Chewing through challenges: Exploring the evolutionary pathways to wood-feeding in insects.

Decaying wood, while an abundant and stable resource, presents considerable nutritional challenges due to its structural rigidity, chemical recalcitrance, and low nitrogen content. Despite these challenges, certain insect lineages have successfully evolved saproxylophagy (consuming and deriving sustenance from decaying wood), impacting nutrient recycling in ecosystems and carbon sequestration dynamics. This study explores the uneven phylogenetic distribution of saproxylophagy across insects and delves into the evolutionary origins of this trait in disparate insect orders. Employing a comprehensive analysis of gut microbiome data, from both saproxylophagous insects and their non-saproxylophagous relatives, including new data from unexplored wood-feeding insects, this Hypothesis paper discusses the broader phylogenetic context and potential adaptations necessary for this dietary specialization. The study proposes the "Detritivore-First Hypothesis," suggesting an evolutionary pathway to saproxylophagy through detritivory, and highlights the critical role of symbiotic gut microbiomes in the digestion of decaying wood.

Species traits elucidate crop pest response to landscape composition: a global analysis.

Recent synthesis studies have shown inconsistent responses of crop pests to landscape composition, imposing a fundamental limit to our capacity to design sustainable crop protection strategies to reduce yield losses caused by insect pests. Using a global dataset composed of 5242 observations encompassing 48 agricultural pest species and 26 crop species, we tested the role of pest traits (exotic status, host breadth and habitat breadth) and environmental context (crop type, range in landscape gradient and climate) in modifying the pest response to increasing semi-natural habitats in the surrounding landscape. For natives, increasing semi-natural habitats decreased the abundance of pests that exploit only crop habitats or that are highly polyphagous. On the contrary, populations of exotic pests increased with an increasing cover of semi-natural habitats. These effects might be related to changes in host plants and other resources across the landscapes and/or to modified top-down control by natural enemies. The range of the landscape gradient explored and climate did not affect pests, while crop type modified the response of pests to landscape composition. Although species traits and environmental context helped in explaining some of the variability in pest response to landscape composition, the observed large interspecific differences suggest that a portfolio of strategies must be considered and implemented for the effective control of rapidly changing communities of crop pests in agroecosystems.

Mesoscale hydrodynamics via stochastic rotation dynamics: comparison with Lennard-Jones fluid.

Stochastic rotation dynamics (SRD) is a relatively recent technique, closely related to lattice Boltzmann, for capturing hydrodynamic fluid flow at the mesoscale. The SRD method is based on simple constituent fluid particle interactions and dynamics. Here we parametrize the SRD fluid to provide a one to one match in the shear viscosity of a Lennard-Jones fluid and present viscosity measurements for a range of such parameters. We demonstrate how to apply the Müller-Plathe reverse perturbation method for determining the shear viscosity of the SRD fluid and discuss how finite system size and momentum exchange rates effect the measured viscosity. The implementation and performance of SRD in a parallel molecular dynamics code is also described.

Liquid crystal nanodroplets in solution.

The aggregation of liquid crystal nanodroplets from a homogeneous solution is studied by molecular dynamics simulations. The liquid crystal particles are modeled as elongated ellipsoidal Gay-Berne particles while the solvent is modeled as spherical Lennard-Jones particles. Extending previous studies of Berardi et al. [J. Chem. Phys. 126, 044905 (2007)], we find that liquid crystal nanodroplets are not stable and that after sufficiently long times the nanodroplets always aggregate into a single large droplet. Results describing the droplet shape and orientation for different temperatures and shear rates are presented. The implementation of the Gay-Berne potential for biaxial ellipsoidal particles in a parallel molecular dynamics code is also briefly discussed.

Shear thinning of nanoparticle suspensions.

Results of large scale nonequilibrium molecular dynamics simulations are presented for nanoparticles in an explicit solvent. The nanoparticles are modeled as a uniform distribution of Lennard-Jones particles, while the solvent is represented by standard Lennard-Jones particles. We present results for the shear rheology of spherical nanoparticles of diameter 10 times that of the solvent for a range of nanoparticle volume fractions. By varying the strength of the interactions between nanoparticles and with the solvent, this system can be used to model colloidal gels and glasses as well as hard spherelike nanoparticles. Effect of including the solvent explictly is demonstrated by comparing the pair correlation function of nanoparticles to that in an implicit solvent. The shear rheology for dumbbell nanoparticles made of two fused spheres is similar to that of single nanoparticle.

Orientational dynamics of water in the nafion polymer electrolyte membrane and its relationship to proton transport.

Orientational anisotropies are calculated from molecular dynamics simulations of bulk water and the Na(+) and H(+) forms of hydrated Nafion and then compared with corresponding experimental values. The extended jump model of Laage and Hynes is applied to water reorientations for each system, and the anisotropies are explored as a product of hydrogen bond restricted "wobble-in-a-cone" reorientations and that due to the discrete jumps of hydrogen bond reorganization. Additionally, the timescales of hydrogen bond switching and proton transport are presented for bulk water and the H(+) form of hydrated Nafion. The short time scale of proton hopping is found to be independent of Nafion water loading, suggesting the short time dynamics of proton hopping are relatively insensitive to the level of hydration. Furthermore, the long time decay for the forward rate of hydrogen bond switching is shown to be identical to the long time decay in the forward rate of proton hopping, for bulk water and all water loadings of Nafion investigated, suggesting a unified process.

