Comparison and Determination of the Content of Mosapride Citrate by Different qNMR Methods.

As a salt-type compound, mosapride citrate's metabolism and side effects are correlated with its salt-forming ratio. Several techniques were developed in this work to compare various quantitative nuclear magnetic resonance (qNMR) methodologies and to quantitatively examine the content of raw materials. Among the qNMR techniques, methods for H NMR and F NMR were developed.

Preparation and optimization of dummy molecularly imprinted polymer-based solid-phase extraction system for selective enrichment of p-toluene sulfonate esters genotoxic impurities.

Sulfonate esters, one class of genotoxic impurities (GTIs), have gained significant attention in recent years due to their potential to cause genetic mutations and cancer. In the current study, we employed the dummy template molecular imprinting technology with a dummy template molecule replacing the target molecule to establish a pretreatment method for samples containing p-toluene sulfonate esters. Through computer simulation and ultraviolet-visible spectroscopy analysis, the optimal functional monomer acrylamide and polymerization solvent chloroform were selected.

Bypassing Formation of Oxide Intermediate via Chemical Vapor Deposition for the Synthesis of an Mn-N-C Catalyst with Improved ORR Activity.

A significant barrier to the commercialization of proton exchange membrane fuel cells (PEMFCs) is the high cost of the platinum-based oxygen reduction reaction (ORR) cathode electrocatalysts. One viable solution is to replace platinum with a platinum-group metal (PGM) free catalyst with comparable activity and durability. However, PGM-free catalyst development is burdened by a lack of understanding of the active site formation mechanism during the requisite high-temperature synthesis step, thus making rational catalyst design challenging.

Periodic Assembly of Diblock Pt-Au Heteronanowires for the Methanol Oxidation Reaction.

Periodic assembly of heterogeneous nanoparticles provides a strategy for integrating distinct nanocatalyst blocks where their synergic effects can be explored for diverse applications. To achieve the synergistic enhancement, an intimate clean interface is preferred which however is usually plagued by the bulky surfactant molecules used in the synthesis and assembly process. Herein, we showed the creation of one-dimensional Pt-Au nanowires (NWs) with periodic alternating Pt and Au nanoblocks, by assembling Pt-Au Janus nanoparticles with the assistance of peptide T7 (Ac-TLTTLTN-CONH).

Functional implication of heat shock protein 70/90 and tubulin in cold stress of Dermacentor silvarum.

Background: The tick Dermacentor silvarum Olenev (Acari: Ixodidae) is a vital vector tick species mainly distributed in the north of China and overwinters in the unfed adult stage. The knowledge of the mechanism that underlies its molecular adaptation against cold is limited. In the present study, genes of hsp70 and hsp90 cDNA, named Dshsp70 and Dshsp90, and tubulin were cloned and characterized from D.

Chemical vapour deposition of Fe-N-C oxygen reduction catalysts with full utilization of dense Fe-N sites.

Replacing scarce and expensive platinum (Pt) with metal-nitrogen-carbon (M-N-C) catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells has largely been impeded by the low oxygen reduction reaction activity of M-N-C due to low active site density and site utilization. Herein, we overcome these limits by implementing chemical vapour deposition to synthesize Fe-N-C by flowing iron chloride vapour over a Zn-N-C substrate at 750 °C, leading to high-temperature trans-metalation of Zn-N sites into Fe-N sites. Characterization by multiple techniques shows that all Fe-N sites formed via this approach are gas-phase and electrochemically accessible.

Reshaping the Cathodic Catalyst Layer for Anion Exchange Membrane Fuel Cells: From Heterogeneous Catalysis to Homogeneous Catalysis.

In anion exchange membrane fuel cells, catalytic reactions occur at a well-defined three-phase interface, wherein conventional heterogeneous catalyst layer structures exacerbate problems, such as low catalyst utilization and limited mass transfer. We developed a structural engineering strategy to immobilize a molecular catalyst tetrakis(4-methoxyphenyl)porphyrin cobalt(II) (TMPPCo) on the side chains of an ionomer (polyfluorene, PF) to obtain a composite material (PF-TMPPCo), thereby achieving a homogeneous catalysis environment inside ion-flow channels, with greatly improved mass transfer and turnover frequency as a result of 100 % utilization of the catalyst molecules. The unique structure of the homogeneous catalysis system comprising interconnected nanoreactors exhibits advantages of low overpotential and high fuel-cell power density.

Evolution Pathway from Iron Compounds to Fe(II)-N Sites through Gas-Phase Iron during Pyrolysis.

Pyrolysis is indispensable for synthesizing highly active Fe-N-C catalysts for the oxygen reduction reaction (ORR) in acid, but how Fe, N, and C precursors transform to ORR-active sites during pyrolysis remains unclear. This knowledge gap obscures the connections between the input precursors and the output products, clouding the pathway toward Fe-N-C catalyst improvement. Herein, we unravel the evolution pathway of precursors to ORR-active catalyst comprised exclusively of single-atom Fe(II)-N sites via in-temperature X-ray absorption spectroscopy.

