Structural and dynamical equilibrium properties of hard board-like particles in parallel confinement.

We performed Monte Carlo and dynamic Monte Carlo simulations to model the diffusion of monodispersed suspensions composed of impenetrable cuboidal particles, specifically hard board-like particles (HBPs), in the presence of parallel hard walls. The impact of the walls was investigated by adjusting the size of the simulation box while maintaining constant packing fractions, fixed at η = 0.150, for systems consisting of HBPs with prolate, dual-shaped, and oblate geometries. We observed that increasing the distance between the walls led to the recovery of an isotropic bulk phase, while local particle organization near the walls remained stable. Due to their shape, oblate HBPs exhibit more efficient anchoring at wall surfaces compared to prolate shapes. The formation of nematic-like particle assemblies near the walls, confirmed by theoretical calculations based on density functional theory, significantly influenced local particle dynamics. This effect was particularly pronounced to the extent that a modest portion of cuboids near the walls tended to diffuse exclusively in planes parallel to the confinement, even more efficiently than observed in the bulk regions.

Application of machine-learning algorithms to predict the transport properties of Mie fluids.

The ability to predict transport properties of fluids, such as the self-diffusion coefficient and viscosity, has been an ongoing effort in the field of molecular modeling. While there are theoretical approaches to predict the transport properties of simple systems, they are typically applied in the dilute gas regime and are not directly applicable to more complex systems. Other attempts to predict transport properties are performed by fitting available experimental or molecular simulation data to empirical or semi-empirical correlations. Recently, there have been attempts to improve the accuracy of these fittings through the use of Machine-Learning (ML) methods. In this work, the application of ML algorithms to represent the transport properties of systems comprising spherical particles interacting via the Mie potential is investigated. To this end, the self-diffusion coefficient and shear viscosity of 54 potentials are obtained at different regions of the fluid-phase diagram. This data set is used together with three ML algorithms, namely, k-Nearest Neighbors (KNN), Artificial Neural Network (ANN), and Symbolic Regression (SR), to find correlations between the parameters of each potential and the transport properties at different densities and temperatures. It is shown that ANN and KNN perform to a similar extent, followed by SR, which exhibits larger deviations. Finally, the application of the three ML models to predict the self-diffusion coefficient of small molecular systems, such as krypton, methane, and carbon dioxide, is demonstrated using molecular parameters derived from the so-called SAFT-VR Mie equation of state [T. Lafitte et al. J. Chem. Phys. 139, 154504 (2013)] and available experimental vapor-liquid coexistence data.

Physical Fitness as a Prognostic Marker for Infectious Events in Kidney Transplant Recipients.

INTRODUCTION: Infectious events are one of the leading causes of death in kidney transplant recipients (KTRs). KTRs have reduced cardiorespiratory fitness (CRF), a predictor for infections in other populations. The aim of this study was to investigate whether CRF and muscle strength are prognostic markers for infectious events in KTRs. METHODS: In this retrospective cohort study, 155 KTRs underwent an incremental, maximal cardiopulmonary exercise test (CPET) 3 months after transplantation. CRF was analyzed with peak oxygen consumption (VO2 peak) while muscle strength with isometric handgrip (HG) test. Laboratory blood samples and drug therapy were collected. The median follow-up period was 54 (interquartile range 38-62) months. Cox regression analyses were performed to evaluate predictors of infectious events adjusting for potential confounders. RESULTS: During this study, severe infectious events occurred in 41 subjects (26.5%). 15.5% (n = 24) of patients had a severely reduced CRF, defined as a VO2 peak below the 5th percentile of the reference values reported for a matched healthy population. The hazard ratio for infectious events in this subgroup was 2.389 (95% CI = 1.188-4.801, p = 0.014), independently of gender, age, BMI, time on dialysis, hemoglobin concentration, eGFR, diabetes, and immunosuppressive regimen. On the contrary, no significant association of HG strength and infections was found. CONCLUSION: Therefore, low CRF may be considered as a modifiable predictor of severe infectious events in KTRs. A CPET should thus be recommended for cardiovascular screening, evaluation of CRF, and tailored exercise prescription to reduce the risk of infections and potentially improve long-term outcomes of transplantation.

