Toxicity of additives present in conventional and biodegradable plastics on soil fauna: a case study of the root lesion nematode Pratylenchus neglectus.

Plastic pollution in terrestrial environments is a growing concern, with an increasing focus on the impact of plastic additives on soil ecosystems. We evaluated the impact of additives from conventional plastics (ACP) and biodegradable plastics (ABP) on the soil nematode, Pratylenchus neglectus. The additives represented five functional classes (antioxidants, colourants, flame retardants, nucleating agents, and plasticisers).

One-pot synthesis and covalent conjugation of methylene blue in mesoporous silica nanoparticles - A platform for enhanced photodynamic therapy.

Photodynamic therapy (PDT) is an emerging clinical modality for diverse disease conditions, including cancer. This technique involves, the generation of cytotoxic reactive oxygen species by a photosensitizer in the presence of light and oxygen. Methylene blue (MB) is a cationic dye with an ability to act as photosensitizing and bioimaging agent.

Use of Silica Nanoparticles for Drug Delivery in Cardiovascular Disease.

Purpose: Cardiovascular disease (CVD) is the leading cause of death worldwide. The current CVD therapeutic drugs require long-term treatment with high doses, which increases the risk of adverse effects while offering only marginal treatment efficacy. Silica nanoparticles (SNPs) have been proven to be an efficient drug delivery vehicle for numerous diseases, including CVD.

Carbohydrate coated fluorescent mesoporous silica particles for bacterial imaging.

This work investigated the synthesis of carbohydrate functionalized methylene blue doped amine grafted mesoporous silica nanoparticles (MB AMSN) and their application in bioimaging. A single-pot synthesis methodology was developed via a modified co-condensation sol-gel technique for simultaneous incorporation of the dye molecule in the nanoparticles, with amine grafting for subsequent functionalization. The obtained nanoparticles (∼ 450 nm) are mesoporous and have a high surface area (538 m/g), pore-volume (0.

Contribution of Binary Organic Layers to Soil Water Repellency: A Molecular Level Perspective.

Soil water repellency (SWR) is an extensively occurring phenomenon on natural and agricultural soils with a severe impact on soil water relations and thus crop yields and ecosystem productivity. It is caused by long chain amphiphilic compounds that originate from plant cuticular waxes. However, the severity of SWR varies with soil physical properties and the concentration of the compounds closely associated with producing hydrophobic coatings on soil surfaces.

Effect of substrate on the mechanical response and adhesion of PEGylated surfaces: insights from all-atom simulations.

Responsive surfaces show potential for many applications; however, the molecular mechanisms of their responsive behavior are often dependent on the nature and properties of the substrate and this dependence is not fully understood. We present a molecular dynamics study on the mechanical response of poly(ethylene glycol) (PEG) grafted on substrates of varying flexibility in "dry" conditions. Our in silico surface loading tests show that when PEG is grafted onto a hard substrate (silica), there is a significant reduction in adhesion to a solid surface, owing to augmented steric repulsions at the interface.

Role of hydrogen in dimerizaton of aluminum clusters: a theoretical study.

We have used density functional theory to investigate how Al(13) cluster dimers can be formed with or without a bridging hydrogen. We have identified several stable dimers in which 0, 1, or 2 hydrogen atoms link two bare clusters together. Each of these structures can adsorb further H atoms in atop sites on the surface of the dimer.

Effect of substituents on the stabilities of multiply-substituted carbon-centered radicals.

The bond dissociation energies (BDEs) and radical stabilization energies (RSEs) which result from 166 reactions that lead to carbon-centered radicals of the type ˙CH(2)X, ˙CHXY and ˙CXYZ, where X, Y and Z are any of the fourteen substituents H, F, Cl, NH(2), OH, SH, CH[double bond, length as m-dash]CH(2), C[triple bond, length as m-dash]CH, BH(2), CHO, COOH, CN, CH(3), and CF(3), were calculated using spin-restricted and -unrestricted variants of the double-hybrid B2-PLYP method with the 6-311+G(3df,2p) basis set. The interactions of substituents X, Y, and Z in both the radicals (˙CXYZ) and in the precursor closed-shell molecules (CHXYZ), as well as the extent of additivity of such interactions, were investigated by calculating radical interaction energies (RIEs), molecule interaction energies (MIEs), and deviations from additivity of RSEs (DARSEs) for a set of 152 reactions that lead to di- (˙CHXY) and tri- (˙CXYZ) substituted carbon-centered radicals. The pairwise quantities describing the effects of pairs of substituents in trisubstituted systems, namely pairwise MIEs (PMIEs), pairwise RIEs (PRIEs) and deviations from pairwise additivity of RSEs (DPARSEs), were also calculated for the set of 61 reactions that lead to trisubstituted radicals (˙CXYZ).

Comparative study of commonly used molecular dynamics force fields for modeling organic monolayers on water.

This study compares the performance of the all-atom molecular dynamics force fields OPLS-AA and COMPASS, and the united-atom GROMOS96 ff53a6 force field, for organic monolayers at aqueous interfaces, as a function of surface density, temperature, and system size. Where possible, comparison with experimental data was undertaken and used to scrutinize the performance of each force field. We find close agreement between the all-atom force fields (OPLS and COMPASS) and experiment for the description of organic monolayers on water.

