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A non-isocyanate synthetic route was used to generate 20 different ionic liquids containing either a carbamate or thiocarbamate functional group. 

ABSTRACT Development of genome-editing tools in diverse microbial species is an important step both in understanding the roles of those microbes in different environments, and in engineering microbes for a variety of applications. Freshwater-specific clades of Actinobacteria are ubiquitous and abundant in surface freshwaters worldwide. Here, we show thatRhodoluna lacicolaandAurantimicrobium photophilum, which represent widespread clades of freshwater Actinobacteria, are naturally transformable. We also show that gene inactivation via double homologous recombination and replacement of the target gene with antibiotic selection markers can be used in both strains, making them convenient and broadly accessible model organisms for freshwater systems. We further show that in both strains, the predicted phytoene synthase is the only phytoene synthase, and its inactivation prevents the synthesis of all pigments. The tools developed here enable targeted modification of the genomes of some of the most abundant microbes in freshwater communities. These genome-editing tools will enable hypothesis testing about the genetics and (eco)physiology of freshwater Actinobacteria and broaden the available model systems for engineering freshwater microbial communities. IMPORTANCETo advance bioproduction or bioremediation in large, unsupervised environmental systems such as ponds, wastewater lagoons, or groundwater systems, it will be necessary to develop diverse genetically amenable microbial model organisms. Although we already genetically modify a few key species, tools for engineering more microbial taxa, with different natural phenotypes, will enable us to genetically engineer multispecies consortia or even complex communities. Developing genetic tools for modifying freshwater bacteria is particularly important, as wastewater, production ponds or raceways, and contaminated surface water are all freshwater systems where microbial communities are already deployed to do work, and the outputs could potentially be enhanced by genetic modifications. Here, we demonstrate that common tools for genome editing can be used to inactivate specific genes in two representatives of a very widespread, environmentally relevant group of Actinobacteria. These Actinobacteria are found in almost all tested surface freshwater environments, where they co-occur with primary producers, and genome-editing tools in these species are thus a step on the way to engineering microbial consortia in freshwater environments. 

Distinguishing ET and PCET processes is challenging. This paper used “protein charge ladders” to show that PCET occurs at the non-redox “structural” zinc sight of SOD1, when a Cu ion displaces Zn. 

A cellulose graft copolymer (cellulose nanoresin) was synthesized by the all-aqueous functionalization of cellouronic acid with poly (vinyl benzyl trimethyl ammonium chloride) (poly(vbTMAC)). Cellulose was oxidized using the highly reported 2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO)-mediated selective C-6 oxidation reaction. Fischer–Speier esterification of cellouronic acid was used to graft poly(vbTMAC) to the cellulosic backbone in a facile click-like mechanism. Synthesis of cellulose nanoresin was confirmed using dynamic light scattering and zeta potential measurements. Conductometric titration was used to determine the carboxylate content of cellouronic acid and the percent functionalization of the cellulose nanoresin, which was 1.69 ± 0.03 mmol/g and 61.2 ± 4%, respectively. Using a disodium fluorescein (NaFL) surrogate adsorbate, the maximum adsorption capacity of CNR was measured to be 26.8 ± 1.3 mg NaFL per gram of CNR with a Langmuir equilibrium binding constant of Ks = 10.5 ± 2 ppm−1. When examined as a thin film membrane, a breakthrough study of CNR showed that equilibrium loading was achieved in less than 30 s, and that > 90% of loading occurred in under 5 s. This data suggests that these films can be used as contact resins for anion-exchange water purification. We show in this work that these films maintain > 99% of loading performance over 40 trials of regeneration and reuse, meaning that these films are green and regenerable. Initial testing shows that CNR is effective at the removal of perfluorooctane sulfonate (PFOS) from water to below our limit of detection of 100 ppt. 

Abstract The synthesis and characterization of a series of polyurethane ionenes using a non‐isocyanate approach is disclosed. Imidazole‐capped, urethane‐containing prepolymers are prepared by first reacting carbonyl diimidazole (CDI) with several poly(propylene glycol) (PPG) diols with variable molecular weight, followed by subsequent reaction with 3‐aminopropylimidazole (API). Polymerization with 1,4‐dibromomethylbenzene followed by anion exchange resulted in the desired polyurethane ionenes bearing the [NTf₂] counteranion as a series of viscous liquids. NMR and FTIR spectroscopy are used to characterize the intermediates and final ionenes, including molecular weight determination by end‐group analysis. A single glass transition temperature (T_g), as determined by differential scanning calorimetry (DSC), is observed for each ionene (−38 to −64 °C) with theT_gdecreasing with increasing PPG molecular weight. Thermogravimetric analysis (TGA) indicated a two‐step decomposition for each ionene, with the first being degradation of the PPG segment, followed by the urethane/ionic segment. Microphase separation is observed from x‐ray scattering profiles with Bragg distances that increased with increasing PPG molecular weight. Ionic conductivity is found to be inversely dependent upon DSCT_gat lower temperatures (RT and below); however, at higher temperatures, conductivity appears to be more dependent upon the ability of ionic aggregates caused by phase separation to interact. 

Nanomaterials have been extensively used in polymer nanocomposite membranes due to the inclusion of unique features that enhance water and wastewater treatment performance. Compared to the pristine membranes, the incorporation of nanomodifiers not only improves membrane performance (water permeability, salt rejection, contaminant removal, selectivity), but also the intrinsic properties (hydrophilicity, porosity, antifouling properties, antimicrobial properties, mechanical, thermal, and chemical stability) of these membranes. This review focuses on applications of different types of nanomaterials: zero-dimensional (metal/metal oxide nanoparticles), one-dimensional (carbon nanotubes), two-dimensional (graphene and associated structures), and three-dimensional (zeolites and associated frameworks) nanomaterials combined with polymers towards novel polymeric nanocomposites for water and wastewater treatment applications. This review will show that combinations of nanomaterials and polymers impart enhanced features into the pristine membrane; however, the underlying issues associated with the modification processes and environmental impact of these membranes are less obvious. This review also highlights the utility of computational methods toward understanding the structural and functional properties of the membranes. Here, we highlight the fabrication methods, advantages, challenges, environmental impact, and future scope of these advanced polymeric nanocomposite membrane based systems for water and wastewater treatment applications. 

The heterodimerization of wild-type (WT) Cu, Zn superoxide dismutase-1 (SOD1) and mutant SOD1 might be a critical step in the pathogenesis of SOD1-linked amyotrophic lateral sclerosis (ALS). Post-translational modifications that accelerate SOD1 heterodimerization remain unidentified. Here, we used capillary electrophoresis to quantify the effect of cysteine-111 oxidation on the rate and free energy of ALS mutant/WT SOD1 heterodimerization. The oxidation of Cys111-β-SH to sulfinic and sulfonic acid (by hydrogen peroxide) increased rates of heterodimerization (with unoxidized protein) by ∼3-fold. Cysteine oxidation drove the equilibrium free energy of SOD1 heterodimerization by up to ΔΔG = −5.11 ± 0.36 kJ mol–1. Molecular dynamics simulations suggested that this enhanced heterodimerization, between oxidized homodimers and unoxidized homodimers, was promoted by electrostatic repulsion between the two “dueling” Cys111-SO2–/SO3–, which point toward one another in the homodimeric state. Together, these results suggest that oxidation of Cys-111 promotes subunit exchange between oxidized homodimers and unoxidized homodimers, regardless of whether they are mutant or WT dimers.