Nonconventional Phases of Colloidal Nanorods with a Soft Corona.

Using computer simulations, we investigate the phase behavior of hard-core spherocylinders with a length-to-diameter ratio L/σ=5 and coated by a soft deformable corona of length λ/σ=1.35. When quasi-two-dimensional layers are formed in smectic and solid phases at low temperatures, the competition between the two intrinsic length scales of the parallel aligned particles leads to the stabilization of different in-plane lattices of nonconventional symmetry, including low-density hexagonal, square, and high-density hexagonal crystals, as well as an intriguing dodecagonal quasicrystal. Our Letter opens up the opportunity to control the assembly of anisotropic nanoparticles into structures with preengineered symmetry-dependent physical properties.

Effect of a Home-Based Exercise Program on Indices of Physical Function and Quality of Life in Elderly Maintenance Hemodialysis Patients.

BACKGROUND: Patients on maintenance hemodialysis (MHD) exhibit muscle wasting and impaired physical function which can be reversed with regular exercise, but accessibility to exercise programs for this unique population is lacking. We assessed the efficacy of a home-based exercise program on a broad range of indices of physical function, quality of life (QoL), and cognitive decline in patients with MHD. DESIGN AND METHODS: Twenty-eight MHD patients, mean age 66 ± 7 years, were randomized to a 12-week home-based, case-managed aerobic and resistance exercise program or to usual care (13 exercise and 15 usual care). Comparisons were made for peak VO2, ventilatory inefficiency, 6-min walk test (6MWT), 1-min sit-to-stand (1STS), muscle strength, body composition, QoL, and cognitive measures. RESULTS: Peak VO2 improved significantly in the exercise group (p = 0.01 between groups); exercise time improved by 41 and 36% at the ventilatory threshold and peak exercise, respectively (p < 0.01 between groups), but there were no differences in ventilatory efficiency. Trends for improvements in 6MWT and 1STS in the exercise group were observed, but no differences were observed in strength or body composition. Among measures of QoL, general health determined by the SF-36 improved in the exercise group, but there were no differences between groups in cognitive function. CONCLUSIONS: MHD patients improved exercise capacity and some indices of QoL following a 12-week home-based exercise program. Home-based exercise is feasible for patients undergoing MHD and may help to obviate accessibility barriers to regular exercise.

A clinical evaluation of VO2 kinetics in kidney transplant recipients.

PURPOSE: Aerobic exercise capacity is reduced in patients with chronic kidney disease, partly due to alterations at the muscular and microvascular level. This study evaluated oxygen uptake (VO2) kinetics as indicator of muscular oxidative metabolism in a population of Kidney Transplant Recipients (KTRs). METHODS: Two groups of KTRs enrolled 3 (n = 21) and 12 months (n = 14) after transplantation and a control group of healthy young adults (n = 16) underwent cardiopulmonary exercise testing on cycle-ergometer. The protocol consisted in two subsequent constant, moderate-load exercise phases with a final incremental test until exhaustion. RESULTS: The time constant of VO2 kinetics was slower in KTRs at 3 and 12 months after transplantation compared to controls (50.4 ± 13.1 s and 43.8 ± 11.6 s vs 28.9 ± 8.4 s, respectively; P < 0.01). Peak VO2 was lower in KTRs evaluated 3 months after transplantation compared to patients evaluated after 1 year (21.3 ± 4.3 and 26.4 ± 8.0 mL/kg/min; P = 0.04). Blood haemoglobin (Hb) concentration was higher in KTRs evaluated at 12 months (12.8 ± 1.7 vs 14.6 ± 1.7 g/dL; P < 0.01). Among KTRs, τ showed a moderate negative correlation with Peak VO2 (ρ = - 0.52) and Oxygen uptake efficiency slope (OUES) (r = - 0.57) while no significant correlation with Hb and peak heart rate. CONCLUSIONS: KTRs show slower VO2 kinetics compared to healthy controls. Hb and peak VO2 seem to improve during the first year after transplantation. VO2 kinetics were significantly associated with indices of cardiorespiratory fitness, but less with central determinants of aerobic capacity, thus suggesting a potential usefulness of adding this index of muscular oxidative metabolism to functional evaluation in KTRs.

