Maize-Brachiaria intercropping: A strategy to supply recycled N to maize and reduce soil N2O emissions?

Nitrogen use in agriculture directly impacts food security, global warming, and environmental degradation. Forage grasses intercropped with maize produce feed for animals and or mulch for no-till systems. Forage grasses may exude nitrification inhibitors. It was hypothesized that brachiaria intercropping increases N recycling and maize grain yield and reduces nitrous oxide (N2O) emissions from soil under maize cropping. A field experiment was set up in December 2016 to test three cropping system (maize monocropped, maize intercropped with Brachiaria brizantha or with B. humidicola) and two N rates (0 or 150 kg ha-1). The grasses were sown with maize, but B. humidicola did not germinate well in the first year. B. brizantha developed slowly during the maize cycle because of shading but expanded after maize was harvested. The experiment was repeated in 2017/2018 when B. humidicola was replanted. N2O and carbon dioxide (CO2) emissions, maize grain yield and N content were measured during the two seasons. After the first maize harvest, the above- and below-ground biomass, C and N content of B. brizantha grown during fall-winter, and the biological nitrification inhibition potential of B. brizantha were evaluated. Maize yield responded to N fertilization (5.1 vs. 9.8 t ha-1) but not to brachiaria intercropping. B. brizantha recycled approximately 140 kg N ha-1 and left 12 t dry matter ha-1 for the second maize crop. However, the 2017/18 maize yields were not affected by the N recycled by B. brizantha, whereas N2O emissions were higher in the plots with brachiaria, suggesting that part of the recycled N was released too early after desiccation. Brachiarias showed no evidence of causing nitrification inhibition. The strategy of intercropping brachiarias did not increase maize yield, although it added C and recycled N in the system.

Computational Reverse-Engineering Analysis for Scattering Experiments on Amphiphilic Block Polymer Solutions.

In this paper, we present a computational reverse-engineering analysis for scattering experiments (CREASE) based on genetic algorithms and molecular simulation to analyze the structure within self-assembled amphiphilic polymer solutions. For a given input comprised of scattering intensity profiles and information about the amphiphilic polymers in solution, CREASE outputs the structure of the self-assembled micelles (e.g., core and corona diameters, aggregation number) as well as the conformations of the amphiphilic polymer chains in the micelle (e.g., blocks' radii of gyration, chain radii of gyration, monomer concentration profiles). First, we demonstrate CREASE's ability to reverse-engineer self-assembled nanostructures for scattering profiles obtained from molecular simulations (or in silico experiments) of generic coarse-grained bead-spring polymer chains in an implicit solvent. We then present CREASE's outputs for scattering profiles obtained from small-angle neutron scattering (SANS) experiments of poly(d-glucose carbonate) block copolymers in solution that exhibit assembly into spherical nanoparticles. The success of this method is demonstrated by its ability to replicate, quantitatively, the results from in silico experiments and by the agreement in micelle core and corona sizes obtained from microscopy of the in vitro solutions. The primary strength of CREASE is its ability to analyze scattering profiles without an off-the-shelf scattering model and the ability to provide chain and monomer level structural information that is otherwise difficult to obtain from scattering and microscopy alone.

Coarse-grained molecular dynamics simulations of α-1,3-glucan.

In this paper we present a computational study of aggregation in aqueous solutions of α-1,3-glucan captured using a coarse-grained (CG) model that can be extended to other polysaccharides. This CG model captures atomistic geometry (i.e., relative placement of the hydrogen bonding donors and acceptors within the monomer) of the α-1,3-glucan monomer, the directional interactions due to the donor-acceptor hydrogen bonds, and their effect on aggregation of multiple α-1,3-glucan chains without the extensive computational resources needed for simulations with atomistic models. Using this CG model, we conduct molecular dynamics simulations to assess the effect of varying α-1,3-glucan chain length and hydrogen bond interaction strengths on the aggregation of multiple chains at finite concentrations in implicit solvent. We quantify the hydrogen bonding strength needed for multiple chains to aggregate, the distribution of inter- and intra-chain hydrogen bonds within the aggregate and in some cases, the shapes of the aggregate. We also explore the effect of substitution/silencing of some randomly selected or specific hydrogen bonding sites in the chain on the aggregation and aggregate structure. In the unmodified α-1,3-glucan solution, the inter-chain hydrogen bonds cause the chains to aggregate into sheets. Random silencing of hydrogen bonding donor sites only increases the hydrogen bond strength needed for aggregation but retains the same aggregate structure as the unmodified chains. Specific silencing of the hydrogen-bonding site on the C6 carbon leads to the chains aggregating into planar sheets that then fold over to form hollow cylinders at intermediate hydrogen bond strength - 4.7 to 5.3 kcal mol-1. These cylindrical aggregates assemble end-to-end to form larger aggregates at higher hydrogen bond strengths.

