Conductivity Diffusivity Research Articles

Understanding the role of aliovalent cation substitution on the li-ion diffusion mechanism in Li6+xP1-xSixS5Br argyrodites.

Due to their high ionic conductivity, lithium-ion conducting argyrodites show promise as solid electrolytes for solid-state batteries. Aliovalent substitution is an effective technique to enhance the transport properties of Li6PS5Br, where aliovalent Si substitution triples ionic conductivity. However, the origin of this experimentally observed increase is not fully understood. Our density functional theory (DFT) study reveals that Si4+ substitution increases Li diffusion by activating Li occupancy in the T4 sites. Redistribution of Li-ions within the lattice results in a more uniform distribution of Li around the T4 and neighboring T5 sites, flattening the energy landscape for diffusion. Since the T4 site is positioned in the intercage jump pathway, an increase in the intercage jump rate is found, which is directly related to the macroscopic diffusion and bulk conductivity. Analysis of neutron diffraction experiments confirms partial T4 site occupancy, in agreement with the computational findings. Understanding the aliovalent substitution effect on interstitials is crucial for improving solid electrolyte ionic conductivity and advancing solid-state battery performance.

Lung function and cardiovascular risk at age 45 in a cohort of the general population

BackgroundImpaired lung function is associated with cardiovascular mortality, but the origins of this association are poorly understood. We investigated associations between lung function and cardiovascular risk scores in a general population cohort of men and women aged 45 years. MethodsParticipants are members of an unselected birth cohort followed to adulthood. Lung function determined at ages 32 and 45 by spirometry, body plethysmography, gas diffusion, and airway conductance were the main predictors. Future cardiovascular risk was estimated at age 45 using a multivariable cardiovascular risk algorithm – PREDICT. Risk scores were log-transformed and used as the dependent variable in linear regression analyses. We investigated cross-sectional associations with lung function at age 45 and longitudinal associations using changes in lung function between ages 32–45 as the predictors. Results863 of 1037 original cohort participants had data for analysis. Low lung volumes (FEV1, FVC, VA, TLC, and FRC) were associated with greater cardiovascular risk scores in the cross-sectional analyses at age 45 and the longitudinal analyses. These associations were stronger in women than in men, were independent of smoking history, and present in never smokers, even after adjusting for body mass index. Associations were not found for measures of airway function (FEV1/FVC ratio and sGaw) or gas transfer (TLco/VA). ConclusionsLow lung volumes at age 45 and accelerated pulmonary function decline are associated with a higher estimated cardiovascular risk scores in mid-adulthood. This association is stronger in women and is not explained by smoking or obesity.

Facile and Low Temperature Synthesis of Nd1.8Sr0.2NiO4-δ Cathode Nanofibers for Intermediate Temperature Solid Oxide Fuel Cells

