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Sample records for alkyl acids pfaas

  1. Activation of mouse and human Peroxisome Proliferator-Activated Receptor-alpha (PPARa) by Perfluoroalkyl Acids(PFAAs): Further investigation of C4-C12 compounds.

    EPA Science Inventory

    Perfluorinated alkyl acids (PFAAs) are manufactured surfactants found globally in the environment and in tissues of humans and wildlife. Several PFAAs adversely affect rodents and activation of PPARa is thought to be their mode of action. Our previous study demonstrated that some...

  2. Bioaccumulation characteristics of perfluoroalkyl acids (PFAAs) in coastal organisms from the west coast of South Korea.

    PubMed

    Hong, Seongjin; Khim, Jong Seong; Wang, Tieyu; Naile, Jonathan E; Park, Jinsoon; Kwon, Bong-Oh; Song, Sung Joon; Ryu, Jongseong; Codling, Garry; Jones, Paul D; Lu, Yonglong; Giesy, John P

    2015-06-01

    Year-round monitoring for perfluoroalkyl acids (PFAAs) along the west coast of South Korea targeting long-term changes in water and coastal organisms has been conducted since 2008. In this study, we present the most recent 5-years of accumulated data and scrutinize the relationship between concentrations in water and biota highlighting bioaccumulation characteristics. Twelve individual PFAAs in samples of water (n=43) and biota (n=59) were quantified by use of HPLC-MS/MS after solid phase extraction. In recent years, concentrations of PFAAs in water have been generally decreasing, but profiles of relative concentrations of individual PFAAs vary among location and year. Bioaccumulation of PFAAs in various organisms including fishes, bivalves, crabs, gastropods, shrimps, starfish, and polychaetes varied among species. However, overall bioaccumulation of PFAAs was dependent on corresponding concentrations of PFAAs in water within an area. In organ-specific distributions of PFAAs, greater concentrations of PFAAs were found in intestine of fish (green eel goby). This result suggests that PFAAs are mainly accumulated via dietary exposure, while greater concentrations were found in gill and intestine of bivalve (oyster) which suggests both waterborne and dietary exposures to these organisms. Concentrations of PFAAs in biota did not decrease over time (2008-2010), indicating that continuing bioaccumulation followed by slow degradation or excretion of PFAAs accumulated in biota. Overall, spatio-temporal distributions of PFAAs in water and bioaccumulation characteristics seemed to be associated with recent restrictions of PFOS-based products and uses of PFBS-based substitutes.

  3. Sequestration and bioavailability of perfluoroalkyl acids (PFAAs) in soils: Implications for their underestimated risk.

    PubMed

    Zhao, Lixia; Zhu, Lingyan; Zhao, Shuyan; Ma, Xinxin

    2016-12-01

    Different from typical hydrophobic organic contaminants (HOCs), perfluoroalkyl acids (PFAAs) are more soluble in water and less partitioned to soil than the HOCs. It remains unclear whether and to what extent PFAAs could be sequestrated in soil. In this study, sequential extraction of PFAAs in soil and bioaccumulation of PFAAs in earthworm were carried out to understand the sequestration and bioavailability of PFAAs in soils with different soil organic matter (SOM) and aged for different time periods (7 and 47d). Sequestration occurred in different degrees depending on the amount and compositions of SOM in soil, structural properties of PFAAs and aging time. Surprisingly, in one peat soil with high fraction of organic carbon (foc, 59%), the PFAAs were completely sequestrated in the soil. Aging might lead to further sequestration of PFAAs in soil with relatively lower foc. As a consequence of sequestration, the bioavailability of PFAAs in peat soils was reduced 3-10 times compared to that in the plain farmland soil. However, the sequestrated PFAAs were still bioaccumulative in earthworms to some extent. The results indicated that the risk of PFAAs in field soil with high content of SOM could be underestimated if only free PFAAs using mild solvent extraction were monitored.

  4. Investigating sources and pathways of perfluoroalkyl acids (PFAAs) in aquifers in Tokyo using multiple tracers.

    PubMed

    Kuroda, Keisuke; Murakami, Michio; Oguma, Kumiko; Takada, Hideshige; Takizawa, Satoshi

    2014-08-01

    We employed a multi-tracer approach to investigate sources and pathways of perfluoroalkyl acids (PFAAs) in urban groundwater, based on 53 groundwater samples taken from confined aquifers and unconfined aquifers in Tokyo. While the median concentrations of groundwater PFAAs were several ng/L, the maximum concentrations of perfluorooctane sulfonate (PFOS, 990 ng/L), perfluorooctanoate (PFOA, 1800 ng/L) and perfluorononanoate (PFNA, 620 ng/L) in groundwater were several times higher than those of wastewater and street runoff reported in the literature. PFAAs were more frequently detected than sewage tracers (carbamazepine and crotamiton), presumably owing to the higher persistence of PFAAs, the multiple sources of PFAAs beyond sewage (e.g., surface runoff, point sources) and the formation of PFAAs from their precursors. Use of multiple methods of source apportionment including principal component analysis-multiple linear regression (PCA-MLR) and perfluoroalkyl carboxylic acid ratio analysis highlighted sewage and point sources as the primary sources of PFAAs in the most severely polluted groundwater samples, with street runoff being a minor source (44.6% sewage, 45.7% point sources and 9.7% street runoff, by PCA-MLR). Tritium analysis indicated that, while young groundwater (recharged during or after the 1970s, when PFAAs were already in commercial use) in shallow aquifers (<50 m depth) was naturally highly vulnerable to PFAA pollution, PFAAs were also found in old groundwater (recharged before the 1950s, when PFAAs were not in use) in deep aquifers (50-500 m depth). This study demonstrated the utility of multiple uses of tracers (pharmaceuticals and personal care products; PPCPs, tritium) and source apportionment methods in investigating sources and pathways of PFAAs in multiple aquifer systems.

  5. Perfluoroalkyl acids (PFAAs) in water and sediment from the coastal regions of Shandong peninsula, China.

    PubMed

    Wan, Yi; Wang, Shiliang; Cao, Xuezhi; Cao, Yuanxin; Zhang, Lu; Wang, Hui; Liu, Jinfeng

    2017-03-01

    Perfluoroalkyl acids (PFAAs) have been observed in various environmental matrices globally in recent years. In this study, the levels, spatial distribution tendencies, and partitioning characteristics of the target 12 PFAAs were investigated in water and sediment from the coastal regions of Shandong peninsula in China, and two sediment core samples were also collected to study the vertical and historical variation of PFAAs. The ranges (means) of total PFAA concentrations were 23.69-148.48 ng/L (76.11 ng/L) in the water and 1.30-11.17 ng/g (5.93 ng/g) in the surface sediment, respectively. Among the target 12 PFAAs, perfluorooctanoic acid (PFOA) was the dominant component in water, followed by perfluorooctane sulfonate (PFOS) and perfluorohexanoic acid (PFHxA). PFOS, perfluoroundecanoic acid, and PFOA were the dominant components in sediment. For their spatial distribution, higher levels of PFAAs were found at the locations close to much developed cities. The PFAA concentrations showed an overall decreasing tendency with depth increase in the two sediment cores, which indicates that the extent of PFAAs pollution is aggravating trend in recent years. Results of the partition coefficient (K d ) show that the compounds with longer carbon chains (C ≥ 7) generally had higher K d values, which suggest that long-chain PFAAs are prone to be adsorbed by sediment. In addition, the Log K d of PFHxA, PFOA, and PFOS were significantly and positively correlated to the salinity of the water. The results of risk assessment suggest appreciable risk of PFAAs to the local ecosystem.

  6. Evaluating the additivity of perfluoroalkyl acids (PFAAs) in binary combinations on peroxisome proliferator-activated receptor-a(PPARa) activation

    EPA Science Inventory

    Perfluoroalkyl acids (PFAAs) are found globally in the environment, detected in humans and wildlife, and are typically present as mixtures of PFAA congeners. Mechanistic studies have found that responses to PFAAs are mediated in part by PPARa. Our previous studies showed that ind...

