Donnellyherndon7354

0% removal of dimethyl phthalate, 3-chlorophenol, bisphenol A, and sulfamethoxazole with a low specific energy consumption of 0.17-0.36 kW·h·g-1. Furthermore, 90.1 ± 0.6% removal of dissolved organic carbon and 83.3 ± 0.9% removal of NH3-N are achieved in the treatment of domestic sewage. The purpose of this work is to present a novel strategy for the regeneration of Fe2+ in the EF process and also to elucidate the role of different N species of the carbonaceous electrode in contributing to the redox cycle of Fe2+/Fe3+.As a novel ultrahigh temperature ceramic, the stability of a high-entropy transition metal carbide under extreme conditions is of great concern to its application. Despite the intense research, the available high-pressure experimental results are few so far. Here, we synthesized the nanocrystalline (Ti0.2Zr0.2Nb0.2Ta0.2Mo0.2)C by a high-pressure solid-state reaction successfully. Meanwhile, synchrotron radiation X-ray diffraction experiments were carried out to explore the phase stability and mechanical response under high pressure. The single cubic B1 phase structure of the high-entropy carbide is retained under extreme hydrostatic pressure. An abnormal cubic-to-cubic phase transition was observed unexpectedly under nonhydrostatic compression. This result reflects the effect of the severe lattice distortion of the initial B1 phase high-entropy carbide and the shear strain caused by deviatoric stress under high nonhydrostatic pressure. The physical mechanism about electronic/magnetic characteristics behind findings is an interesting issue for future studies.When optimizing nanocarriers, structural motifs that are beneficial for the respective type of cargo need to be identified. Here, succinoyl tetraethylene pentamine (Stp)-based lipo-oligoaminoamides (OAAs) were optimized for the delivery of plasmid DNA (pDNA). Structural variations comprised saturated fatty acids with chain lengths between C2 and C18 and terminal cysteines as units promoting nanoparticle stabilization, histidines for endosomal buffering, and disulfide building blocks for redox-sensitive release. Biophysical and tumor cell culture screening established clear-cut relationships between lipo-OAAs and characteristics of the formed pDNA complexes. Based on the optimized alternating Stp-histidine backbones, lipo-OAAs containing fatty acids with chain lengths around C6 to C10 displayed maximum gene transfer with around 500-fold higher gene expression than that of C18 lipo-OAA analogues. Promising lipo-OAAs, however, showed only moderate in vivo efficiency. In vitro testing in 90% full serum, revealing considerable inhibition of lytic and gene-transfer activity, was found as a new screening model predictive for intravenous applications in vivo.Polyubiquitin is a multifunctional protein tag formed by the covalent conjugation of ubiquitin molecules. Due to the high rigidity of the ubiquitin fold, the ubiquitin moieties in a polyubiquitin chain appear to be structurally equivalent to each other. It is therefore unclear how a specific ubiquitin moiety in a chain may be preferentially recognized by some proteins, such as the kinase PINK1. Here we show that there is structural dynamic heterogeneity in the two ubiquitin moieties of K48-linked diubiquitin by NMR spectroscopic analyses. Our analyses capture subunit-asymmetric structural fluctuations that are not directly related to the closed-to-open transition of the two ubiquitin moieties in diubiquitin. Strikingly, these newly identified heterogeneous structural fluctuations may be linked to an increase in susceptibility to phosphorylation by PINK1. Coupled with the fact that there are almost no differences in static tertiary structure among ubiquitin moieties in a chain, the observed subunit-specific structural fluctuations may be an important factor that distinguishes individual ubiquitin moieties in a chain, thereby aiding both efficiency and specificity in post-translational modifications.Herein, we describe capsule polymer particles with precisely controlled pH-responsive release properties prepared directly via the interfacial photo-cross-linking of spherical poly(2-diethylaminoethyl methacrylate-co-2-cinnamoylethyl methacrylate) (P(DEAEMA-CEMA)) particles. In the interfacial photo-cross-linking, photoreactive cinnamoyl groups in the polymer particles were cross-linked via [2π + 2π] cycloaddition reactions at the polymer/water interface, showing that the shell-cross-linked hollow polymer particles can be directly prepared from spherical polymer particles. The approach has fascinating advantages such as using minimal components, simplicity, and not requiring sacrificial template particles and toxic solvents. The following important observations are made (I) encapsulated materials were stably retained in the capsule particles under neutral pH conditions; (II) encapsulated materials were released from the capsule particles under acidic pH conditions; (III) the release kinetics of encapsulated materials were controlled by the pH conditions; i.e., immediate and sustained release was achieved by varying the acidity of the aqueous media; (IV) the photoirradiation time did not significantly affect the release kinetics under different pH conditions; and (V) the pH-responsive release properties were regulated by changing the polymer composition in P(DEAEMA-CEMA). Furthermore, by exploiting the pH-responsiveness, capsule particles are successfully obtained via an all-aqueous process from spherical polymer particles. Cerdulatinib The advantages of the all-aqueous encapsulation process allowed the water-soluble biomacromolecules such as DNA and saccharides to be successfully encapsulated in the P(DEAEMA-CEMA) hollow particles. With this simple interfacial photo-cross-linking strategy, we envision the ready synthesis of sophisticated