Unifying the Hydrogen Evolution and Oxidation Reactions Kinetics in Base by Identifying the Catalytic Roles of Hydroxyl-Water-Cation Adducts.

Despite the fundamental and practical significance of the hydrogen evolution and oxidation reactions (HER/HOR), their kinetics in base remain unclear. Herein, we show that the alkaline HER/HOR kinetics can be unified by the catalytic roles of the adsorbed hydroxyl (OH)-water-alkali metal cation (AM) adducts, on the basis of the observations that enriching the OH abundance via surface Ni benefits the HER/HOR; increasing the AM concentration only promotes the HER, while varying the identity of AM affects both HER/HOR. The presence of OH-(HO) -AM in the double-layer region facilitates the OH removal into the bulk, forming OH-(HO) -AM as per the hard-soft acid-base theory, thereby selectively promoting the HER.

X-Ray Absorption Spectroscopy Characterizations on PGM-Free Electrocatalysts: Justification, Advantages, and Limitations.

Transition metals embedded in nitrogen-doped carbon matrices (denoted as M-N-C) are the leading platinum group metal (PGM)-free electrocatalysts for the oxygen reduction reaction (ORR) in acid, and are the most promising candidates for replacing platinum in practical devices such as fuel cells. Two of the long-standing puzzles in the field are the nature of active sites for the ORR and the reaction mechanism. Poor understanding of the structural and mechanistic basis for the exceptional ORR activity of M-N-C electrocatalysts impedes rational design for further improvements.

Roles of Mo Surface Dopants in Enhancing the ORR Performance of Octahedral PtNi Nanoparticles.

Doping with a transition metal was recently shown to greatly boost the activity and durability of PtNi/C octahedral nanoparticles (NPs) for the oxygen reduction reaction (ORR), but its specific roles remain unclear. By combining electrochemistry, ex situ and in situ spectroscopic techniques, density functional theory calculations, and a newly developed kinetic Monte Carlo model, we showed that Mo atoms are preferentially located on the vertex and edge sites of Mo-PtNi/C in the form of oxides, which are stable within the wide potential window of the electrochemical cycle. These surface Mo oxides stabilize adjacent Pt sites, hereby stabilizing the octahedral shape enriched with (111) facets, and lead to increased concentration of Ni in subsurface layers where they are protected against acid dissolution.

Experimental Proof of the Bifunctional Mechanism for the Hydrogen Oxidation in Alkaline Media.

Realization of the hydrogen economy relies on effective hydrogen production, storage, and utilization. The slow kinetics of hydrogen evolution and oxidation reaction (HER/HOR) in alkaline media limits many practical applications involving hydrogen generation and utilization, and how to overcome this fundamental limitation remains debatable. Here we present a kinetic study of the HOR on representative catalytic systems in alkaline media.

Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction.

Single-atom catalysts with full utilization of metal centers can bridge the gap between molecular and solid-state catalysis. Metal-nitrogen-carbon materials prepared via pyrolysis are promising single-atom catalysts but often also comprise metallic particles. Here, we pyrolytically synthesize a Co-N-C material only comprising atomically dispersed cobalt ions and identify with X-ray absorption spectroscopy, magnetic susceptibility measurements and density functional theory the structure and electronic state of three porphyrinic moieties, CoNC, CoNC and CoNC.

Resolving the Iron Phthalocyanine Redox Transitions for ORR Catalysis in Aqueous Media.

Metal macrocycles are among the most important catalytic systems in electrocatalysis and biocatalysis owing to their rich redox chemistry. Precise understanding of the redox behavior of metal macrocycles in operando is essential for fundamental studies and practical applications of this catalytic system. Here we present electrochemical data for the representative iron phthalocyanine (FePc) in both aqueous and nonaqueous media coupled with in situ Raman and X-ray absorption analyses to challenge the traditional notion of the redox transition of FePc at the low potential end in aqueous media by showing that it arises from the redox transition of the ring.

Cold tolerance and biochemical response of unfed Dermacentor silvarum ticks to low temperature.

The important pathogen vector Dermacentor silvarum is widely distributed in China. However, the tick's adaptation to low winter temperatures remains poorly understood. We therefore investigated the cold hardiness and physiological and biochemical responses of D.

Unraveling the Nature of Sites Active toward Hydrogen Peroxide Reduction in Fe-N-C Catalysts.

Fe-N-C catalysts with high O reduction performance are crucial for displacing Pt in low-temperature fuel cells. However, insufficient understanding of which reaction steps are catalyzed by what sites limits their progress. The nature of sites were investigated that are active toward H O reduction, a key intermediate during indirect O reduction and a source of deactivation in fuel cells.

Metal and Metal Oxide Interactions and Their Catalytic Consequences for Oxygen Reduction Reaction.

Many industrial catalysts are composed of metal particles supported on metal oxides (MMO). It is known that the catalytic activity of MMO materials is governed by metal and metal oxide interactions (MMOI), but how to optimize MMO systems via manipulation of MMOI remains unclear, due primarily to the ambiguous nature of MMOI. Herein, we develop a Pt/NbO/C system with tunable structural and electronic properties via a modified arc plasma deposition method.

