Crossover Density Research Articles

Iron complex with multiple negative charges ligand for ultrahigh stability and high energy density alkaline all-iron flow battery

Alkaline all-iron flow batteries (AIFBs) are highly attractive for large-scale and long-term energy storage due to the abundant availability of raw materials, low cost, inherent safety, and decoupling of capacity and power. However, a stable iron anolyte is still being explored to address complex decomposition, ligand crossover, and energy density to improve battery performance. Herein, a promising metal-organic complex, Fe(NTHPS), consisting of FeCl3 and 3,3',3''-nitrilotris(2-hydroxypropane-1-sulfonate) (NTHPS), is specifically designed for alkaline all-iron flow battery. The NTHPS exhibits strong binding strength with iron ions, resulting in ultrahigh stability during the charge-discharge process. AIFB based on the [Fe(CN)6]4- catholyte and Fe(NTHPS) showcases an exceptionally high capacity retention of 97.8% after 2000 cycles (0.0011% per cycle), maintaining high coulombic efficiency near 100%. Furthermore, with a solubility as high as 1.82 mol L-1, the Fe(NTHPS) anolyte demonstrates an ultra-high theoretical capacity of 47.23 Ah L-1. This multiple negative charges ligand not only resolves existing barrier associated with AIFBs, but also provides valuable insight for their commercial application.

Construction of PtAg‐on‐Au Heterostructured Nanoplates for Improved Electrocatalytic Activity of Formic Acid Oxidation

AbstractDirect formic acid fuel cells have attracted significant attention due to their low fuel crossover, high safety, and high theoretical power density among all proton‐exchange membrane fuel cells. Numerous efforts have been dedicated to studying formic acid oxidation, particularly in the fabrication of high‐performance electrocatalysts with economical utilization of Pt metal. In this work, we report a synthetic strategy to create PtAg dots supported on plate‐like Au nanoparticles and explore their applications in electrocatalytic formic acid oxidation. The highly dispersed nature of the catalytic Pt centers and the successful construction of PtAg−Au trimetallic interfaces makes the current nanostructure an ideal system to allow for a synergetic effect between Pt, Au, and Ag, leading to improved electrocatalysis. Compared with commercial Pt/C, our PtAg‐on‐Au heterogenous nanoplates exhibit superior mass activity, along with enhanced reaction kinetics and long‐term durability for FAOR in an acidic medium. Density functional theory (DFT) simulation results indicate that AgPtAu(111) exhibits a relatively high activity for HCOOH oxidation into CO2 among the various Au‐based catalysts. This work provides a viable strategy for constructing Pt‐based electrocatalysts with controlled Pt ensembles, offering insights into the development of fuel cell catalysts that make highly efficient use of costly noble metals.

Canonical and noncanonical roles of Hop1 are crucial for meiotic prophase in the fungus Sordaria macrospora.

We show here that in the fungus Sordaria macrospora, the meiosis-specific HORMA-domain protein Hop1 is not essential for the basic early events of chromosome axis development, recombination initiation, or recombination-mediated homolog coalignment/pairing. In striking contrast, Hop1 plays a critical role at the leptotene/zygotene transition which is defined by transition from pairing to synaptonemal complex (SC) formation. During this transition, Hop1 is required for maintenance of normal axis structure, formation of SC from telomere to telomere, and development of recombination foci. These hop1Δ mutant defects are DSB dependent and require Sme4/Zip1-mediated progression of the interhomolog interaction program, potentially via a pre-SC role. The same phenotype occurs not only in hop1Δ but also in absence of the cohesin Rec8 and in spo76-1, a non-null mutant of cohesin-associated Spo76/Pds5. Thus, Hop1 and cohesins collaborate at this crucial step of meiotic prophase. In addition, analysis of 4 non-null mutants that lack this transition defect reveals that Hop1 also plays important roles in modulation of axis length, homolog-axis juxtaposition, interlock resolution, and spreading of the crossover interference signal. Finally, unexpected variations in crossover density point to the existence of effects that both enhance and limit crossover formation. Links to previously described roles of the protein in other organisms are discussed.