Shear-Induced Alignment of Janus Particle Lamellar Structures.

Control over the alignment of colloidal structures plays a crucial role in advanced reconfigurable materials. In this work, we study the alignment of Janus particle lamellar structures under shear flow via Brownian dynamics simulations. Lamellar alignment (orientation relative to flow direction) is measured as a function of the Péclet number (Pe)-the ratio of the viscous shear to the Brownian forces-the particle volume fraction, and the strength of the anisotropic interaction potential made dimensionless with thermal energy. Under conditions where lamellar structures are formed, three orientation regimes are observed: (1) random orientation for very small Pe, (2) parallel orientation-lamellae with their normals parallel to the direction of the velocity gradient-for intermediate values of Pe, and (3) perpendicular orientation-lamellae with their normals parallel to the vorticity direction-for large Pe. To understand the alignment mechanism, we carry out a scaling analysis of competing torques between a pair of particles in the lamellar structure. Our results suggest that the change of parallel to perpendicular orientation is independent of the particle volume fraction and is caused by the hydrodynamic and Brownian torques on the particles overcoming the torques resulting from the interparticle interactions. This initial study of shear-induced alignment on lamellar structures formed by Janus colloidal particles also opens the door for future applications where a reversible actuator for structure orientation is required.

Phase diagram of Janus particles: The missing dimension of pressure anisotropy.

Brownian dynamics simulations of single-patch Janus particles under sedimentation equilibrium reveal that the phases found at fixed temperature and volume fraction are extremely sensitive to small changes in lateral box dimension. We trace this sensitivity to an uncontrolled parameter, namely, the pressure component parallel to the hexagonally ordered layers formed through sedimentation. We employ a flexible-cell constant-pressure scheme to achieve explicit control over this usually overlooked parameter, enabling the estimation of phase behavior under given pressure anisotropy. Our results show an increase in the stability range of an orientationally ordered lamellar phase with lateral layer compression and suggest a novel mechanism to control solid-solid phase transitions with negligible change in system volume, thus showing prospect for design of novel structures and switchable crystals from anisotropic building blocks.

Rotator-to-Lamellar Phase Transition in Janus Colloids Driven by Pressure Anisotropy.

We demonstrate through Brownian dynamics simulations a phase transition in plastic crystalline assemblies of Janus spheres through controlled pressure anisotropy. When the pressure in plane with hexagonally ordered layers is increased relative to that normal to the layers, a rapid first-order rotator-to-lamellar transition of Janus sphere orientation occurs at constant temperature. We show that the underlying mechanism closely follows the Maier-Saupe theory, originally developed for isotropic-to-nematic transition in positionally disordered materials but here applied to positionally ordered ones. Since the transition involves almost no translational diffusion or volume change, and occurs rapidly by particle rotation, the results should help guide the design of rapidly switchable colloidal crystals.

Putative binding mode of Escherichia coli exopolyphosphatase and polyphosphates based on a hybrid in silico/biochemical approach.

The exopolyphosphatase of Escherichia coli processively and completely hydrolyses long polyphosphate chains to ortho-phosphate. Genetic surveys, based on the analysis of single ppx(-) or ppk(-) mutants and on the double mutant, demonstrate a relationship between these genes and the survival capacity. The exopolyphosphatase belongs to the ASKHA protein superfamily, hence, its active site is well known; however, the knowledge of the way in which this enzyme binds polyP remains incomplete. Here we present different computational approaches, site-direct mutagenesis and kinetic data to understand the relationship between structure and function of exopolyphosphatase. We propose H(378) as a fundamental gatekeeper for the recognition of long chain polyphosphate.

Rich Janus colloid phase behavior under steady shear.

