will be on reports published since the last review on Li-S batteries. This review is meant to be helpful for beginners as well as useful for those doing research in the field, and will delineate some of the cutting-edge adaptations of many avenues that are being pursued to improve the performance and safety of Li-S batteries.

A composite was prepared from biomass and waste sulfur from fossil fuel refining. The composite has higher compressive and flexural strength than portland cement. Avoiding expensive biomass separation and achieving metrics exceeding those of commercial products is a notable step towards a green economy.

Renewably-sourced, recyclable materials that can replace or extend the service life of existing technologies are essential to accomplish humanity's quest for sustainable living. In this contribution, remeltable composites were prepared in a highly atom-economical reaction between plant-derived terpenoid alcohols (10 wt% citronellol, geraniol, or farnesol) and elemental sulfur (90 wt%). Investigation into the microstructures led to elucidation of a mechanism for terpenoid polyene cyclization initiated by sulfur-centered radicals. The formation of these cyclic structures contributes significantly to understanding the mechanical properties of the materials and the extent to which linear versus crosslinked network materials are formed. The terpenoid–sulfur composites can be thermally processed at low temperatures of 120 °C without loss of mechanical properties, and the farnesol–sulfur composite so processed exhibits compressive strength 70% higher than required of concrete for residential building. The terpenoid–sulfur composites also resist degradation by oxidizing acid under conditions that disintegrate many commercial composites and cements. In addition to being stronger and more chemically resistant than some commercial products, the terpenoid–sulfur composites can be used to improve the acid resistance of mineral-based Portland cement as well. These terpenoid–sulfur composites thus hold promise as elements of sustainable construction on their own or as additives to extend the operational life of existing technologies, while the cyclization behaviour could be an important contributor in other polymerizations of terpenoids.

A simple approach to a high sulfur-content material from biomass-derived guaiacol and waste sulfur is introduced. This direct reaction of elemental sulfur with an anisole derivative lacking olefins or halogen leaving groups expands the monomer scope beyond existing routes to high sulfur-content materials.

Lignocellulosic biomass holds a tremendous opportunity for transformation into carbon-negative materials, yet the expense of separating biomass into its cellulose and lignin components remains a primary economic barrier to biomass utilization. Herein is reported a simple procedure to convert several biomass-derived materials into robust, recyclable composites through their reaction with elemental sulfur by inverse vulcanization, a process in which olefins are crosslinked by sulfur chains. In an effort to understand the chemistry and the parameters leading to the strength of these composites, sulfur was reacted with four biomass-derivative comonomers: (1) unmodified peanut shell powder, (2) allyl peanut shells, (3) ‘mock’ allyl peanut shells (a mixture containing independently-prepared allyl cellulose and allyl lignin), or (4) peanut shells that have been defatted by extraction of peanut oil. The reactions of these materials with sulfur produce the biomass–sulfur composites PSx, APSx, mAPSx and dfPSx, respectively, where x = wt% sulfur in the monomer feed. The influence of biomass : sulfur ratio was assessed for PSx and APSx. Thermal/mechanical properties of composites were evaluated for comparison to commercial materials. Remarkably, unmodified peanut shell flour can simply be heated with elemental sulfur to produce composites having flexural/compressive strengths exceeding those of Portland cement, an effect traced to the presence of olefin-bearing peanut oil in the peanut shells. When allylated peanut shells are used in this process, a composite having twice the compressive strength of Portland cement is attained.

This report introduces a new approach to high sulfur-content materials. This route, RASP (radical-induced aryl halide/sulfur polymerization), expands the substrate scope beyond olefins required for the traditional inverse vulcanization route to such materials. RASP allows direct reaction of two unmodified industrial waste products to give lignin–sulfur composites.