Chiral crossover versus chiral density wave in dense nuclear matter

We employ a model based on nucleonic and mesonic degrees of freedom to discuss the competition between isotropic and anisotropic phases in cold and dense matter. Assuming isotropy, the model exhibits a chiral phase transition which is of second order in the chiral limit and becomes a crossover in the case of a realistic pion mass. This observation crucially depends on the presence of the nucleonic vacuum contribution. Allowing for an anisotropic phase in the form of a chiral density wave can disrupt the smooth crossover. We identify the regions in the parameter space of the model where a chiral density wave is energetically preferred. A high-density reappearance of the chiral density wave with unphysical behavior, as seen in previous studies, is avoided by a suitable renormalization scheme. A nonzero pion mass tends to disfavor the anisotropic phase compared to the chiral limit and we find that, within our model, the chiral density wave is only realized for baryon densities of at least about 6 times nuclear saturation density. Published by the American Physical Society 2024

Immobilized hindered amine radical scavenger for durability enhancement of perfluorosulfonic acid membrane in PEMFCs

Membrane durability is one of the crucial considerations that restrict the development of proton exchange membrane fuel cells (PEMFCs). The widely used and inexpensive stabilizer hindered amine 4-amino-2,2,6,6-tetramethylpiperidine (TEMP) was selected as the free radical scavenger and tethered onto the skeleton of carboxyl-functionalized metal-organic frameworks for addressing its migration problem. The resulted inorganic-organic hybrid dopant (UIO-66-TEMP) was then incorporated into the Nafion matrix to alleviate the attacks of free radicals on the membrane in the fuel cell working circumstances. Besides the improved mechanical strength and oxidative stability, and restricted water swelling and hydrogen crossover, the resulted hybrid membranes also possess excellent proton conductivity up to 176 mS cm−1, endowing them with high power density up to 612.78 mW cm−2, 1.5 times higher than recast Nafion. After accelerated durability testing for 120 h, the OCV decay rate of the hybrid membranes decreased to 0.74 mV h−1, only 40% of recast Nafion (1.89 mV h−1). Meanwhile, the optimized hybrid membrane still maintained a high peak power density of 463.62 mW cm−2 and a low hydrogen crossover density of 4.44 mA cm−2, which were superior to recast Nafion after OCV durability tests. Hindered amines can be “regenerated” by the “Denisov cycle” to ensure that they can be used sustainably in the fuel cell. The results demonstrate that the novel UIO-66-TEMP decorated with hindered amine radical scavengers are promising nanofillers for mitigating the membrane degradation and improving the proton conductivity, thereby significantly enhancing the performance and durability of PEMFCs.

Triple-Stranded DNA As a Structural Element in DNA Origami.

Molecular self-assembly with DNA origami offers an attractive route to fabricate arbitrary three-dimensional nanostructures. In DNA origami, B-form double-helical DNA domains (dsDNA) are commonly linked with covalent phosphodiester strand crossovers to build up three-dimensional objects. To expand the palette of structural motifs in DNA origami, here we describe hybrid duplex-triplex DNA motifs as pH-dependent building blocks in DNA origami. We investigate design rules for incorporating triplex forming oligonucleotides and noncanonical duplex-triplex crossovers in multilayer DNA origami objects. We use single-particle cryoelectron microscopy to elucidate the structural basis of triplex domains and of duplex-triplex crossovers. We find that duplex-triplex crossovers can complement and fully replace the canonical duplex-duplex crossovers within DNA origami objects, for example, to increase the crossover density for potentially greater rigidity and reduced interhelical spacing, and to create connections at sites where conventional crossovers may be undesirable. We also show the pH-induced formation of a DNA origami object stabilized entirely by triplex-mediated strand crossovers.

Hadron-quark phase transition in neutron star by combining the relativistic Brueckner-Hartree-Fock theory and Dyson-Schwinger equation approach

Starting from the relativistic Brueckner-Hartree-Fock theory for nuclear matter and the Dyson-Schwinger equation approach for quark matter, the possible hadron-quark phase transition in the interior of a neutron star is explored. The first-order phase transition and crossover are studied by performing the Maxwell construction and three-window construction respectively. The mass-radius relation and the tidal deformability of the hybrid star are calculated and compared to the joint mass-radius observation of a neutron star and the constraints from gravitational wave detection. For the Maxwell construction, no stable quark core is found in the interior of a neutron star. For the three-window construction, the parameters of the smooth interpolation function are chosen in such a way to keep the thermodynamic stability and lead to a moderate crossover density region. To support a two-solar-mass neutron star under the three-window construction, the effective width of medium screening effects in quark matter should be around 0.35 GeV.