Proton solvation and transport in aqueous and biomolecular systems: insights from computer simulations.

The excess proton in aqueous media plays a pivotal role in many fundamental chemical (e.g., acid-base chemistry) and biological (e.g., bioenergetics and enzyme catalysis) processes. Understanding the hydrated proton is, therefore, crucial for chemistry, biology, and materials sciences. Although well studied for over 200 years, excess proton solvation and transport remains to this day mysterious, surprising, and perhaps even misunderstood. In this feature article, various efforts to address this problem through computer modeling and simulation will be described. Applications of computer simulations to a number of important and interesting systems will be presented, highlighting the roles of charge delocalization and Grotthuss shuttling, a phenomenon unique in many ways to the excess proton in water.

Amphiphilic character of the hydrated proton in methanol-water solutions.

The hydrated proton was studied in methanol-water solutions of varying methanol concentrations using the multistate empirical valence bond simulation method. Amphiphile-like behavior of the hydrated proton was noted from its anisotropic association with the methanol methyl groups. Molecular length immiscibility was also characterized through the enumeration of water and protonated water clusters. Excess proton diffusion was calculated across the varying methanol concentrations and found to be in good agreement with experiment after correcting for nuclear quantum effects.

Characterization of the solvation and transport of the hydrated proton in the perfluorosulfonic acid membrane nafion.

The solvation and transport properties of the sulfonate-hydronium ion pair have been studied in hydrated Nafion through molecular dynamics simulation. Explicit proton and charge delocalization of the excess proton transport, via the Grotthuss hopping mechanism, were treated using the self-consistent multistate empirical valence bond (SCI-MS-EVB) method. The nature of the sulfonate-hydronium ion pair was characterized through analysis of free-energy profiles. It was found that, in general, the excess proton is solvated between two water molecules of a Zundel moiety while in the contact ion pair position, but then it transitions to an Eigen-like configuration in the solvent-separated pair position. Furthermore, the positive charge associated with the excess proton passes between the contact and solvent-separated ion pair positions through the Grotthuss mechanism rather than simple vehicular diffusion. The total proton diffusion was decomposed into vehicular and Grotthuss components and were found to be of the same relative magnitude, but with a strong negative correlation resulting in a smaller overall diffusion. Correlated motions between the ion pair were examined through the distinct portion of the van Hove correlation function, and a characteristic time scale of approximately 425 ps was observed. Additionally, the association of the hydrated proton with the hydrophobic polymer backbone suggests its amphiphile-like behavior (see Acc. Chem. Res. 2006, 39, 143; Phys. Rev. 1954, 95, 249; J. Chem. Phys. 2005, 123, 084309).

Development of the Diabetes Technology Society Blood Glucose Monitor System Surveillance Protocol.

BACKGROUND: Inaccurate blood glucsoe monitoring systems (BGMSs) can lead to adverse health effects. The Diabetes Technology Society (DTS) Surveillance Program for cleared BGMSs is intended to protect people with diabetes from inaccurate, unreliable BGMS products that are currently on the market in the United States. The Surveillance Program will provide an independent assessment of the analytical performance of cleared BGMSs. METHODS: The DTS BGMS Surveillance Program Steering Committee included experts in glucose monitoring, surveillance testing, and regulatory science. Over one year, the committee engaged in meetings and teleconferences aiming to describe how to conduct BGMS surveillance studies in a scientifically sound manner that is in compliance with good clinical practice and all relevant regulations. RESULTS: A clinical surveillance protocol was created that contains performance targets and analytical accuracy-testing studies with marketed BGMS products conducted by qualified clinical and laboratory sites. This protocol entitled "Protocol for the Diabetes Technology Society Blood Glucose Monitor System Surveillance Program" is attached as supplementary material. CONCLUSION: This program is needed because currently once a BGMS product has been cleared for use by the FDA, no systematic postmarket Surveillance Program exists that can monitor analytical performance and detect potential problems. This protocol will allow identification of inaccurate and unreliable BGMSs currently available on the US market. The DTS Surveillance Program will provide BGMS manufacturers a benchmark to understand the postmarket analytical performance of their products. Furthermore, patients, health care professionals, payers, and regulatory agencies will be able to use the results of the study to make informed decisions to, respectively, select, prescribe, finance, and regulate BGMSs on the market.

Structure of hydrated Na-Nafion polymer membranes.