Exercise-Based Cardiac Rehabilitation Programs in Heart Failure Patients.

Exercise training is recommended for patients with heart failure by major societies' guidelines. It improves exercise capacity and quality of life, reduces symptoms of depression, can improve survival, and reduce the risk for hospitalizations. Exercise-based cardiac rehabilitation can be offered with different modalities, such as continuous or interval aerobic training, resistance, and inspiratory muscle training. The intervention must follow an accurate evaluation of the patient's cardiovascular conditions and functional capacity. Despite the multiple benefits of exercise training, there is a lack of adherence to exercise-based programs, due to socioeconomic factors, patients' characteristics, and lack of referral.

Self-assembly of freely-rotating polydisperse cuboids: unveiling the boundaries of the biaxial nematic phase.

Colloidal cuboids have the potential to self-assemble into biaxial liquid crystal phases, which exhibit two independent optical axes. Over the last few decades, several theoretical works have predicted the existence of a wide region of the phase diagram where the biaxial nematic phase would be stable, but imposed rather strong constraints on the particle rotational degrees of freedom. In this work, we use molecular simulation to investigate the impact of size dispersity on the phase behaviour of freely-rotating hard cuboids, here modelled as self-dual-shaped nanoboards. This peculiar anisotropy, exactly in between the oblate and prolate geometry, has been proposed as the most appropriate to promote phase biaxiality. We observe that size dispersity radically changes the phase behaviour of monodisperse systems and leads to the formation of an elusive biaxial nematic phase, being found in a large region of the packing fraction vs. polydispersity phase diagram. Although our results confirm the tendencies reported in past experimental observations on colloidal dispersions of slightly prolate goethite particles, they cannot reproduce the direct isotropic-to-biaxial nematic phase transition observed in these experiments.

Biaxial nematics of hard cuboids in an external field.

By computer simulation, we model the phase behaviour of colloidal suspensions of board-like particles under the effect of an external field and assess the still disputed occurrence of the biaxial nematic (NB) liquid crystal phase. The external field promotes the rearrangement of the initial isotropic (I) or uniaxial nematic (NU) phase and the formation of the NB phase. In particular, very weak field strengths are sufficient to spark a direct I-NB or NU-NB phase transition at the self-dual shape, where prolate and oblate particle geometries fuse into one. By contrast, forming the NB phase at any other geometry requires stronger fields and thus reduces the energy efficiency of the phase transformation. Our simulation results show that self-dual shaped board-like particles with moderate anisotropy are able to form NB liquid crystals under the effect of a surprisingly weak external stimulus and suggest a path to exploit low-energy uniaxial-to-biaxial order switching.

Brownian dynamics simulations of oblate and prolate colloidal particles in nematic liquid crystals.

It is well known that understanding the transport properties of liquid crystals is crucial to optimize their performance in a number of technological applications. In this work, we analyze the effect of shape anisotropy on the diffusion of rodlike and disklike particles by Brownian dynamics simulations. To this end, we compare the dynamics of prolate and oblate nematic fluids incorporating particles with the same infinite-dilution translational or rotational diffusion coefficients. Under these conditions, which are benchmarked against the standard case of identical aspect ratios, we observe that prolate particles display faster dynamics than oblate particles at short and long time scales. Nevertheless, when compared at identical infinite-dilution translational diffusion coefficients, oblate particles are faster than their prolate counterparts at short-to-intermediate time scales, which extend over almost three time decades. Both oblate and prolate particles exhibit an anisotropic diffusion with respect to the orientation of the nematic director. More specifically, prolate particles show a fast diffusion in the direction parallel to the nematic director, while their diffusion in the direction perpendicular to it is slower. By contrast, the diffusion of oblate particles is faster in the plane perpendicular to the nematic director. Finally, in the light of our recent study on the long-time Gaussian and Fickian diffusion in nematic systems, we map the decay of the autocorrelation functions and their fluctuations over the time scales of our simulations to ponder the existence of mobile clusters of particles and the occurrence of collective motion.