Construction of gradient catalyst layer anode by incorporating covalent organic framework to improve performance of direct methanol fuel cells

Improving cell performance is the most demanded task in direct methanol fuel cell (DMFC) research, although this fuel cell has several intrinsic features like high energy density, moderate operating temperature and environmentally friendly operation. The catalyst layer (CL) is the site of electrochemical reactions directly affecting the cell performance. Accordingly, the structure and preparation of the CL are crucial in optimizing performance. In this study, a novel gradient catalyst layer (G-CL) for the anode of DMFC is developed and better performance is obtained compared with that of single catalyst layer (S-CL) anode. A G-CL anode is composed of an outer CL of covalent organic framework (COF) materials-mixed catalyst near the microporous layer (MPL) and a conventional inner CL near the membrane side. Different loading of Pt catalyst in the two layers. Therefore, in the G-CL structure, there existed a catalyst concentration gradient and porosity gradient. Anode electrodes are characterized morphologically and electrochemically and the performance of individual cells containing such G-CL designs is measured. The results indicate that incorporation of the appropriate amount of COF materials enables the outer CL not only to have a larger electrochemical surface area (ECSA) and expose more catalytic active sites but also holds a strong proton transfer ability to improve the methanol oxidation reaction (MOR) performance. Due to the presence of the inner layer of the CL formed the methanol gradient oxidation process. With the same platinum-ruthenium (Pt–Ru) catalyst loading, the 5 wt.% COF G-CL anode structure exhibited lower methanol crossover and higher power density (nearly 11% increment) compared with that of the S-CL anode with high methanol concentration (8 M) at 60 °C, showing the promising potential in further applications.

Effect of architecture disorder on the elastic response of two-dimensional lattice materials.

We examine how disordering joint position influences the linear elastic behavior of lattice materials via numerical simulations in two-dimensional beam networks. Three distinct initial crystalline geometries are selected as representative of mechanically isotropic materials with low connectivity, mechanically isotropic materials with high connectivity, and mechanically anisotropic materials with intermediate connectivity. Introducing disorder generates spatial fluctuations in the elasticity tensor at the local (joint) scale. Proper coarse-graining reveals a well-defined continuum-level scale elasticity tensor. Increasing disorder aids in making initially anisotropic materials more isotropic. The disorder impact on the material stiffness depends on the lattice connectivity: Increasing the disorder softens lattices with high connectivity and stiffens those with low connectivity, without modifying the scaling between elastic modulus and density (linear scaling for high connectivity and cubic scaling for low connectivity). Introducing disorder in lattices with intermediate fixed connectivity reveals both scaling: the linear scaling occurs for low density, the cubic one at high density, and the crossover density increases with disorder. Contrary to classical formulations, this work demonstrates that connectivity is not the sole parameter governing elastic modulus scaling. It offers a promising route to access novel mechanical properties in lattice materials via disordering the architectures.

Regulation of Msh4-Msh5 association with meiotic chromosomes in budding yeast.

In the baker's yeast Saccharomyces cerevisiae, most of the meiotic crossovers are generated through a pathway involving the highly conserved mismatch repair related Msh4-Msh5 complex. To understand the role of Msh4-Msh5 in meiotic crossing over, we determined its genome wide in vivo binding sites in meiotic cells. We show that Msh5 specifically associates with DSB hotspots, chromosome axes, and centromeres on chromosomes. A basal level of Msh5 association with these chromosomal features is observed even in the absence of DSB formation (spo11Δ mutant) at the early stages of meiosis. But efficient binding to DSB hotspots and chromosome axes requires DSB formation and resection and is enhanced by double Holliday junction structures. Msh5 binding is also correlated to DSB frequency and enhanced on small chromosomes with higher DSB and crossover density. The axis protein Red1 is required for Msh5 association with the chromosome axes and DSB hotspots but not centromeres. Although binding sites of Msh5 and other pro-crossover factors like Zip3 show extensive overlap, Msh5 associates with centromeres independent of Zip3. These results on Msh5 localization in wild type and meiotic mutants have implications for how Msh4-Msh5 works with other pro-crossover factors to ensure crossover formation.