  7. Dietary predictors and plasma concentrations of perfluorinated alkyl acids in a Singapore population.

    PubMed

    Liu, Yu; Su, Jin; van Dam, Rob M; Prem, Kiesha; Hoong, Joey Y S; Zou, Li; Lu, Yonghai; Ong, Choon Nam

    2017-03-01

    Perfluorinated alkyl acids (PFAAs), a family of man-made organofluorinated compounds, have drawn much attention due to their ubiquitous existence in the environment and their bioaccumulation potential. Here, we examined the plasma concentrations of thirteen PFAAs in a healthy population (N = 270) in Singapore, and investigated the association between major food groups and plasma PFAA concentrations. We detected eight types of PFAAs in more than 75% of all samples (N = 270), and their median concentrations ranged from 0.05 to 8.34 ng mL(-1). Age- and gender-related differences were observed for the three dominant PFAAs, i.e., perfluorooctanesulfonic acid (PFOS), perfluorohexane sulfonate (PFHxS) and perfluorooctanoate acid (PFOA), with concentrations being higher in men and older adults. Multiple linear regression analyses showed that fish, shellfish, red meat and poultry were associated with increased PFAAs concentrations in plasma, whereas grains and soy products showed inverse associations with PFAAs. Further, significant correlations were observed between various long-chain PFAAs and plasma concentrations of omega-3 fatty acids, suggesting seafood was a significant source of these PFAAs, within this population. Future studies on diet exposure to PFAAs are encouraged to focus more on the effects on diet pattern.

  8. Survey of perfluoroalkyl acids (PFAAs) and their precursors present in Japanese consumer products.

    PubMed

    Ye, Feng; Zushi, Yasuyuki; Masunaga, Shigeki

    2015-05-01

    Perfluoroalkyl acids (PFAAs) and their precursors have been used in various consumer products. However, limited information regarding their occurrence and concentration levels in products is available. In this study, we investigated 18 PFAAs and 14 PFAA precursors in various categories of consumer products purchased in Japan. Relatively high total concentrations of PFAAs and their precursors were found in sprays for fabrics and textiles (acid (PFOS), N-methyl perfluorooctane sulfonamidoethanol (MeFOSE) was detected in a higher frequency (8%) and in greater concentrations (PFAAs emitted from consumer products may be underestimated if the occurrence of PFAA precursors is not considered. In addition to PFAA precursors, long chain perfluoroalkyl carboxylic acids (PFCAs) (carbon chain length⩾7) were also detected in greater concentrations than short chain PFCAs (⩽6). This result suggests that consumer products are one of the important sources of long-chain PFCAs in the environment.

  9. Getting on with persistent pollutants: Decreasing trends of perfluoroalkyl acids (PFAAs) in sewage sludge.

    PubMed

    Ulrich, Hanna; Freier, Korbinian P; Gierig, Michael

    2016-10-01

    Sewage sludge can be a relevant source of perfluoroalkyl acids (PFAAs) for the environment. In order to reduce emissions from this source, Bavarian authorities enforced in 2008 an analysis of PFAAs from sewage sludge derived from municipal wastewater treatment plants (WWTPs). 4981 sludge samples from 1165 different WWTPs were analyzed between 2008 and 2013 for 11 PFAAs compounds. During this period, 71 WWTPs exceeded the precautionary limit of 125 μg kg(-1) dm of total PFAAs in sludge samples at least once with a decreasing tendency. The yearly exceedances of the investigated WWTPs decreased from 6% in 2008 to 0.8% in 2013. At the same time, the percentage of uncontaminated WWTPs increased from 33% to 65%. Perfluorooctane sulfonic acid (PFOS) was the predominant compound found in 41% of all sludge samples. Perfluorodecanoic acid (PFDA) was detected in 19% and Perfluorooctanoic acid (PFOA) in 7%. Very high PFAAs concentrations (>500 μg kg(-1) dm) in sewage sludge were generally caused by firefighting foams containing PFAAs or emissions from PFAAs-using industries including metal plating, textile, leather or paper industries. Trend analyses of the six year period show that PFAAs contamination in sewage sludge clearly decreased for 47% of the WWTPs. However, for 16% of the WWTPs an increasing trend was detected, even though the concentration levels were below the precautionary limit. During the six years of investigation the load of total PFAAs in sewage sludge was reduced by more than 90%, from 17 t a(-1) in 2008 to 1.5 t a(-1) in 2013.

  10. Evaluation of additivity of binary mixtures of perfluoroalkyl acids (PFAAs) on peroxisome proliferator-activated receptor-alpha (PPARa) activation in vitro

    EPA Science Inventory

    Perfluoroalkyl acids (PFAAs) are found globally in the environment and in animal tissues, and are present as mixtures of PFAA congeners. Mechanistic studies have found that in vivo effects of PFAAs are mediated by PPARL. Our previous studies showed that individual PFAAs activate ...

  11. Occurrence, temporal trends, and half-lives of perfluoroalkyl acids (PFAAs) in occupational workers in China

    NASA Astrophysics Data System (ADS)

    Fu, Jianjie; Gao, Yan; Cui, Lin; Wang, Thanh; Liang, Yong; Qu, Guangbo; Yuan, Bo; Wang, Yawei; Zhang, Aiqian; Jiang, Guibin

    2016-12-01

    Paired serum and urine samples were collected from workers in a fluorochemical plant from 2008 to 2012 (n = 302) to investigate the level, temporal trends, and half-lives of PFAAs in workers of a fluorochemical plant. High levels of perfluorohexane sulfonate (PFHxS), perfluorooctanoic acid (PFOA), and perfluorooctanesulfonate (PFOS) were detected in serum with median concentrations of 764, 427, and 1725 ng mL‑1, respectively. The half-lives of PFAAs in workers were estimated by daily clearance rates and annual decline rates of PFAAs in serum by a first-order model. The geometric mean and median value for PFHxS, PFOA, and PFOS were 14.7 and 11.7, 4.1 and 4.0, 32.6 and 21.6 years, respectively, by the daily clearance rates, and they were 3.6, 1.7, and 1.9 years estimated by annual decline rates. The half-lives estimated by the limited clearance route information could be considered as the upper limits for PFAAs, however, the huge difference between two estimated approaches indicated that there were other important elimination pathways of PFAAs other than renal clearance in human. The half-lives estimated by annual decline rates in the present study were the shortest values ever reported, and the intrinsic half-lives might even shorter due to the high levels of ongoing exposure to PFAAs.

  12. Occurrence, temporal trends, and half-lives of perfluoroalkyl acids (PFAAs) in occupational workers in China

    PubMed Central

    Fu, Jianjie; Gao, Yan; Cui, Lin; Wang, Thanh; Liang, Yong; Qu, Guangbo; Yuan, Bo; Wang, Yawei; Zhang, Aiqian; Jiang, Guibin

    2016-01-01

    Paired serum and urine samples were collected from workers in a fluorochemical plant from 2008 to 2012 (n = 302) to investigate the level, temporal trends, and half-lives of PFAAs in workers of a fluorochemical plant. High levels of perfluorohexane sulfonate (PFHxS), perfluorooctanoic acid (PFOA), and perfluorooctanesulfonate (PFOS) were detected in serum with median concentrations of 764, 427, and 1725 ng mL−1, respectively. The half-lives of PFAAs in workers were estimated by daily clearance rates and annual decline rates of PFAAs in serum by a first-order model. The geometric mean and median value for PFHxS, PFOA, and PFOS were 14.7 and 11.7, 4.1 and 4.0, 32.6 and 21.6 years, respectively, by the daily clearance rates, and they were 3.6, 1.7, and 1.9 years estimated by annual decline rates. The half-lives estimated by the limited clearance route information could be considered as the upper limits for PFAAs, however, the huge difference between two estimated approaches indicated that there were other important elimination pathways of PFAAs other than renal clearance in human. The half-lives estimated by annual decline rates in the present study were the shortest values ever reported, and the intrinsic half-lives might even shorter due to the high levels of ongoing exposure to PFAAs. PMID:27905562

  13. Extraction of perfluorinated alkyl acids from human serum for determination of the combined xenoestrogenic transactivity: a method development.

