Sulfur Polymers Meet Poly(ionic liquid)s: Bringing New Properties to Both Polymer Families.

Sulfur-containing polymers and poly(ionic liquid)s are emerging macromolecules with unique properties and applications. This article shows the first integration of these two polymer families, leading to materials with a unique combination of properties. The synthetic strategy toward sulfur-containing poly(ionic liquid)s involves first the copolymerization of elemental sulfur with 4-vinylbenzyl chloride and subsequent quaternization of the alkyl chloride group using N-methyl imidazole. The synthetic pathway is completed by the anion exchange reaction of the poly(sulfur-co-4-vinylbenzyl imidazolium chloride) by a sulphonamide anion. The obtained polymers are fully characterized by NMR, FTIR, SEC, DSC, and TGA. The sulfur poly(ionic liquid)s combine some properties related to its poly(ionic liquid) nature, such as anion-dependent solubility (water vs organic solvents) and high ionic conductivity as well as properties related to its sulfur content, such as redox activity.

Injection Molding of Low-Density Polyethylene (LDPE) as a Model Polymer: Effect of Molding Parameters on the Microstructure and Crystallinity.

Due to its relatively simple structure, low-density polyethylene (LDPE) can be considered as a model polymer for the study of its properties. Herein, the effect of processing variables on the microstructure and crystallinity of injection-molded LDPE specimens was quantitatively determined. The polymer was injected at different temperature conditions in the barrel and the mold. The specimens were characterized by scanning electron microscopy and X-ray diffraction. With the data obtained, an analysis of variance (ANOVA) was carried out, and response surface graphs (SRP) were constructed to quantify and to observe the behavior of the processing variables, respectively. Different models were obtained to predict the effect of the experimental factors on the response variables. The results showed that the interaction of the two temperatures has the greatest effect on the size of the spherulite, while the temperature of the mold affects the crystallinity. The SRP showed different behaviors: for the spherulite, the size increases with the mold temperature, while for the crystallinity, higher values were observed at an intermediate mold temperature and a low melt temperature. The results presented herein are valuable for setting empirical relations between the microstructure, crystallinity, and the molding conditions of LDPE.

Room-Temperature Self-Standing Cellulose-Based Hydrogel Electrolytes for Electrochemical Devices.

The trend of research towards more sustainable materials is pushing the application of biopolymers in a variety of unexplored fields. In this regard, hydrogels are attracting significant attention as electrolytes for flexible electrochemical devices thanks to their combination of ionic conductivity and mechanical properties. In this context, we present the use of cellulose-based hydrogels as aqueous electrolytes for electrochemical devices. These materials were obtained by crosslinking of hydroxyethyl cellulose (HEC) with divinyl sulfone (DVS) in the presence of carboxymethyl cellulose (CMC), creating a semi-IPN structure. The reaction was confirmed by NMR and FTIR. The small-amplitude oscillatory shear (SAOS) technique revealed that the rheological properties could be conveniently varied by simply changing the gel composition. Additionally, the hydrogels presented high ionic conductivity in the range of mS cm-1. The ease of synthesis and processing of the hydrogels allowed the assembly of an all-in-one electrochromic device (ECD) with high transmittance variation, improved switching time and good color efficiency. On the other hand, the swelling ability of the hydrogels permits the tuning of the electrolyte to improve the performance of a printed Zinc/MnO2 primary battery. The results prove the potential of cellulose-based hydrogels as electrolytes for more sustainable electrochemical devices.

Characterisation of HRas local signal transduction networks using engineered site-specific exchange factors.

Ras GTPases convey signals from different types of membranes. At these locations, different Ras isoforms, interactors and regulators generate different biochemical signals and biological outputs. The study of Ras localisation-specific signal transduction networks has been hampered by our inability to specifically activate each of these Ras pools. Here, we describe a new set of site-specific tethered exchange factors, engineered by fusing the RasGRF1 CDC25 domain to sub-localisation-defining cues, whereby Ras pools at specific locations can be precisely activated. We show that the CDC25 domain has a high specificity for activating HRas but not NRas and KRas. This unexpected finding means that our constructs mainly activate endogenous HRas. Hence, their use enabled us to identify distinct pathways regulated by HRas in endomembranes and plasma membrane microdomains. Importantly, these new constructs unveil different patterns of HRas activity specified by their subcellular localisation. Overall, the targeted GEFs described herein constitute ideal tools for dissecting spatially-defined HRas biochemical and biological functions.

Poly(anthraquinonyl sulfides): High Capacity Redox Polymers for Energy Storage.

Redox polymers with high energy storage capacity are searched in order to diminish the weight to the actual batteries. Poly(anthraquinonyl sulfide) PAQS is a popular redox polymer which has shown a high performance cathode for lithium, sodium and magnesium batteries. Although PAQS cathodes show high cycling stability it has a relatively low theoretical specific capacity of 225 mAh/g. In this paper we show the synthesis and characterization of new poly(anthraquinonyl sulfides) PAQxS in an attempt to improve the specific capacity of PAQS. Thus, a series of PAQxS polymers with different polysulfide segment lengths (x between 2 and 9 sulfur atoms) have been synthesized in high yields by reacting in situ formed sodium polysulfides with 1,5-dicholoroanthraquinone. The poly(anthraquinonyl sulfides) powders were characterized by ATR-FTIR, solid state 13C NMR for the organic part and Raman spectroscopy for the chalcogenide part. This characterization confirmed the chemical structure of the PAQxS based on an anthraquinone moiety bind together by polysulfide segments. The electrochemical characterization showed a dual reversible redox mechanism associated with both the anthraquinone and polysulfide electrochemistry. Finally, lithium coin cell battery test of the PAQxS redox polymers as cathodes indicated that the capacity of poly(anthraquinonyl sulfides) showed very high experimental initial capacity values above 600 mAh/g, less capacity loss than sulfur cathodes, and higher steady state capacity than PAQS.

Inverse Vulcanization of Sulfur using Natural Dienes as Sustainable Materials for Lithium-Sulfur Batteries.

Lithium-sulfur batteries are among the most promising next-generation battery systems due to the high capacity of sulfur as cathodic material. Beyond its interesting intrinsic properties, sulfur possesses a very low conductivity and complex electrochemistry, which involves the high solubility of the lithium sulfides in the electrolyte. These two characteristics are at the core of a series of limitations of its performance as active cathode material, which leads to batteries with low cyclability. Recently, inverse vulcanized sulfur was shown to retain capacity far better than elemental sulfur, leading to batteries with excellent cyclability. Nevertheless, the diene co-monomers used so far in the inverse vulcanization process are man-made molecules. Herein, a tentative work on exploring inverse vulcanization using two naturally available monomers, diallyl sulfide and myrcene, is presented. The inverse vulcanization of sulfur was successfully completed, and the resulting polymers were characterized by FTIR, NMR spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. Afterwards these polymers were tested as cathodic materials in lithium-sulfur cells. The sulfur-natural dienes materials exhibited high capacity at different C rates and high lifetime over 200 cycles with very high capacity retention at a moderate C rate of C/5. Altogether, these materials made from inexpensive and abundant chemicals are an excellent option as sustainable materials for electrochemical energy storage.