We study the assembly of single-patch colloidal Janus particles under steady shear flow via Brownian dynamics simulations. In the absence of flow, by varying the Janus patch size and the range and strength of the anisotropic interaction potential, Janus colloids form different aggregates such as micelles, wormlike clusters, vesicles and lamellae. Under shear flow we observe rearrangement, deformation, and break-up of aggregates. At small and intermediate Péclet (Pe) numbers-the ratio between shear and Brownian forces-the competition between rearrangement, deformation, and break-up favors the growth of micelles and vesicles increasing mean cluster size, which is consistent with a previous numerical study of Janus particles under shear. This initial shear-induced growth causes micelles and vesicles to reach a maximum cluster size at Pe ≈ 1 and Pe ≈ 10, respectively. After this growth micelles dissociate continuously to reach a dilute colloidal "gas phase" at Pe ≈ 10 while vesicles dissociate into micelles with high aspect ratio at Pe ≈ 10 and finally break-up into a gas phase at Pe ≈ 30. Wormlike clusters initially break-up into micelles with high aspect ratio at Pe ≈ 0.1, and proceed to finally reach a gas phase at Pe ≈ 10. Lamellae initially break into smaller lamellae that align with the flow in the velocity-velocity-gradient plane and finally break-up into a gas phase at Pe ≈ 100. The different cluster sizes and morphologies observed as functions of interaction range, Janus patch size, interaction strength, and shear rate, open new actuation routes for reconfigurable materials and applications.

Binding kinetics of lock and key colloids.

Using confocal microscopy and first passage time analysis, we measure and predict the rates of formation and breakage of polymer-depletion-induced bonds between lock-and-key colloidal particles and find that an indirect route to bond formation is accessed at a rate comparable to that of the direct formation of these bonds. In the indirect route, the pocket of the lock particle is accessed by nonspecific bonding of the key particle with the lock surface, followed by surface diffusion leading to specific binding in the pocket of the lock. The surprisingly high rate of indirect binding is facilitated by its high entropy relative to that of the pocket. Rate constants for forward and reverse transitions among free, nonspecific, and specific bonds are reported, compared to theoretical values, and used to determine the free energy difference between the nonspecific and specific binding states.

Phase behavior of Janus colloids determined by sedimentation equilibrium.

We investigate the phase behavior of short-range interacting isotropic particles and single-patch Janus particles via simulations of sedimentation equilibrium, which allows for a rapid assessment of the equation of state and phase behavior directly from simulation. The methodology is tested against results by traditional methods and is found to yield good agreement for isotropic interactions. The method is then used to study single-patch Janus particles with different interaction strengths and patch sizes with particle area coverage greater than ∼0.63. Our results show an interplay between translational and orientational order. We observe a lamellar phase, a fluid phase and a rotator close-packed structure. The lamellar phase is shown to have a different range of stability than previously observed in simulation studies for systems of similar and longer-ranged interactions.

Self-consistent colloidal energy and diffusivity landscapes in macromolecular solutions.

We report a dynamic analysis to simultaneously measure colloidal forces and hydrodynamic interactions in the presence of both adsorbed and unadsorbed macromolecules. A Bayesian inference method is used to self-consistently obtain the position-dependent potential energy (i.e., energy landscape) and diffusivity (i.e., diffusivity landscape) from measured colloidal trajectories normal to a wall. Measurements are performed for particles and surfaces with adsorbed polyethylene oxide (PEO) copolymer as a function of unadsorbed PEO homopolymer concentration. Energy landscapes are well described by a steric repulsion between adsorbed brushes and depletion attraction due to unadsorbed macromolecules. Diffusivity landscapes show agreement with predicted short-range permeable brush models and long-range mobilities determined by the bulk solution viscosity. Lower than expected mobilities in the vicinity of overlapping depletion layers are attributed to interactions of adsorbed and unadsorbed macromolecules altering nonconservative lubrication forces.

Anomalous silica colloid stability and gel layer mediated interactions.

Total internal reflection microscopy (TIRM) is used to measure SiO2 colloid ensembles over a glass microscope slide to simultaneously obtain interactions and stability as a function of pH (4-10) and NaCl concentration (0.1-100 mM). Analysis of SiO2 colloid Brownian height excursions yields kT-scale potential energy vs separation profiles, U(h), and diffusivity vs separation profiles, D(h), and determines whether particles are levitated or irreversibly deposited (i.e., stable). By including an impermeable SiO2 "gel layer" when fitting van der Waals, electrostatic, and steric potentials to measured net potentials, gel layers are estimated to be ~10 nm thick and display an ionic strength collapse. The D(h) results indicate consistent surface separation scales for potential energy profiles and hydrodynamic interactions. Our measurements and model indicate how SiO2 gel layers influence van der Waals (e.g., dielectric properties), electrostatics (e.g., shear plane), and steric (e.g., layer thickness) potentials to understand the anomalous high ionic strength and high pH stability of SiO2 colloids.