Solid oxide fuel cells (SOFCs) are usually operated at high temperatures (800-1000 °C). As the overall efficiency of SOFC is governed by thermodynamics and kinetics during operation, reducing the operating temperature to 500-650 °C causes significant increase in the electrode polarization losses especially at cathode due to high activation energy towards oxygen reduction reaction (ORR) at cathode, which eventually reduces the overall cell performance. Addressing increased polarization losses at relatively low temperatures (500-650 °C) has been the key issue and a focus of many groups over past couple of decades. Conventional cathode materials lose their ORR activity and so discarded for intermediate temperature (IT)-SOFC application. In this regard, mixed ionic-electronic conductors (MIECs) offer high thermal and chemical stability along with high oxygen diffusion and good electronic conductivity at IT [1,2]. In addition, Ruddlesden-Popper (RP) type MIECs with A2BO4 structure have been demonstrated as promising cathode for IT- SOFCs due to their unique structure, rapid oxygen surface exchange kinetics, and excellent stability in atmosphere. Particularly Nd2NiO4+δ oxides offer an excellent oxygen diffusion coupled with high surface exchange coefficients and comparable thermal expansion coefficients with those of oxygen-ion conductors (YSZ and CGO) [2]. Enhanced electronic conductivity and electrochemical performance have been demonstrated for partial replacement of Nd with Sr in our previous reports [3].Albeit, the intrinsic material properties such as electrochemical catalytic activity and electrical conductivity are of primary importance, an actual electrode performance strongly depends on its microstructure. Therefore, in addition to using high catalytic and conductive materials, achieving an extremely high-power density, thus, requires a finely controlled electrode microstructure, to expand the electrochemically active triple-phase boundary (TPB). Recently, electrospinning has been considered as an efficient, cost effective and promising method for synthesis of ceramic nanofibers. Pertinent literature suggests that SOFC with cathode nanofiber has superior/better performance (nearly doubled power density and significant reduced polarization resistance) compared to powder type electrodes. Selection of suitable cathode materials with modified microstructure (nanofibers) would facilitate more electrochemically active sites for the oxygen reduction at relatively low temperatures <650 °C.In this paper we synthesized Nd1.8Sr0.2NiO4-δ (NSNO) cathode nanofibers using electrospinning technique and compared its electrochemical performance with NSNO nanopowder. Practically, 10 wt.% Polyvinylpyrrolidone (PVP) solution was prepared by dissolving it in ethanol, to which stoichiometric amounts of Nd-nitrate, Sr-nitrate, Ni-nitrate (total weight percentage of metal salts- 3 wt%) were added, together with some deionized water. The mixture was then stirred for 10 h at room temperature on a magnetic stirrer to obtain a homogeneous sol. The sol was loaded into the electrospinning syringe. Distance between the spinneret and the collector was fixed at 25 cm and the high-voltage supply was maintained at 30 kV. The spinning rate was controlled at 5 ml h- 1 by a syringe pump. The obtained nanofibers were dried at 80 °C for 12 h, then sintered at 900 °C for 2 h in air to obtain single-phase NSNO.The obtained nanofibers were characterized using room temperature XRD, XPS, SEM and dc electrical conductivity (400-650 °C). In addition, electrochemical impedance spectroscopy studies on symmetric cells were carried out as a function of temperature (400-650 °C). Improved electrochemical performance is attributed to enhanced electrochemical active sites for ORR due to nanofibers and optimum porosity.

Life Cost Assessment of Using Binders of Sulfide-Based All Solid-State Lithium Batteries for Lithium-Ion Batteries

PVDF is commonly a binder used for cathode materials in generation 3 Li ion batteries due to the good binding ability to active material and the current collector with reasonable electrochemical stability and maintaining facile lithium transport. However, organic solvent N-methyl pyrrolidone (NMP) is required for the preparation of slurry in order to dissolve PVDF [1]. These drawbacks of high cost and environmental issues are worsened by the fact that PVDF can easily react with components of liquid electrolytes with possible formation of LiF leading to the unstable performance [2]. Furthermore, fluorinated polymers are considered an environmental risk and are a major concern for recycling efforts [3]. Therefore, reducing the use of polyvinylidene difluoride binder in combination with toxic and expensive N-methyl pyrrolidone (NMP) organic solvent, resulting in safe use and utilization during the battery manufacturing process, is the aim of this work. Here, the sulfide solid state binders are attractive candidates for the anode and cathode composites from the point of view of environmentally friendly use of materials, low cost, and easy electrode processing with subsequent disposal. This study reports the performance of the cathode and anode materials applied to these types of binders and reference binders of polyvinylidene difluoride (PVDF) for these as-obtained samples for lithium-ion batteries. The obtained cathode and anode materials are analyzed by XRD and SEM methods. The electrochemical performance of the obtained electrodes is tested by galvanostatic cycling, cyclic voltammetry, and electrochemical impedance spectroscopy. The obtained electrodes exhibit stable electrochemical performance due to the better uniform distribution of electrode particles with strong adhesion to the current collector for long cycle life and stable formed SEI layer compared to the PVDF-based sample. In addition, these samples maintain stable cycle life after various rate capabilities due to the facilitated lithium-ion diffusion and electronic conductivity. Acknowledgments This work was supported by the financial support of the Austrian Federal Ministry for Climate Action, Environment, Energy, Mobility, Innovation and Technology.

