We describe a 100% efficient moving-wire interface for on-line coupling of high performance liqui... more We describe a 100% efficient moving-wire interface for on-line coupling of high performance liquid chromatography which transmits 100% of carbon in non-volatile analytes to a CO 2 gas accepting ion source. This interface accepts a flow of analyte in solvent, evaporates the solvent, combusts the remaining analyte, and directs the combustion products to the instrument of choice. Effluent is transferred to a periodically indented wire by a coherent jet to increase efficiency and maintain peak resolution. The combustion oven is plumbed such that gaseous combustion products are completely directed to an exit capillary, avoiding the loss of combustion products to the atmosphere. This system achieves the near complete transfer of analyte at HPLC flow rates up to 125 μL/min at a wire speed of 6 cm/s. This represents a 30x efficiency increase and 8x maximum wire loading compared to the spray transfer technique used in earlier moving wire interfaces.
Numerous people have contributed to this project. First, we thank David Eisen (USACE), Andy Fishe... more Numerous people have contributed to this project. First, we thank David Eisen (USACE), Andy Fisher (UCSC), Buck King (Harding ESE) and Larry Friend (Harding ESE) for sharing their wide knowledge of Fort Ord hydrogeology. We further thank Harding ESE (Buck King, Larry Friend, and Ed Heistand) for their generous and efficient work to supply LBNL with monitoring data from OU 1. This report was improved by comments and reviews by Chris Doughty (LBNL), Rohit Salve (LBNL), and Marcelo Lippmann (LBNL). We thank Maria Fink and Diana Swantek (LBNL) for assistance with document conversion and CD preparation. The encouragement and thorough and prompt review comments of Jim Gill (UCSC) improved this report. We further thank Bashar Alhajjar (CTC) for his interest in our work and efficient management of this project.
The Building 834 Complex at the Lawrence Livermore National Laboratory (LLNL) Site 300, has been ... more The Building 834 Complex at the Lawrence Livermore National Laboratory (LLNL) Site 300, has been used by the weapons development programs at LLNL as a testing facility for measuring component response to environmental stresses such as extreme temperature. The heat-exchange system at the facility used trichloroethene TCE, at times with adjuvants, as the primary heat-transfer media for over 20 years. Accidental spills, pipe failures, and seal blowouts over that period contributed to a substantial contaminant plume in a perched water-bearing zone underlying the Complex. Individual wells near the source area have produced ground water samples with TCE concentrations exceeding 800,000 ppb. In the last several years, the authors have developed a modular ground water and soil vapor extraction system for remediating the plume source area. The modular facility design permits the testing of new technologies to expedite remediation, and/or reduce the quantity of hazardous wastes generated as b...
Bioorganic & Medicinal Chemistry Letters, Feb 1, 2016
N,N-Diallyltryptamine (DALT) and 5-methoxy-N,N-diallyltryptamine (5-MeO-DALT) are two tryptamines... more N,N-Diallyltryptamine (DALT) and 5-methoxy-N,N-diallyltryptamine (5-MeO-DALT) are two tryptamines synthesized and tested by Alexander Shulgin. In self-experiments, 5-MeO-DALT was reported to be psychoactive in the 12-20 mg range, while the unsubstituted compound DALT had few discernible effects in the 42-80 mg range. Recently, 5-MeO-DALT has been used in nonmedical settings for its psychoactive effects, but these effects have been poorly characterized and little is known of its pharmacological properties. We extended the work of Shulgin by synthesizing additional 5-substituted-DALTs. We then compared them to DALT and 5-MeO-DALT for their binding affinities at 45 cloned receptors and transporter proteins. Based on in vitro binding affinity, we identified 27 potential receptor targets for the 5-substituted-DALT compounds. Five of the DALT compounds had affinity in the 10-80 nM range for serotonin 5-HT 1A and 5-HT 2B receptors, while the affinity of DALT itself at 5-HT 1A receptors was slightly lower at 100 nM. Among the 5-HT 2 subtypes, the weakest affinity was at 5-HT 2A receptors, spanning 250-730 nM. Five of the DALT compounds had affinity in the 50-400 nM range for serotonin 5-HT 1D , 5-HT 6 , and 5-HT 7 receptors; again, it was the unsubstituted DALT that had the weakest affinity at all three subtypes. The test drugs had even weaker affinity for 5-HT 1B , 5-HT 1E , and 5-HT 5A subtypes and little or no affinity for the 5-HT 3 subtype. These compounds also had generally nanomolar affinities for adrenergic a 2A , a 2B , and a 2C receptors, sigma receptors r 1 and r 2 , histamine H 1 receptors, and norepinephrine and serotonin uptake transporters. They also bound to other targets in the nanomolar-to-low micromolar range. Based on these binding results, it is likely that multiple serotonin receptors, as well as several nonserotonergic sites are important for the psychoactive effects of DALT drugs. To learn whether any quantitative structure-affinity relationships existed, we evaluated correlations among physicochemical properties of the congeneric 5-substituted-DALT compounds. The descriptors included electronic (r p), hydrophobic (p), and steric (CMR) parameters. The binding affinity at 5-HT 1A , 5-HT 1D , 5-HT 7 , and j opioid receptors was positively correlated with the steric volume parameter CMR. At a 2A , a 2B , and a 2C receptors, and at the histamine H 1 receptor, binding affinity was correlated with the Hammett substituent parameter r p ; higher affinity was associated with larger r p values. At the r 2 receptor, higher affinity was correlated with increasing p. These correlations should aid in the development of more potent and selective drugs within this family of compounds.