    PubMed

    Bjerregaard-Olesen, Christian; Bossi, Rossana; Bech, Bodil Hammer; Bonefeld-Jørgensen, Eva Cecilie

    2015-06-01

    Humans are exposed to perfluorinated alkyl acids (PFAAs) through food, drinking water, consumer products, dust, etc. The human metabolism and excretion of the long-chain PFAAs is slow with half-lives up to 8.8years. Studies suggest that the PFAAs are potential endocrine-disrupting compounds that might affect human health. We developed a method for extraction of PFAAs from human serum with simultaneous removal of endogenous sex hormones. The developed method includes solid phase extraction, liquid/liquid extraction, HPLC fractionation and weak anion exchange. The method was validated by extraction of seven persistent PFAAs spiked to human male serum obtaining mean recoveries between 49.6% and 78.6%. Using an estrogen receptor (ER) transactivation luciferase reporter gene assay, analysis of the extracted PFAA serum fraction from three pregnant women showed the ER-active endogenous hormones were removed. The developed method was further documented by extraction of the PFAAs from the serum of 18 Danish pregnant women. The PFAA fraction from three of the 18 samples significantly induced the ER-transactivity. Upon co-exposure with the natural ER-ligand 17β-estradiol (E2), 17 of the 18 PFAA fractions caused a significant further increase of the E2 induced ER-transactivity. In conclusion, we developed a method to extract PFAAs from human serum, and the method documentation suggested that PFAAs at the levels found in human serum can transactivate the ER.

  14. Bioaccumulation of perfluorinated alkyl acids: observations and models.

    PubMed

    Ng, Carla A; Hungerbühler, Konrad

    2014-05-06

    In this review, we consider the two prevailing hypotheses for the mechanisms that control the bioaccumulation of perfluorinated alkyl acids (PFAAs). The first assumes that partitioning to membrane phospholipids, which have a higher affinity for charged species than neutral storage lipids, can explain the high bioaccumulation potential of these compounds. The second assumes that interactions with proteins--including serum albumin, liver fatty acid binding proteins (L-FABP), and organic anion transporters--determine the distribution, accumulation and half-lives of PFAAs. We consider three unique phenomena to evaluate the two models: (1) observed patterns of tissue distribution in the laboratory and field, (2) the relationship between perfluorinated chain length and bioaccumulation, and (3) species- and gender-specific variation in elimination half-lives. Through investigation of these three characteristics of PFAA bioaccumulation, we show the strengths and weaknesses of the two modeling approaches. We conclude that the models need not be mutually exclusive, but that protein interactions are needed to explain some important features of PFAA bioaccumulation. Although open questions remain, further research should include perfluorinated alkyl substances (PFASs) beyond the long-chain PFAAs, as these substances are being phased out and replaced by a wide variety of PFASs with largely unknown properties and bioaccumulation behavior.

  15. In situ fate and partitioning of waterborne perfluoroalkyl acids (PFAAs) in the Youngsan and Nakdong River Estuaries of South Korea.

    PubMed

    Hong, Seongjin; Khim, Jong Seong; Park, Jinsoon; Kim, Minhee; Kim, Woong-Ki; Jung, Jinho; Hyun, Seunghun; Kim, Jeong-Gyu; Lee, Hyojin; Choi, Heeseon J; Codling, Garry; Giesy, John P

    2013-02-15

    Concentrations, distributions, fate, and partitioning of perfluoroalkyl acids (PFAAs) were investigated in surface water (n=34) collected from the Youngsan and Nakdong River Estuaries of South Korea. Thirteen individual PFAAs in water and suspended solids (SS) were quantified by use of HPLC-MS/MS. PFAAs were detected in all samples, which indicated that they were widely distributed in the study area. Greater concentrations of PFAAs were found at some inland sites which seemed to be affected by direct input from point sources, such as wastewater treatment plants, and/or indirect diffusive sources, such as surface runoff. Spatial distributions of PFAAs in estuaries along transects toward the open sea demonstrated that these chemicals were transported to the outer region primarily by water discharged during the rainy season. Field-based partition coefficients (K(d)) for long-chain PFAAs (C≥8) were significantly correlated with salinity (r(2)=0.48 to 0.73, p<0.01); K(d) values increased exponentially as a function of salinity. Due to the 'salting-out' effect, PFAAs were largely scavenged by adsorption onto SS and/or sediments in estuarine environments. In addition, values for K(d) of those PFAAs were directly proportional to the number of carbon atoms in the PFAAs. Salting constants of selected PFAAs were notably greater than those of other environmental organic contaminants, which indicated that adsorption of PFAAs is largely associated with salinity. Overall, the results of the present study will provide better understanding of the fate and transport of PFAAs in the zone of salinity boundary that can be used for developing fate models of PFAAs in the coastal marine environment.

  16. Testing for departures from additivity in mixtures of perfluoroalkyl acids (PFAAs)

    EPA Science Inventory

    This study is a follow-up to a paper by Carr, et al. that determined a design structure to optimally test for departures from additivity in a fixed ratio mixture of four perfluoroalkyl acids (PFAAs) using an in vitro transiently-transfected COS- 1 PPARa reporter model with an NHA...

  17. Perfluorinated alkyl acids in the plasma of South African crocodiles (Crocodylus niloticus).

    PubMed

    Christie, Ian; Reiner, Jessica L; Bowden, John A; Botha, Hannes; Cantu, Theresa M; Govender, Danny; Guillette, Matthew P; Lowers, Russell H; Luus-Powell, Wilmien J; Pienaar, Danie; Smit, Willem J; Guillette, Louis J

    2016-07-01

    Perfluorinated alkyl acids (PFAAs) are environmental contaminants that have been used in many products for over 50 years. Interest and concern has grown since 2000 on the widespread presence of PFAAs, when it was discovered that PFAAs were present in wildlife samples around the northern hemisphere. Since then, several studies have reported PFAAs in wildlife from many locations, including the remote regions of Antarctica and the Arctic. Although there are a multitude of studies, few have reported PFAA concentrations in reptiles and wildlife in the Southern Hemisphere. This study investigated the presence of PFAAs in the plasma of Nile crocodiles (Crocodylus niloticus) from South Africa. Crocodiles were captured from five sites in and around the Kruger National Park, South Africa, and plasma samples examined for PFAAs. Perfluorooctane sulfonate (PFOS) was the most frequent PFAA detected; with median values of 13.5 ng/g wet mass in crocodiles. In addition to PFOS, long chain perfluorinated carboxylic acids were also detected. Correlations between total length and PFAA load were investigated, as were differences in PFAA accumulation between sexes. No correlations were seen between crocodile size, nor were there sex-related differences. Spatial differences were examined and significant differences were observed in samples collected from the different sites (p < 0.05). Flag Boshielo Dam had the highest PFOS measurements, with a median concentration of 50.3 ng/g wet mass, when compared to the other sites (median concentrations at other sites below 14.0 ng/g wet mass). This suggests a point source of PFOS in this area.

  18. Spatial distribution and partition of perfluoroalkyl acids (PFAAs) in rivers of the Pearl River Delta, southern China.