(Invited) On Non-equilibrium Thermodynamics in Electrochemical Systems

Much of our understanding of physical behavior of materials is based on the concept of equilibrium, which lies at the heart of classical thermodynamics, condensed matter physics, and modern reaction kinetics. If a thermodynamic system is in equilibrium conditions, which is the situation when an energy system (e.g., a fuel cell or a battery) is under open circuit voltage, the surface and bulk of the electrode are only subject to fluctuation of thermodynamic qualities. For the cases that are not at equilibrium, but are close to it, Onsager established linear reciprocal relationships between flux and thermodynamic force for a thermodynamic system in nonequilibrium states. These linear relationships are manifested in transport phenomena, which are non-equilibrium processes, such as ion diffusion and heat conduction.When an electrochemical reaction takes place at an electrode of a fuel cell, electrolyzer, or battery, the thermodynamic system is far away from equilibrium. Therefore, the thermodynamic states of the surface and bulk of an electrode are subject to external thermodynamic forces. As a result, in an active electrode, the electrochemical reaction on the surface causes all thermodynamic variables to change in both the surface and the bulk. In this talk, I will use solid oxide cells and lithium-ion batteries as an example to address three questions related to materials in non-equilibrium thermodynamic states: (i) how do fast kinetics and high current in an operating electrochemical cell affect the thermodynamic states of its material constituents, (ii) whether or not the state of non-equilibrium can remain stable with constant flow of matter and energy, and (iii) what is the origin that governs activity and stability in solid oxide cells?

Entropy optimized flow subject to variable fluid characteristics and convective conditions

Background and objectiveNanofluids possess significant enhancement in nanomaterial properties such as convective heat transfer coefficient, thermal conductivity (which increases volumetric fraction of nanoparticles) and diffusivity at reasonable nanoparticle concentration. Nanofluids provide interesting new opportunities to develop nanotechnology-based operative coolants for different kinds of innovative applications. Hydromagnetic radiative flow of nanomaterial by curved stretched sheet is addressed in presence of Darcy-Forchheimer relation. Heat generation and dissipation are deliberated. Variable mass diffusivity and thermal conductivity behaviors are under consideration. Convective conditions are taken into account. Random diffusion and thermophoresis behaviors are considered. Dufour and Soret behaviors are taken. Binary chemical reaction and thermal radiation are explored. Entropy rate is taken into consideration. MethodologyNonlinear formulation is reduced to ordinary differential system. Convergent solutions for nonlinear ordinary systems are developed invoking Optimal homotopy analysis method (OHAM). ResultsImpacts for influential parameters regarding fluid flow, pressure, thermal distribution, entropy and concentration are discussed. Larger magnetic variable has reverse behavior on entropy rate and pressure. Higher magnetic field intensifies thermal distribution whereas reverse effect noted for liquid flow. Thermal distribution has increasing trend for Dufour number and variable thermal conductivity. Concentration reduces for random motion and Schmidt number. Concentration has increasing behavior for Soret number and variable mass diffusivity parameter. Larger estimation of thermal Biot number has same impact on thermal distribution and entropy. Increasing behaviors of entropy rate and concentration for solutal Biot number are observed. Bejan number reduces against Brinkman number whereas opposite trend holds for radiation parameter.

Structure of aqueous alkali metal halide electrolyte solutions from molecular simulations of phase-transferable polarizable models

The structure of aqueous solutions of alkali metal halides is studied under ambient thermodynamic conditions and concentrations from infinite dilution to supersaturation using molecular dynamics simulations of phase-transferable polarizable models. The results of the solution densities, radial distribution functions, 3D spatial distribution functions, the properties of hydrogen and other noncovalent bonds in solutions, hydration numbers, coordination numbers, numbers of contact cation-anion pairs, and other statistics of the number of ions hydrated simultaneously by a shared water molecule are systematically presented. In particular, the results show and quantify how the strengths of the hydration bonds of different ions vary and how the hydration numbers decrease with increasing concentration in parallel with an increase in the number of contact cation-anion pairs. In most cases, they completely compensate for the loss of water-ion bonds by an increase in cation-anion bonds. An exception are solutions based on the Li+ cation, which retain a solid hydration shell even at high concentrations. This behavior is conceptualized on the basis of three imaginary driving forces: the first dominating at low concentrations and causing full hydration of the ions, the second representing a lack of water necessary for full hydration of the ions and increasing with increasing concentration, and the third attracting counterions to the water-unoccupied sites of the hydration shells and also increasing with concentration. This concept can be used not only to understand the structural behavior of homogeneous electrolytes in thermodynamic equilibrium but also to study phenomena that involve preferential adsorption of ions on electrodes, in nanochannels, or porous materials. The data obtained for the number and strength of hydration bonds and ion pairs can also be used in further studies to elucidate the diffusion behavior, viscosity, and conductivity of aqueous electrolyte solutions.

