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The synthesis of stereochemically pure oximes, amines, saturated and unsaturated cyanomethyl compounds, and methylaminomethyl compounds at the C9 position in 3-hydroxy-N-phenethyl-5-phenylmorphans provided μ-opioid receptor (MOR) agonists with varied efficacy and potency. One of the most interesting compounds, (2-((1S,5R,9R)-5-(3-hydroxyphenyl)-2-phenethyl-2-azabicyclo[3.3.1]nonan-9-yl)acetonitrile), was found to be a potent partial MOR agonist (EC50 = 2.5 nM, %Emax = 89.6%), as determined in the forskolin-induced cAMP accumulation assay. Others ranged in potency and efficacy at the MOR, from nanomolar potency with a C9 cyanomethyl compound (EC50 = 0.85 nM) to its totally inactive diastereomer, and three compounds exhibited weak MOR antagonist activity (the primary amine 3, the secondary amine 8, and the cyanomethyl compound 41). Many of the compounds were fully efficacious; their efficacy and potency were affected by both the stereochemistry of the molecule and the specific C9 substituent. Most of the MOR agonists were selective in their receptor interactions, and only a few had δ-opioid receptor (DOR) or κ-opioid receptor (KOR) agonist activity. Only one compound, a C9-methylaminomethyl-substituted phenylmorphan, was moderately potent and fully efficacious as a KOR agonist (KOR EC50 = 18 nM (% Emax = 103%)).

The El Rio Spreading Grounds, an area of artificial recharge, lies within a regional groundwater depression. It consists of ten small ponds surrounded by eight production wells. A deliberate tracer experiment using sulfur hexafluoride (SF6) and an isotope of helium (3He) was conducted to determine groundwater flow. The tracer was continuously injected into one pond for one week prior to a ~50 day period of no recharge. At the time of the experiment, the artificial recharge rate through the highly permeable alluvial sediments which underlie the ponds was ~4 m day-1 and the water table was ~12 m below the ground surface. Tracer breakthrough curves from the production wells indicate that the plume remained near (within 500 m) the injection site during the 18 month experiment. Its movement was influenced by a number of factors. First, variable groundwater production in the production wells cause frequent changes in the water level, and thus, rates and direction of the plume flow respond to local groundwater cones of depression. Second, additional recharge events, which were free of tracer, create groundwater mounds that block the transport of the tracer to specific production wells. Noble gas concentrations in the groundwater were much higher than in the pond due to the dissolution of trapped air. However, significant retardation (absolute and relative) of the gas tracers was not detected. Breakthrough curves of SF6 and 3He at two nearby production wells (within ~10 m of the pond) were very similar and suggest that nonequilibrium gas transfer was occurring between the percolating water and trapped air. At one well screened between 50 and 90 m below ground, both tracers were detected after 5 days and reached a maximum at ~24 days. Despite potential dilution caused by mixing within the production well, the maximum concentration observed at this well was ~33% of the mean pond concentration. More than 50% of the SF6 recharged was recovered by the production wells during this 18 month experiment. The experiment demonstrates that at artificial recharge sites with high infiltration rates and moderately deep water tables, transport times between recharge locations and wells determined with gas tracer experiments are reliable.

A dual gas tracer experiment using sulfur hexafluoride (SF6) and an isotope of helium (3He) and measurements of dissolved noble gases was performed at the El Rio spreading grounds to examine gas transport and trapped air below an artificial recharge pond with a very high recharge rate (approximately 4 m day(-1)). Noble gas concentrations in the groundwater were greater than in surface water due to excess air formation showing that trapped air exists below the pond. Breakthrough curves of SF6 and 3He at two nearby production wells were very similar and suggest that nonequilibrium gas transfer was occurring between the percolating water and the trapped air. At one well screened between 50 and 90 m below ground, both tracers were detected after 5 days and reached a maximum at approximately 24 days. Despite the potential dilution caused by mixing within the production well, the maximum concentration was approximately 25% of the mean pond concentration. More than 50% of the SF6 recharged was recovered by the production wells during the 18 month long experiment. Our results demonstrate that at artificial recharge sites with high infiltration rates and moderately deep water tables, transport times between recharge locations and wells determined with gas tracer experiments are reliable.

