Molecularly imprinting sol-gel materials for DDT using both a noncovalent and a covalent approach was examined. A nonpolar porous sol-gel network was created through the use of the bridged polysilsesquioxane, bis-(trimethoxysilylethyl)benzene (BTEB), as the principal sol-gel component. Noncovalent molecular imprinting was deemed unsuccessful, presumably because of the lack of strong intermolecular interactions that can be established between the DDT and the sol-gel precursor. A covalent imprinting strategy was employed by generating a sacrificial spacer through the reaction of two 3-isocyanatopropyltriethoxysilanes with one of two different template molecules: 4,4'-ethylenedianiline (EDA) or 4,4'-ethylidenebisphenol (EBP). After formation of the sol-gel, the bonds linking the spacer template to the matrix were cleaved in a manner that generated a pocket of the appropriate size bordered by amine groups that could aid in the binding of DDT through weak hydrogen bonding interactions. Experiments indicated that DDT could be bound selectively by such an approch. To generate a sensor, an environmentally sensitive fluorescent probe, 7-nitrobenz-2-oxa-1,3-diazole, (NBD) located adjacent to the DDT binding site was used to transduce the binding of analyte. EDA-imprinted sol-gels, deposited as films on glass microscope slides, were shown to quantitatively detect DDT in water to a limit-of-detection of 50 ppt with a response time of <60 s. Repeat measurements could be made with the same sensing films after rinsing with acetone between each measurement. The EDA sensing material was selective for DDT and other structurally similar molecules. However, the sensing film design was limited by the relatively minor changes in fluorescence intensity upon binding DDT. This situation may be remedied by an alternative methodology that can facilitate attachment of the NBD fluorophore in an optimal position proximal to the binding pocket.

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A fluorescence-based chemical sensor for fluorene was created by molecularly imprinting a sol-gel comprising the bridged silsesquioxane, bis(trimethoxysilylethyl)benzene. The template was covalently bound to the sol-gel matrix using a fluorene analogue functionalized silane. After chemical removal of template via cleavage of a carbamate linkage, an amine group was left that provided an attachment site for the environmentally sensitive fluorescent probe 7-nitrobenz-2-oxa-1,3-diazole (NBD). Fluorene binding was detected by a change in NBD fluorescence intensity induced by a difference in the local polarity around the probe when the recognition site is filled. Such an approach eliminated response to nonspecific binding to the matrix. Sensing films deposited on glass slides were shown to have response times of <60 s and detection limits below 10 parts-per-trillion. Binding experiments demonstrated that the materials had good selectivity for fluorene over close structural analogues including naphthalene, fluoranthene, and anthracene. However, the sensing design is limited by a lack of reversibility following fluorene binding.

Abstract. This study was conducted to: (1) determine the probable cause of several areas of stressed and dead vegetation adjacent to a 15-yr-old reject coal pile in western South Carolina and (2) identify the factors limiting successful revegetation of the site. Data from an earlier study suggested that solution pH, total dissolved solids (TDS) and electrical conductivity (EC), and/or elevated trace element concentrations may have contributed to the stress and dieback. Soil water in the two vegetation kill zones is saline (TDS > 10000 mg L -l and EC > 4 dS m-l), highly acidic (soil pH < 3.5), and high in A1 and Mn (AI conc. > 200 mg L -1 and Mn conc. > 10 mg L-I). Soil water in areas of sparse vegetation is brackish (TDS > 1000 mg L -~ and EC > 2 dS m 1) and acidic (soil pH < 4.0), with elevated A1 values (> 40.5 mg A1 L-~). Tissue samples were collected from volunteer loblolly pine (Pinus taeda L.) seedlings growing in the study area and analyzed for essential and non-essential elements. Seedling tissues did not contain abnormal concentrations of nutrients or trace elements. The strong relationship between the zones of vegetation stress and dieback and solution pH and soluble salt concentrations, and the lack of excessive metal accumulations by tree seedlings which have become established in the less toxic portions of the study area, suggest that low solution pH and high soluble salts are more important factors limiting plant establishment on this site than solution metal concentrations. The results of this study demonstrate the importance of site hydrology in determining the impacts of coal waste disposal on adjacent ecosystems.

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