Transport properties evaluation of pore-scale GDLs for PEMFC using orthogonal design method

Gas diffusion layer (GDL) is an essential component of proton exchange membrane fuel cells, serving the functions of gas-water transport, thermal-electrical conduction and mechanical support. The various microstructural characteristics of the GDL have coupled and complex impact on transport properties, which is not comprehensively considered in previous studies. This study combines stochastically reconstruction techniques, pore-scale modeling and orthogonal design method to evaluate the coupling effect of multiple microstructural characteristics on transport properties, and determine the impact degree of each microstructural characteristics, including fiber diameter, porosity, GDL thickness, fiber orientation coefficient, binder and PTFE content. Finally, new mathematical models are developed and validated to predict and optimize the anisotropic transport properties accurately and rapidly by considering the coupling effect of multiple microstructural characteristics. The results showed that porosity has higher impact degree on gas diffusion and heat conduction than other microstructural characteristics. The combinations of microstructural parameters are optimized to achieve higher performance, with thermal conductivity and gas diffusivity increased by ≥139% and 62%, respectively. The prediction mathematical models are validated with the error ranging from 1% to 8%, which can predict transport properties and optimize the GDL microstructure accurately and rapidly.

Exploring the responses of crop photosynthesis to CO2 elevation at the molecular, physiological, and morphological levels toward increasing crop production

Exploring the impact of elevated CO2 on photosynthesis is vital for understanding plant responses to climate change. In C3 plants, elevated CO2 concentrations generally enhance CO2 assimilation by increasing chloroplast CO2 concentration. However, the underlying mechanisms are complex since photosynthesis involves multiple physiological processes operating at different time scales and varying among plant species. In this review, we focused on the responses of key photosynthetic processes in crop, including CO2 diffusion conductances such as stomatal conductance (gs), mesophyll conductance (gm), photochemical reactions, the Calvin-Benson cycle, and related metabolic pathways. Short-term exposure to elevated CO2 often decreases gs and gm while increasing the electron transport rate. However, long-term exposure to elevated CO2 can decrease photosynthetic capacity due to coordinated downregulation of multiple processes, particularly when the sink‒source ratio declines. To enhance plant productivity under elevated CO2, it is crucial to maintain or enhance sink activity and understand the CO2 response mechanisms at the molecular, physiological, and morphological levels. This review provides an update on the short- and long-term responses of gs, gm, electron transport system, and carbon assimilation metabolism to elevated CO2. Furthermore, it offers a perspective on improving crop production in the future with elevated CO2 levels.

Analysis of Forchheimer Effect for Double Diffusive Convection With Dusty Fluids and MHD

An attempt has been made to analyze the effect of second order resistance for a steady, dusty fluid considering magnetohydrodynamic (MHD) and also the characteristics of fluid like permeability, porosity, solutal diffusivity and thermal conductivity being varied. Here the basic equations are coupled, non-linear Partial Differential Equations (PDEs), which are changed by similarity transformations to higher order Ordinary Differential Equations (ODE). After being transformed the higher order ODE that where obtained are resolved numerically. Shooting technique is employed here and the values are tabulated for various pertinent parameter variations. The effects of the inertia, concentration and interaction, mixed convection, magnetic and many other parameters are discussed and plotted graphs for velocity, concentration and temperature. The magnetic force enhances velocity. It was found that the present study correlates with the existence results.

Resonant interactions involving local vibrational modes in crystals

When an impurity with a light mass is inserted into a crystal, it can undergo a high-frequency oscillation referred to as a local vibrational mode (LVM). A Fermi resonance may occur between the LVM and lower-frequency modes of the defect. The LVM may also interact with phonons or the electromagnetic field. Understanding these interactions can help model and control diffusion, defect reactions, and thermal conductivity. LVMs have been probed in semiconductors using pressure and alloying as experimental parameters, resulting in anticrossing between localized and extended vibrational modes. These types of vibrational interactions could play an important role in the stability and thermal properties of organic–inorganic hybrid semiconductors. The coupling between an LVM and electromagnetic wave yields an “LVM polariton,” an excitation that has significant vibrational and electric-field amplitudes.