Comparison of cardiovascular screening guidelines for middle-aged/older adults.

PURPOSE: Although both European (EACPR) and American (ACSM) Scientific Societies have devised cardiovascular protocols for the assessment of "middle-aged/older" individuals who are about to participate in sports or physical exercise, there are no data regarding the guidelines' sensitivity of these measures. The aim of this study was to compare the outcomes of different international screening protocols. METHODS: This observational cross-sectional study evaluated 525 subjects (80% males; median age 50 [35-85] years) seeking medical certification before participating in sports or regular exercise. The screening protocol consisted in completing a personal history profile, a physical examination, a resting ECG, a maximal exercise test, and, when required, additional instrumental evaluations. The effectiveness of the current EACPR as well as the former and new ACSM guidelines was thereby analyzed. RESULTS: The full screening protocol uncovered 100 previously undetected cardiovascular conditions (main pathologies detected: 21 coronary artery disease (CAD), 14 arterial hypertension, 38 complex arrhythmias). When the European guideline was used, 49% of these conditions went undetected, including 10 CAD. When the former American guideline was used, 29% (6 CAD) went undetected; when the recently updated edition was used, 50% including 11 CAD went undetected. CONCLUSION: The former ACSM guideline demonstrated a higher diagnostic sensitivity than the newer version and the EACPR guideline. Current screening protocols might be adapted for subjects performing high-intensity exercise due to their higher risk for cardiovascular and exercise-associated adverse events. The use of an incremental ECG-monitored maximal exercise test seems to improve these screening outcomes.

Dynamic Monte Carlo algorithm for out-of-equilibrium processes in colloidal dispersions.

Colloids have a striking relevance in a wide spectrum of industrial formulations, spanning from personal care products to protective paints. Their behaviour can be easily influenced by extremely weak forces, which disturb their thermodynamic equilibrium and dramatically determine their performance. Motivated by the impact of colloidal dispersions in fundamental science and formulation engineering, we have designed an efficient Dynamic Monte Carlo (DMC) approach to mimic their out-of-equilibrium dynamics. Our recent theory, which provided a rigorous method to reproduce the Brownian motion of colloids by MC simulations, is here generalised to reproduce the Brownian motion of colloidal particles during transitory unsteady states, when their thermodynamic equilibrium is significantly modified. To this end, we investigate monodisperse and bidisperse rod-like particles in the isotropic phase and apply an external field that forces their reorientation along a common direction and induces an isotropic-to-nematic phase transition. We also study the behaviour of the system once the external field is removed. Our simulations are in excellent quantitative agreement with Brownian Dynamics simulations when the DMC results are rescaled with a time-dependent acceptance ratio, which depends on the strength of the applied field.

Phase behaviour of hard board-like particles.

We examine the phase behaviour of colloidal suspensions of hard board-like particles (HBPs) as a function of their shape anisotropy, and observe a fascinating spectrum of nematic, smectic, and columnar liquid-crystalline phases, whose formation is entirely driven by excluded volume effects. We map out the phase diagram of short and long HBPs by gradually modifying their shape from prolate to oblate and investigate the long-range order of the resulting morphologies along the phase directors and perpendicularly to them. The intrinsic biaxial nature of these particles promotes the formation of translationally ordered biaxial phases, but does not show solid evidence that it would, per se, promote the formation of the biaxial nematic phase. Our simulations shed light on the controversial existence of the discotic smectic phase, whose layers are as thick as the minor particle dimension, which is stable in a relatively large portion of our phase diagrams. Additionally, we modify the Onsager theory to describe the isotropic-nematic phase transition of freely rotating biaxial particles as a function of the particle width, and find a relatively strong first-order signature, in excellent agreement with our simulations. In an attempt to shed light on the elusive formation of the biaxial nematic phase, we apply this theory to predict the uniaxial-biaxial nematic phase transition and confirm, again in agreement with simulations, the prevailing stability of the translationally ordered smectic phase over the orientationally ordered biaxial nematic phase.