    PubMed

    Liu, Baolin; Zhang, Hong; Xie, Liuwei; Li, Juying; Wang, Xinxuan; Zhao, Liang; Wang, Yanping; Yang, Bo

    2015-08-15

    This study investigated the occurrence of perfluoroalkyl acids (PFAAs) in surface water from 67 sampling sites along rivers of the Pearl River Delta in southern China. Sixteen PFAAs, including perfluoroalkyl carboxylic acids (PFCAs, C5-14, C16 and C18) and perfluoroalkyl sulfonic acids (PFSAs, C4, C6, C8 and C10) were determined by high performance liquid chromatography-negative electrospray ionization-tandem mass spectrometry (HPLC/ESI-MS/MS). Total PFAA concentrations (∑ PFAAs) in the surface water ranged from 1.53 to 33.5 ng·L(-1) with an average of 7.58 ng·L(-1). Perfluorobutane sulfonic acid (PFBS), perfluorooctanoic acid (PFOA), and perfluorooctane sulfonic acid (PFOS) were the three most abundant PFAAs and on average accounted for 28%, 16% and 10% of ∑ PFAAs, respectively. Higher concentrations of ∑ PFAAs were found in the samples collected from Jiangmen section of Xijiang River, Dongguan section of Dongjiang River and the Pearl River flowing the cities which had very well-developed manufacturing industries. PCA model was employed to quantitatively calculate the contributions of extracted sources. Factor 1 (72.48% of the total variance) had high loading for perfluorohexanoic acid (PFHxA), perfluoropentanoic acid (PFPeA), PFBS and PFOS. For factor 2 (10.93% of the total variance), perfluorononanoic acid (PFNA) and perfluoroundecanoic acid (PFUdA) got high loading. The sorption of PFCAs on suspended particulate matter (SPM) increased by approximately 0.1 log units for each additional CF2 moiety and that on sediment was approximately 0.8 log units lower than the SPM logKd values. In addition, the differences in the partition coefficients were influenced by the structure discrepancy of absorbents and influx of fresh river water. These data are essential for modeling the transport and environmental fate of PFAAs.

  19. Multi-generational xenoestrogenic effects of Perfluoroalkyl acids (PFAAs) mixture on Oryzias latipes using a flow-through exposure system.

    PubMed

    Lee, Jin Wuk; Lee, Jae-Woo; Shin, Yu-Jin; Kim, Ji-Eun; Ryu, Tae-Kwon; Ryu, Jisung; Lee, Jaean; Kim, Pilje; Choi, Kyunghee; Park, Kyunghwa

    2017-02-01

    To elucidate the multi-generational estrogenic potential of Perfluoroalkyl acids (PFAAs) mixture, vitellogenin (VTG) expression, growth indices, histological alteration, fecundity, hatching rate, larval survival rate, and sex ratio of Japanese medaka (Oryzias latipes) were investigated by exposing the fish to a mixture of perfluorooctane sulfonate (PFOS), perfluroroctanoic acid (PFOA), perfluorobutane sulfonate (PFBS), and perfluorononanoic acid (PFNA) for three generations (238 days). Mixture composition is in the ratio of 1:1:1:1. In addition, whole body burden for each PFAA was analyzed. According to the results, concentrated levels of the PFAAs in both F1 and F2 generation O. latipes were ordered PFOS > PFNA > PFOA > PFBS at both low concentration (0.5 μg/L) and high concentration (5 μg/L), whereas a significant difference in whole body burden based on sex or generation was not detected. Significant induction of VTG expression in F2 and the decline of the gonad somatic index (GSI) in F1 were observed following PFAAs mixture exposure (p < 0.05, one-way ANOVA). Furthermore, suppression level of reproduction rate relative to the control increased as generation was transferred to the next in response to PFAAs mixture or 17 β-estradiol exposure, with the inhibition of hatchability observed in the F1 generation. The PFAA high concentration caused significant alteration of F1 generation sex ratio, suggesting the adverse effect of PFAA in population level (Chi-square test, P > 0.05). Overall, this study demonstrated that PFAA mixture could have the potential of multi-generational endocrine disruptors in O. latipes.

  20. Uptake of perfluorinated alkyl acids by hydroponically grown lettuce (Lactuca sativa).

    PubMed

    Felizeter, Sebastian; McLachlan, Michael S; de Voogt, Pim

    2012-11-06

    An uptake study was carried out to assess the potential human exposure to perfluorinated alkyl acids (PFAAs) through the ingestion of vegetables. Lettuce (Lactuca sativa) was grown in PFAA-spiked nutrient solutions at four different concentrations, ranging from 10 ng/L to 10 μg/L. Eleven perfluorinated carboxylic acids (PFCAs) and three perfluorinated sulfonic acids (PFSAs) were analyzed by HPLC-MS/MS. At the end of the experiment, the major part of the total mass of each of the PFAAs (except the short-chain, C4-C7, PFCAs) taken up by plants appeared to be retained in the nonedible part, viz. the roots. Root concentration factors (RCF), foliage/root concentration factors (FRCF), and transpiration stream concentration factors (TSCF) were calculated. For the long chained PFAAs, RCF values were highest, whereas FRCF were lowest. This indicates that uptake by roots is likely governed by sorption of PFAAs to lipid-rich root solids. Translocation from roots to shoots is restricted and highly depending on the hydrophobicity of the compounds. Although the TSCF show that longer-chain PFCAs (e.g., perfluorododecanoic acid) get better transferred from the nutrient solution to the foliage than shorter-chain PFCAs (e.g., perfluoroheptanoic acid), the major fraction of longer-chain PFCAs is found in roots due to additional adsorption from the spiked solution. Due to the strong electron-withdrawing effect of the fluorine atoms the role of the negative charge of the dissociated PFAAs is likely insignificant.

  1. The overnight effect of dietary energy balance on postprandial plasma free amino acid (PFAA) profiles in Japanese adult men.

    PubMed

    Nishioka, Manabu; Imaizumi, Akira; Ando, Toshihiko; Tochikubo, Osamu

    2013-01-01

    The plasma free amino acid (PFAA) profile is affected by various nutritional conditions, such as the dietary energy balance. Regarding the clinical use of PFAA profiling, it is of concern that differences in food ingestion patterns may generate systematic errors in a plasma amino acid profile and constitute a confounding factor in assessment. In this study, the overnight impact of the dietary energy balance on the postprandial plasma amino acid profile was investigated to elucidate in particular the effects of high protein meals typical in Japanese cuisine. We conducted diet-controlled, crossover trials in eleven healthy male volunteers aged 40-61 y. They consumed either a normal meal (meal N) or high protein meal (meal H) at dinner. Forearm venous blood was collected, and plasma amino acid concentrations were measured before dinner and the next morning. We found that a high protein meal in the evening that contained 40% energy would significantly increase the PFAA concentration the next morning, even more than 12 hours after the meal. Among amino acids, the most significant difference was observed in the branched-chain amino acids (BCAAs) and in some urea-cycle related compounds. If the subject consumed the high protein diet at dinner, the PFAA profile after overnight fasting might be still affected by the meal even 12 hours after the meal, suggesting that the PFAA profile does not reflect the subject's health condition, but rather the acute effect of high protein ingestion.

  2. Perfluorinated alkylated acids in groundwater and drinking water: identification, origin and mobility.

    PubMed

    Eschauzier, Christian; Raat, Klaasjan J; Stuyfzand, Pieter J; De Voogt, Pim

    2013-08-01

    Human exposure to perfluorinated alkylated acids (PFAA) occurs primarily via the dietary intake and drinking water can contribute significantly to the overall PFAA intake. Drinking water is produced from surface water and groundwater. Waste water treatment plants have been identified as the main source for PFAA in surface waters and corresponding drinking water. However, even though groundwater is an important source for drinking water production, PFAA sources remain largely uncertain. In this paper, we identified different direct and indirect sources of PFAA to groundwater within the catchment area of a public supply well field (PSWF) in The Netherlands. Direct sources were landfill leachate and water draining from a nearby military base/urban area. Indirect sources were infiltrated rainwater. Maximum concentrations encountered in groundwater within the landfill leachate plume were 1.8 μg/L of non branched perfluorooctanoic acid (L-PFOA) and 1.2 μg/L of perfluorobutanoic acid (PFBA). Sum concentrations amounted to 4.4 μg/L total PFAA. The maximum concentration of ΣPFAA in the groundwater originating from the military camp was around 17 ng/L. Maximum concentrations measured in the groundwater halfway the landfill and the PWSF (15 years travel distance) were 29 and 160 ng/L for L-PFOA and PFBA, respectively. Concentrations in the groundwater pumping wells (travel distance >25 years) were much lower: 0.96 and 3.5 ng/L for L-PFOA and PFBA, respectively. The chemical signature of these pumping wells corresponded to the signature encountered in other wells sampled which were fed by water that had not been in contact with potential contaminant sources, suggesting a widespread diffuse contamination from atmospheric deposition.

