Modelling of interactions of polar and nonpolar pollutants with soil minerals and soil organic matter

Environmental pollution of soils by organic contaminants such as pesticides is one of the serious problems of our civilization. Contaminants can undergo various physical, chemical and biological transformation processes in soils governing behaviour, distribution, and fate of organic species in environment and subsequent environmental risks. Mechanistic understanding of molecular interactions of organic pollutants with main soil components represents a key factor for estimating the behaviour of contaminants in soils. Molecular modelling offers an opportunity to investigate and characterize various details of these interactions at molecular level providing specifications, which are difficult to obtain at the experimental level. This work represents a comprehensive overview of our investigations of the molecular interactions of organic contaminants with selected soil components. Particularly, we focused on the characterization of the structure and the surface complexation of the phenoxyacetic acid derivatives (herbicides MCPA and 2,4-D) and typical soil minerals such as clay minerals (kaolinite and montmorillonite) and iron oxyhydroxides (goethite and lepidocrocite). Further, interactions of several representative nonpolar polycyclic aromatic hydrocarbons (e.g. naphthalene, anthracene, pyrene, and phenanthrene) with iron oxyhydroxides were modelled, as well. It was found that in case of polar species, hydrogen bonds and electrostatic interactions play an important role in the formation of the surface complexes. In case of nonpolar PAHs, dispersion forces dominate in the planar stacking of the PAHs molecules on mineral surfaces. Another study focused at a complex 3D model representing humic substances firstly, featuring polar hydrophilic and nonpolar hydrophobic domains and also a nanopore SOM structure. This model was taken to simulate trapping and interactions of MCPA (polar) and naphthalene (nonpolar) species inside of the nanopore. It was found that MCPA is preferentially stabilized close to polar functional groups (carboxyl) whereas naphthalene interacts mostly with nonpolar aliphatic chains through dispersion interactions

Supercritical fluid technology as a tool to prepare gradient multifunctional architectures towards regeneration of osteochondral injuries

Platelet lysates (PLs) are a natural source of growth factors (GFs) known for its stimulatory role on stem cells which can be obtained after activation of platelets from blood plasma. The possibility to use PLs as growth factor source for tissue healing and regeneration has been pursued following different strategies. Platelet lysates are an enriched pool of growth factors which can be used as either a GFs source or as a three-dimensional (3D) hydrogel. However, most of current PLs-based hydrogels lack stability, exhibiting significant shrinking behavior. This chapter focuses on the application of supercritical fluid technology to develop three-dimensional architectures of PL constructs, crosslinked with genipin. The proposed technology allows in a single step operation the development of mechanically stable porous structures, through chemical crosslinking of the growth factors present in the PL pool, followed by supercritical drying of the samples. Furthermore gradient structures of PL-based structures with bioactive glass are also presented and are described as an interesting approach to the treatment of osteochondral defects.info:eu-repo/semantics/publishedVersio

An autonomous chemically fuelled small-molecule motor

Molecular machines are among the most complex of all functional molecules and lie at the heart of nearly every biological process. A number of synthetic small-molecule machines have been developed, including molecular muscles, synthesizers, pumps, walkers, transporters and light-driven and electrically driven rotary motors. However, although biological molecular motors are powered by chemical gradients or the hydrolysis of adenosine triphosphate (ATP), so far there are no synthetic small-molecule motors that can operate autonomously using chemical energy (that is, the components move with net directionality as long as a chemical fuel is present). Here we describe a system in which a small molecular ring (macrocycle) is continuously transported directionally around a cyclic molecular track when powered by irreversible reactions of a chemical fuel, 9-fluorenylmethoxycarbonyl chloride. Key to the design is that the rate of reaction of this fuel with reactive sites on the cyclic track is faster when the macrocycle is far from the reactive site than when it is near to it. We find that a bulky pyridine-based catalyst promotes carbonate-forming reactions that ratchet the displacement of the macrocycle away from the reactive sites on the track. Under reaction conditions where both attachment and cleavage of the 9-fluorenylmethoxycarbonyl groups occur through different processes, and the cleavage reaction occurs at a rate independent of macrocycle location, net directional rotation of the molecular motor continues for as long as unreacted fuel remains. We anticipate that autonomous chemically fuelled molecular motors will find application as engines in molecular nanotechnology.</p

Evaluating the Labor-Market Effects of Compulsory Military Service – A Regression-Discontinuity Approach

We identify the causal effect of compulsory military service on conscripts' subsequent labor-market outcomes by exploiting the regression-discontinuity design of the military draft in Germany during the 1950s. Unbiased estimates of military service on lifetime earnings, wages, and employment are obtained by comparing men born before July 1, 1937 (the White Cohort) who were exempted from compulsory military service to men who were born on or shortly after this threshold date and hence faced a positive probability of being drafted. We find that the putative earnings advantage and wage premium of those who served in the armed forces vanish when selection effects are taken into account

Evaluation of interactive in-car systems in immersive environments

In the coming few years, electronic innovation like driver assistance and information system as well as driving X-by-wire will radically change the development of car technology and the face of driving. Short development cycles and changing market demands require a fast and flexible prototyping, while the introduction of further communication, information and entertainment technology in cars makes it necessary to adjust their human machine interface into the driving context. For answering these demands the Fraunhofer Institute of Industry Engineering IAO developed a highly flexible virtual prototyping and testing system based on driving simulators. These systems can integrate several further interfaces via "Switchboard and therefore allow to flexibly introduce further data sources allowing a fast adaptability testing scenarios. This virtual prototyping and testing system has already been effective, tried and tested in several international research projects: Within SAVE, IN-ARTE and COMUNICAR a human-machine interface has been created for driver assistance systems and advanced media interaction devices. These interfaces were developed from the very beginning parallel to the technological system concept. A virtual prototype was designed after analyzing the user requirements and consequently run through a user test. The list of defects obtained from this trial will help to optimize the prototype and serves as input for further development phases