Rational Design of High-Loading Electrodes with Superior Performances Toward Practical Application for Energy Storage Devices.

High-loading electrodes play a crucial role in designing practical high-energy batteries as they reduce the proportion of non-active materials, such as current separators, collectors, and battery packaging components. This design approach not only enhances battery performance but also facilitates faster processing and assembly, ultimately leading to reduced production costs. Despite the existing strategies to improve rechargeable battery performance, which mainly focus on novel electrode materials and high-performance electrolyte, most reported high electrochemical performances are achieved with low loading of active materials (<2mgcm-2). Such low loading, however, fails to meet application requirements. Moreover, when attempting to scale up the loading of active materials, significant challenges are identified, including sluggish ion diffusion and electron conduction kinetics, volume expansion, high reaction barriers, and limitations associated with conventional electrode preparation processes. Unfortunately, these issues are often overlooked. In this review, the mechanisms responsible for the decay in the electrochemical performance of high-loading electrodes are thoroughly discussed. Additionally, efficient solutions, such as doping and structural design, are summarized to address these challenges. Drawing from the current achievements, this review proposes future directions for development and identifies technological challenges that must be tackled to facilitate the commercialization of high-energy-density rechargeable batteries.

Divergences in leaf CO2 diffusion conductance and water use efficiency of soybean coping with water stress and its interaction with N addition

Drought and nitrogen (N) additions have been shown to affect plant photosynthesis, but the effect of their interaction on CO2 diffusion conductance (i.e., stomatal conductance, gsc, mesophyll conductance, gm) and water use efficiency (WUE) at the leaf level (i.e., instantaneous water use efficiency, WUEins; intrinsic water use efficiency, WUEint) has rarely been reported. Herein, we examined the interactive effects of drought and N addition on gsc and gm and WUE (i.e., WUEins and WUEint) in soybean (Glycine max (Linn.) Merr.) and analysed the interaction mechanisms mitigating water stress based on leaf anatomy and molecular activity. Drought decreased gsc,gm and WUEins, but N addition had a positive interactive effect with water stress on leaf physiological traits. The variables gsc, gm and WUEins were significantly increased by the additions of 7.5 and 15.0 g urea m−2 under moderate water stress (MW) conditions (P < 0.05), but they decreased under the interaction effect of SW and N addition. The decreased Tcw and increased Sm and Sc under the water stress × N addition interaction positively affected gm, and the increased SS dominated the gsc increase. In addition, these positive effects were further enhanced with increased AQP, CA and Rubisco activities and a decrease in the ABA content. Accordingly, moderate soil N additions of 7.5 and 15.0 g urea m−2 greatly mitigated the negative effects of droughts, especially the MW effects, by enhancing CO2 diffusion conductance and WUE.

Synthesis and characterization of functionally graded SiC-mullite thermal material

SiC-mullite is considered for high temperature applications due to its high mechanical strength and thermal shock-resistance. However, maintaining these properties is challenged by the high processing temperature requirement for the formation and densification of the mullite phase which leads to abundant surface oxidation of SiC into cristobalite. Cristobalite has relatively poor mechanical strength and thermal properties compared to SiC. Herein, we report on using coal fly ash as a source of alumina (Al2O3) that reacts in situ with the silica (SiO2), oxidation product of SiC. The instantaneous mullite formation on the surface of SiC facilitated due to the presence of minor concentrations of metal oxides in coal fly ash, resulted in a strong bonding zone between the two phases at relatively low temperature. In this work, SiC was mixed with coal fly ash at weight ratios of 90SiC/10ash, 85SiC/15ash, 80SiC/20ash, and 75SiC/25ash and sintered at 1400 °C. Measurements of mechanical properties showed that the 85SiC/15ash composition had the highest mechanical strength among samples. XRD analysis showed the phase composition of thermally treated 85SiC/15ash to be 81.8 wt% SiC, 11.4 wt% mullite, and 6.8 wt% cristobalite. SEM-EDX revealed a concentration gradient of Al in the cristobalite which enhanced formation of functionally graded bonding zones between phases and resulted in SiC-mullite composite with high thermomechanical properties. The compressive strength, nanoindentation elastic modulus, and Vickers hardness were 434 ± 20 MPa, 370.9 ± 22.6 GPa, and 11.5 ± 1.2 GPa respectively. The thermal shock resistance test showed high dimensional and mechanical stabilities after quenching in liquid nitrogen (−196 °C) from 1400 °C. The SiC-mullite composite showed low thermal expansion co-efficient from 3.17 × 10−7/K to 5.615 × 10−6/K when the sample was heated from 182 K to 354 K. The specific heat capacity, thermal diffusivity, and thermal conductivity were 7.83 ± 0.0014 J/g.K, 1.04 ± 0.013 mm2/s, and 17 W/m.K at 100 °C, respectively. The SiC-mullite composite exhibited moderate electrical conductivity of 3.48 × 10−2 S/m at 1000 °C.