Journal of the Botanical Research Institute of Texas, 2011
A phytochemical analytical study was conducted to address the question of whether Lophophora will... more A phytochemical analytical study was conducted to address the question of whether Lophophora williamsii (peyote) plants from Chihuahuan Desert populations in the Trans-Pecos region of West Texas exhibited higher tissue concentrations of mescaline than plants from Tamaulipan Thornscrub populations of South Texas. This question is of cultural significance to the Native American peyote religion, which involves the ingestion of peyote as a psychopharmacologically active sacrament. Tissue samples were field-collected from 10 individuals in each of four L. williamsii populations, two of which were located in the Chihuahuan Desert, and two of which were located in the Tamaulipan Thornscrub ecoregion. For each of the four populations, the tissue samples from 10 individual plants were pooled, the alkaloids were extracted, and the average mescaline concentration of the population was determined by HPLC. There was limited geographic variation in mescaline concentration; the highest concentrati...
The increased interest in N,N-dialkyl tryptamines is a reflection of their diverse range of biolo... more The increased interest in N,N-dialkyl tryptamines is a reflection of their diverse range of biologically active properties. Deuterated derivatives are of interest for use as internal standards in bioanalytical or pharmacological assays. The present study reports on the synthesis of twelve novel 5-ethoxy-N,N-dialkyl-[α,α,β,β-H 4 ]-tryptamines and their [α,α,β,β-D 4 ]-counterparts following the Speeter and Anthony procedure. The normally time-consuming reduction step was carried out in 5 min under microwave-accelerated conditions. Good yields were obtained using tetrahydrofuran as the solvent at 150 • C. The resulting 24 tryptamines have been characterized by 1D/2D nuclear magnetic resonance spectroscopy and gas chromatography ion trap mass spectrometry. Differential fragmentation of side-chain-related iminium ions has been observed as a key principle. Because many N,N-dialkyltryptamines are available outside of traditional pharmaceutical supply chains as so-called 'research chemicals', the availability, as standards, of these new N,N-dialkyltryptamines will aid in identifiying novel tryptamines arising from these other souces. They should therefore be of immediate value within forensic, research, and public health contexts.
Author(s): Oldenburg, Curt M.; Daley, Paul F.; Freifeld, Barry M.; Hinds, Jennifer; Jordan, Prest... more Author(s): Oldenburg, Curt M.; Daley, Paul F.; Freifeld, Barry M.; Hinds, Jennifer; Jordan, Preston D.
Seven-year-old ponderosa pine (Pinus ponderosa Dougl. ex P. Laws.) saplings and one- and two-year... more Seven-year-old ponderosa pine (Pinus ponderosa Dougl. ex P. Laws.) saplings and one- and two-year-old ponderosa pine seedlings of a Sierra Nevada and a Rocky Mountain seed source, respectively, were exposed to CO(2)-enriched atmospheres in an outdoor open-top chamber facility for 2.5 years. Seedling growth (main stem diameter, height, volume) increased with increasing CO(2) concentration, though the two populations exhibited different patterns of response. By the beginning of the last growth season, however, the trees under the highest CO(2) concentrations showed signs of stress that included accelerated needle abscision, chlorosis, and apparent alteration of tolerance to heat. The stress response is at least partly attributable to elevated foliar temperatures resulting from CO(2)-induced stomatal closure, which in turn lowered transpirational cooling of needles.