  3. Development and validation of a method for the quantification of extractable perfluoroalkyl acids (PFAAs) and perfluorooctane sulfonamide (FOSA) in textiles.

    PubMed

    van der Veen, Ike; Weiss, Jana M; Hanning, Anne-Charlotte; de Boer, Jacob; Leonards, Pim E G

    2016-01-15

    In textiles, like outdoor clothing, per- and polyfluoroalkyl substances (PFASs) are often used for durable water repellency (DWR) of the final products. The analytical performance to determine the concentration of these chemicals available for exposure to humans and to the environment need to be established. Here a method for the extraction and analysis of one class of PFASs, namely perfluoroalkyl acids (PFAAs), in outdoor clothing was developed and validated. The PFAAs which were validated, included perfluoroalkyl carboxylic acids (PFCAs) (C4-C14), and perfluoroalkane sulfonic acids (PFSAs) (C4, C6, C7, C8). In addition, perfluorooctane sulfonamide (FOSA) was included in this study. The method was based on an organic solvent extraction and analysis by high-performance liquid chromatography-tandem mass spectrometry (LC-MS/MS). No further cleaning was needed. Two commonly used organic solvent compositions were evaluated for the optimal extraction, i.e. methanol and acetone/acetonitrile (80:20, v/v), and the number and duration of the sequential extractions were optimized. Results showed that two sequential extractions with 5mL methanol and an extraction time of 30min gave an optimal performance with an extraction efficiency of >90%. The influence of matrix on the quantification of PFAAs was studied. This indicated ion suppression due to different matrix effects or sorption behavior to specific textile samples. Validation of the entire method showed overall recoveries of>80% and relative standard deviations (RSDs) of<9% (n=3) for repeatability and <20% (n=3) for reproducibility. This is the first validation of an analytical method for the analysis of extractable PFCAs, PFSAs and FOSA associated to textiles, which is of high importance due to the regulation of PFAAs in textile.

  4. PPAR involvement in PFAA developmental toxicity

    EPA Science Inventory

    Perfluoroalkyl acids (PFAAs) are found in the environment and in serum of wildlife and humans. Perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorooctane sulfonate (PFOS) are developmentally toxic in rodents. The effects of in utero exposure include increas...

  5. Occurrence and distribution of perfluoroalkyl acids (PFAAs) in surface water and sediment of a tropical coastal area (Bay of Bengal coast, Bangladesh).

    PubMed

    Habibullah-Al-Mamun, Md; Ahmed, Md Kawser; Raknuzzaman, Mohammad; Islam, Md Saiful; Negishi, Junya; Nakamichi, Shihori; Sekine, Makoto; Tokumura, Masahiro; Masunaga, Shigeki

    2016-11-15

    This study reports the first evidence of perfluoroalkyl acids (PFAAs) in surface waters and sediments collected from the coastal area of Bangladesh. Fifteen target PFAAs, including C4-14-PFCAs (perfluoroalkyl carboxylates) and C4, C6, C8, and C10-PFSAs (perfluoroalkyl sulfonates), were quantified by HPLC-MS/MS. The ΣPFAAs in surface water and sediment samples were in the range of 10.6 to 46.8ng/L and 1.07 to 8.15ng/gdw, respectively. PFOA in water (3.17-27.8ng/L) and PFOS in sediment samples (0.60-1.14ng/gdw) were found to be the most abundant PFAAs, and these concentrations were comparable to or less than most other reported values, particularly those recorded from the coastal areas of China, Japan, Korea and Spain. The majority of the monitored PFAAs did not show clear seasonal variation. The southeastern part (Cox's Bazar and Chittagong) of the Bangladeshi coastal area was more contaminated with PFAAs than the southern (Meghna Estuary) and southwestern parts (Sundarbans). Industrial and municipal wastewater effluents, ship breaking and port activities were identified as potential sources of the PFAA contamination in this region. Field-based sediment water distribution coefficients (KD) were calculated and corrected for organic carbon content (KOC), which reduced the variability between samples. The values of log KD (1.63-2.88) and log KOC (4.02-5.16) were higher than previously reported values, which may indicate that the partitioning of PFAAs in a tropical coastal ecosystem is different from other ecosystems, such as temperate and sub-tropical regions. Although a preliminary environmental hazard assessment indicated that PFOA or PFOS levels do not currently exceed the acute safety thresholds, we should keep in mind that they are bioavailable and can accumulate in the food chain. Therefore, the ubiquity of PFAAs in the coastal area of Bangladesh warrants further studies characterizing their specific sources and the potential long-term risks they present to both

  6. THE DEVELOPMENT OF AN IN VITRO ASSAY FOR EVALUATING THE BINDING OF PERFLUOROALKYL ACIDS (PFAAS) TO THE PEROXISOME PROLIFERATOR-ACTIVATED RECEPTORS (PPARS)

    EPA Science Inventory

    The purpose of this work was to evaluate the binding of PFAAs to PPAR receptors and determine the potential for activation or antagonism of the pathway during embryonic development. Activation of mouse and human PPAR isoforms by perfluorooctanoic acid (PFOA) and perfluorooctanes...

  7. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl...

  8. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl...

  9. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl...

  10. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl...

  11. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl...

  12. ACTIVATION ASSAY FOR PEROXISOME PROLIFERATOR-ACTIVATED RECEPTOR- ALPHA (PPARÁ) BY PERFLUOROALKYL ACIDS (PFAAS) IN COS-1 CELLS

    EPA Science Inventory

    PFAAs have been found to elicit various physiological effects including peroxisome proliferation, indicating the mechanism of action for these chemicals could involve PPAR. This study investigates the ability of PFAAs to bind and activate mouse and human PPARα in COS-1 cell...

  13. Alkyl phosphonic acids and sulfonic acids in the Murchison meteorite

    NASA Technical Reports Server (NTRS)

    Cooper, George W.; Onwo, Wilfred M.; Cronin, John R.

    1992-01-01

    Homologous series of alkyl phosphonic acids and alkyl sulfonic acids, along with inorganic orthophosphate and sulfate, are identified in water extracts of the Murchison meteorite after conversion to their t-butyl dimethylsilyl derivatives. The methyl, ethyl, propyl, and butyl compounds are observed in both series. Five of the eight possible alkyl phosphonic acids and seven of the eight possible alkyl sulfonic acids through C4 are identified. Abundances decrease with increasing carbon number as observed of other homologous series indigenous to Murchison. Concentrations range downward from approximately 380 nmol/gram in the alkyl sulfonic acid series, and from 9 nmol/gram in the alkyl phosphonic acid series.

  14. Perfluorinated Alkyl Acids in Plasma of American Alligators (Alligator Mississippiensis) from Florida and South Carolina

    NASA Technical Reports Server (NTRS)

    Bangma, Jacqueline T.; Bowden, John A.; Brunell, Arnold M.; Christie, Ian; Finnell, Brendan; Guillette, Matthew P.; Jones, Martin; Lowers, Russell H.; Rainwater, Thomas R.; Reiner, Jessica L.; Wilkinson, Philip M.; Guillette, Louis J., Jr.