Driving sustainable energy storage: A multi-scale investigation of methane hydrate formation with green promoters and innovative reactor design

Synthetic Gas hydrates are promising materials for safe and compact energy storage but their wide-scale application is hindered by slow formation kinetics. We investigated the effect of green kinetic promoters of H-SSZ-13 zeolite, L-tryptophan, L-leucine, and L-methionine in a novel reactor design to accelerate hydrate formation at 6 MPa. In (NSR), H-SSZ-13 and L-tryptophan showed superior performance over L-leucine and L-methionine. While H-SSZ-13 showed the lowest average (t90) of 286 mins and the highest volumetric capacity of 115 V/V at 283 K, its kinetic performance, along with other promoters, dropped significantly at 293 K. We introduced a new (FBR) equipped with light (MFP) to increase gas diffusion and thermal conductivity. The combined effect of (FBR)-(MFP) reactor with zeolite significantly improved the kinetics overcoming (NSR) drawbacks. At 293.15 K, H-SSZ-13 zeolite promoter showed superior performance reducing the induction time and (t90) to 3 and 154 mins, respectively. Furthermore, it exploited 88.6%, and 96% of the sII clathrates volumetric storage capacity at 293 K and 283 K, respectively. Finally, we showed that the synthesized hydrates can be stored at atmospheric pressure for 4 months without significant methane loss. This multi-scale approach is paving the way for scaling up green and economical gas hydrate technology.

Mesophyll conductance limits photosynthesis in fluctuating light under combined drought and heat stresses.

Drought and heat stresses usually occur concomitantly in nature, with increasing frequency and intensity of both stresses expected due to climate change. The synergistic agricultural impacts of these compound climate extremes are much greater than those of the individual stresses. However, the mechanisms by which drought and heat stresses separately and concomitantly affect dynamic photosynthesis have not been thoroughly assessed. To elucidate this, we used tomato (Solanum lycopersicum) seedlings to measure dynamic photosynthesis under individual and compound stresses of drought and heat. Individual drought and heat stresses limited dynamic photosynthesis at the stages of diffusional conductance to CO2 and biochemistry, respectively. However, the primary limiting factor for photosynthesis shifted to mesophyll conductance under the compound stresses. Compared with the control, photosynthetic carbon gain in fluctuating light decreased by 38%, 73%, and 114% under the individual drought, heat, and compound stresses, respectively. Therefore, compound stresses caused a greater reduction in photosynthetic carbon gain in fluctuating light conditions than individual stress. These findings highlight the importance of mitigating the effects of compound climate extremes on crop productivity by targeting mesophyll conductance and improving dynamic photosynthesis.

Insulin resistance without coexisting hyperglycaemia is not independently associated with cardiorespiratory fitness or its components in women