Comparing demographics, clinical characteristics, and hospital outcomes by vaccine uptake status: A single-institution cross-sectional study.

Vaccination against Coronavirus disease 2019 (COVID-19) has been the cornerstone of reducing morbidity and mortality of this disease, as it has been shown to decrease the risk of viral transmission, severity of disease, hospitalization, and intubation. However, true understanding of its impact is skewed by heterogeneous vaccine administration due to lack of equitable access, vaccine hesitancy, and varying social determinants of health. Therefore, this study aims to identify groups that are less likely to be vaccinated and understand whether the resultant differences in vaccination rates affect morbidity and mortality in socially marginalized COVID-19 patients. A retrospective cohort analysis was performed on a randomized and stratified population of 939 COVID-19 patients from January 2021 to December 2021. Bivariate analysis and logistic regression were used to assess demographic and clinical characteristic trends in unvaccinated, partially vaccinated, and fully vaccinated groups. No one age (P = .21), gender (P = .9), race (P = .12), ethnicity (P = .09), or health insurance status (P = .13) group was more vaccinated than the other. Similarly, no subgroup was at increased odds of intubation (P = .08) or death. However, patients with all categories of comorbidities including cardiopulmonary disease (P = <.001, effect size .17), renal disease (P = <.001, effect size 0.138), metabolic disease (P = .04), and immunocompromised (P = .01) states were found to have significantly higher vaccination rates. Our study also shows that full vaccination protects against mortality and decreases the odds of intubation by 55% (adjusted odds ratio = 0.453, P value = .015) compared to no vaccination or partial vaccination. Findings from this study show an encouraging trend that sicker patients had higher rates of vaccination against COVID-19. This trend highlights the need for further identification of motivators that may be applied to vaccine-hesitant populations, which can help guide population-level policy, increase vaccination campaign yield, and reach for health equity.

Leadership in a hospital of the Andalusian Public Health System.

OBJECTIVE: To analyse, from a gender perspective, the characteristics and perception of the effects of leadership of nurses in a hospital of the Andalusian Public Health System. METHODOLOGY: Qualitative study with a phenomenological approach. The participants were nurses in care and intermediate positions with a contract of more than 6 months. A qualitative content analysis was carried out. Four phases were established for data analysis, from which 5 categories resulted. NVivo 11 software was used to analyse the dialogues. RESULTS: The participants' discourses endow the leader with characteristics that define him as a reference person. The contribution of middle management is necessary for the achievement of the objectives of the care units and the cohesion of the group, although this group perceives it only in relation to the management of resources. Access to management positions is not linked to gender. CONCLUSIONS: The participants' discourses endow the leader with characteristics that define him as a reference person. The contribution of middle management is necessary for the achievement of the objectives of the care units and the cohesion of the group, although this group perceives it only in relation to the management of resources. Access to management positions is not linked to gender.

Colloidal cluster crystallization dynamics.

The crystallization dynamics of a colloidal cluster is modeled using a low-dimensional Smoluchowski equation. Diffusion mapping shows that two order parameters are required to describe the dynamics. Using order parameters as metrics for condensation and crystallinity, free energy, and diffusivity landscapes are extracted from brownian dynamics simulations using bayesian inference. Free energy landscapes are validated against Monte Carlo simulations, and mean first-passage times are validated against dynamic simulations. The resulting model enables a low-dimensional description of colloidal crystallization dynamics.

A Smoluchowski model of crystallization dynamics of small colloidal clusters.

We investigate the dynamics of colloidal crystallization in a 32-particle system at a fixed value of interparticle depletion attraction that produces coexisting fluid and solid phases. Free energy landscapes (FELs) and diffusivity landscapes (DLs) are obtained as coefficients of 1D Smoluchowski equations using as order parameters either the radius of gyration or the average crystallinity. FELs and DLs are estimated by fitting the Smoluchowski equations to Brownian dynamics (BD) simulations using either linear fits to locally initiated trajectories or global fits to unbiased trajectories using Bayesian inference. The resulting FELs are compared to Monte Carlo Umbrella Sampling results. The accuracy of the FELs and DLs for modeling colloidal crystallization dynamics is evaluated by comparing mean first-passage times from BD simulations with analytical predictions using the FEL and DL models. While the 1D models accurately capture dynamics near the free energy minimum fluid and crystal configurations, predictions near the transition region are not quantitatively accurate. A preliminary investigation of ensemble averaged 2D order parameter trajectories suggests that 2D models are required to capture crystallization dynamics in the transition region.