    2016-01-01

    This study aimed to quantitate fourteen perfluoroalkyl acids (PFAAs) in 125 adult American alligators at twelve sites across the southeastern US. Of those fourteen PFAAs, nine were detected in 65% - 100% of the samples: PFOA, PFNA, PFDA, PFUnA, PFDoA, PFTriA, PFTA, PFHxS, and PFOS. Males (across all sites) showed significantly higher concentrations of four PFAAs: PFOS (p = 0.01), PFDA (p = 0.0003), PFUnA (p = 0.021), and PFTriA (p = 0.021). Concentrations of PFOS, PFHxS, and PFDA in plasma were significantly different among the sites in each sex. Alligators at Merritt Island National Wildlife Refuge and Kiawah Nature Conservancy both exhibited some of the highest PFOS concentrations (medians 99.5 ng/g and 55.8 ng/g respectively) in plasma measured to date in a crocodilian species. A number of positive correlations between PFAAs and snout-vent length (SVL) were observed in both sexes suggesting PFAA body burdens increase with increasing size. In addition, several significant correlations among PFAAs in alligator plasma may suggest conserved sources of PFAAs at each site throughout the greater study area. This study is the first to report PFAAs in American alligators, reveals potential PFAA hot spots in Florida and South Carolina, and provides and additional contaminant of concern when assessing anthropogenic impacts on ecosystem health.

  15. Evidence for the Involvement of Xenobiotic-responsive Nuclear Receptors in Transcriptional Effects Upon Perfluoroalkyl Acid Exposure in Diverse Species.

    EPA Science Inventory

    Humans and other species have detectable body burdens of a number of perfluorinated alkyl acids (PFAA) including perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). In mouse and rat liver these compounds elicit transcriptional and phenotypic effects similar to pe...

  16. Evidence for the Involvement of Xenobiotic-response Nuclear Receptors in Transcriptional Effects Upon Perfluroroalkyl Acid Exposure in Diverse Species

    EPA Science Inventory

    Humans and ecological species have been found to have detectable body burdens of a number of perfluorinated alkyl acids (PFAA) including perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). In mouse and rat liver these compounds elicit transcriptional and phenotyp...

  17. Mechanisms of perfluoroalkyl acid (PFAA) toxicity: Involvement of peroxisome proliferator activator receptor alpha (PPAR) molecular signals.

    EPA Science Inventory

    Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are members of a family of environmentally persistent perfluorinated compounds and are found in the serum of wildlife and humans. PFOS and PFOA are developmentally toxic in rats and mice. Exposure in utero reduces...

  18. PFAA Days III Meeting Report and Highlights

    EPA Science Inventory

    The Office of Research and Development (ORD) at the U.S. Environmental Protection Agency (U.S. EPA) sponsored a symposium on perfluoroalkyl acids (PFAAs) on June 8-10, 2010 at the Research Triangle Park, NC. The goals ofthe symposium were to share and review the latest research ...

  19. PFAA Days II Meeting Report and Highlights

    EPA Science Inventory

    The Office of Research and Development at the U.S. Environmental Protection Agency (U.S. EPA) sponsored a workshop on perfluoroalkyl acids (PFAAs) on June 3-4, 2008 at the Research Triangle Park, NC. The goals of the workshop were to review the research progress made with the P...

  20. Iron-Catalyzed Decarboxylative Alkyl Etherification of Vinylarenes with Aliphatic Acids as the Alkyl Source.

    PubMed

    Jian, Wujun; Ge, Liang; Jiao, Yihang; Qian, Bo; Bao, Hongli

    2017-03-20

    Because of the lack of effective alkylating reagents, alkyl etherification of olefins with general alkyl groups has not been previously reported. In this work, a variety of alkyl diacyl peroxides and peresters generated from aliphatic acids have been found to enable the first iron-catalyzed alkyl etherification of olefins with general alkyl groups. Primary, secondary and tertiary aliphatic acids are suitable for this reaction, delivering products with yields up to 97 %. Primary and secondary alcohols react well, affording products in up to 91 % yield.

  1. An ultra-sensitive method for the analysis of perfluorinated alkyl acids in drinking water using a column switching high-performance liquid chromatography tandem mass spectrometry.

    PubMed

    Dasu, Kavitha; Nakayama, Shoji F; Yoshikane, Mitsuha; Mills, Marc A; Wright, J Michael; Ehrlich, Shelley

    2017-04-21

    In epidemiological research, it has become increasingly important to assess subjects' exposure to different classes of chemicals in multiple environmental media. It is a common practice to aliquot limited volumes of samples into smaller quantities for specific trace level chemical analyses. A novel method was developed for the determination of 14 perfluorinated alkyl acids (PFAAs) in small volumes (10mL) of drinking water using off-line solid phase extraction (SPE) pre-treatment followed by on-line pre-concentration on a WAX column before analysis on column-switching high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). In general, large volumes (100-1000mL) have been used for the analysis of PFAAs in drinking water. The current method requires approximately 10mL of drinking water concentrated by using an SPE cartridge and eluted with methanol. A large volume injection of the extract was introduced on to a column-switching HPLC-MS/MS using a mix-mode SPE column for the trace level analysis of PFAAs in water. The recoveries for most of the analytes in the fortified laboratory blanks ranged from 73±14% to 128±5%. The lowest concentration minimum reporting levels (LCMRL) for the 14 PFAAs ranged from 0.59 to 3.4ng/L. The optimized method was applied to a pilot-scale analysis of a subset of drinking water samples from an epidemiological study. These samples were collected directly from the taps in the households of Ohio and Northern Kentucky, United States and the sources of drinking water samples are both surface water and ground water, and supplied by different water distribution facilities. Only five PFAAs, perfluoro-1-butanesulfonic acid (PFBS), perfluoro-1- -hexanesulfonic acid (PFHxS), perfluoro-1-octanesulfonic acid (PFOS), perfluoro-n-heptanoic acid (PFHpA) and perfluoro-n-octanoic acid (PFOA) are detected above the LCMRL values. The median concentrations of these five PFAAs detected in the samples was ≤4.1ng/L with PFOS at 7.6ng

  2. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... alkyl esters (generic name). 721.1875 Section 721.1875 Protection of Environment ENVIRONMENTAL... esters (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  3. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... alkyl esters (generic name). 721.1875 Section 721.1875 Protection of Environment ENVIRONMENTAL... esters (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  4. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... alkyl esters (generic name). 721.1875 Section 721.1875 Protection of Environment ENVIRONMENTAL... esters (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  5. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... alkyl esters (generic name). 721.1875 Section 721.1875 Protection of Environment ENVIRONMENTAL... esters (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  6. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... alkyl esters (generic name). 721.1875 Section 721.1875 Protection of Environment ENVIRONMENTAL... esters (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  7. PROCESS FOR PRODUCING ALKYL ORTHOPHOSPHORIC ACID EXTRACTANTS

    DOEpatents

    Grinstead, R.R.

    1962-01-23

    A process is given for producing superior alkyl orthophosphoric acid extractants for use in solvent extraction methods to recover and purify various metals such as uranium and vanadium. The process comprises slurrying P/sub 2/O/ sub 5/ in a solvent diluent such as kerosene, benzene, isopropyl ether, and the like. An alipbatic alcohol having from nine to seventeen carbon atoms, and w- hcrein ihc OH group is situated inward of the terminal carbon atoms, is added to the slurry while the reaction temperature is mainiained below 60 deg C. The alcohol is added in the mole ratio of about 2 to l, alcohol to P/sub 2/O/sub 5/. A pyrophosphate reaotion product is formed in the slurry-alcohol mixture. Subsequently, the pyrophosphate reaction product is hydrolyzed with dilute mineral acid to produce the desired alkyl orthophosphoric aeid extractant. The extraetant may then be separated and utilized in metal-recovery, solvent- extraction processes. (AEC)

  8. Ligand-Accelerated ortho-C–H Alkylation of Arylcarboxylic Acids Using Alkyl Boron Reagents

    PubMed Central

    Thuy-Boun, Peter S.; Villa, Giorgio; Dang, Devin; Richardson, Paul; Su, Shun; Yu, Jin-Quan

    2013-01-01

    A protocol for the Pd(II)-catalyzed ortho-C–H alkylation of phenylacetic and benzoic acids using alkylboron reagents is disclosed. Mono-protected amino acid ligands (MPAA) were found to significantly promote reactivity. Both potassium alkyltrifluoroborates and alkylboronic acids were compatible coupling partners. The possibility of a radical alkyl transfer to Pd(II) was also investigated. PMID:24124892

  9. Corrosion abatement in sulfuric acid alkylation unit horizontal contactors

    SciTech Connect

    Schutt, H.U.