Understanding the onset of negative electronic compressibility in single-band and two-band two-dimensional electron gases: Application to LaAlO3/SrTiO3

We investigate the effects of two electronic bands at the negative electronic compressibility (NEC) in a two-dimensional electron gas (2DEG). We use a simple homogeneous model with Coulombic interactions and first-order multi-band coupling to examine the role of effective mass and relative permittivity in relation to the critical carrier density, where compressibility turns negative. We demonstrate that the population of a second band, along with the presence of inter-band coupling, can dramatically change the cross-over carrier density. Given the difficulty in determining and confirming multi-band electronic systems, this model provides a potential method for identifying multi-band electronic systems using precise bulk electronic properties measurements. To help illustrate this method, we apply our results to the observed NEC in the 2D electron gas at the interface of LaAlO$_3$/SrTiO$_3$ (LAO/STO) and determine that, for the known parameters of LAO/STO, the system is likely a realization of a two-band 2D electron gas. Furthermore, we provide general limits on the inter-band coupling with respect to the electronic band population.

Penetration mechanism of cells by vertical nanostructures.

Cell penetration by high aspect-ratio vertical nanostructures such as nanowires and nanopillars provides a powerful method for accessing the cell interior for delivery and sensing. However, there is a lack of studies on the understanding of the mechanism of cell membrane penetration and how design nanostructures to optimize the efficiency of penetration remains unclear. Here, we propose an analytical model to elucidate the mechanism of cells penetration by analyzing the free-energy change of cells adhered to the nanostructures surface. Furthermore, we provide a simple method to evaluate the crossover radius or density for cell membrane penetration. By introducing a dimensionless parameter, i.e., adhesion area factor, we investigated the effects of the radius and distribution densities of nanostructures on cell membrane penetration which is determined by the competition between adhesion energy and deformation energy. Besides, a diagram of the distribution of cell penetration and no penetration is obtained. From the cell penetration diagram, one can determine easily and intuitively the relations of cell penetration state with the radius and distribution densities of nanostructures. Our theoretical results seem to show broad agreement with experimental observations, which implies that these studies would provide useful guidance to the design of nanopatterned surfaces for biomedical applications.

Following the effect of braid architecture on performance and damage of carbon fibre/epoxy composite tubes during torsional straining

The torsional performance of bi-axially braided carbon fibre reinforced polymer (CFRP) tubes as a function of braid architecture is investigated. It is found that for a given braid pattern, the 45° braided CFRP tubes have higher shear moduli and lower shear strength than the 35° braids. In general, 2/2 (regular) braided CFRP tubes exhibit both higher shear strength and higher shear modulus than 1/1 (diamond) braids. However, beyond the peak load, the shear strength of 2/2 braided CFRPs exhibits sudden and steep drops, resulting in a lower remnant shear strength than 1/1 structures after the shear strain exceeds 4.5%. Moreover, the damage evolution is monitored in-situ by synchrotron X-ray computed tomography during torsional straining. It shows that for a 2/2 structure, inter-tow debonded regions are vertically interconnected allowing rapid crack propagation and strength drops, whereas for the 1/1 braid they are distributed in a chequer board pattern causing a more gradual loss of strength. The fibre/matrix interfacial strength and tow cross-over density play key roles in the torsional failure of 1/1 and 2/2 braided CFRP tubes, as the former controls damage initiation and the latter controls damage propagation.

Design and synthesis of pleated DNA origami nanotubes with adjustable diameters.

DNA origami allows for the synthesis of nanoscale structures and machines with nanometre precision and high yields. Tubular DNA origami nanostructures are particularly useful because their geometry facilitates a variety of applications including nanoparticle encapsulation, the construction of artificial membrane pores and as structural scaffolds that can uniquely spatially arrange nanoparticles in circular, linear and helical arrays. Here we report a system of parametrization for the design of radially symmetric DNA origami nanotubes with adjustable diameter, length, crossover density, pleat angle and chirality. The system is implemented into a computational algorithm that provides a practical means to navigate the complex geometry of DNA origami nanotube design. We apply this in the design, synthesis and characterization of novel DNA origami nanotubes. These include structures with pleated walls where the same number of duplexes can form nanotubes with different diameters, and to vary the diameter within the same structure. We also construct nanotubes that can be reconfigured into different chiral shapes. Finally, we explore the effect of strain on the local and global geometry of DNA origami nanotubes and demonstrate how pleated walls can provide a strategy to rigidify nanotubes and to construct closely packed parallel duplexes.

