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. Subsequently, a dummy template molecularly imprinted polymer (DMIP) was prepared by the precipitation polymerization method, and the polymer was characterized in morphology, particle size, and composition. The results of the adsorption and enrichment study demonstrated that the DMIP has high adsorption capability (Q = 7.88 mg/g) and favorable imprinting effects (IF = 1.37); Further, it could simultaneously adsorb three p-toluene sulfonate esters. The optimal adsorption conditions were obtained by conditional optimization of solid-phase extraction (SPE). A pH 7 solution was selected as the loading condition, the methanol/1 % phosphoric acid solution (20:80, v/v) was selected as the washing solution, and acetonitrile containing 10 % acetic acid in 6 mL was selected as the elution solvent. Finally, we determined methyl p-toluene sulfonate alkyl esters, ethyl p-toluene sulfonate alkyl esters, and isopropyl p-toluene sulfonate alkyl esters in tosufloxacin toluene sulfonate and capecitabine at the 10 ppm level (relative to 1 mg/mL active pharmaceutical ingredient (API) samples) by using DMIP-based SPE coupled with HPLC. This approach facilitated the selective enrichment of p-toluene sulfonate esters GTIs from complex API samples.

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. Herein we demonstrate in-temperature X-ray absorption spectroscopy (XAS) to unravel the mechanism of site evolution during pyrolysis for a manganese-based catalyst. We show the transformation from an initial state of manganese oxides (MnOx) at room temperature, to the emergence of manganese-nitrogen (MnN4) site beginning at 750 °C, with its continued evolution up to the maximum temperature of 1000 °C. The competition between the MnOx and MnN4 is identified as the primary factor governing the formation of MnN4 sites during pyrolysis. This knowledge led us to use a chemical vapor deposition (CVD) method to produce MnN4 sites to bypass the evolution route involving the MnOx intermediates. The Mn-N-C catalyst synthesized via CVD shows improved ORR activity over the Mn-N-C synthesized via traditional synthesis by the pyrolysis of a mixture of Mn, N, and C precursors.

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-CONH2). It is demonstrated that the Pt-Au NWs showed much-improved performance in the methanol oxidation reaction (MOR), exhibiting 5.3 times higher specific activity and 2.5 times higher mass activity than the current state-of-the-art commercial Pt/C catalyst. In addition, the periodic heterostructure also improves the stability of Pt-Au NWs in the MOR, where the Pt-Au NWs retained 93.9% of their initial mass activity much higher than commercial Pt/C (30.6%).

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. silvarum, and their functions in cold stress were further evaluated. METHODS: The genome of the heat shock proteins and tubulin of D. silvarum were sequenced and analyzed using bioinformatics methods. Each group of 20 ticks were injected in triplicate with Dshsp90-, Dshsp70-, and tubulin-derived dsRNA, whereas the control group was injected with GFP dsRNA. Then, the total RNA was extracted and cDNA was synthesized and subjected to RT-qPCR. After the confirmation of knockdown, the ticks were incubated for 24 h and were exposed to - 20 °C lethal temperature (LT50), and then the mortality was calculated. RESULTS: Results indicated that Dshsp70 and Dshsp90 contained an open reading frame of 345 and 2190 nucleotides that encoded 114 and 729 amino acid residues, respectively. The transcript Dshsp70 showed 90% similarity with that identified from Dermacentor variabilis, whereas Dshsp90 showed 85% similarity with that identified from Ixodes scapularis. Multiple sequence alignment indicates that the deduced amino acid sequences of D. silvarum Hsp90, Hsp70, and tubulin show very high sequence identity to their corresponding sequences in other species. Hsp90 and Hsp70 display highly conserved and signature amino acid sequences with well-conserved MEEVD motif at the C-terminal in Hsp90 and a variable C-terminal region with a V/IEEVD-motif in Hsp70 that bind to numerous co-chaperones. RNA interference revealed that the mortality of D. silvarum was significantly increased after injection of dsRNA of Dshsp70 (P = 0.0298) and tubulin (P = 0.0448), whereas no significant increases were observed after the interference of Dshsp90 (P = 0.0709). CONCLUSIONS: The above results suggested that Dshsp70 and tubulin play an essential role in the low-temperature adaptation of ticks. The results of this study can contribute to the understanding of the survival and acclimatization of overwintering ticks.