High sulfur-content materials (HSMs) have been investigated for a plethora of applications owing to a combination of desirable properties and the low cost of waste sulfur as a starting monomer. Whereas extended sulfur catenates are unstable with respect to orthorhombic sulfur (S8 rings) at STP, oligomeric/polymeric sulfur chains can be stabilized when they are confined in a supporting matrix. The vast majority of reported HSMs have been made by inverse vulcanization of sulfur and olefins. In the current case, a radical aryl halide–sulfur polymerization (RASP) route was employed to form an HSM (XS81) by copolymerizing elemental sulfur with the xylenol derivative 2,4-dimethyl-3,5-dichlorophenol (DDP). XS81 is a composite of which 81 wt% is sulfur, wherein the sulfur is distributed between cross-linking chains averaging four sulfur atoms in length and trapped sulfur that is not covalently attached to the network. XS81 (flexural strength = 2.0 MPa) exhibits mechanical properties on par with other HSMs prepared by inverse vulcanization. Notably, XS81 retains mechanical integrity over many heat-recast cycles, making it a candidate for facile recyclability. This is the first report of an HSM comprising stabilized polymeric sulfur that has been successfully prepared from a small molecular comonomer by RASP. Preparation of XS81 thus demonstrates a new route to access HSMs using small molecular aryl halides, a notable expansion beyond the olefins required for the well-studied inverse vulcanization route to HSMs from small molecular comonomers.

Two tetraarylphosphonium polyelectrolytes having perfluorocyclobutyl units in their backbones have been prepared in which the counteranion is either bromide (PFP·Br) or bis(trifluoromethyl)sulfonimide (PFP·NTf₂). These polymers exhibit high thermal stability as assessed by thermogravimetric analysis, with a decomposition temperature of 460 °C for PFP·NTf₂. Even after heating at 300 °C for 72 h, PFP·NTf₂ shows no signs of degradation detectable by nuclear magnetic resonance spectrometry. As is typical for many tetraarylphosphonium species, films of these polymers can be quite resistant to degradation by alkaline solution. Upon alkaline challenge by exposure to 6 M NaOH at 65 °C for 24 h, for example, only 16% of the phosphonium centers in PFP·NTf₂ are degraded, making PFP·NTf₂ one of the most alkaline‐stable phosphonium polymers to date. Despite having ionic backbones, PFP·Br and PFP·NTf₂ exhibit very low critical surface energies of 26.1 and 22.9 mJ m⁻¹, respectively. These values are on par with the values for poly(vinylene fluoride) and dimethylsiloxane. Such low surface energy polycations capable of high alkaline stability may find application as components of alkaline fuel cell membranes. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2267–2272

A series of 10 polythiophene derivatives is reported, in which each polymer has a different percentage of carboxylic acid‐bearing repeat units. The properties of these polymers are explored under acidic conditions, where the carboxylic acid moieties remain neutral, and under basic conditions, where the carboxylic acid units become anionic carboxylates. The properties that are examined for both solutions and films include UV–vis absorption spectroscopy, photoluminescence spectroscopy, and red‐edge optical band gaps. All the properties studied are strongly dependent both on protonation state and percentage of carboxylic acid/carboxylate side chains along the polymer backbone. The anionic form of each polythiophene derivative was also used in layer‐by‐layer film deposition with a cationic phosphonium polyelectrolyte. The film growth process was studied by spectroscopic techniques to assess the influence of side‐chain composition on the film growth and optical properties. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019

Terpenoids are potentially sustainable replacements for petrochemical olefins. Sulfur is a waste product produced in large quantities from fossil fuel refining. Several composites with attractive properties have recently been made from terpenoids and sulfur. This report details the extent to which the ratio of sulfur to terpenoid and the terpenoid olefin content influences the thermal and mechanical properties of such terpenoid-sulfur composites. The terpenoids selected were diunsaturated geraniol and triunsaturated farnesol that, upon their inverse vulcanization with elemental sulfur, yield composites GerSx and FarSx, respectively (x = wt % sulfur). The wt % sulfur in the monomer feed was varied from 30–95 for this study, providing twelve materials. Mechanical analysis of these materials was undertaken by compressive and tensile strength techniques. Differential scanning calorimetric analysis revealed both polymeric and orthorhombic sulfur present in the materials with glass transition temperatures (Tg) of −37 °C to −13 °C and melt temperatures (Tm) of 119 to 104 °C. The crystallinity of composites decreases as the weight fraction of sulfur decreases and composites having the highest olefin content exhibit no detectable crystalline microstructures. The compressive strength of the materials showed increasing strength for higher olefin-content materials for both GerSx (with compressive strength of up to 32 MPa) and FarSx (with compressive strength of up to 43 MPa). The improved strength with increasing olefin content levels off at around 80–85% of terpenoid, after which point both tensile and compressive strength diminish.