... Potential consequences of virus infection for shade-sun acclimation in leaves Auteur(s) / Aut... more ... Potential consequences of virus infection for shade-sun acclimation in leaves Auteur(s) / Author(s). OSMOND CB ; BERRY JA ; BALACHANDRAN S. ; BUÊCHEN-OSMOND C. ; DALEY PF ; HODGSON RAJ ; Affiliation(s) du ou des auteurs / Author(s) Affiliation(s). ...
We have carried out numerical simulations of three-dimensional nonisothermal flow around an in si... more We have carried out numerical simulations of three-dimensional nonisothermal flow around an in situ heatbased flow sensor to investigate how formation heterogeneities can affect the interpretation of ground water flow velocities from this instrument. The flow sensor operates by constant heating of a 0.75-m-long, 5-cm-diameter cylindrical probe, which contains 30 thermistors in contact with the formation. The temperature evolution at each thermistor can be inverted to obtain an estimate of the ground water flow velocity vector using the standard interpretive method, which assumes that the formation is homogeneous. Analysis of data from heat-based flow sensors installed in a sand aquifer at the Former Fort Ord Army Base near Monterey, California, suggested an unexpected component of downward flow. The magnitudes of the vertical velocities were expected to be much less than those of the horizontal velocities at this site because the sensors were installed just above a clay aquitard. Nu...
Field tests of a remote fiber optic chemical sensor have recently been completed. The sensor has ... more Field tests of a remote fiber optic chemical sensor have recently been completed. The sensor has measured trace quantities of organohalides in the vadose zone and groundwater. Due to its toxicological importance and accessibility, a specific contaminant monitored was trichloroethylene (TCE). Two elements considered in these field measurements included temperature and carbon dioxide (CO[sub 2]) fluctuations. The effects of these properties on the sensor have been modeled in the lab. These results were used in the final determination of TCE concentration. Department of Energy (DOE) sites where remediation work is in progress provided opportunities for testing the sensor. One test was conducted in the vadose zone over sampling wells at the Savannah River Plant DOE integrated test site. Measurements were made before and several months after remediation procedures were in progress. A series of wells was selected with discretely screened depth intervals. Data were collected over a range o...
We describe a 100% efficient moving-wire interface for on-line coupling of high performance liqui... more We describe a 100% efficient moving-wire interface for on-line coupling of high performance liquid chromatography which transmits 100% of carbon in non-volatile analytes to a CO 2 gas accepting ion source. This interface accepts a flow of analyte in solvent, evaporates the solvent, combusts the remaining analyte, and directs the combustion products to the instrument of choice. Effluent is transferred to a periodically indented wire by a coherent jet to increase efficiency and maintain peak resolution. The combustion oven is plumbed such that gaseous combustion products are completely directed to an exit capillary, avoiding the loss of combustion products to the atmosphere. This system achieves the near complete transfer of analyte at HPLC flow rates up to 125 μL/min at a wire speed of 6 cm/s. This represents a 30x efficiency increase and 8x maximum wire loading compared to the spray transfer technique used in earlier moving wire interfaces.
Numerous people have contributed to this project. First, we thank David Eisen (USACE), Andy Fishe... more Numerous people have contributed to this project. First, we thank David Eisen (USACE), Andy Fisher (UCSC), Buck King (Harding ESE) and Larry Friend (Harding ESE) for sharing their wide knowledge of Fort Ord hydrogeology. We further thank Harding ESE (Buck King, Larry Friend, and Ed Heistand) for their generous and efficient work to supply LBNL with monitoring data from OU 1. This report was improved by comments and reviews by Chris Doughty (LBNL), Rohit Salve (LBNL), and Marcelo Lippmann (LBNL). We thank Maria Fink and Diana Swantek (LBNL) for assistance with document conversion and CD preparation. The encouragement and thorough and prompt review comments of Jim Gill (UCSC) improved this report. We further thank Bashar Alhajjar (CTC) for his interest in our work and efficient management of this project.