We use molecular dynamics simulations to investigate the structure of the hydrated Na-Nafion membranes. The membrane is "prepared" by starting with the Nafion chains placed on a cylinder having the water inside it. Minimizing the energy of the system leads to a filamentary hydrophilic domain whose structure depends on the degree of hydration. At 5 wt % water the system does not have enough water molecules to solvate all the ions that could be formed by the dissociation of the -SO3Na groups. As a result, the -SO3Na groups aggregate with the water to form very small droplets that do not join into a continuous phase. The size of the droplets is between 5 and 8 A. As the amount of water present in the membrane is increased, the membrane swells, and SO3Na has an increasing tendency to dissociate into ions. Furthermore, a transition to a percolating hydrophilic network is observed. In the percolating structure, the water forms irregular curvilinear channels branching in all directions. The typical dimension of the cross section of these channels is about 10-20 A. Calculated neutron scattering from the simulated system is in qualitative agreement with experiment. In all simulations, the pendant sulfonated perfluorovinyl side chains of the Nafion hug the walls of the hydrophilic channel, while the sulfonate groups point toward the center of the hydrophilic phase. The expulsion of the side chains from the hydrophilic domain is favored because it allows better interaction between the water molecules. We have also examined the probability of finding water molecules around the Na+ and the -SO3(-) ions as well as the probability of finding other water molecules next to a given water molecule. These probabilities are much broader than those found in bulk water or for one ion in bulk water (calculated with the potentials used in the present simulation). This is due to the highly inhomogeneous nature of the material contained in the small hydrophilic pores.

Excess proton solvation and delocalization in a hydrophilic pocket of the proton conducting polymer membrane nafion.

Solvation properties of the hydrated excess proton are studied in a hydrophilic pocket of Nafion 117 through a series of molecular dynamics simulations. The multistate empirical valence bond (MS-EVB) methodology, which enables the delocalization of the excess proton through the Grotthuss hopping mechanism, was employed for one of the excess protons in the simulation cell. Simulations were performed such that "classical" nondissociable hydronium cations and a single excess proton treated with the MS-EVB methodology were at a concentration ratio of 39:1. Two degrees of hydration of the Nafion polymer electrolyte membrane were simulated, each displaying the same marked difference between the solvation structures of the classical versus MS-EVB treated (Grotthuss shuttling) excess proton species. These differences are attributed to the solvent dynamics needed to transfer the cation between the solvent separated and contact pair positions about the sulfonic acid counterion. The results demonstrate that it is generally impossible to describe the low pH conditions in the hydrophilic domains of Nafion without the explicit treatment of Grotthuss delocalization in the underlying molecular dynamics model for the excess protons.

Shear rheology of extended nanoparticles.

Nonequilibrium molecular-dynamics simulations are presented for the shear rheology of suspensions of extended "jack"-shaped nanoparticles in an explicit solvent. The shear viscosity is measured for two jack-shaped nanoparticle suspensions for volume fractions from 0.01 to 0.15 and compared to spherical nanoparticles of the same mass. Large differences, in some cases, orders of magnitude, are observed for both the equilibrium viscosity and diffusion constant as the shape of the nanoparticle is varied. The source of enhanced viscosity is the very large effective volume swept out by these extended nanoparticles which allows them to become highly entangled even at low volume fraction.

The properties of ion-water clusters. II. Solvation structures of Na+, Cl-, and H+ clusters as a function of temperature.

Ion-water-cluster properties are investigated both through the multistate empirical valence bond potential and a polarizable model. Equilibrium properties of the ion-water clusters H+(H2O)100, Na+(H2O)100, Na+(H2O)20, and Cl-(H2O)17 in the temperature region 100-450 K are explored using a hybrid parallel basin-hopping and tempering algorithm. The effect of the solid-liquid phase transition in both caloric curves and structural distribution functions is investigated. It is found that sodium and chloride ions largely reside on the surface of water clusters below the cluster melting temperature but are solvated into the interior of the cluster above the melting temperature, while the solvated proton was found to have significant propensity to reside on or near the surface in both the liquid- and solid-state clusters.

A bond-order analysis of the mechanism for hydrated proton mobility in liquid water.

Bond-order analysis is introduced to facilitate the study of cooperative many-molecule effects on proton mobility in liquid water, as simulated using the multistate empirical valence-bond methodology. We calculate the temperature dependence for proton mobility and the total effective bond orders in the first two solvation shells surrounding the H(5)O(2) (+) proton-transferring complex. We find that proton-hopping between adjacent water molecules proceeds via this intermediate, but couples to hydrogen-bond dynamics in larger water clusters than previously anticipated. A two-color classification of these hydrogen bonds leads to an extended mechanism for proton mobility.

The properties of ion-water clusters. I. The protonated 21-water cluster.

The ab initio atom-centered density-matrix propagation approach and the multistate empirical valence bond method have been employed to study the structure, dynamics, and rovibrational spectrum of a hydrated proton in the "magic" 21 water cluster. In addition to the conclusion that the hydrated proton tends to reside on the surface of the cluster, with the lone pair on the protonated oxygen pointing "outwards," it is also found that dynamical effects play an important role in determining the vibrational properties of such clusters. This result is used to analyze and complement recent experimental and theoretical studies.