Herein we report high strength composites prepared by reaction of sulfur, plant oils (either canola oil or sunflower oil) and brown grease. Brown grease is a high-volume, low value animal fat rendering coproduct that represents one of the most underutilized products of agricultural animal processing. Chemically, brown grease is primarily comprised of triglycerides and fatty acids. The inverse vulcanization of the unsaturated units in triglycerides/fatty acids upon their reaction with sulfur yields CanBG

Anion exchange membranes (AEMs) are becoming increasingly common in electrochemical energy conversion and storage systems around the world (EES). Proton-/cation-exchange membranes (which conduct positive charged ions such as H+ or Na+) have historically been used in many devices such as fuel cells, electrolysers, and redox flow batteries. High capital costs and the use of noble metal catalysts are two of the current major disadvantages of polymer electrolyte membrane (PEM)-based systems. AEMs may be able to overcome the limitations of conventional PEMs. As a result, polymers with anion exchange properties have recently attracted a lot of attention due to their significant benefits in terms of transitioning from a highly acidic to an alkaline environment, high kinetics for oxygen reduction and fuel oxidation in an alkaline environment, and lower cost due to the use of non-precious metals. The aim of this research was to learn more about the development of a new AEM based on poly tetraarylphosphonium ionomers (pTAP), which has high ionic conductivity, alkaline stability, thermal stability, and good mechanical properties, making it a more cost-effective and stable alternative to conventional and commercial AEMs. A simple solution casting method was used to build novel anion exchange composite membranes with controlled thicknesses using the synthesized pTAP with polysulfone (PS). To ensure their suitability for use as an electrolyte in alkaline electrochemical systems, the composite membranes were characterized using FTIR, XRD, water uptake, ionic conductivity, and alkaline stability. At 40 °C, the PS/pTAP 40/60 percent membrane had a maximum ionic conductivity of 4.2 mS/cm. The thermal and mechanical stability of the composite membranes were also examined, with no substantial weight loss observed up to 150 °C. These findings pave the way for these membranes to be used in a wide variety of electrochemical applications.

Lignin is the second-most abundant biopolymer in nature and remains a severely underutilized waste product of agriculture and paper production. Sulfur is the most underutilized byproduct of petroleum and natural gas processing industries. On their own, both sulfur and lignin exhibit very poor mechanical properties. In the current work, a strategy for preparing more durable composites of sulfur and lignin, LSx, is described. Composites LSx were prepared by reaction of allyl lignin with elemental sulfur, whereby some of the sulfur forms polysulfide crosslinks with lignin to yield a three-dimensional network. Even relatively small quantities (

The properties of phosphonium polyelectrolytes (PELs) were evaluated in an effort to assess the influence of both side chain and main chain composition. The influence of side chain was examined by comparing properties of a series of PELs having hydrophobic octyloxy side chains to those of structural analogues lacking the side chains. The influence exerted by backbone flexibility/length of spacer between charges was revealed by comparing properties of two series of polymers with a variable number of methylene units between phosphonium charge‐bearing sites. Side chain composition and spacing between phosphonium units lead to noteworthy influence on thermal stability, glass transition, and crystallinity. The molecular structure of PELs also correlates with trends in film morphology and critical surface energy of PEL dip‐cast films. Sensitivity of morphology to humidity or water in the casting solvent was observed. Supramolecular assembly of films via layer‐by‐layer deposition of PELs alternating with anionic polythiophene derivative layers was also undertaken. The linearity of film growth, amount of material deposited in each bilayer, polycation:polyanion ratio, and film roughness all show noteworthy trends that depend on both the presence/absence of side chains and on spacing between ionic centers. The relationship between side chain and spacer on bactericidal activity against Staphylococcus aureus and Escherichia coli was assessed. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 24–34