[1] The relationship between the chemical and isotopic composition of groundwater and residence times was used to understand the temporal variability in stream hydrochemistry in Sagehen basin, California. On the basis of the relationship between groundwater age and [Ca2+], the mean residence time of groundwater feeding Sagehen Creek during base flow is approximately 28 years. [Cl-]:[Ca2+] ratios in Sagehen Creek can be used to distinguish between two important processes: changes in the apparent age of groundwater discharging into the creek and dilution with snowmelt. The mean residence time of groundwater discharging into the creek is approximately 15 years during snowmelt periods. The results from this study have implications for hydrograph separation studies as groundwater is not a single, well-mixed chemical component but rather is a variable parameter that predictably depends on groundwater residence time. Most current models of catchment hydrochemistry do not account for chemical and isotopic variability found within the groundwater reservoir. In addition, this study provides valuable insight into the long-term hydrochemical response of a catchment to perturbations as catchment-flushing times are related to the mean residence time of water in a basin. Copyright 2005 by the American Geophysical Union.

Critical for the management of artificial recharge operations is detailed knowledge of ground water dynamics near spreading areas. Geochemical tracer techniques including stable isotopes of water, tritium/helium-3 (T/3He) dating, and deliberate gas tracer experiments are ideally suited for these investigations. These tracers were used to evaluate flow near an artificial recharge site in northern Orange County, California, where approximately 2.5 x 10(8) m3 (200,000 acre-feet) of water are recharged annually. T/3He ages show that most of the relatively shallow ground water within 3 km of the recharge facilities have apparent ages < 2 years; further downgradient apparent ages increase, reaching > 20 years at approximately 6 km. Gas tracer experiments using sulfur hexafluoride and xenon isotopes were conducted from the Santa Ana River and two spreading basins. These tracers were followed in the ground water for more than two years, allowing subsurface flow patterns and flow times to be quantified. Results demonstrate that mean horizontal ground water velocities range from < 1 to > 4 km/year. The leading edges of the tracer patch moved at velocities about twice as fast as the center of mass. Leading edge velocities are important when considering the potential transport of microbes and other "time sensitive" contaminants and cannot be determined easily with other methods. T/3He apparent ages and tracer travel times agreed within the analytical uncertainty at 16 of 19 narrow screened monitoring wells. By combining these techniques, ground water flow was imaged with time scales on the order of weeks to decades.

Springs in Sagehen basin, California, were used to document the effect of chemical weathering on the chemical evolution and composition of groundwater in a high elevation catchment. Geochemical tracer ages were determined with chlorofluorocarbons (CFCs) and tritium/3 He dating techniques. The spring water ages range from less than 5 years to almost 40 years. Mass balance calculations performed by NETPATH were combined with spring water ages to calculate chemical weathering rates observed throughout the basin, which range from 0.0116 to 0.0018 and from 0.0036 to 0.0006 mmol 1-1 year-1, for plagioclase and hornblende, respectively. Major cation concentrations, pH, and spring water conductivity were found to correlate positively (R2 = 0.7) with spring water age. This suggests that shallow groundwater, as represented by the springs, is a chemically evolving system. © 2001 Elsevier Science B.V. All rights reserved.

An extensive suite of isotopic and geochemical tracers in groundwater has been used to provide hydrologic assessments of the hierarchy of flow systems in aquifers underlying the central Great Plains (southeastern Colorado and western Kansas) of the United States and to determine the late Pleistocene and Holocene paleotemperature and paleorecharge record. Hydrogeologic and geochemical tracer data permit classification of the samples into late Holocene, late Pleistocene-early Holocene, and much older Pleistocene groups. Paleorecharge rates calculated from the Cl concentration in the samples show that recharge rates were at least twice the late Holocene rate during late Pleistocene-early Holocene time, which is consistent with their relative depletion in 16O and D. Noble gas (Ne, Ar, Kr, Xe) temperature calculations confirm that these older samples represent a recharge environment approximately 5°C cooler than late Holocene values. These results are consistent with the global climate models that show a trend toward a warmer, more arid climate during the Holocene. (C) 2000 University of Washington.