Chemical vapour deposition of Fe-N-C oxygen reduction catalysts with full utilization of dense Fe-N4 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-N4 sites into Fe-N4 sites. Characterization by multiple techniques shows that all Fe-N4 sites formed via this approach are gas-phase and electrochemically accessible. As a result, the Fe-N-C catalyst has an active site density of 1.92 × 1020 sites per gram with 100% site utilization. This catalyst delivers an unprecedented oxygen reduction reaction activity of 33 mA cm-2 at 0.90 V (iR-corrected; i, current; R, resistance) in a H2-O2 proton exchange membrane fuel cell at 1.0 bar and 80 °C.

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. This strategy of reshaping of the catalyst layer structure may serve as a new platform for applications of many molecular catalysts in fuel cells.

Evolution Pathway from Iron Compounds to Fe1(II)-N4 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 Fe1(II)-N4 sites via in-temperature X-ray absorption spectroscopy. The Fe precursor transforms to Fe oxides below 300 °C and then to tetrahedral Fe1(II)-O4 via a crystal-to-melt-like transformation below 600 °C. The Fe1(II)-O4 releases a single Fe atom that diffuses into the N-doped carbon defect forming Fe1(II)-N4 above 600 °C. This vapor-phase single Fe atom transport mechanism is verified by synthesizing Fe1(II)-N4 sites via "noncontact pyrolysis" wherein the Fe precursor is not in physical contact with the N and C precursors during pyrolysis.

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 (OHad)-water-alkali metal cation (AM+) adducts, on the basis of the observations that enriching the OHad 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 OHad-(H2O) x-AM+ in the double-layer region facilitates the OHad removal into the bulk, forming OH--(H2O) x-AM+ as per the hard-soft acid-base theory, thereby selectively promoting the HER. It can be detrimental to the HOR as per the bifunctional mechanism, as the AM+ destabilizes the OHad, which is further supported by the CO oxidation results. This new notion may be important for alkaline electrochemistry.

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. Recently, synchrotron-based X-ray absorption spectroscopy (XAS) has been successfully implemented to shed some light on these two issues. In this context, a critical review is given to detail the contribution of XAS to the advancement of the M-N-C electrocatalysis to highlight its advantages and limitations.

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. Consequently, the favorable Pt3Ni(111) structure for the ORR is stabilized on the surface of PtNi/C NPs in acid against voltage cycling. Significantly, the unusual potential-dependent oxygen coverage trend on Mo-doped PtNi/C NPs as revealed by the surface-sensitive Δµ analysis suggests that the Mo dopants may also improve the ORR kinetics by modifying the coordination environments of Pt atoms on the surface. Our studies point out a possible way to stabilize the favorable shape and composition established on conceptual catalytic models in practical nanoscale catalysts.

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, CoN4C12, CoN3C10,porp and CoN2C5. The O2 electro-reduction and operando X-ray absorption response are measured in acidic medium on Co-N-C and compared to those of a Fe-N-C catalyst prepared similarly. We show that cobalt moieties are unmodified from 0.0 to 1.0 V versus a reversible hydrogen electrode, while Fe-based moieties experience structural and electronic-state changes. On the basis of density functional theory analysis and established relationships between redox potential and O2-adsorption strength, we conclude that cobalt-based moieties bind O2 too weakly for efficient O2 reduction.Nitrogen-doped carbon materials with atomically dispersed iron or cobalt are promising for catalytic use. Here, the authors show that cobalt moieties have a higher redox potential, bind oxygen more weakly and are less active toward oxygen reduction than their iron counterpart, despite similar coordination.

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. Electrochemical measurements show that the HOR rate of Pt-Ru/C and Ru/C systems is decoupled to their hydrogen binding energy (HBE), challenging the current prevailing HBE mechanism. The alternative bifunctional mechanism is verified by combined electrochemical and in situ spectroscopic data, which provide convincing evidence for the presence of hydroxy groups on surface Ru sites in the HOR potential region and its key role in promoting the rate-determining Volmer step. The conclusion presents important references for design and selection of HOR catalysts.

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. Our data unequivocally demonstrate that the electron is shuttled to the Pc ring via the Fe(II)/Fe(I) redox center. The Fe(II)/Fe(I) redox transition of FePc in aqueous media is indiscernible by normal spectroscopic methods owing to the lack of a suitable axial ligand to stabilize the Fe(I) state.

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

Fe-N-C catalysts with high O2 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 H2 O2 reduction, a key intermediate during indirect O2 reduction and a source of deactivation in fuel cells. Catalysts comprising different relative contents of FeNx Cy moieties and Fe particles encapsulated in N-doped carbon layers (0-100 %) show that both types of sites are active, although moderately, toward H2 O2 reduction. In contrast, N-doped carbons free of Fe and Fe particles exposed to the electrolyte are inactive. When catalyzing the ORR, FeNx Cy moieties are more selective than Fe particles encapsulated in N-doped carbon. These novel insights offer rational approaches for more selective and therefore more durable Fe-N-C catalysts.