The Influence of Marginalization on Cultural Attitudes and Trash Disposal Practices in Esfuerzo de Paraíso of the Dominican Republic: A Qualitative Interview Study.

The inadequate management of municipal solid waste (MSW) in fast-developing nations is a major public health problem. Trash collection is often inconsistent, leaving residents to use unsafe disposal methods such as incineration or unregulated dumping. The issue is especially pronounced in marginalized communities, where public service provision is scarce. Past research has identified factors that perpetuate harmful disposal practices. The current study expanded on previous work by exploring how individuals' perceptions of political, spatial, and economic marginalization affected their agency with regards to waste management. Researchers focused on a marginalized community in the Dominican Republic known as Esfuerzo de Paraíso. There, they conducted semi-structured interviews to explore residents' perceptions of marginalization at the individual, interpersonal, community, and institutional levels, and its effects on their agency. A qualitative coding process revealed that most community members were discontent with their trash disposal practices, but that long-standing marginalization left them feeling ill equipped to generate change at the individual level. Interviewees believed that change should be initiated at the community level and implemented with the support of institutional-level actors, namely the municipal government. Residents did not identify any non-governmental organizations as possible sources of help, which may suggest a limited view of institutional support networks.

Concentrated diffusing colloidal probes of Ca2+-dependent cadherin interactions.

We report video microscopy measurements and inverse simulation analyses of specific Ca(2+)-dependent interactions between N-cadherin fragments attached to supported lipid bilayer-coated silica colloids in quasi-2D concentrated configurations. Our results include characterization of the bilayer formation and fluidity and the attachment of active extracellular cadherin fragments on bilayers. Direct measurements of interaction potentials show nonspecific macromolecular repulsion between cadherin fragments in the absence of Ca(2+) and irreversible bilayer fusion via cadherin-mediated attraction at >100 µM Ca(2+). Analysis of Ca(2+)-dependent N-cadherin bond formation in quasi-2D concentrated configurations using inverse Monte Carlo and Brownian Dynamics simulations show measurable attraction starting at 0.1 µM Ca(2+), a concentration significantly below previously reported values.

Charged micelle depletion attraction and interfacial colloidal phase behavior.

Ensemble total internal reflection microscopy (TIRM) is used to directly measure the evolution of colloid-surface depletion attraction with increasing sodium dodecyl sulfate (SDS) concentration near the critical micelle concentration (CMC). Measured potentials are well described by a modified Asakura-Oosawa (AO) depletion potential in addition to electrostatic and van der Waals contributions. The modified AO potential includes effects of electrostatic interactions between micelles and surfaces via effective depletant dimensions in an excluded volume term and partitioning in an osmotic pressure term. Directly measured colloid-surface depletion potentials are used in Monte Carlo (MC) simulations to capture video microscopy (VM) measurements of micelle-mediated quasi-two-dimensional phase behavior including fluid, crystal, and gel microstructures. Our findings provide information to develop more rigorous and analytically simple models of depletion attraction in charged micellar systems.

Fokker-Planck analysis of separation dependent potentials and diffusion coefficients in simulated microscopy experiments.

Total internal reflection microscopy (TIRM) and video microscopy (VM) are methods for nonintrusively measuring weak colloidal interactions important to many existing and emerging applications. Existing analyses of TIRM measured single particle trajectories can be used to extract particle-surface potentials and average particle diffusion coefficients. Here we develop a Fokker-Planck (FP) formalism to simultaneously extract both particle-surface interaction potentials and position dependent diffusion coefficients. The FP analysis offers several advantages including capabilities to measure separation dependent hydrodynamic interactions and nonequilibrium states that are not possible with existing analyses. The FP analysis is implemented to analyze Brownian dynamic simulations of single particle TIRM and VM experiments in several configurations. Relative effects of spatial and temporal sampling on the correct interpretation of both conservative and dissipative forces are explored and show a broad range of applicability for accessible experimental systems. Our results demonstrate the ability to extract both static and dynamic information from microscopy measurements of isolated particles near surfaces, which provides a foundation for further investigation of particle ensembles and nonequilibrium systems.