Monolayer structure and evaporation resistance: a molecular dynamics study of octadecanol on water.

This study examines intermolecular interactions of a monolayer of octadecanol (CH(3)(CH(2))(17)OH) on water as a function of surface density and temperature, using classical molecular dynamics simulations. We observe increased interaction between the alkyl chains (van der Waals) and hydroxyl groups (H-bonding) with increased surface density, which leads to increased order and packing within the monolayer. We also identified clear trends in the intermolecular interactions, ordering and packing of the monolayer molecules as a function of temperature.

DFT study of H adsorption on magnesium-doped aluminum clusters.

In this study we use density functional theory (DFT) to investigate the properties and H adsorption characteristics of structural isomers of the magnesium-doped aluminum cluster, Al(12)Mg. Our results show that the exohedral structure (exo-MgAl(12)) is significantly lower in energy (1.59 eV) than the endohedral structure (endo-Al(12)Mg); however, the exohedral structure shows significant structural distortion.

First principles investigation of H addition and abstraction reactions on doped aluminum clusters.

We have investigated axial interactions of H(2) with Al(12)X (X = Mg, Al, and Si) clusters and found that homolytic dissociation leading to Al(12)XH and H atom proceeds without a barrier but is an extremely endothermic process. The calculated difference in energy of the addition and abstraction reactions indicates that any Al(12)X-based hydrogen storage technology that involves predissociation of H(2) will be limited by the competing processes. We have also discovered that while there is a modest barrier for dissociation of H(2) on a single Al(12)Mg cluster to give the dihydride, the process occurs spontaneously between two closely spaced Al(12)Mg clusters, resulting in the formation of two Al(12)MgH species.

Comparison of embedded atom method potentials for small aluminium cluster simulations.

In this paper, we present a comparison of the performance of a series of embedded atom method potentials for the evaluation of bulk and small aluminium cluster geometries and relative energies, against benchmark density functional theory calculations. In general, the non-pairwise potential-B (NP-B), which was parametrized against Al cluster data, performs the best.

Dissociative adsorption of hydrogen molecule on aluminum clusters: effect of charge and doping.

The dissociative chemisorption of molecular hydrogen on charged and neutral aluminum clusters Al12X (X = Mg, Al, Si) was investigated using DFT and a modified G3(MP2)-RAD procedure. Reaction barriers and enthalpies were determined for both neutral and singly charged clusters. The lowest barrier for dissociative adsorption of H2 on a neutral cluster was found for the Al12Mg cluster, whereas the highest barrier was found to be on the closed-shell Al12Si.

Performance of numerical basis set DFT for aluminum clusters.

We have investigated and compared the ability of numerical and Gaussian-type basis sets combined with density functional theory (DFT) to accurately describe the geometries, binding energies, and electronic properties of aluminum clusters, Al12XHn (X = Al, Si; n = 0, 1, 2). DFT results are compared against high-level benchmark calculations and experimental data where available. Properties compared include geometries, binding energies, ionization potentials, electron affinities, and HOMO-LUMO gaps.

Classical molecular dynamics study of [60]fullerene interactions with silica and polyester surfaces.

This study examines the interaction of neutral and charged fullerenes with model silica and polyester surfaces. Molecular dynamics simulations at 298 K indicate that van der Waals forces are sufficiently strong in most cases to cause physisorption of the neutral fullerene particle onto the surfaces. The fullerenes are unable to penetrate the rigid silica surface but are generally able to at least partially infiltrate the flexible polymer surface by opening surface cavities.

Adhesion between graphite and modified polyester surfaces: a theoretical study.

This study examines the adhesion of graphite to functionalized polyester surfaces using a range of qualitative and quantitative measures of theoretical adhesion. Modifications to the polyester surfaces include the addition of hydroxyl, carboxyl, or fluorine substituents with coverages of 0.4 and 0.

Inhibition of peptidylglycine alpha-amidating monooxygenase by exploitation of factors affecting the stability and ease of formation of glycyl radicals.

Peptidylglycine alpha-amidating monooxygenase catalyzes the biosynthesis of peptide hormones through radical cleavage of the C-terminal glycine residues of the corresponding prohormones. We have correlated ab initio calculations of radical stabilization energies and studies of free radical brominations with the extent of catalysis displayed by peptidylglycine alpha-amidating monooxygenase, to identify classes of inhibitors of the enzyme. In particular we find that, in closely related systems, the substitution of glycolate for glycine reduces the calculated radical stabilization energy by 34.

Comparison of the kinetics and thermodynamics for methyl radical addition to C=C, C=O, and C=S double bonds.

The barriers, enthalpies, and rate constants for the addition of methyl radical to the double bonds of a selection of alkene, carbonyl, and thiocarbonyl species (CH(2)=Z, CH(3)CH=Z, and (CH(3))(2)C=Z, where Z = CH(2), O, or S) and for the reverse beta-scission reactions have been investigated using high-level ab inito calculations. The results are rationalized with the aid of the curve-crossing model. The addition reactions proceed via early transition structures in all cases.