Molecular Dynamics Simulations of Different Nanoparticles at Substrates.

We report the results of large-scale molecular dynamics simulations of adsorption nanoparticles on solid surfaces. The particles were modeled as stiff aggregates of spherical segments. Three types of particles were studied: rods, rectangles, and triangles built of the same number of segments. We show how the particle shape affects the adsorption, the structure of the surface layer, and the degree of the removal of particles from the solvent. The systems with different segment-segment and segment-surface interactions and different concentrations of particles were investigated. The ordered structures formed in adsorption monolayers were also analyzed. The results are consistent with experimental observations.

Janus Ligand-Tethered Nanoparticles at Liquid-Liquid Interfaces.

We investigate the structural properties of Janus ligand-tethered nanoparticles at liquid-liquid interfaces using coarse-grained molecular dynamics simulations. The effect of interactions between different chains and liquids is discussed. We consider the Janus particles with symmetrical interactions with the liquids which correspond to supplementary wettability and particles with uncorrelated interactions. Simulation results indicate that the Janus hairy particles trapped in the interface region have different configurations characterized by the vertical displacement distance, the orientation of the Janus line relative to the interface, and the particle shape. The Janus hairy particles present abundant morphologies, including dumbbell-like and typical core-shell, at the interface. The shape of adsorbed particles is analyzed in detail. The simulation data are compared with those predicted by a simple phenomenological approach. This work can promote the applications of Janus hairy particles in nanotechnology.

Hybrid Nanoparticles at Fluid-Fluid Interfaces: Insight from Theory and Simulation.

Hybrid nanoparticles that combine special properties of their different parts have numerous applications in electronics, optics, catalysis, medicine, and many others. Of the currently produced particles, Janus particles and ligand-tethered (hairy) particles are of particular interest both from a practical and purely cognitive point of view. Understanding their behavior at fluid interfaces is important to many fields because particle-laden interfaces are ubiquitous in nature and industry. We provide a review of the literature, focusing on theoretical studies of hybrid particles at fluid-fluid interfaces. Our goal is to give a link between simple phenomenological models and advanced molecular simulations. We analyze the adsorption of individual Janus particles and hairy particles at the interfaces. Then, their interfacial assembly is also discussed. The simple equations for the attachment energy of various Janus particles are presented. We discuss how such parameters as the particle size, the particle shape, the relative sizes of different patches, and the amphiphilicity affect particle adsorption. This is essential for taking advantage of the particle capacity to stabilize interfaces. Representative examples of molecular simulations were presented. We show that the simple models surprisingly well reproduce experimental and simulation data. In the case of hairy particles, we concentrate on the effects of reconfiguration of the polymer brushes at the interface. This review is expected to provide a general perspective on the subject and may be helpful to many researchers and technologists working with particle-laden layers.

Shape Transformations and Self-Assembly of Hairy Particles under Confinement.

Molecular dynamics simulations are used to investigate the behavior of polymer-tethered nanoparticles between two inert or attractive walls. The confinement in pores creates new possibilities for controlling the shape transformation of individual hairy particles and their self-organization. We introduce a minimalistic model of the system; only chain-wall interactions are assumed to be attractive, while the others are softly repulsive. We show how the shape of isolated particles can be controlled by changing the wall separation and the strength of the interaction with the surfaces. For attractive walls, we found two types of structures, "bridges" and "mounds". The first structures are similar to flanged spools in which the chains are connected with both walls and form bridges between them. We observed various bridges, symmetrical and asymmetrical spools, hourglasses, and pillars. The bridge-like structures can be "nano-oscillators" in which the cores jump from one wall to the other. We also study the self-assembly of a dense fluid of hairy particles in slit-like pores and analyze how the system morphology depends on interactions with the surfaces and the wall separation. The hairy particles form layers parallel to the walls. Different ordered structures, resembling two-dimensional crystalline lattices, are reported. We demonstrate that hairy particles are a versatile soft component forming a variety of structures in the slits.

Adsorption of Polymer-Tethered Particles on Solid Surfaces.

We explore the behavior of polymer-tethered particles on solid surfaces using coarse-grained molecular dynamics simulations. Segment-segment, segment-core, and core-core interactions are assumed to be purely repulsive, while the segment-substrate interactions are attractive. We analyze changes in the internal structure of single hairy particles on the surfaces with the increasing strength of the segment-substrate interactions. For this purpose, we calculate the density profiles along the x, y, z axes and the mass dipole moments. The adsorbed hairy particles are found to be symmetrical in a plane parallel to the substrate but strongly asymmetric in the vertical direction. On stronger adsorbents, the particle canopies become flattened and the cores lie closer to the wall. We consider the adsorption of hairy nanoparticles dispersed in systems of different initial particle densities. We show how the strength of segment-substrate interactions affects the structure of the adsorbed phase, the particle-wall potential of the average force, the excess adsorption isotherms, and the real adsorption isotherms.