Network polymers of sulfur and poly(4-allyloxystyrene), PAOSx (x = percent by mass sulfur, where x is varied from 10–99), were prepared by reaction between poly(4-allyloxystyrene) with thermal homolytic ring-opened S8 in a thiol-ene-type reaction. The extent to which sulfur content and crosslinking influence thermal/mechanical properties was assessed. Network materials having sulfur content below 50% were found to be thermosets, whereas those having >90% sulfur content are thermally healable and remeltable. DSC analysis revealed that low sulfur-content materials exhibited neither a Tg nor a Tm from −50 to 140 °C, whereas higher sulfur content materials featured Tg or Tm values that scale with the amount of sulfur. DSC data also revealed that sulfur-rich domains of PAOS90 are comprised of sulfur-crosslinked organic polymers and amorphous sulfur, whereas, sulfur-rich domains in PAOS99 are comprised largely of α-sulfur (orthorhombic sulfur). These conclusions are further corroborated by CS2-extraction and analysis of extractable/non-extractable fractions. Calculations based on TGA, FT-IR, H2S trapping experiments, CS2-extractable mass, and elemental combustion microanalysis data were used to assess the relative percentages of free and crosslinked sulfur and average number of S atoms per crosslink. Dynamic mechanical analyses indicate high storage moduli for PAOS90 and PAOS99 (on the order of 3 and 6 GPa at −37 °C, respectively), with a mechanical Tg between −17 °C and 5 °C. A PAOS99 sample retains its full initial mechanical strength after at least 12 pulverization-thermal healing cycles, making it a candidate for facile repair and recyclability.

A series of eight tetraarylphosphonium polyelectrolytes (TPELs) has been successfully synthesized by polymerization of diphenylphosphine and bis(aryl triflate)s. The bis(aryl triflate)s are readily prepared from bisphenols, some of which are commodity feedstocks such as bisphenol A. The polymerization via palladium catalyzed P–C bond formation produces degrees of polymerization up to 65. All polymeric triflates have reasonable thermal stability in the range of 350–450 °C. The stability of the TPELs to alkaline solution is strongly depending on the spacer between adjacent phosphonium sites. Polymers with electron-releasing and bulky substituent para- to the phosphonium site have improved stability while those with electron-withdrawing substituent para- to phosphonium site have decreased alkaline stability due to decomposition via a nucleophilic aromatic substitution pathway. These findings have important ramifications for the design of ionomers for alkaline exchange membrane fuel cells and related electrochemical energy conversion devices. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017

Lignin is the most abundant aromatic biopolymer and is the sustainable feedstock most likely to supplant petroleum-derived aromatics and downstream products. Rich in functional groups, lignin is largely peerless in its potential for chemical modification towards attaining target properties. Lignin’s crosslinked network structure can be exploited in composites to endow them with remarkable strength, as exemplified in timber and other structural elements of plants. Yet lignin may also be depolymerized, modified, or blended with other polymers. This review focuses on substituting petrochemicals with lignin derivatives, with a particular focus on applications more significant in terms of potential commercialization volume, including polyurethane, phenol-formaldehyde resins, lignin-based carbon fibers, and emergent melt-processable waste-derived materials. This review will illuminate advances from the last eight years in the prospective utilization of such lignin-derived products in a range of application such as adhesives, plastics, automotive components, construction materials, and composites. Particular technical issues associated with lignin processing and emerging alternatives for future developments are discussed.