Life Cycle of Hirst, 1926 (Acari: Ixodidae) under Laboratory Conditions.

This study investigated the development characteristics of under laboratory conditions. The time taken for to complete the whole life cycle was 110.2 days on average, and the average developmental durations of larvae and nymphs were 17.

Highly Active and Stable Fe-N-C Catalyst for Oxygen Depolarized Cathode Applications.

Anion immunity toward the oxygen reduction reaction (ORR) has tremendous implications in electrocatalysis with applications for fuel cells, metal-air batteries, and oxygen depolarized cathodes (ODCs) in the anodic evolution of chlorine. The necessity of exploring ORR catalysts with immunity to anion adsorption is particularly significant considering that platinum group metal (PGM) catalysts are costly and highly vulnerable to impurities such as halides. Herein, we report a metal organic framework (MOF)-derived Fe-N-C catalyst that exhibits a dramatically improved half-wave potential of 240 mV compared to the state-of-the-art RhS/C catalyst in a rotating disk electrode in the presence of Cl.

Asymmetric Volcano Trend in Oxygen Reduction Activity of Pt and Non-Pt Catalysts: In Situ Identification of the Site-Blocking Effect.

Proper understanding of the major limitations of current catalysts for oxygen reduction reaction (ORR) is essential for further advancement. Herein by studying representative Pt and non-Pt ORR catalysts with a wide range of redox potential (E) via combined electrochemical, theoretical, and in situ spectroscopic methods, we demonstrate that the role of the site-blocking effect in limiting the ORR varies drastically depending on the E of active sites; and the intrinsic activity of active sites with low E have been markedly underestimated owing to the overlook of this effect. Accordingly, we establish a general asymmetric volcano trend in the ORR activity: the ORR of the catalysts on the overly high E side of the volcano is limited by the intrinsic activity; whereas the ORR of the catalysts on the low E side is limited by either the site-blocking effect and/or intrinsic activity depending on the E.

Ultrafine jagged platinum nanowires enable ultrahigh mass activity for the oxygen reduction reaction.

Improving the platinum (Pt) mass activity for the oxygen reduction reaction (ORR) requires optimization of both the specific activity and the electrochemically active surface area (ECSA). We found that solution-synthesized Pt/NiO core/shell nanowires can be converted into PtNi alloy nanowires through a thermal annealing process and then transformed into jagged Pt nanowires via electrochemical dealloying. The jagged nanowires exhibit an ECSA of 118 square meters per gram of Pt and a specific activity of 11.

Experimental Observation of Redox-Induced Fe-N Switching Behavior as a Determinant Role for Oxygen Reduction Activity.

The commercialization of electrochemical energy conversion and storage devices relies largely upon the development of highly active catalysts based on abundant and inexpensive materials. Despite recent achievements in this respect, further progress is hindered by the poor understanding of the nature of active sites and reaction mechanisms. Herein, by characterizing representative iron-based catalysts under reactive conditions, we identify three Fe-N4-like catalytic centers with distinctly different Fe-N switching behaviors (Fe moving toward or away from the N4-plane) during the oxygen reduction reaction (ORR), and show that their ORR activities are essentially governed by the dynamic structure associated with the Fe(2+/3+) redox transition, rather than the static structure of the bare sites.

Improved Oxygen Reduction Activity and Durability of Dealloyed PtCo Catalysts for Proton Exchange Membrane Fuel Cells: Strain, Ligand, and Particle Size Effects.

The development of active and durable catalysts with reduced platinum content is essential for fuel cell commercialization. Herein we report that the dealloyed PtCo/HSC and PtCo/HSC nanoparticle (NP) catalysts exhibit the same levels of enhancement in oxygen reduction activity (~4-fold) and durability over pure Pt/C NPs. Surprisingly, ex situ high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) shows that the bulk morphologies of the two catalysts are distinctly different: D-PtCo/HSC catalyst is dominated by NPs with solid Pt shells surrounding a single ordered PtCo core; however, the D-PtCo/HSC catalyst is dominated by NPs with porous Pt shells surrounding multiple disordered PtCo cores with local concentration of Co.

Composite Ni/NiO-CrO Catalyst for Alkaline Hydrogen Evolution Reaction.

We report a Ni-Cr/C electrocatalyst with unprecedented mass-activity for the hydrogen evolution reaction (HER) in alkaline electrolyte. The HER kinetics of numerous binary and ternary Ni-alloys and composite Ni/metal-oxide/C samples were evaluated in aqueous 0.1 M KOH electrolyte.

Spectroscopic Measurements of the Relative Pt Skin Thicknesses and Porosities of Dealloyed PtM (Ni, Co) Electrocatalysts.

X-ray adsorption near edge structure (XANES) data at the Co or Ni K-edge, analyzed using the Δ difference procedure, are reported for dealloyed PtCo and PtNi catalysts (six different catalysts at different stages of life). All catalysts meet the 2017 DOE beginning of life target Pt mass activity target (>0.44 A mg), but exhibit varying activities and durabilities.