Curvature dependence of the effect of ionic functionalization on the attraction among nanoparticles in dispersion

Solubilization of nanoparticles facilitates nanomaterial processing and enables new applications. An effective method to improve dispersibility in water is provided by ionic functionalization.We explore how the necessary extent of functionalization depends on the particle geometry. Using molecular dynamics/umbrella sampling simulations, we determine the effect of the solute curvature on solventaveraged interactions among ionizing graphitic nanoparticles in aqueous dispersion. We tune the hydrophilicity of molecular-brush coated fullerenes, carbon nanotubes, and graphane platelets by gradually replacing a fraction of the methyl end groups of the alkyl coating by the ionizing –COOK or –NH3Cl groups. To assess the change in nanoparticles’ dispersibility in water, we determine the potential-of-mean-force profiles at varied degrees of ionization. When the coating comprises only propyl groups, the attraction between the hydrophobic particles intensifies from spherical to cylindrical to planar geometry. This is explained by the increasing fraction of surface groups that can be brought into contact and the reduced access to water molecules, both following the above sequence. When ionic groups are added, however, the dispersibility increases in the opposite order, with the biggest effect in the planar geometry and the smallest in the spherical geometry. These results highlight the important role of geometry in nanoparticle solubilization by ionic functionalities, with about twice higher threshold surface charge necessary to stabilize a dispersion of spherical than planar particles. At 25%–50% ionization, the potential of mean force reaches a plateau because of the counterion condensation and saturated brush hydration. Moreover, the increase in the fraction of ionic groups can weaken the repulsion through counterion correlations between adjacent nanoparticles. High degrees of ionization and concomitant ionic screening gradually reduce the differences among surface interactions in distinct geometries until an essentially curvature-independent dispersion environment is created. Insights into tuning nanoparticle interactions can guide the synthesis of a broad class of nonpolar nanoparticles, where solubility is achieved by ionic functionalization

Dynamics at a Janus interface

Electric field effects on water interfacial properties abound, ranging from electrochemical cells to nanofluidic devices to membrane ion channels. On the nanoscale, spontaneous orientational polarization of water couples with field alignment, resulting in an asymmetric wetting behavior of opposing surfacesa field-induced analogue of a chemically generated Janus interface. Using atomistic simulations, we uncover a new and significant field polarity (sign) dependence of the dipolar- orientation polarization dynamics in the hydration layer. Applying electric fields across a nanoparticle, or a nanopore, can lead to close to 2 orders of magnitude difference in response times of water polarization at opposite surfaces. Typical time scales are within the O(10−1) to O(10) picosecond regime. Temporal response to the field change also reveals strong coupling between local polarization and interfacial density relaxations, leading to a nonexponential and in some cases, nonmonotonic response. This work highlights the surprisingly strong asymmetry between reorientational dynamics at surfaces with incoming and outgoing fields, which is even more pronounced than the asymmetry in static properties of a field-induced Janus interface

Climatic cycles recorded in the Middle Eocene hemipelagites from a Dinaric foreland basin of Istria (Croatia)

Middle Eocene hemipelagic marls from the Pazin-Trieste Basin, a foreland basin of the Croatian Dinarides, display repetitive alternations of two types of marls with different resistance to weathering. This study focuses on the chemical composition, stable isotopes, and palynomorph content of these marls in order to better understand the nature of their cyclic deposition and to identify possible paleoenvironmental drivers responsible for their formation. The less resistant marls (LRM) have consistently lower carbonate content, lower δ18O and δ13C values, and more abundant dinoflagellate cysts than the more resistant marls (MRM). We interpret these differences between the two marl types to be a result of climatic variations, likely related to Milankovitch oscillations. Periods with wetter climate, associated with increased continental runoff, detrital and nutrient influx produced the LRM. Higher nutrient supply sparked higher dinoflagellate productivity during these times, while reduced salinity and stratification of the water column may have hampered the productivity of calcareous nannoplankton and/or planktonic foraminifera. In contrast, the MRM formed during dryer periods which favoured higher carbonate accumulation rates. This study provides new information about the sedimentary record of short-scale climate variations reflected in wet-dry cycles during an overall warm, greenhouse Earth

Multifaceted Water Dynamics in Spherical Nanocages

We present a new method to study position- dependent, anisotropic diffusion tensors inside spherically confined systems—a geometry that is common to many chemical nanoreactors. We use this method to elucidate the surprisingly rich solvent dynamics of confined water. The spatial variation of the strongly anisotropic diffusion predicted by the model agrees with the results of explicit molecular dynamics simulations. The same approach can be directly transferred to the transport of solutes to and from reaction sites located at nanoreactor interfaces. We com- plement our study by a detailed analysis of wa- ter hydrogen bond kinetics, which is intimately coupled to diffusion. Despite the inhomogene- ity in structure and translational dynamics in- side our nanocages, a single set of well-defined rate constants is sufficient to accurately describe the kinetics of hydrogen bond breaking and for- mation. We find that once system size effects have been eliminated, the residence times of wa- ter molecules inside the coordination shell of a hydrogen bond partner are well correlated to average diffusion constants obtained from the procedure above

Floral temperature and optimal foraging: is heat a feasible floral reward for pollinators?