Abstract Background Insulin resistance (IR) is a globally prevalent condition in which tissues’ response to insulin is diminished. Cardiorespiratory fitness (peak O2 uptake (VO2peak)) is determined by Fick’s equation (VO2 = cardiac output (CO) × arteriovenous O2 difference (Ca-vO2) = heart rate × stroke volume (SV) × Ca-vO2) and diffusion law (VO2 = diffusive O2 conductance (DO2) × constant k × venous O2 pressure (PvO2)). Several studies suggest an association between IR and decreased VO2peak, but the association has been questioned by analyses taking account of body size and composition, and potential mechanisms behind the association are unknown. Purpose To test a hypothesis that IR is not independently associated with VO2peak or its components. Methods Fifty of 144 women, who had participated in baseline experiments of three intervention studies, were included in this retrospective cross-sectional study; see Table 1 for subject characteristics. The inclusion criteria were age 18-40 years, body mass index 18.5-40 kg/m2, Caucasian origin, and available data on key measures. The exclusion criteria were diseases, medications, and other factors possibly affecting VO2peak. We measured haemoglobin, fasting glucose, and fasting insulin concentrations (blood), assessed IR (homeostasis model assessment (HOMA-IR)), and measured body size and composition (bioimpedance). The subjects performed an incremental cycling test to volitional fatigue; we measured ventilatory gas exchange (spiroergometry), arterial O2 saturation (oximetry), and SV and CO (impedance cardiography), and calculated Ca-vO2, DO2, and PvO2. We analysed VO2peak and its components as absolute (e.g. L/min) and ratiometrically scaled values (e.g. mL/min/kg), and when appropriate, also as allometrically scaled values (e.g. mL/min/kg^x, where 0 &amp;lt; x &amp;lt; 1) after identifying optimal variable-specific exponents. Results VO2peak scaled to body mass (BM) as well as SVpeak and COpeak scaled to body surface area (BSA) were inversely associated with the body size variables they were scaled to (all P &amp;lt; 0.013). Contrariwise, this was not the case when we optimally scaled VO2peak to fat-free mass (FFM), SVpeak to FFM^0.55, COpeak to FFM^0.50, and DO2peak to FFM (all 0.066 &amp;lt; P &amp;lt; 0.977). HOMA-IR was inversely associated with VO2peak scaled to BM but not in a multivariate analysis, whereas HOMA-IR was not associated with VO2peak scaled to FFM (Table 2); we made alike observations with SVpeak and COpeak (data not shown). Further, VO2peak scaled to BM as well as SVpeak and COpeak scaled to BSA were or tended to be up to 15 % higher in a group with HOMA-IR&amp;lt;3.0 than in a group with HOMA-IR≥3.0, while other peak exercise data did not differ between the groups (Table 1). Conclusion Body size and composition significantly affect conclusions drawn regarding VO2peak and its components. Taking this into account, IR without coexisting hyperglycaemia is not independently associated with VO2peak or its components in women.Table 1Table 2

Sex differences in the peripheral determinants of oxygen uptake in heart failure with preserved ejection fraction

Abstract Background A hallmark feature of heart failure with preserved ejection fraction (HFpEF) is exercise intolerance. Data from non-invasive, whole-body cardiopulmonary exercise testing indicates that females with HFpEF have reduced VO2 secondary to a to lower cardiac output and arterial-to-venous oxygen content difference (∆a-vO2) at maximal effort compared to males with HFpEF [1]. Thus, in addition to cardiac limitations, peripheral/non-cardiac limitations may be important contributors to reduced peak aerobic power (VO2) in females with HFpEF; however, these peripheral mechanisms of exercise intolerance are not fully understood. Given that HFpEF disproportionately affects older females, identifying sex differences in the limitations to exercise is especially important. Purpose Using dynamic single leg knee extension (SLKE) exercise to isolate peripheral determinants of oxygen transport and utilization, we sought to test the hypothesis that females with HFpEF have lower leg VO2 at peak SLKE resulting from smaller increases Δa-vO2 and muscle oxygen diffusive conductance (DMO2) compared to males. Methods Eighteen females (69 ± 7 years) and 13 males (73 ± 6 years) with HFpEF performed a maximal SLKE exercise test on a custom ergometer. LBF (duplex Doppler ultrasound) was measured at the common femoral artery and leg VO2 was determined as the product of LBF and ∆a-vO2 (femoral venous catheter). DMO2 was calculated as leg VO2/2x leg venous oxygen pressure (PvO2). Thigh lean and fat mass (TLM and TFM, respectively) was measured using dual energy x-ray absorptiometry. Group differences between the two sexes were compared using an unpaired t-test and significance was set at p&amp;lt;0.05. Results Body mass, body mass index, and TLM were not different between groups (p &amp;gt; 0.05 for all), however TFM was higher in females (p&amp;lt;0.001; Table 1). At rest, ∆a-vO2 was lower in females (p = 0.001), whereas heart rate, mean arterial blood pressure, femoral LBF, and leg VO2 were not different between groups (p&amp;gt;0.05 for all; Table 1). Peak workload was lower in females compared to males (13 ± 5 vs 20 ± 7 watts, p = 0.011). At peak SLKE, leg VO2 was lower in females (185 ± 57 vs 286 ± 91 ml/min, Figure 1) due to lower ∆a-vO2 (9.7 ± 1.8 vs 12.3 ± 2.5 ml O2/dl blood, p = 0.003) and LBF (1918 ± 576 vs 2382 ± 872 ml/min, p = 0.084). DMO2 at peak SLKE was also lower in females (3.6 ± 1.2 vs 6.3 ± 1.8 ml/min/mmHg, Figure 1) suggesting sex differences in both convective and diffusive oxygen transport. Moreover, when normalized to TLM, the difference in peak leg VO2 between the sexes persisted (28.2 ± 6.5 vs 41.5 ± 10.9 ml/kg/min; p = 0.004). Conclusion These data highlight that that the lower peak oxygen extraction (∆a-vO2) and diffusion (DMO2) in females with HFpEF contribute to sex-dependent differences in exercise intolerance. Further studies investigating potential sex-specific impairments in the muscle-vascular interface in HFpEF are warranted.Table 1Figure 1