Effective short-range Coulomb correction to model the aggregation behavior of ionic surfactants.

We present a short-range correction to the Coulomb potential to investigate the aggregation of amphiphilic molecules in aqueous solutions. The proposed modification allows to quantitatively reproduce the distribution of counterions above the critical micelle concentration (CMC) or, equivalently, the degree of ionization, α, of the micellar clusters. In particular, our theoretical framework has been applied to unveil the behavior of the cationic surfactant C24H49N2O2 (+) CH3SO4 (-), which offers a wide range of applications in the thriving and growing personal care market. A reliable and unambiguous estimation of α is essential to correctly understand many crucial features of the micellar solutions, such as their viscoelastic behavior and transport properties, in order to provide sound formulations for the above mentioned personal care solutions. We have validated our theory by performing extensive lattice Monte Carlo simulations, which show an excellent agreement with experimental observations. More specifically, our coarse-grained model is able to reproduce and predict the complex morphology of the micelles observed at equilibrium. Additionally, our simulation results disclose the existence of a transition from a monodisperse to a bidisperse size distribution of aggregates, unveiling the intriguing existence of a second CMC.

Insight into the Viscoelasticity of Self-Assembling Smectic Liquid Crystals of Colloidal Rods from Active Microrheology Simulations.

The rheology of colloidal suspensions is of utmost importance in a wide variety of interdisciplinary applications in formulation technology, determining equally interesting questions in fundamental science. This is especially intriguing when colloids exhibit a degree of long-range positional or orientational ordering, as in liquid crystals (LCs) of elongated particles. Along with standard methods, microrheology (MR) has emerged in recent years as a tool to assess the mechanical properties of materials at the microscopic level. In particular, by active MR one can infer the viscoelastic response of a soft material from the dynamics of a tracer particle being dragged through it by external forces. Although considerable efforts have been made to study the diffusion of guest particles in LCs, little is known about the combined effect of tracer size and directionality of the dragging force on the system's viscoelastic response. By dynamic Monte Carlo simulations, we apply active MR to investigate the viscoelasticity of self-assembling smectic (Sm) LCs consisting of rodlike particles. In particular, we track the motion of a spherical tracer whose size is varied within a range of values matching the system's characteristic length scales and being dragged by constant forces that are parallel, perpendicular, or at 45° to the nematic director. Our results reveal a uniform value of the effective friction coefficient as probed by the tracer at small and large forces, whereas a nonlinear, force-thinning regime is observed at intermediate forces. However, at relatively weak forces the effective friction is strongly determined by correlations between the tracer size and the structure of the host fluid. Moreover, we also show that external forces forming an angle with the nematic director provide additional details that cannot be simply inferred from the mere analysis of parallel and perpendicular forces. Our results highlight the fundamental interplay between tracer size and force direction in assessing the MR of Sm LC fluids.

Respiratory gas kinetics in patients with congestive heart failure during recovery from peak exercise.