particulate materials for broad application in advanced research fields.We demonstrate liquid-liquid phase separation involving both coacervation and coil-to-globule phase transition of a thermoresponsive polymer. By focusing a near-infrared laser beam into an aqueous solution of poly(N-isopropylacrylamide) (PNIPAM), a single phase-separated polymer microdroplet can be formed and stably trapped at the focal point. Such droplet formation is induced by a local elevation in temperature (induced by a photothermal effect) and an optical force. The technique allows us to selectively analyze a single polymer droplet trapped at the focal point. In this study, we applied this technique to poly(N,N-diethylacrylamide) (PDEA) in water and generated a double-layered PDEA droplet. Such an inhomogeneous and complex microstructure has not been previously observed both in steady-state heating of a PDEA solution and in the PNIPAM system. Moreover, we used micro-Raman spectroscopy to clarify that PDEA underwent dehydration due to a coil-to-globule phase transition. Despite this, the polymer concentration (Cpoly) of the trapped PDEA droplet was very low and was around 30 wt %. Cpoly depended on the molecular weight of PDEA and the laser power that regulates the temperature elevation. These results strongly indicate that PDEA undergoes coacervation in addition to a coil-to-globule phase transition. This study will help provide us with a fundamental understanding of the phase separation mechanisms of thermoresponsive polymers.Electrochemical disinfection-a method in which chemical oxidants are generated in situ via redox reactions on the surface of an electrode-has attracted increased attention in recent years as an alternative to traditional chemical dosing disinfection methods. Because electrochemical disinfection does not entail the transport and storage of hazardous materials and can be scaled across centralized and distributed treatment contexts, it shows promise for use both in resource limited settings and as a supplement for aging centralized systems. In this Critical Review, we explore the significance of treatment context, oxidant selection, and operating practice on electrochemical disinfection system performance. We analyze the impacts of water composition on oxidant demand and required disinfectant dose across drinking water, centralized wastewater, and distributed wastewater treatment contexts for both free chlorine- and hydroxyl-radical-based systems. Drivers of energy consumption during oxidant generation are identified, and the energetic performance of experimentally reported electrochemical disinfection systems are evaluated against optimal modeled performance. We also highlight promising applications and operational strategies for electrochemical disinfection and propose reporting standards for future work.Serine hydrolases cleave peptide and ester bonds and are ubiquitous in nature, with applications in biotechnology, in materials, and as drug targets. The serine hydrolase two-step mechanism employs a serine-histidine-aspartate/glutamate catalytic triad, where the histidine residue acts as a base to activate poor nucleophiles (a serine residue or a water molecule) and as an acid to allow the dissociation of poor leaving groups. This mechanism has been the subject of debate regarding how histidine shuttles the proton from the nucleophile to the leaving group. To elucidate the reaction mechanism of serine hydrolases, we employ quantum mechanics/molecular mechanics-based transition path sampling to obtain the reaction coordinate using the Aspergillus niger feruloyl esterase A (AnFaeA) as a model enzyme. The optimal reaction coordinates include terms involving nucleophilic attack on the carbonyl carbon and proton transfer to, and dissociation of, the leaving group. During the reaction, the histidine residue undergoes a reorientation on the time scale of hundreds of femtoseconds that supports the "moving histidine" mechanism, thus calling into question the "ring flip" mechanism. We find a concerted mechanism, where the transition state coincides with the tetrahedral intermediate with the histidine residue pointed between the nucleophile and the leaving group. Moreover, motions of the catalytic aspartate toward the histidine occur concertedly with proton abstraction by the catalytic histidine and help stabilize the transition state, thus partially explaining how serine hydrolases enable poor nucleophiles to attack the substrate carbonyl carbon. Rate calculations indicate that the second step (deacylation) is rate-determining, with a calculated rate constant of 66 s-1. Overall, these results reveal the pivotal role of active-site dynamics in the catalytic mechanism of AnFaeA, which is likely similar in other serine hydrolases.Chemists visualize chemical reactions as motion along one-dimensional "reaction coordinates" over free energy barriers. Various rate theories, such as transition state theory and the Kramers theory of diffusive barrier crossing, differ in their assumptions regarding the mathematical specifics of this motion. Direct experimental observation of the motion along reaction coordinates requires single-molecule experiments performed with unprecedented time resolution. Toward this goal, recent single-molecule studies achieved time resolution sufficient to catch biomolecules in the act of crossing free energy barriers as they fold, bind to their targets, or undergo other large structural changes, offering a window into the elusive reaction "mechanisms". This Perspective describes what we can learn (and what we have already learned) about barrier crossing dynamics through synergy of single-molecule experiments, theory, and molecular simulations. In particular, I will discuss how emerging experimental data can be used to answer several questions of principle.