Translational and rotational diffusion of rod shaped molecules by molecular dynamics simulations

The results of molecular dynamics simulations of the dynamical evolution of assemblies of linear rigid rods of variable aspect ratio, a, and number density, ρ, in the isotropic phase are reported. The rods consist of m equally spaced sites interacting with the Weeks-Chandler-Andersen repulsive pair potential, where 2 < m < 16. With increasing m, features specific to long rods, such as anisotropic self-diffusion, become apparent. There is also an increasing separation between the characteristic relaxation times of the torque, angular velocity, and reorientational time correlation functions with increasing density. The latter is exponential at high densities even for dimers. The isotropic translational diffusion coefficient, Di, and rotational diffusion coefficient, Dr, are reported as a function of m and ρ or volume fraction, ξ. The mDi data scale with ξ throughout much of the simulated range, while the rotational diffusion coefficients scale approximately as m3Dr against ρ at low densities but as ∼m6Dr at high ρ, consistent with theories of colloidal and noncolloidal rod-containing liquids. The crossover density between the two regimes is parameterized in analytic form. The probability distribution functions for displacements and angular jumps in a given time show evidence of non-Gaussian behavior with increasing density. The shear viscosity and Di scale approximately as m and m-1, respectively, in the semidilute regime, which is consistent with a Stokes-Einstein-like relationship. At high concentrations, a frustrated or glassy structure formed in which the rods were randomly oriented.

The High Temperature Crossover for General 2D Coulomb Gases

We consider $N$ particles in the plane influenced by a general external potential that are subject to the Coulomb interaction in two dimensions at inverse temperature $\beta$. At large temperature, when scaling $\beta=2c/N$ with some fixed constant $c>0$, in the large-$N$ limit we observe a crossover from Ginibre's circular law or its generalization to the density of non-interacting particles at $\beta=0$. Using several different methods we derive a partial differential equation of generalized Liouville type for the crossover density. For radially symmetric potentials we present some asymptotic results and give examples for the numerical solution of the crossover density. These findings generalise previous results when the interacting particles are confined to the real line. In that situation we derive an integral equation for the resolvent valid for a general potential and present the analytic solution for the density in case of a Gaussian plus logarithmic potential.

Integrated vector control of Aedes aegypti mosquitoes around target houses

BackgroundThe developing fetuses of pregnant women are at high risk of developing serious birth defects following Zika virus infections. We applied an Integrated Vector Control (IVC) approach using source reduction, larviciding, and mass trapping with non-insecticidal sticky traps to protect targeted houses by reducing the density of female Aedes aegypti mosquitoes.MethodsWe tested the hypothesis that Ae. aegypti density could be reduced to below three female mosquitoes/trap/week around a target house in the center of a circular area with a 150 m radius using IVC. Two non-adjacent areas within the same neighbourhood were selected and randomly designated as the treatment or control areas. Sentinel Autocidal Gravid Ovitraps (SAGO traps) were placed in each study area and were sampled weekly from May to November, during the 2016 Zika epidemic in Puerto Rico. The experimental design was longitudinal with pre-and post-IVC treatment observations between treatment and control areas, and a partial cross-over design, where IVC was applied to the original control area after 2 months to determine if Ae. aegypti density converged to levels observed in the treatment area. Pools of female Ae. aegypti mosquitoes were analyzed by RT-PCR to detect Zika, dengue and chikungunya virus RNA.ResultsOverall, pre-treatment mosquito densities in the inner (0–50 m; 15.6 mosquitoes/trap/week), intermediate (50–100 m; 18.1) and outer rings (100–150 m; 15.6) were reduced after treatment to 2.8, 4.1, and 4.3 in the inner, middle, and outer rings, respectively. Density at the target house in the treatment area changed from 27.7 mosquitoes/trap/week before IVC to 2.1 after IVC (92.4% reduction), whereas after treating the original control area (cross-over) density changed from 22.4 to 3.5 (84.3% reduction). Vector reductions were sustained in both areas after IVC. Zika virus was detected in Ae. aegypti, but the low incidence of the virus precluded assessing the impact of IVC on Zika transmission during the study.ConclusionsApplying IVC to circular areas that were surrounded by untreated areas significantly decreased the number of mosquitoes around target houses located in the center. Gravid Ae. aegypti females in the center of the 150 m areas fell below threshold levels that possibly protect against novel invading arboviruses, such as chikungunya and Zika.