BACKGROUND: Cardiopulmonary Exercise Testing (CPX) is essential for the assessment of exercise capacity for patients with Chronic Heart Failure (CHF). Respiratory gas and hemodynamic parameters such as Ventilatory Efficiency (VE/VCO2 slope), peak oxygen uptake (peak VO2), and heart rate recovery are established diagnostic and prognostic markers for clinical populations. Previous studies have suggested the clinical value of metrics related to respiratory gas collected during recovery from peak exercise, particularly recovery time to 50% (T1/2) of peak VO2. The current study explores these metrics in detail during recovery from peak exercise in CHF. METHODS: Patients with CHF who were referred for CPX and healthy individuals without formal diagnoses were assessed for inclusion. All subjects performed CPX on cycle ergometers to volitional exhaustion and were monitored for at least five minutes of recovery. CPX data were analyzed for overshoot of respiratory exchange ratio (RER=VCO2/VO2), ventilatory equivalent for oxygen (VE/VO2), end-tidal partial pressure of oxygen (PETO2), and T1/2 of peak VO2 and VCO2. RESULTS: Thirty-two patients with CHF and 30 controls were included. Peak VO2 differed significantly between patients and controls (13.5 ± 3.8 vs. 32.5 ± 9.8 mL/Kg*min-1, p < 0.001). Mean Left Ventricular Ejection Fraction (LVEF) was 35.9 ± 9.8% for patients with CHF compared to 61.1 ± 8.2% in the control group. The T1/2 of VO2, VCO2 and VE was significantly higher in patients (111.3 ± 51.0, 132.0 ± 38.8 and 155.6 ± 45.5s) than in controls (58.08 ± 13.2, 74.3 ± 21.1, 96.7 ± 36.8s; p < 0.001) while the overshoot of PETO2, VE/VO2 and RER was significantly lower in patients (7.2 ± 3.3, 41.9 ± 29.1 and 25.0 ± 13.6%) than in controls (10.1 ± 4.6, 62.1 ± 17.7 and 38.7 ± 15.1%; all p < 0.01). Most of the recovery metrics were significantly correlated with peak VO2 in CHF patients, but not with LVEF. CONCLUSIONS: Patients with CHF have a significantly blunted recovery from peak exercise. This is reflected in delays of VO2, VCO2, VE, PETO2, RER and VE/VO2, reflecting a greater energy required to return to baseline. Abnormal respiratory gas kinetics in CHF was negatively correlated with peak VO2 but not baseline LVEF.

Frustration of the isotropic-columnar phase transition of colloidal hard platelets by a transient cubatic phase.

Using simulations and theory, we show that the cubatic phase is metastable for three model hard platelets. The locally favored structures of perpendicular particle stacks in the fluid prevent the formation of the columnar phase through geometric frustration resulting in vitrification. Also, we find a direct link between structure and dynamic heterogeneities in the cooperative rotation of particle stacks, which is crucial for the devitrification process. Finally, we show that the lifetime of the glassy cubatic phase can be tuned by surprisingly small differences in particle shape.

Long-time relaxation dynamics in nematic and smectic liquid crystals of soft repulsive colloidal rods.

Understanding the relaxation dynamics of colloidal suspensions is crucial to identifying the elements that influence the mobility of their constituents, assessing their macroscopic response across the relevant time and length scales, and thus disclosing the fundamentals underpinning their exploitation in formulation engineering. In this work, we specifically assess the impact of long-ranged ordering on the relaxation dynamics of suspensions of soft repulsive rodlike particles, which are able to self-organize into nematic and smectic liquid-crystalline phases. Rods are modeled as soft repulsive spherocylinders with a length-to-diameter ratio L^{★}=5, interacting via the truncated and shifted Kihara potential. By performing dynamic Monte Carlo simulations, we analyze the effect of translational and orientational order on the diffusion of the rods along the relevant directions imposed by the morphology of the background phases. To provide a clear picture of the resulting dynamics, we assess its dependence on temperature, which can dramatically determine the response time of the system relaxation and the self-diffusion coefficients of the rods. The computation of the van Hove correlation functions allows us to identify the existence of rods that diffuse significantly faster than the average and whose concentration can be accurately adjusted by a suitable choice of temperature.

Structural relaxation dynamics of colloidal nanotrimers.

By Molecular Dynamics simulation, we investigate the dynamics of isotropic fluids of colloidal nanotrimers whose interactions are described by varying the strength of attractive and repulsive terms of the Mie potential. To provide a consistent comparison between the systems described by different force fields, we determine the phase diagram and critical points of each system, characterize the morphology of high-density liquid phases at the same reduced temperature and density, and finally investigate their long-time relaxation dynamics. In particular, we detect an especially complex dynamics that reveals the existence of slow and fast nanotrimers and the resulting occurrence of non-Gaussianity, which develops at intermediate timescales. Deviations from Gaussianity are temporary and vanish within the timescales of the system's density fluctuations decay, when a Fickian-like diffusion regime is eventually observed.