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Bolton Mikkelsen posted an update 2 weeks, 3 days ago
Assessment of cytotoxicity showed that etoposide nanoparticles with PGA85%C18 were more potent than an equivalent amount of free drug. This screening method to match polymers to drugs to monitor based drug and polymer interactions thus resulted in the formulation of nanoparticles with higher drug loading and slower release and potential for further development for clinical applications.Understanding water wetting layers on solid surfaces is essential for many natural and industrial processes. Takinib Here we find a helical ice monolayer with every six water molecules helically arranged along the normal of the basal plane by performing an intensive structural search based on ab initio calculations. The helical ice is more stable than all previous models of monolayer and bilayer ices in a wide range of water densities both in vacuum and on weakly interacting substrates due to a stronger network of hydrogen bonds enabled by the helical geometry. More compelling is the fact that this model adequately explains a recent experimental ice monolayer grown on graphite in terms of the lattice parameter, water density, and Moiré pattern. The helical character in the new ice model echoes previously reported helical motifs in one-dimensional ice structures and suggests an unexpected capability of hydrogen bonds in driving the surface reconstruction of ice structures.A simple and straightforward approach to synthesize oil-in-water (O/W) emulsions under high salinity and temperature using zwitterion-functionalized latexes are presented in this work. First, well-defined functionalized latexes were synthesized by emulsifier-free emulsion copolymerization in the presence of precursor sulfobetaine comonomer using brine as a continuous phase. The surface-functionalized latex particles were then characterized by DLS, SEM, TEM, XPS, and TGA. The functionalized latex exhibited antipolyelectrolyte behavior in high salinity brine and at high temperatures. The effects of salinity, temperature, and pH on the long-term stability of the particles were investigated. Further, to evaluate the potential in high salinity brine and high temperature, the saltphilic functionalized latexes were utilized to stabilize the oil/brine (O/W) interface without any other additives. The latex enabled the formation of a stable Pickering emulsion system with low solid content ( less then 0.02% w/w) in the presence of 50% v/v n-decane. The functionalized latexes were self-assembled at the O/W interface as a spherical colloidosome in high salinity brine through hydrophobic interactions and irreversible adsorption. The supraparticles were imaged with SEM, providing an insight that the exterior of the emulsion droplets is stabilized by the saltphilic latex particles, forming a protective layer at the oil-water interface through electrostatic repulsion. The antipolyelectrolyte latex can be utilized as a novel emulsion stabilizer, which can provide a versatile alternative for applications in a complex environment such as high salinity, temperature, and low or high pH.We previously reported the development of an electron-deficient olefin (EDO) ligand, Fro-DO, that promotes the generation of quaternary carbon centers via Ni-catalyzed Csp3-Csp3 cross-coupling with aziridines. By contrast, electronically and structurally similar EDO ligands such as dimethyl fumarate and electron-deficient styrenes afford primarily β-hydride elimination side reactivity. Only a few catalyst systems have been identified that promote the formation of quaternary carbons via Ni-catalyzed Csp3-Csp3 cross-coupling. Although Fro-DO represents a promising ligand in this regard, the basis for its superior performance is not well understood. Here we describe a detailed mechanistic study of the aziridine cross-coupling reaction and the role of EDO ligands in facilitating Csp3-Csp3 bond formation. This analysis reveals that cross-coupling proceeds by a Ni0/II cycle with a NiII azametallacyclobutane catalyst resting state. Turnover-limiting C-C reductive elimination occurs from a spectroscopically observable NiII-dialkyl intermediate bound to the EDO. Computational analysis shows that Fro-DO accelerates turnover limiting reductive elimination via LUMO lowering. However, it is no more effective than dimethyl fumarate at reducing the barrier to Csp3-Csp3 reductive elimination. Instead, Fro-DO’s unique reactivity arises from its ability to associate favorably to NiII intermediates. Natural bond order second-order perturbation theory analysis of the catalytically relevant NiII intermediate indicates that Fro-DO binds to NiII through an additional stabilizing donor-acceptor interaction between its sulfonyl group and NiII. Design of new ligands to evaluate this proposal supports this model and has led to the development of a new and tunable ligand framework.We developed a clustered regularly interspaced short palindromic repeats (CRISPR)/retron system for multiplexed generation of substitution mutations by coutilization of a retron system that continuously expresses donor DNA and a CRISPR/Cas9 cassette that induces cleavage at target genomic loci. Our system efficiently introduces substitution mutation in the Escherichia coli genome in a high-throughput manner. These substitution mutations can be tracked by analysis of retron plasmid sequences without laborious amplification of individual edited loci. We demonstrated that our CRISPR/retron system can introduce thousands of mutations in a single experiment and be used for screening phenotypes related to chemical responses or fitness changes. We expect that our system could facilitate genome-scale substitution screenings.The bubbles electrochemically generated by gas evolution reactions are commonly driven off the electrode by buoyancy, a weak force used to overcome bubble adhesion barriers, leading to low gas-transporting efficiency. Herein, a Janus electrode with asymmetric wettability has been prepared by modifying two sides of a porous stainless-steel mesh electrode, with superhydrophobic polytetrafluoroethylene (PTFE) and Pt/C (or Ir/C) catalyst with well-balanced hydrophobicity, respectively, affording unidirectional transportation of as-formed gaseous hydrogen and oxygen from the catalyst side to the gas-collecting side during water splitting. “Bubble-free” electrolysis was realized while “floating” the Janus electrode on the electrolyte. Antibuoyancy through-mesh bubble transportation was observed while immersing the electrode with the PTFE side downward. The wettability gradient within the electrode endowed sticky states of bubbles on the catalyst side, resulting in efficient bubble-free gas transportation with 15-fold higher current density than submerged states.