The preparation and photophysical properties of two heavier main group element analogues of boron-dipyrromethene (BODIPY) chromophores are described. Specifically, we have prepared dipyrrin complexes of dichlorogallate (GADIPY) or phenylphosphenium (PHODIPY) units. Whereas cationic PHODIPY is labile, decomposing to a phosphine over time, GADIPY is readily prepared in good yield as a crystalline solid having moderate air- and water-stability. Crystallographically characterized GADIPY displays intense green photoluminescence (λem = 505 nm, Φem = 0.91 in toluene). These inaugural heavier main group element analogues of BODIPY offer a glimpse into the potential for elaboration to a panoply of chromophores with diverse photophysical properties.

A host of emerging cementitious products derived from waste materials or sustainable precursors have drawn increasing interest in response to economic, social and regulatory pressures. Among the more well-studied and abundant of such cement products are sulfur cements and pozzolans like fly ash, silica fume, ground granulated blast furnace slag, and metakaolin. For the current study, oleic acid was combined with these compounds to make a series of pastes. Oleic acid is an attractive additive because it is a primary constituent of low value, high-volume by-products of biodiesel production and animal product rendering. The current work is thus a comparative study of pastes prepared by heating sulfur and oleic acid with either ordinary Portland cement or one of the pozzolan-extended cements. The mechanical properties of the cured sulfur-oleic acid pastes were assessed by dynamic mechanical analysis to provide stress-strain curves both before and after acid challenge. All of the blocks prepared from the pastes retain significantly more mechanical strength (up to 100%) after exposure to strong oxidizing acid solutions than does ordinary Portland cement. Surface damage to these sulfur cement blocks can be healed to varying extents by thermal annealing, as assessed by optical microscopy.

A debromination–chain polymerization–debromination (DPD) route to poly( p -phenylene vinylene) (PPV) derivatives is reported. In contrast to existing chain polymerization routes for the preparation of PPV derivatives, this route takes advantage of a symmetric monomer to preclude head-to-head or tail-to-tail coupling that ultimately leads to alkyne or alkyl defects in the polymer chain. Mechanistic studies were performed and revealed that the DPD route can be carried out with the desirable intermediacy of a soluble, isolable polymer precursor. Unsubstituted PPV, poly( p -(2,5-dihexyloxyphenylene)vinylene) and a PPV derivative with a sterically encumbering side chain were all readily prepared by the new DPD route.

Three phosphonium polyelectrolytes have been prepared wherein the flexibility of the spacer between charge-bearing phosphonium units was varied from 1,2-ethyl to 1,4-phenyl to 1,1′-ferrocenyl. The influence of inter-phosphonium spacer flexibility on the ability of the polyelectrolyte to form ordered films via layer-by-layer supramolecular assembly with anionic polythiophene and anionic poly(p-phenylenevinylene) derivatives was also assessed through a combination of UV−visible spectroscopy and atomic force microscopy. The more flexible ionic polymers were found to be capable of forming thicker films and to maintain growth linearity up to at least 800 bilayers in some cases. © 2015 Society of Chemical Industry

A P-C bond-forming reaction has been applied to the convenient preparation of tetraarylphosphonium polyelectrolytes (TPELs) from aryl dihalides and diphenylphosphine. A TPEL having a thermal decomposition temperature of 460 °C that is also stable to heating at 65 °C in 6 M NaOH(aq) for at least 24 h has been prepared by this method.

