Academic literature on the topic 'Dendrimers. Chemical kinetics. Nuclear magnetic resonance spectroscopy'

Nuclear magnetic resonance (NMR) spectroscopy is one of the most powerful experimental methods available for atomic and molecular level structure elucidation. It is a powerful technique in that it is a noninvasive probe that can be used to identify individual compounds, aid in determining structures of large macromolecules, such as proteins, and examine the kinetics of certain reactions. NMR spectroscopy takes advantage of the magnetic properties of the observed nucleus that are influenced not only by its chemical environment, but also by physical interactions with its environment. Both can be examined by measuring specific NMR parameters such as coupling constants, relaxation times, or changes in chemical shifts. As NMR techniques and instrumentation advance, NMR spectroscopy is becoming more important in the environmental sciences, tackling problems and questions that previously were difficult to answer. For example, sensitivity enhancement techniques increase the ability to examine a sample without chemical or physical pretreatment. A sample examined in this manner is in its original state and is unaffected by chemical or physical reactions caused by the pretreatment procedure. Despite its increasing popularity and numerous advantages, NMR spectroscopy can be a mysterious, and at times daunting, technique. The purpose of this chapter is to provide an overview of basic NMR theory and background for the uninitiated. It is hoped that it will provide enough information to those unfamiliar with NMR and its terminology for them to find the remaining chapters understandable and interesting. Those who desire a greater understanding are referred to the many textbooks on solution-state NMR, solid-state NMR, and the application of NMR to geochemistry, soil chemistry, oils and coals, and carbonaceous solids. The advance that led to NMR spectroscopy came in 1939 with resonance experiments by Rabi and coworkers, who demonstrated the property of nuclear spin. In 1945, the research groups of Bloch and Purcell independently obtained the first nuclear resonance signals. For this they won the 1952 Nobel prize. The first application of NMR spectroscopy in the field of humic substance research was 1H NMR of liquids. González-Vila et al. were the first to apply 13C solution-state NMR to natural humic acids.

Modern agricultural practices have contributed to the accumulation of herbicides, pesticides and their decomposition products in the soil. These pollutants are known to interact with soil organic matter to form covalent and/or noncovalent bonding associations. The covalent bonds are thought to result from addition or oxidative coupling reactions, some of which may be catalyzed by oxidoreductive enzymes. Noncovalent associations include such interactions as ion exchange, hydrogen bonding, protonation, charge transfer, ligand exchange, coordination through metal ions, van der Waals forces, and hydrophobic bonding. The association of pollutants with soil organic matter is an area of study that is of extreme interest for two reasons. First, dissolved organic matter present in lakes and streams is known to enhance the solubility of pollutants, which poses a real threat to the quality of fresh water supplies. Therefore, if we are to predict the movement of pollutants in the water table we need to have a mechanistic understanding of their interactions with dissolved humic materials. Second, early studies had indicated that some pollutants chemically bind to humic materials, thus reducing the risk of further transport and dispersion. If this chemical binding of the pollutants is irreversible, then this process may serve as a natural means for their detoxification. Regardless of the type of association, the first task in any mechanistic study is to characterize the reaction products structurally. In the case of noncovalent binding mechanisms, studies have focused on the physical characteristics of the process and not on the structure of the associated pollutant. Association studies are used to determine the sorption kinetics and transport of pollutants as well as their association constants. These types of studies utilize various techniques such as batch sorption, gas-purge desorption, column adsorption, and miscible displacement. All of these techniques are only capable of providing quantitative information on the amount of pollutant sorbed by a substrate. The study of the covalent binding of pollutants to humic substances has utilized 14C labeling in addition to various spectrometric techniques such as ultraviolet (UV) difference, fluorescence polarization and infrared (IR) spectroscopy.