    1997-09-01

    The need to increase throughput in alkylation plants has resulted in higher operating temperatures and higher water levels in alkylation acids than projected by design. Combined with higher flow rates, the more severe process environment causes carbon steel to corrode at increased rates. Carbon steel is the main material of construction for horizontal contactors (Stratco reactors). A leak to the atmosphere in the hydraulic end cone of one contactor and the realization that basic corrosion data are not available for high throughput process conditions in alkylation units prompted a laboratory study to develop the lacking expertise. Corrosion in alkylation unit horizontal contactors is successfully mitigated by saturating fresh alkylation acid with ferrous sulfate.

  10. PFAAs in fish and other seafood products from Icelandic waters.

    PubMed

    Jörundsdóttir, Hrönn; Halldorsson, Thorhallur I; Gunnlaugsdottir, Helga

    2014-01-01

    Perfluorinatedalkyl acids (PFAAs) are of growing concern due to possible health effects on humans. Exposure assessments indicate that fish consumption is one of the major sources of perfluorooctane sulfonate (PFOS) exposure to humans, one of the major PFASs, whereas concerns of overestimation of this exposure source have been raised. Therefore, PFAAs concentrations in fish from the North Atlantic (Icelandic fishing grounds) in the flesh of different fish species were investigated along with more detailed analyses of tissue concentrations in cod (Gadus morhua) and lumpfish (Cyclopterus lumpus). Further, fish feed was investigated as a possible source of PFAAs in aquaculture by examining fish meal as feed ingredient. No PFAAs were detected in the edible part of all fish samples, except for PFOS in pollock (Pollachius virens, 0,05 ng/g wet weight). PFOS was the only PFAA detected in the fish meal samples with the exception of PFOSA in blue whiting (Micromesistius poutassou) meal (0,45 ng/g dry weight (d.w.)), where the PFOS concentration was 1,3-13 ng/g d.w. in the capelin (Mallotus villosus) and mackerel (Scomber scombrus) meal samples. The conclusions of the study are that fish commonly consumed from the Icelandic fishing grounds are unlikely to be an important source of PFAAs exposure.

  11. An overview of the properties of fatty acid alkyl esters

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Fatty acid alkyl esters of plant oils, especially in the form of methyl esters, have numerous applications with fuel use having received the most attention in recent times due to the potential high volume. Various properties imparted by neat fatty acid alkyl esters have been shown to influence fuel ...

  12. Deaminative and decarboxylative catalytic alkylation of amino acids with ketones.

    PubMed

    Kalutharage, Nishantha; Yi, Chae S

    2013-12-16

    It cuts two ways: The cationic [Ru-H] complex catalyzes selective coupling of α- and β-amino acids with ketones to form α-alkylated ketone products. The reaction involves CC and CN bond cleavage which result in regio- and stereoselective alkylation using amino acids. A broad substrate scope and high functional-group tolerance is demonstrated.

  13. Corrosion abatement in sulfuric acid alkylation unit horizontal contactors

    SciTech Connect

    Schutt, H.U.

    1999-03-01

    A leak to the atmosphere in the hydraulic end cone of a horizontal contactor and the realization that basic corrosion data are not available for high-throughput process conditions in alkylation units prompted a laboratory study to develop the lacking expertise. Corrosion in the horizontal contractor of an alkylation unit was mitigated successfully by saturating fresh alkylation acid with ferrous sulfate (FeSO{sub 4}).

  14. Comparative description of PFAA developmental toxicity: An update

    EPA Science Inventory

    The perfluoroalkyl acids (PFAAs) are a family of fluorocarbons consisting of a perfluorinated carbon tail (typically 4-12 carbons in length) and an acidic functional moiety, usually carboxylate or sulfonate. These compounds have excellent surface tension reducing properties and h...

  15. Benefits of the stirred, autorefrigerated reactor in sulfuric acid alkylation

    SciTech Connect

    Ackerman, S.; Lerner, H.; Zaczepinski, S.

    1996-12-01

    Alkylation is a process which combines propylenes, butylenes, and pentylenes with isobutane in the presence of an acid catalyst (H{sub 2}SO{sub 4} or HF) to produce a premium quality gasoline blendstock. The alkylation process was developed in the late 1930`s and processing capacity grew tremendously during World War II in response to demand for aviation gasoline. Since that time, alkylation capacity has steadily grown to supply an important motor gasoline component. Now, more than 50 years later, alkylation is in the spotlight again for reformulated gasoline. Alkylate is a high octane, low sensitivity, low RVP, totally paraffinic material which represents the ideal blendstock for modern gasoline manufacture. Two types of modern reactor systems are currently offered for license to the refining industry for sulfuric acid alkylation. These are the stirred, autorefrigerated system offered by Exxon Research and Engineering (ERE) and the indirect, or effluent refrigerated system offered by others. By means of a case study example, this paper discusses the autorefrigerated reaction system and its benefits.

  16. DETERMINING A ROBUST D-OPTIMAL DESIGN FOR TESTING FOR DEPARTURE FROM ADDITIVITY IN A MIXTURE OF FOUR PFAAS

    EPA Science Inventory

    Our objective was to determine an optimal experimental design for a mixture of perfluoroalkyl acids (PFAAs) that is robust to the assumption of additivity. Of particular focus to this research project is whether an environmentally relevant mixture of four PFAAs with long half-liv...

  17. Activation of mouse and human peroxisome proliferator-activated receptor-alpha (PPARα) by perfluoroalkyl acids (PFAAs) of 5, 7, 8, 11, and 12 carbon chain lengths in C05-1 cells.

    EPA Science Inventory

    PFAAs are surfactants that have been found globally in the environment and in tissues of humans and wildlife. They adversely affect perinatal survival and development in rodents and PPARα is involved in inducing these effects. Our previous study demonstrated that some PFAAs activ...

  18. 40 CFR 721.6475 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkyl polycarboxylic acids, esters... Significant New Uses for Specific Chemical Substances § 721.6475 Alkyl polycarboxylic acids, esters with... chemical substances identified generically as alkyl polycarboxylic acids, esters with ethoxylated...

  19. 40 CFR 721.6475 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl polycarboxylic acids, esters... Significant New Uses for Specific Chemical Substances § 721.6475 Alkyl polycarboxylic acids, esters with... chemical substances identified generically as alkyl polycarboxylic acids, esters with ethoxylated...

  20. 40 CFR 721.6475 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkyl polycarboxylic acids, esters... Significant New Uses for Specific Chemical Substances § 721.6475 Alkyl polycarboxylic acids, esters with... chemical substances identified generically as alkyl polycarboxylic acids, esters with ethoxylated...

  1. 40 CFR 721.10437 - Sulfonic acid, linear xylene alkylate, mono, sodium salts (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Sulfonic acid, linear xylene alkylate... Significant New Uses for Specific Chemical Substances § 721.10437 Sulfonic acid, linear xylene alkylate, mono... chemical substances identified generically as sulfonic acid, linear xylene alkylate, mono, sodium...