The Building 834 Complex at the Lawrence Livermore National Laboratory (LLNL) Site 300, has been ... more The Building 834 Complex at the Lawrence Livermore National Laboratory (LLNL) Site 300, has been used by the weapons development programs at LLNL as a testing facility for measuring component response to environmental stresses such as extreme temperature. The heat-exchange system at the facility used trichloroethene TCE, at times with adjuvants, as the primary heat-transfer media for over 20 years. Accidental spills, pipe failures, and seal blowouts over that period contributed to a substantial contaminant plume in a perched water-bearing zone underlying the Complex. Individual wells near the source area have produced ground water samples with TCE concentrations exceeding 800,000 ppb. In the last several years, the authors have developed a modular ground water and soil vapor extraction system for remediating the plume source area. The modular facility design permits the testing of new technologies to expedite remediation, and/or reduce the quantity of hazardous wastes generated as b...
Bioorganic & Medicinal Chemistry Letters, Feb 1, 2016
N,N-Diallyltryptamine (DALT) and 5-methoxy-N,N-diallyltryptamine (5-MeO-DALT) are two tryptamines... more N,N-Diallyltryptamine (DALT) and 5-methoxy-N,N-diallyltryptamine (5-MeO-DALT) are two tryptamines synthesized and tested by Alexander Shulgin. In self-experiments, 5-MeO-DALT was reported to be psychoactive in the 12-20 mg range, while the unsubstituted compound DALT had few discernible effects in the 42-80 mg range. Recently, 5-MeO-DALT has been used in nonmedical settings for its psychoactive effects, but these effects have been poorly characterized and little is known of its pharmacological properties. We extended the work of Shulgin by synthesizing additional 5-substituted-DALTs. We then compared them to DALT and 5-MeO-DALT for their binding affinities at 45 cloned receptors and transporter proteins. Based on in vitro binding affinity, we identified 27 potential receptor targets for the 5-substituted-DALT compounds. Five of the DALT compounds had affinity in the 10-80 nM range for serotonin 5-HT 1A and 5-HT 2B receptors, while the affinity of DALT itself at 5-HT 1A receptors was slightly lower at 100 nM. Among the 5-HT 2 subtypes, the weakest affinity was at 5-HT 2A receptors, spanning 250-730 nM. Five of the DALT compounds had affinity in the 50-400 nM range for serotonin 5-HT 1D , 5-HT 6 , and 5-HT 7 receptors; again, it was the unsubstituted DALT that had the weakest affinity at all three subtypes. The test drugs had even weaker affinity for 5-HT 1B , 5-HT 1E , and 5-HT 5A subtypes and little or no affinity for the 5-HT 3 subtype. These compounds also had generally nanomolar affinities for adrenergic a 2A , a 2B , and a 2C receptors, sigma receptors r 1 and r 2 , histamine H 1 receptors, and norepinephrine and serotonin uptake transporters. They also bound to other targets in the nanomolar-to-low micromolar range. Based on these binding results, it is likely that multiple serotonin receptors, as well as several nonserotonergic sites are important for the psychoactive effects of DALT drugs. To learn whether any quantitative structure-affinity relationships existed, we evaluated correlations among physicochemical properties of the congeneric 5-substituted-DALT compounds. The descriptors included electronic (r p), hydrophobic (p), and steric (CMR) parameters. The binding affinity at 5-HT 1A , 5-HT 1D , 5-HT 7 , and j opioid receptors was positively correlated with the steric volume parameter CMR. At a 2A , a 2B , and a 2C receptors, and at the histamine H 1 receptor, binding affinity was correlated with the Hammett substituent parameter r p ; higher affinity was associated with larger r p values. At the r 2 receptor, higher affinity was correlated with increasing p. These correlations should aid in the development of more potent and selective drugs within this family of compounds.
Journal of the Botanical Research Institute of Texas, 2011
A phytochemical analytical study was conducted to address the question of whether Lophophora will... more A phytochemical analytical study was conducted to address the question of whether Lophophora williamsii (peyote) plants from Chihuahuan Desert populations in the Trans-Pecos region of West Texas exhibited higher tissue concentrations of mescaline than plants from Tamaulipan Thornscrub populations of South Texas. This question is of cultural significance to the Native American peyote religion, which involves the ingestion of peyote as a psychopharmacologically active sacrament. Tissue samples were field-collected from 10 individuals in each of four L. williamsii populations, two of which were located in the Chihuahuan Desert, and two of which were located in the Tamaulipan Thornscrub ecoregion. For each of the four populations, the tissue samples from 10 individual plants were pooled, the alkaloids were extracted, and the average mescaline concentration of the population was determined by HPLC. There was limited geographic variation in mescaline concentration; the highest concentrati...
