Sorption of cefdinir, memantine, praziquantel and trimethoprim in sediment and soil samples.

The everyday use of various pharmaceuticals to treat humans or animals means that they are increasingly found in the environment. Contamination of the soil can cause the active ingredients to be strongly sorbed to the soil or sediment. In the worst case, they can also be expected to occur in the aquatic environment due to their different polarity. In this study, four drugs from different therapeutic classes (trimetoprim, memantine, cefdinir, praziquantel) were used in dissolved form in two sediment and three soil samples to obtain data that can describe their fate and behavior in the environment. The sorption affinities of the pharmaceuticals were described using linear, Freundlich and Dubinin-Radushkevich sorption isotherms. The highest Kd values were obtained for cefdinir, while memantine and praziquantel tended to be present in water due to their very low sorption coefficients. The studied influence of pH showed a negative trend for memantine and trimetoprim, while an increase in ionic strength resulted in higher Kd values for all drugs. The sorption mechanism for all tested samples was best described by the pseudo-secondary kinetic model (R2 > 0.9999).

Benzil Photoperoxidations in Polymer Films and Crosslinking by the Resultant Benzoyl Peroxides in Polystyrene and Other Polymers.

Benzil (BZ) can be converted almost quantitatively to benzoyl peroxide (BP) in aerated polymer films upon irradiation at >400 nm (i.e., the long-wavelength edge of the n→π* absorption band of BZ, where BP does not absorb). Here, we summarize results for the photoperoxidation of BZ structures with molecular oxygen, principally in glassy polymer matrices. Some of the polymers are doped directly with BZ or its derivatives, and others, contain covalently attached BZ pendant groups from which BP groups are derived. While the decomposition of low-molecular-weight BP doped into polymer films (such as those of polystyrene (PS)) results in a net decrease in polymer molecular weight, thermal decomposition of pendant BP groups is an efficient method for chain crosslinking. Crosslinking of PS films doped with a molecule containing two covalently linked BZ or BP groups proceeds in a similar fashion. Free radicals from the covalently attached BP allow grafting of new monomers, as well. Additionally, the use of radiation filtered through masks has been used to create patterns of polymers on solid surfaces. Crosslinking of photodegradable poly(phenyl vinyl ketone) with BP structures obtained by photoperoxidation of BZ structures for the preparation of photodegradable polymer networks is described as well. In sum, the use of BZ and BP and their derivatives offers simple and convenient routes for modifying polymer chains and, especially, for crosslinking them. Specific applications of each use and process are provided. Although applications with PS are featured here, the methodologies described are amenable to a wide variety of other polymers.

Synthesis and photooxidation of styrene copolymer bearing camphorquinone pendant groups.

(±)-10-Methacryloyloxycamphorquinone (MCQ) was synthesized from (±)-10-camphorsulfonic acid either by a known seven-step synthetic route or by a novel, shorter five-step synthetic route. MCQ was copolymerized with styrene (S) and the photochemical behavior of the copolymer MCQ/S was compared with that of a formerly studied copolymer of styrene with monomers containing the benzil (BZ) moiety (another 1,2-dicarbonyl). Irradiation (λ > 380 nm) of aerated films of styrene copolymers with monomers containing the BZ moiety leads to the insertion of two oxygen atoms between the carbonyl groups of BZ and to the formation of benzoyl peroxide (BP) as pendant groups on the polymer backbone. An equivalent irradiation of MCQ/S led mainly to the insertion of only one oxygen atom between the carbonyl groups of camphorquinone (CQ) and to the formation of camphoric anhydride (11) covalently bound to the polymer backbone. While the decomposition of pendant BP groups formed in irradiated films of styrene copolymers with pendant BZ groups leads to crosslinking, only small molecular-weight changes in irradiated MCQ/S were observed.

Photo-crosslinking of polyethylene by mono- and diacetophenone derivatives and their precursors.

The efficiency of photochemical crosslinking of low-density polyethylene (PE) films by molecules containing one or two acetophenone groups and their precursors have been correlated with the relative rates of carbonyl group depletion under equivalent irradiation conditions. The acetophenone derivatives are found to be equally or more efficient than benzophenone as crosslinkers of PE. Because some additives are not thermodynamically equilibrated in the PE matrices and crystallize on standing at 30 degrees C, doped films were irradiated usually as soon as possible after their preparation. However, others were aged to determine the influence of equilibration on the efficiency of crosslinking. Thus, the effect of crystallization of some of the crosslinker additives in the PE matrices and the competition between photochemical addition of the carbonyl groups to C-H or C=C bonds of the polymer were investigated. GC-MS and FTIR analyses of photoproducts from irradiation of alkanophenones bearing a gamma-hydrogen atom in PE films showed that (intramolecular) Norrish Type II splitting and Yang cyclization processes proceed efficiently, and are more rapid than subsequent intermolecular hydrogen abstraction reactions by the acetophenone photoproducts.