Loss of Drosophila Mei-41/ATR Alters Meiotic Crossover Patterning.

Meiotic crossovers must be properly patterned to ensure accurate disjunction of homologous chromosomes during meiosis I. Disruption of the spatial distribution of crossovers can lead to nondisjunction, aneuploidy, gamete dysfunction, miscarriage, or birth defects. One of the earliest identified genes involved in proper crossover patterning is Drosophila mei-41, which encodes the ortholog of the checkpoint kinase ATR. Analysis of hypomorphic mutants suggested the existence of crossover patterning defects, but it was not possible to assess this in null mutants because of maternal-effect embryonic lethality. To overcome this lethality, we constructed mei-41 null mutants in which we expressed wild-type Mei-41 in the germline after completion of meiotic recombination, allowing progeny to survive. We find that crossovers are decreased to about one-third of wild-type levels, but the reduction is not uniform, being less severe in the proximal regions of chromosome 2L than in medial or distal 2L or on the X chromosome. None of the crossovers formed in the absence of Mei-41 require Mei-9, the presumptive meiotic resolvase, suggesting that Mei-41 functions everywhere, despite the differential effects on crossover frequency. Interference appears to be significantly reduced or absent in mei-41 mutants, but the reduction in crossover density in centromere-proximal regions is largely intact. We propose that crossover patterning is achieved in a stepwise manner, with the crossover suppression related to proximity to the centromere occurring prior to and independently of crossover designation and enforcement of interference. In this model, Mei-41 has an essential function in meiotic recombination after the centromere effect is established but before crossover designation and interference occur.

Effects of film growth kinetics on grain coarsening and grain shape.

We study models of grain nucleation and coarsening during the deposition of a thin film using numerical simulations and scaling approaches. The incorporation of new particles in the film is determined by lattice growth models in three different universality classes, with no effect of the grain structure. The first model of grain coarsening is similar to that proposed by Saito and Omura [Phys. Rev. E 84, 021601 (2011)PLEEE81539-375510.1103/PhysRevE.84.021601], in which nucleation occurs only at the substrate, and the grain boundary evolution at the film surface is determined by a probabilistic competition of neighboring grains. The surface grain density has a power-law decay, with an exponent related to the dynamical exponent of the underlying growth kinetics, and the average radius of gyration scales with the film thickness with the same exponent. This model is extended by allowing nucleation of new grains during the deposition, with constant but small rates. The surface grain density crosses over from the initial power law decay to a saturation; at the crossover, the time, grain mass, and surface grain density are estimated as a function of the nucleation rate. The distributions of grain mass, height, and radius of gyration show remarkable power law decays, similar to other systems with coarsening and particle injection, with exponents also related to the dynamical exponent. The scaling of the radius of gyration with the height h relative to the base of the grain show clearly different exponents in growth dominated by surface tension and growth dominated by surface diffusion; thus it may be interesting for investigating the effects of kinetic roughening on grain morphology. In growth dominated by surface diffusion, the increase of grain size with temperature is observed.

Density Affects the Nature of the Hexatic-Liquid Transition in Two-Dimensional Melting of Soft-Core Systems

We find that both continuous and discontinuous hexatic-liquid transitions can happen in the melting of two-dimensional solids of soft-core disks. For three typical model systems, Hertzian, harmonic, and Gaussian-core models, we observe the same scenarios. These systems exhibit reentrant crystallization (melting) with a maximum melting temperature T_{m} happening at a crossover density ρ_{m}. The hexatic-liquid transition at a density smaller than ρ_{m} is discontinuous. Liquid and hexatic phases coexist in a density interval, which becomes narrower with increasing temperature and tends to vanish approximately at T_{m}. Above ρ_{m}, the transition is continuous, in agreement with the Kosterlitz-Thouless-Halperin-Nelson-Young theory. For these soft-core systems, the nature of the hexatic-liquid transition depends on density (pressure), with the melting at ρ_{m} being a plausible transition point from discontinuous to continuous hexatic-liquid transition.