A suite of chemical and isotope tracers (dissolved noble gases, stable isotopes of water, radiocarbon, and CI) have been analyzed along a flow path in the Dakota aquifer system to determine likely recharge sources, ground water residence times, and the extent of mixing between local and intermediate flow systems, presumably caused by large well screens. Three water types were distinguished with the tracers, each having a very different history. Two of the water types were found in south-eastern Colorado where the Dakota is poorly confined. The tracer data suggest that the first group recharged locally during the last few thousand years and the second group was composed of ground water that recharged earlier during a cooler climate, presumably during the last glacial period (LGP) and mixed aged water. The paleotemperature record archived in this groundwater system indicates that south-eastern Colorado was about 5°C cooler during the LGP than during the late Holocene. Similar temperature changes derived from dissolved noble gases in other aquifer systems have been reported earlier for the south-western United States. The third water type was located down gradient of the first two in the confined Dakota in western and central Kansas. Groundwater residence time of this water mass is on the order of 104-105 yrs and its recharge location is near the Colorado and Kansas border down gradient of the other water types. The study shows the importance of using multiple tracers when investigating ground water systems.

Electrodegradation of atrazine in water was performed using homemade (PA and PB) and purchased (PC) boron-doped diamond anodes. The degradation was monitored off-line by analyzing total organic carbon and high performance liquid chromatography with diode array detector (HPLC-DAD) and at-line by UV spectroscopy. The spectra were recorded every 2 min. The rank deficiency problem was resolved by assembling an augmented column-wise matrix. HPLC was employed to separate the original and byproducts degradation components. Aiming the same goal, multivariate curve resolution - alternating least squares (MCR-ALS) was applied to resolve the UV spectroscopic data. Comparison between HPLC and MCR-ALS separations is presented. By using MCR-ALS the spectra of atrazine and two byproducts were successfully resolved and the resulted concentration profiles properly represented the system studied. The ALS explained variance (R2) for PA, PB and PC was equal to 99.99% for all of them and the lack of fit for PA, PB and PC were 0.39, 0.34 and 0.54 respectively. The correlation (R) between the recovered and pure spectra were calculate for each electrodegradation, validating the MCR-ALS results. The average R was equal to 0.997. The spectral and concentration profiles described with this new approach are in agreement with HPLC-DAD results. The proposed method is an alternative to classical analyses for monitoring of the degradation process, mainly due to the simplicity, fast results and economy.

Este artigo traz uma análise nas propriedades eletroquímicas dos Nanotubos de Carbono de Paredes Múltiplas (MWCNT’s) autossustentáveis, visando sua aplicação na confecção de dispositivos Supercapacitores. Os grupos foram produzidos em um único processo, via deposição química fase-vapor (CVD), e caracterizados através de análise eletroquímica via potenciostato em uma célula de testes especial desenvolvida pelo grupo. Os dados aqui apresentados são um complemento ao trabalho já publicado no Journal of Electronic Materials, e trazem a análise de desempenho do material sob diferentes condições de trabalho. Com isso, este trabalho contribui dando um passo a mais na obtenção de dispositivos Supercapacitores de alta potência, oferecendo uma alternativa com tempo de recarga muito inferior às baterias convencionais.

Down syndrome (DS) is the most common genetically-defined cause of intellectual disability. Neurodevelopmental deficits displayed by individuals with DS are generally global, however, disproportionate deficits in cognitive processes that depend heavily on the hippocampus and prefrontal cortex are also well documented. Additionally, DS is associated with relative strengths in visual processing and visuospatial short-term memory, and weaknesses in the verbal domain. Although reports of pharmacological rescuing of learning and memory deficits in mouse models of DS abound in the literature, proving the principle that cognitive ability of persons with DS can be boosted through pharmacological means is still an elusive goal. The design of customized batteries of neuropsychological efficacy outcome measures is essential for the successful implementation of clinical trials of potential cognitive enhancing strategies. Here, we review the neurocognitive phenotype of individuals with DS and major broad-based test batteries designed to quantify specific cognitive domains in these individuals, including the one used in a pilot trial of the drug memantine. The main goal is to illustrate the essential considerations in planning trials to enhance cognitive functions in individuals with DS, which should also have implications for the design of similar studies in individuals with other forms of intellectual disability.