Effects of land use and climate on carbon and nitrogen pool partitioning in European mountain grasslands.

European mountain grasslands are increasingly affected by land-use changes and climate, which have been suggested to exert important controls on grassland carbon (C) and nitrogen (N) pools. However, so far there has been no synthetic study on whether and how land-use changes and climate interactively affect the partitioning of these pools amongst the different grassland compartments. We analyzed the partitioning of C and N pools of 36 European mountain grasslands differing in land-use and climate with respect to above- and belowground phytomass, litter and topsoil (top 23 cm). We found that a reduction of management intensity and the abandonment of hay meadows and pastures increased above-ground phytomass, root mass and litter as well as their respective C and N pools, concurrently decreasing the fractional contribution of the topsoil to the total organic carbon pool. These changes were strongly driven by the cessation of cutting and grazing, a shift in plant functional groups and a related reduction in litter quality. Across all grasslands studied, variation in the impact of land management on the topsoil N pool and C/N-ratio were mainly explained by soil clay content combined with pH. Across the grasslands, below-ground phytomass as well as phytomass- and litter C concentrations were inversely related to the mean annual temperature; furthermore, C/N-ratios of phytomass and litter increased with decreasing mean annual precipitation. Within the topsoil compartment, C concentrations decreased from colder to warmer sites, and increased with increasing precipitation. Climate generally influenced effects of land use on C and N pools mainly through mean annual temperature and less through mean annual precipitation. We conclude that site-specific conditions need to be considered for understanding the effects of land use and of current and future climate changes on grassland C and N pools.

Adsorption on Ligand-Tethered Nanoparticles.

We use coarse-grained molecular dynamics simulations to study adsorption on ligand-tethered particles. Nanoparticles with attached flexible and stiff ligands are considered. We discuss how the excess adsorption isotherm, the thickness of the polymer corona, and its morphology depend on the number of ligands, their length, the size of the core, and the interaction parameters. We investigate the adsorption-induced structural transitions of polymer coatings. The behavior of systems involving curved and flat "brushes" is compared.

Adsorption-induced co-assembly of hairy and isotropic particles.

We use coarse-grained molecular dynamics simulations to study the behavior of polymer-tethered particles immersed in fluids of isotropic particles. Particles modified with weakly anchored, mobile ligands are considered. We discuss how the concentration of fluid particles affects the morphology of an isolated hairy particle. It is shown that hairy particles present different morphologies including typical core-shell, octopus-like and corn-like, depending on fluid-segment interactions and the fluid density. The mechanism of changes in the shape of hairy particles is explained. The reconfiguration of the polymer corona arises from adsorption of fluid particles "on chains". The adsorbed fluid particles form bridges between the chains. This causes the mobile ligands to merge into clusters on the core surface. A part of the core remains empty so the hairy particle becomes a Janus-like object. We also study co-assembly in mixtures of hairy and isotropic particles. Depending on the strength of fluid-segment interactions, hairy particles with fluid particles trapped inside their coronas remain isolated or form mixed clusters of different structures. The aggregation of hairy particles results from the formation of bridges between chains belonging to different cores by fluid particles.

Molecular dynamics simulations of mono-tethered particles at solid surfaces.

We use molecular dynamics simulations to study the behavior of mono-tethered nanoparticles on solid surfaces. In our model particle-particle and particle-chain interactions are repulsive, while chain-chain interactions are attractive. Two surfaces are considered: the first one attracts particles and the other attracts chains. Excess adsorption isotherms are presented for both the surfaces and different lengths of tethers. The mechanism of adsorption is discussed. We find that depending on the assumed parameters the mono-tethered particles can be adsorbed as single particles or as different aggregates. Our main goal is to explore the structure of surface films. We show that the morphology of the adsorbed layer depends mainly on the type of the surface but the influence of the particle diameter, the chain length and the density is also important. We prove that the shape of aggregates changes near the substrate. For certain parameters the aggregates can break under the influence of the surface.

Fate of PAHs in the vicinity of aluminum smelter.