Advances in catalyst and electrolyte materials for hydrogen fuel cells are driving performance gains and cost reductions that are helping to bring hydrogen fuel-cell technology to market. Research on new materials is always a combination of synthesis and characterization, where characterization must eventually include incorporation of materials into an operating fuel cell. It is at this stage that research on leading-edge new materials often stalls, because conventional fuel-cell tests require relatively large amounts of material, e.g. several grams of a new catalyst and tens to hundreds of grams of ionomer, corresponding to many tens of square centimeters of membrane area, are required to run a comprehensive set of tests as is necessary to assure reproducibility and examine behavioral trends. These amounts of material are often not available in early-stage synthetic work, which means that characterization uses other approximate approaches, e.g. rotating disk electrode (RDE) voltammetry to study catalyst activity, with true fuel-cell testing often being delayed until syntheses may be scaled up. This situation is unfortunate because approximate tests often do not adequately screen materials. It would be desirable to run preliminary fuel-cell tests at an early stage to gain a better idea of materials properties before making decisions regarding which materials to scale up. This contribution will present our recent work building and using a miniature PEM fuel-cell test fixture that uses only very small amounts of material to conduct a true solvent-free fuel-cell test. The cell is fabricated from a conventional compression-style fitting and uses 5/8 inch diameter graphite or metal rods for gas delivery and for making electric contact with the electrodes. Membrane-electrode assemblies (MEAs) are made from 3/4-inch diameter PEM disks, typically cut from Nafion ionomer membrane, onto which carbon-cloth-based electrodes are bonded by hot pressing. Electrode diameters range from 1/8 to 3/8 inch. The presentation will include recent published work demonstrating reproducibility and select MEA characterization data, including in-situ voltammetry to assess electrochemically active surface area (ECSA) of catalysts and polarization curve measurements that are easily obtained using conventional linear sweep voltammetry with a conventional laboratory potentiostat. This situation is in contrast to conventional fuel-cell testing that requires specialized instrumentation with passage of very large currents, e.g. tens of amperes. Very recent work using the cells in hydrogen pump configuration will also be presented. This configuration is particularly useful for measuring resistances to proton transport through ionomers in the direction through the membrane plane, in contrast to most measurements which focus on in-plane resistance, because it is easier to measure. Very recent work on the synthesis and properties of new tetra-aryl-phosphonium (TAP) alkaline ionomers which are expected have high alkaline stability and to be good hydroxide-ion conductors, and on the effect of single graphene layers embedded in Nafion membranes on proton and other ion conduction through the Nafion membranes, will also be presented.

Two π-conjugated polymers featuring main-chain m-phenylene linkers as well as iodo substituents were initially prepared. The presence of the iodo functionality allowed for the preparation of six additional polymers from the initial two iodo-substituted polymers via facile post-polymerization modification using Sonogashira-type coupling chemistry. The post-polymerization modification led to crosslinking, to the incorporation of a pyridyl-bearing functionality for potential use as a ligand for transition metals or to the introduction of a ferrocenyl substituent as a possible redox-active unit. The m-phenylene units were incorporated into the polymer main-chain structure in order to periodically disrupt conjugation, thereby allowing for more uniformity in the effective conjugation length and thus in absorption and emission profiles. The thermal stability and photophysical properties of all eight polymers, as well as the stimuli-responsiveness of relevant materials to nitroaromatics and metal ions, are reported. © 2015 Society of Chemical Industry

Three ionic polymers featuring main chain tetraarylphosphonium units have been prepared by an underexplored polymerisation route that employs Ni-catalysed P–C bond formation. The three polymers include chromophores comprised of 2,5-dihexyloxy-p-phenylene, 9,9-dioctyl-2,7-fluorenylene, or 2,7-fluorenone segments between phosphonium sites so that the composite ionic polymers exhibit absorption and photoluminescence in the UV-visible region of the spectrum. The photophysical properties of the materials were evaluated to assess the applicability of the polymers for optoelectronic applications. The wettability and critical surface energies of dip-coated neat polymer films were also determined from contact angle measurements.

A series of seven cationic polymers have been prepared wherein the length of spacer between charge-bearing sites has been varied. Thermal stability of the polymers was characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The length of spacer has obvious effect on thermal stability as well as on the extent of crystallinity as revealed by X-ray powder diffraction. The cationic polymers were tested for their ability to form supramolecularly-assembled films with an anionic polythiophene derivative by a layer-by-layer (LbL) deposition process. Film growth was followed by spectroscopic techniques and surface morphologies were examined by atomic force microscopy (AFM). Interesting dependence of film morphology and composition was observed depending on whether an even- or odd-number of methylene spacers was present between charge-bearing sites.