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. silvarum ticks exposed to low temperatures. The results indicated that the lower lethal temperatures (LT50s) for larvae, nymphs, females and males were -16.9°C, -15.8°C, -20.0°C and -20.1°C, respectively. The discriminating temperatures (resulting in 20% survival) for larvae, nymphs, females and males were -18.5°C, -20.0°C, -21.7°C and -22.6°C, respectively. The supercooling temperature points (at which body fluids spontaneously freeze) of larvae, nymphs, females and males averaged -20.0°C, -23.5°C, -24.2°C and -23.9°C, respectively. These results indicate that adult ticks are more tolerant to cold than the immatures. Low-temperature stress can enhance adult cold hardiness and trigger decreases in glycogen and protein in both females and males, whereas nymphs displayed different biochemical responses, including an increase in water and total fat content. An increase of glycerol observed in nymphs and females suggests that glycerol is important for cold hardiness. The findings of this study will help to define the dispersal limits for D. silvarum and thus inform the need for tick control efforts.

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/NbOx/C system with tunable structural and electronic properties via a modified arc plasma deposition method. We unravel the nature of MMOI by characterizing this system under reactive conditions utilizing combined electrochemical, microscopy, and in situ spectroscopy. We show that Pt interacts with the Nb in unsaturated NbOx owing to the oxygen deficiency in the MMO interface, whereas Pt interacts with the O in nearly saturated NbOx, and further interacts with Nb when the oxygen atoms penetrate into the Pt cluster at elevated potentials. While the Pt-Nb interactions do not benefit the inherent activity of Pt toward oxygen reduction reaction (ORR), the Pt-O interactions improve the ORR activity by shortening the Pt-Pt bond distance. Pt donates electrons to NbOx in both Pt-Nb and Pt-O cases. The resultant electron eficiency stabilizes low-coordinated Pt sites, hereby stabilizing small Pt particles. This determines the two characteristic features of MMO systems: dispersion of small metal particles and high catalytic durability. These findings contribute to our understandings of MMO catalytic systems.

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

This study investigated the development characteristics of Dermacentor everestianus under laboratory conditions. The time taken for D. everestianus to complete the whole life cycle was 110.2 days on average, and the average developmental durations of larvae and nymphs were 17.1 days and 29.5 days, respectively. The summation of the prefeeding, feeding, and preoviposition periods of females was 17.8 days, and the oviposition and egg incubation lasted for 18.1 days and 27.7 days, respectively. A highly positive correlation was observed between the weight of engorged female and the number of egg mass laid (r=0.947). The reproductive efficiency index and the reproductive fitness index were 7.1 and 6.1, respectively.

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 RhxSy/C catalyst in a rotating disk electrode in the presence of Cl-. The Fe-N4 active sites in Fe-N-C are intrinsically immune to Cl- poisoning, in contrast to Pt/C, which is severely susceptible to Cl- poisoning. As a result, the activity of Fe-N-C decreases only marginally in the presence of Cl-, far exceeding that of Pt/C. The viability of this catalyst as ODCs is further demonstrated in real-life hydrochloric acid electrolyzers using highly concentrated HCl solution saturated with Cl2 gas as the electrolyte. The introduction of Fe-N-C materials as ODC catalysts here overcomes the limitations of (i) the low intrinsic ORR activity of RhxSy/C as the state-of-the-art ODC catalyst; (ii) the vulnerability to Cl- poisoning of Pt/C as the state-of-the-art ORR catalyst; and (iii) the high cost of precious metals in these two materials, resulting in a cost-effective ODC catalyst with the overall performance exceeding that of all previously reported materials.

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 (Eredox) 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 Eredox of active sites; and the intrinsic activity of active sites with low Eredox 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 Eredox side of the volcano is limited by the intrinsic activity; whereas the ORR of the catalysts on the low Eredox side is limited by either the site-blocking effect and/or intrinsic activity depending on the Eredox.

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 11.5 milliamperes per square centimeter for ORR (at 0.9 volts versus reversible hydrogen electrode), yielding a mass activity of 13.6 amperes per milligram of Pt, nearly double previously reported best values. Reactive molecular dynamics simulations suggest that highly stressed, undercoordinated rhombus-rich surface configurations of the jagged nanowires enhance ORR activity versus more relaxed surfaces.