Investigation has been carried out in the vicinity of an aluminum smelter located in the industrialized town of Konin. Concentrations of 14 polycyclic aromatic hydrocarbons (PAHs) were determined in grass, spruce needles, and soil collected in the period of the smelter operation and several years after its closing. Significant changes in the quantity of PAHs and their profiles observed in the two measuring periods, stressing the importance of aluminum production with regard to PAH emission. It was confirmed by very high values of the carcinogenic potential (CP) found for PAHs accumulated in grass and soil when compared to the values found in urban and remote sites. PAH ratio rates used as a tool for identifying emission sources showed a pyrogenic origin of PAHs in both periods; the ratios in the period of the smelter running activity were similar to those found in other studies carried out near aluminum smelters. Grass turned out to be a good biomonitor of PAHs similarly to commonly used leaves of various tree species. The use of four age classes of spruce needles, some of which were subjected to emission from the smelter, showed that such approach could serve as an analysis tool for describing retrospective pollution.

Self-assembly of hairy disks in two dimensions - insights from molecular simulations.

We report the results of large scale molecular dynamics simulations conducted for sparsely grafted disks in two-dimensional systems. The main goal of this work is to show how the ligand mobility influences the self-assembly of particles decorated with short chains. We also analyze the impact of the chain length on the structure of dense phases. A crossover between the systems controlled by the core-core or by the segment-segment interactions is discussed. We prove that the ligand mobility determines the structure of the system. The particles with fixed tethers are found to order into different structures, an amorphous phase, hexagonal or honeycomb lattices, and a "spaghetti"-like phase containing single strings of cores, depending on the length of attached chains. The disks with mobile monomers assemble into a hexagonal structure, while the particles with longer mobile chains attached to them form a lamellar phase consisting of double strings of cores.

Interspecific differences in foliar 1 PAHs load between Scots pine, birch, and wild rosemary from three polish peat bogs.

Pine needles are one of the most commonly used bioindicators of polycyclic aromatic hydrocarbons (PAHs) in the environment. Therefore, the main objective of the current research was the assessment of PAHs accumulation potential of Scots pine (Pinus sylvestris L.) needles in comparison to wild rosemary (Rhododendron tomentosum Harmaja) and birch (Betula spp.) leaves. Our study was carried out on three peat bogs subjected to different degree of anthropopression, which gave us also the opportunity to identify local emission sources. Pine needles had the lowest accumulation potential from all the studied species. The highest accumulation potential, and hence carcinogenic potential, was observed for wild rosemary leaves. As far as emission sources are concerned, the most pronounced influence on atmospheric PAHs loads had traditional charcoal production, resulting in great influx of heavy PAHs. Observed seasonal changes in PAHs concentrations followed the pattern of winter increase, caused mainly by heating season, and summer decrease, caused mainly by volatilization of light PAHs.

Forest floor vegetation response to nitrogen deposition in Europe.

Chronic nitrogen (N) deposition is a threat to biodiversity that results from the eutrophication of ecosystems. We studied long-term monitoring data from 28 forest sites with a total of 1,335 permanent forest floor vegetation plots from northern Fennoscandia to southern Italy to analyse temporal trends in vascular plant species cover and diversity. We found that the cover of plant species which prefer nutrient-poor soils (oligotrophic species) decreased the more the measured N deposition exceeded the empirical critical load (CL) for eutrophication effects (P = 0.002). Although species preferring nutrient-rich sites (eutrophic species) did not experience a significantly increase in cover (P = 0.440), in comparison to oligotrophic species they had a marginally higher proportion among new occurring species (P = 0.091). The observed gradual replacement of oligotrophic species by eutrophic species as a response to N deposition seems to be a general pattern, as it was consistent on the European scale. Contrary to species cover changes, neither the decrease in species richness nor of homogeneity correlated with nitrogen CL exceedance (ExCLemp N). We assume that the lack of diversity changes resulted from the restricted time period of our observations. Although existing habitat-specific empirical CL still hold some uncertainty, we exemplify that they are useful indicators for the sensitivity of forest floor vegetation to N deposition.

Contamination of Polish national parks with heavy metals.

The paper presents results of screening analysis of all Polish national parks (23) contamination with Cd, Cu, Pb and Zn on the basis of a three-level characteristic of heavy metal presence in Norway spruce stands: accumulation on the needle surface, concentration of heavy metals in spruce needles and concentration of bioavailable heavy metals in the soil. Based on the obtained results, the classification of forest ecosystem hazard in national parks with heavy metals was made using synthetic indicators. It was found out that Babiogórski, Magurski, Ojcowski and Gorczanski National Parks, located in the southern part of the country, were the most polluted with heavy metals. It is probably due to a higher industrial activity in this part of Poland and the transboundary transport of air pollutants. A little lower level of pollution was observed in Kampinoski National Park located in the middle of the country. The concentration of heavy metals found in needles from national parks does not seem to be harmful for the health status of the trees. Statistically significant correlation between all parameters, which was found for cadmium--the most mobile of the analysed elements--shows that this metal can be proposed as a marker to reflect present effect of industrial emission on forests.