Abstract 13736: Whole Body versus Small Muscle Mass Exercise Training in Patients With Heart Failure With Preserved Ejection Fraction: Impact on Peripheral Responses to Exercise

Background: Patients with heart failure with preserved ejection fraction (HFpEF) have reduced peak aerobic power (VO 2 ) during whole body exercise due in part to smaller increases in blood flow (BF) and arterial-to-venous oxygen difference (Δa-vO 2 ). We recently demonstrated that 8wks of single leg knee extension (SLKE) exercise training was effective in improving whole body VO 2 by increasing Δa-vO 2 in HFpEF; whether SLKE training induces greater peripheral adaptations compared to traditionally prescribed whole-body (i.e., cycle) training is unknown. Hypothesis: SLKE training will result in larger improvements in peak leg VO 2 , leg BF, and Δa-vO 2 during a SLKE peak exercise test vs cycle training. Methods: We recruited 16 patients with HFpEF (71 ± 6yr, 5 males) and randomized them to cycle or SLKE training 3-4 days/wk for 16wk. Before and after the intervention we quantified leg BF (ultrasound), femoral venous O 2 partial pressure (PvO 2 ) and saturation (IV catheter) during incremental SLKE peak exercise to determine peak leg VO 2, Δa-vO 2, and skeletal muscle diffusive conductance (DMO 2 ; leg VO 2 /[2x leg PvO 2 ]). Results: SLKE (n=9) and cycle (n=7) groups were matched for age and sex. Both groups increased peak workload during the SLKE exercise test (34±8%; mean ± SE; p=0.005). There was a main effect of training such that peak DMO 2 improved in both groups (cycle: 45±19%; SLKE: 12±3%; see Figure 1 ). Peak Δa-vO 2 also improved (main effect of training, p=0.002); however, this was greater in response to cycle compared to SLKE training (12±3% vs 3±2%; interaction effect, p=0.035). Conclusion: These preliminary data indicate that both types of training improve leg DMO 2 ; however, greater improvements in O 2 extraction occurred with cycle training. The differences in the peripheral adaptations may be attributed to a larger exercise “dose” in the cycle trained group. This data highlights that both modalities are effective components of exercise prescription for patients with HFpEF.

Electrotransport Properties of Perfluorinated Cation-Exchange Membranes of Various Thickness.

The present work discusses the influence of the thickness of MF-4SK perfluorinated sulfonic cation-exchange membranes on their electrotransport properties in hydrochloric acid solutions. It is found that diffusion permeability and conductivity are primarily determined with the specific water content of the membranes and increase with their increase. Analysis of the contribution of reverse diffusion through the membrane to the value of the limiting current shows that it can reach 20% for membranes with a thickness of 60 μm. A study of the characteristics of the fuel cell with perfluorinated membranes of different thicknesses shows that the membrane thickness affects both the ohmic resistance of the membrane-electrode assembly and the diffusion limitations of proton transport in polymer electrolytes.