The increased interest in N,N-dialkyl tryptamines is a reflection of their diverse range of biolo... more The increased interest in N,N-dialkyl tryptamines is a reflection of their diverse range of biologically active properties. Deuterated derivatives are of interest for use as internal standards in bioanalytical or pharmacological assays. The present study reports on the synthesis of twelve novel 5-ethoxy-N,N-dialkyl-[α,α,β,β-H 4 ]-tryptamines and their [α,α,β,β-D 4 ]-counterparts following the Speeter and Anthony procedure. The normally time-consuming reduction step was carried out in 5 min under microwave-accelerated conditions. Good yields were obtained using tetrahydrofuran as the solvent at 150 • C. The resulting 24 tryptamines have been characterized by 1D/2D nuclear magnetic resonance spectroscopy and gas chromatography ion trap mass spectrometry. Differential fragmentation of side-chain-related iminium ions has been observed as a key principle. Because many N,N-dialkyltryptamines are available outside of traditional pharmaceutical supply chains as so-called 'research chemicals', the availability, as standards, of these new N,N-dialkyltryptamines will aid in identifiying novel tryptamines arising from these other souces. They should therefore be of immediate value within forensic, research, and public health contexts.
Author(s): Oldenburg, Curt M.; Daley, Paul F.; Freifeld, Barry M.; Hinds, Jennifer; Jordan, Prest... more Author(s): Oldenburg, Curt M.; Daley, Paul F.; Freifeld, Barry M.; Hinds, Jennifer; Jordan, Preston D.
Seven-year-old ponderosa pine (Pinus ponderosa Dougl. ex P. Laws.) saplings and one- and two-year... more Seven-year-old ponderosa pine (Pinus ponderosa Dougl. ex P. Laws.) saplings and one- and two-year-old ponderosa pine seedlings of a Sierra Nevada and a Rocky Mountain seed source, respectively, were exposed to CO(2)-enriched atmospheres in an outdoor open-top chamber facility for 2.5 years. Seedling growth (main stem diameter, height, volume) increased with increasing CO(2) concentration, though the two populations exhibited different patterns of response. By the beginning of the last growth season, however, the trees under the highest CO(2) concentrations showed signs of stress that included accelerated needle abscision, chlorosis, and apparent alteration of tolerance to heat. The stress response is at least partly attributable to elevated foliar temperatures resulting from CO(2)-induced stomatal closure, which in turn lowered transpirational cooling of needles.
... Potential consequences of virus infection for shade-sun acclimation in leaves Auteur(s) / Aut... more ... Potential consequences of virus infection for shade-sun acclimation in leaves Auteur(s) / Author(s). OSMOND CB ; BERRY JA ; BALACHANDRAN S. ; BUÊCHEN-OSMOND C. ; DALEY PF ; HODGSON RAJ ; Affiliation(s) du ou des auteurs / Author(s) Affiliation(s). ...
We have carried out numerical simulations of three-dimensional nonisothermal flow around an in si... more We have carried out numerical simulations of three-dimensional nonisothermal flow around an in situ heatbased flow sensor to investigate how formation heterogeneities can affect the interpretation of ground water flow velocities from this instrument. The flow sensor operates by constant heating of a 0.75-m-long, 5-cm-diameter cylindrical probe, which contains 30 thermistors in contact with the formation. The temperature evolution at each thermistor can be inverted to obtain an estimate of the ground water flow velocity vector using the standard interpretive method, which assumes that the formation is homogeneous. Analysis of data from heat-based flow sensors installed in a sand aquifer at the Former Fort Ord Army Base near Monterey, California, suggested an unexpected component of downward flow. The magnitudes of the vertical velocities were expected to be much less than those of the horizontal velocities at this site because the sensors were installed just above a clay aquitard. Nu...
Field tests of a remote fiber optic chemical sensor have recently been completed. The sensor has ... more Field tests of a remote fiber optic chemical sensor have recently been completed. The sensor has measured trace quantities of organohalides in the vadose zone and groundwater. Due to its toxicological importance and accessibility, a specific contaminant monitored was trichloroethylene (TCE). Two elements considered in these field measurements included temperature and carbon dioxide (CO[sub 2]) fluctuations. The effects of these properties on the sensor have been modeled in the lab. These results were used in the final determination of TCE concentration. Department of Energy (DOE) sites where remediation work is in progress provided opportunities for testing the sensor. One test was conducted in the vadose zone over sampling wells at the Savannah River Plant DOE integrated test site. Measurements were made before and several months after remediation procedures were in progress. A series of wells was selected with discretely screened depth intervals. Data were collected over a range o...
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