Band 2, Heft 11 -

The halogen bond, corresponding to an attractive interaction between an electrophilic region in a halogen (X) and a nucleophile (B) yielding a R−X⋯B contact, found applications in many fields such as supramolecular chemistry, crystal engineering, medicinal chemistry, and chemical biology. Their large range of applications also led to an increased interest in their study using computational methods aiming not only at understanding the phenomena at a fundamental level, but also to help in the interpretation of results and guide the experimental work. Herein, a succinct overview of the recent theoretical and experimental developments is given starting by discussing the nature of the halogen bond and the latest theoretical insights on this topic. Then, the effects of the surrounding environment on halogen bonds are presented followed by a presentation of the available method benchmarks. Finally, recent experimental applications where the contribution of computational chemistry was fundamental are discussed, thus highlighting the synergy between the lab and modeling techniques.

Soil is loose skin of the Earth, located between the lithosphere and atmosphere, which originated from parent material under the influence of pedogenetic processes. As a conditionally renewable natural resource, soil has a decisive influence on sustainable development of global economy, especially on sustainable agriculture and environmental protection. In recent decades, a growing interest prevails for non-production soil functions, primarily those relating to environmental protection. It especially refers to protection of natural resources whose quality depends directly on soil and soil management. Soil contamination is one of the most dangerous forms of soil degradation with the consequences that are reflected in virtually the entire biosphere, primarily at heterotrophic organisms, and also at mankind as a food consumer. Contamination is correlated with the degree of industrialization and intensity of agrochemical usage. It is typically caused by industrial activity, agricultural chemicals or improper disposal of waste. The negative effects caused by pollution are undeniable: reduced agricultural productivity, polluted water sources and raw materials for food are only a few of the effects of soil degradation, while almost all human diseases (excluding AIDS) may be partly related to the transport of contaminants, in the food chain or the air, to the final recipients - people, plants and animals. The remediation of contaminated soil is a relatively new scientific field which is strongly developing in the last 30 years and becoming a more important subject. In order to achieve quality remediation of contaminated soil it is very important to conduct an inventory as accurately as possible, that is, to determine the current state of soil contamination.

This publication reviews some relevant features related with the redox activity of two inorganic compounds: [XM 12 O 40 ] q - (Keggin structure) and [X 2 M 18 O 62 ] q - (Wells-Dawson structure). These are two well-known specimens of the vast Polyoxometalate (POM) family, which has been the subject of extensive experimental and theoretical research owing to their unmatched properties. In particular, their redox activity focus a great deal of attention from scientists due to their prospective related applications. POMs are habitually seen as ‘electron sponges’ since many of them accept several electrons without losing their chemical identity. This makes them excellent models to study mechanisms of electrochemical nature. Their redox properties depend on: (i) the type and number of transition metal atoms in the structure, (ii) the basicity of the first reduced species and, occasionally, of the fully oxidized species; (iii) the size of the molecule, (iv) the overall negative charge of the POM, and (v) the size of the central heteroatom. In the last years, important collaboration between the experimental and theoretical areas has been usual on the development of POM science. In the present chapter three of these synergies are highlighted: the influence of the internal heteroatom upon the redox potentials of Keggin anions; the dependence of the redox waves of Fe-substituted Wells-Dawson compounds with pH; and the role of electron delocalization and pairing in mixed-metal Mo/W Wells-Dawson compounds in their ability to accept electrons. In these three cases, a complete understanding of the problem would not have been possible without the mutual benefit of experimental and computational data.

For most people, microorganisms are out of sight and therefore out of mind but they are large, extremely diverse group of organisms, they are everywhere and are the dominant form of life on planet Earth. Almost every surface is colonized by microorganisms, including our skin; however most of them are harmless to humans. Some microorganisms can live in boiling hot springs, whereas others form microbial communities in frozen sea ice. Among their many roles, microorganisms are necessary for biogeochemical cycling, soil fertility, decomposition of dead plants and animals and biodegradation of many complex organic compounds present in the environment. Environmental microbiology is concerned with the study of microorganisms in the soil, water and air and their application in bioremediation to reduce environmental pollution through the biological degradation of pollutants into non-toxic or less toxic substances. Field of environmental microbiology also covers the topics such as microbially induced biocorrosion, biodeterioration of constructing materials and microbiological quality of outdoor and indoor air.

High-resolution infrared (IR) spectroscopy is essential to the analysis of molecular rotation-vibration spectra. The high-resolution spectra deliver much information about structure and dynamic of molecules, but often they are very complex. For nonrigid molecules the complexity arises from transition tunneling splittings. Methylamine is a classic example of a nonrigid molecule in which two large amplitude motions, inversion and torsion, occur simultaneously. It has six equivalent potential minima, for which an effective vibration-inversion-torsion-rotation Hamiltonian has been developed. In the chapter assignment and analysis of several spectral regions of methylamine have been briefly presented explaining the assigning techniques and theoretical treatment of experimental lines.

Azobenzene is by far the most studied photochromic molecule and its applications range from optical storage to bio-engineering. To exploit the great potential of azobenzene, one must achieve deep understanding of its photochemistry as single molecule in solution AS WELL AS in-chain moiety and pendent group in macromolecular structures. With the advent of computer-aided simulation scientists have been able to match experimental data with computational models. In this chapter, a review on the modeling of azobenzene-containing molecules in different conditions and environments IS provided with a special focus on advanced applications of photo-controllable materials, such as molecular machines and photoactivation of bio-molecules.