As well as nutritional rewards, some plants also reward ectothermic pollinators with warmth. Bumble bees have some control over their temperature, but have been shown to forage at warmer flowers when given a choice, suggesting that there is some advantage to them of foraging at warm flowers (such as reducing the energy required to raise their body to flight temperature before leaving the flower). We describe a model that considers how a heat reward affects the foraging behaviour in a thermogenic central-place forager (such as a bumble bee). We show that although the pollinator should spend a longer time on individual flowers if they are warm, the increase in total visit time is likely to be small. The pollinator's net rate of energy gain will be increased by landing on warmer flowers. Therefore, if a plant provides a heat reward, it could reduce the amount of nectar it produces, whilst still providing its pollinator with the same net rate of gain. We suggest how heat rewards may link with plant life history strategies

Line Transect Surveys Underdetect Terrestrial Mammals: Implications for the Sustainability of Subsistence Hunting

Conservation of Neotropical game species must take into account the livelihood and food security needs of local human populations. Hunting management decisions should therefore rely on abundance and distribution data that are as representative as possible of true population sizes and dynamics. We simultaneously applied a commonly used encounter-based method and an infrequently used sign-based method to estimate hunted vertebrate abundance in a 48,000-km² indigenous landscape in southern Guyana. Diurnal direct encounter data collected during three years along 216, four-kilometer -long transects consistently under-detected many diurnal and nocturnal mammal species readily detected through sign. Of 32 species analyzed, 31 were detected by both methods; however, encounters did not detect one and under-detected another 12 of the most heavily hunted species relative to sign, while sign under-detected 12 never or rarely collected species relative to encounters. The six most important game animals in the region, all ungulates, were not encountered at 11–40% of village and control sites or on 29–72% of transects where they were detected by sign. Using the sign methodology, we find that tapirs, one of the terrestrial vertebrates considered most sensitive to overexploitation, are present at many sites where they were never visually detected during distance sampling. We find that this is true for many other species as well. These high rates of under-detection suggest that behavioral changes in hunted populations may affect apparent occurrence and abundance of these populations. Accumulation curves (detection of species on transects) were much steeper for sign for 12 of 16 hunted species than for encounters, but that pattern was reversed for 12 of 16 species unhunted in our area. We conclude that collection of sign data is an efficient and effective method of monitoring hunted vertebrate populations that complements encounter and camera-trapping methods in areas impacted by hunting. Sign surveys may be the most viable method for large-scale, management-oriented studies in remote areas, particularly those focused on community-based wildlife management.Data Availability Statement: Data not provided includes village names, hunters, and hunting details due to ethical human rights concerns linked to indigenous peoples of the area. Agreements with indigenous people limit data to use by our research group. All other relevant data are within the paper and its Supporting Information files

Deconstructing classical water models at interfaces and in bulk

Using concepts from perturbation and local molecular field theories of liquids we divide the potential of the SPC/E water model into short and long ranged parts. The short ranged parts define a minimal reference network model that captures very well the structure of the local hydrogen bond network in bulk water while ignoring effects of the remaining long ranged interactions. This deconstruction can provide insight into the different roles that the local hydrogen bond network, dispersion forces, and long ranged dipolar interactions play in determining a variety of properties of SPC/E and related classical models of water. Here we focus on the anomalous behavior of the internal pressure and the temperature dependence of the density of bulk water. We further utilize these short ranged models along with local molecular field theory to quantify the influence of these interactions on the structure of hydrophobic interfaces and the crossover from small to large scale hydration behavior. The implications of our findings for theories of hydrophobicity and possible refinements of classical water models are also discussed

Dynamics of nanoscale droplets on moving surfaces

We use molecular dynamics (MD) simulations to investigate the dynamic wetting of nanoscale water droplets on moving surfaces. The density and hydrogen bonding profiles along the direction normal to the surface are reported, and the width of the water depletion layer is evaluated first for droplets on three different static surfaces: silicon, graphite, and a fictitious superhydrophobic surface. The advancing and receding contact angles, and contact angle hysteresis, are then measured as a function of capillary number on smooth moving silicon and graphite surfaces. Our results for the silicon surface show that molecular displacements at the contact line are influenced greatly by interactions with the solid surface and partly by viscous dissipation effects induced through the movement of the surface. For the graphite surface, however, both the advancing and receding contact angles values are close to the static contact angle value and are independent of the capillary number; i.e., viscous dissipation effects are negligible. This finding is in contrast with the wetting dynamics of macroscale water droplets, which show significant dependence on the capillary number

Hydrogen-Bond Driven Loop-Closure Kinetics in Unfolded Polypeptide Chains

Characterization of the length dependence of end-to-end loop-closure kinetics in unfolded polypeptide chains provides an understanding of early steps in protein folding. Here, loop-closure in poly-glycine-serine peptides is investigated by combining single-molecule fluorescence spectroscopy with molecular dynamics simulation. For chains containing more than 10 peptide bonds loop-closing rate constants on the 20–100 nanosecond time range exhibit a power-law length dependence. However, this scaling breaks down for shorter peptides, which exhibit slower kinetics arising from a perturbation induced by the dye reporter system used in the experimental setup. The loop-closure kinetics in the longer peptides is found to be determined by the formation of intra-peptide hydrogen bonds and transient β-sheet structure, that accelerate the search for contacts among residues distant in sequence relative to the case of a polypeptide chain in which hydrogen bonds cannot form. Hydrogen-bond-driven polypeptide-chain collapse in unfolded peptides under physiological conditions found here is not only consistent with hierarchical models of protein folding, that highlights the importance of secondary structure formation early in the folding process, but is also shown to speed up the search for productive folding events