  2. 40 CFR 721.10437 - Sulfonic acid, linear xylene alkylate, mono, sodium salts (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Sulfonic acid, linear xylene alkylate... Significant New Uses for Specific Chemical Substances § 721.10437 Sulfonic acid, linear xylene alkylate, mono... chemical substances identified generically as sulfonic acid, linear xylene alkylate, mono, sodium...

  3. Synthesis of Alkyl Methylphosphonic Acid Esters

    SciTech Connect

    Mong, Gary M.; Harvey, Scott D.; Campbell, James A.

    2005-08-01

    This manuscript describes a simple synthesis and purification of cyclohexyl methylphosphonic and isopropyl methylphosphonic acids that provides high purity (>95% purity) product in gram quantities. Based on needs for improved analytical methods for indirect detection of nerve agent use, there is an increasing demand for these nerve agent hydrolysis products. These products are not commercially available. Synthesis is based on reaction of equimolar amounts of alcohol with methylphosphonic dichloride in toluene followed by the addition of excess water (two mole equivalents). The product was then extracted from the resulting aqueous layer into chloroform. The extraction scheme proved highly effective in removing unreacted starting materials and reaction by-products.

  4. The Effect of Supercritical Fluids on Solid Acid Catalyst Alkylation

    SciTech Connect

    Ginosar, Daniel Michael; Thompson, David Neil; Burch, Kyle Coates; Zalewski, D. J.

    2002-05-01

    The alkylation of isobutane with trans-2-butene was explored over six solid acid catalysts in the liquid, near-critical liquid, and supercritical regions through the addition of an inert cosolvent to the reaction feed mixture. The addition of supercritical cosolvents did not result in sustained catalytic alkylation activity. A modest improvement in product yield was obtained with the addition of methane in the modified-liquid region; however, catalyst longevity and product selectivity were decreased compared to cosolvent-free liquid conditions. This paper describes the catalyst screening and selection process, an exploration of catalyst performance with varying concentrations of methane, and an examination of the effects of seven supercritical fluids on catalyst performance. The catalysts included two zeolites, two sulfated metal oxides, and two Nafion catalysts. Three hydrocarbons, two fluorocarbons, carbon dioxide, and sulfur hexafluoride were explored as inert cosolvents added to the reaction mixture.

  5. 40 CFR 721.10664 - Alkenedioic acid dialkyl ester, reaction products with alkenoic acid alkyl esters and diamine...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkenedioic acid dialkyl ester, reaction products with alkenoic acid alkyl esters and diamine (generic). 721.10664 Section 721.10664... Alkenedioic acid dialkyl ester, reaction products with alkenoic acid alkyl esters and diamine (generic)....

  6. 40 CFR 721.10664 - Alkenedioic acid dialkyl ester, reaction products with alkenoic acid alkyl esters and diamine...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkenedioic acid dialkyl ester, reaction products with alkenoic acid alkyl esters and diamine (generic). 721.10664 Section 721.10664... Alkenedioic acid dialkyl ester, reaction products with alkenoic acid alkyl esters and diamine (generic)....

  7. Solid-acid alkylation process development is at a crucial stage

    SciTech Connect

    Rao, P.; Vatcha, S.R.

    1996-09-09

    The refining industry is seeking more environmentally acceptable and economical methods of producing reformulated gasoline (RFG). Alkylate, the cleanest gasoline-blending stream produced in a refinery, is a prime blend stock for RFG production. Alkylation with solid acid catalysts has potential environmental and safety advantages over conventional liquid-acid alkylation. This is especially true for the HF alkylation process. Difficult technical challenges must be overcome in the next few years to achieve a commercially successful solid-acid alylation process. Substantial innovations in catalysts, catalyst regeneration, reactor design, and product separation will be required for solid catalyst processes to replace the incumbent processes, which are being improved continually. The paper discusses background, HF alkylation, H{sub 2}SO{sub 4} alkylation, solid-acid catalysts, reaction mechanism, activity and selectivity, feedstock effects, catalyst life, resistance to poisons, reactors and processes, business issues, and R and D guidelines.

  8. 40 CFR 721.6477 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... with ethoxylated fatty alcohols, reaction products with maleic anhydride. 721.6477 Section 721.6477... Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic... identified generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols,...

  9. 40 CFR 721.6477 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... with ethoxylated fatty alcohols, reaction products with maleic anhydride. 721.6477 Section 721.6477... Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic... identified generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols,...

  10. 40 CFR 721.6477 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... with ethoxylated fatty alcohols, reaction products with maleic anhydride. 721.6477 Section 721.6477... Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic... identified generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols,...

  11. 40 CFR 721.6477 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... with ethoxylated fatty alcohols, reaction products with maleic anhydride. 721.6477 Section 721.6477... Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic... identified generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols,...

  12. 40 CFR 721.6477 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... with ethoxylated fatty alcohols, reaction products with maleic anhydride. 721.6477 Section 721.6477... Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic... identified generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols,...

  13. 40 CFR 721.10126 - Alkyl amino substituted triazine amino substituted benezenesulfonic acid reaction product with...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl amino substituted triazine...

  14. 40 CFR 721.10126 - Alkyl amino substituted triazine amino substituted benezenesulfonic acid reaction product with...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkyl amino substituted triazine...

  15. 40 CFR 721.10126 - Alkyl amino substituted triazine amino substituted benezenesulfonic acid reaction product with...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkyl amino substituted triazine...

  16. 40 CFR 721.10126 - Alkyl amino substituted triazine amino substituted benezenesulfonic acid reaction product with...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl amino substituted triazine...

  17. 40 CFR 721.10126 - Alkyl amino substituted triazine amino substituted benezenesulfonic acid reaction product with...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkyl amino substituted triazine...

  18. Boron-Catalyzed N-Alkylation of Amines using Carboxylic Acids.

    PubMed

    Fu, Ming-Chen; Shang, Rui; Cheng, Wan-Min; Fu, Yao

    2015-07-27

    A boron-based catalyst was found to catalyze the straightforward alkylation of amines with readily available carboxylic acids in the presence of silane as the reducing agent. Various types of primary and secondary amines can be smoothly alkylated with good selectivity and good functional-group compatibility. This metal-free amine alkylation was successfully applied to the synthesis of three commercial medicinal compounds, Butenafine, Cinacalcet. and Piribedil, in a one-pot manner without using any metal catalysts.

  19. 75 FR 50926 - 2-propenoic acid, 2-methyl-, C12-16-alkyl esters, telomers with 1-dodecanethiol, polyethylene...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-08-18

    ... AGENCY 40 CFR Part 180 2-propenoic acid, 2-methyl-, C12-16-alkyl esters, telomers with 1-dodecanethiol... tolerance for residues of 2-propenoic acid, 2-methyl-, C12-16- alkyl esters, telomers with 1-dodecanethiol... residues of 2-propenoic acid, 2-methyl-, C12-16-alkyl esters, telomers with 1-dodecanethiol,...

  20. Alkylation by propylene oxide of deoxyribonucleic acid, adenine, guanosine and deoxyguanylic acid

    PubMed Central

    Lawley, P. D.; Jarman, M.

    1972-01-01

    1. Propylene oxide reacts with DNA in aqueous buffer solution at about neutral pH to yield two principal products, identified as 7-(2-hydroxypropyl)guanine and 3-(2-hydroxypropyl)adenine, which hydrolyse out of the alkylated DNA at neutral pH values at 37°C. 2. These products were obtained in quantity by reactions between propylene oxide and guanosine or adenine respectively. 3. The reactions between propylene oxide and adenine in acetic acid were parallel to those between dimethyl sulphate and adenine in neutral aqueous solution; the alkylated positions in adenine in order of decreasing reactivity were N-3, N-1 and N-9. A method for separating these alkyladenines is described. 4. Deoxyguanylic acid sodium salt was alkylated at N-7 by propylene oxide in neutral aqueous solution. 5. The nature of the side chain in the principal alkylation products was established by mass spectrometry, and the nature of the products is consistent with their formation by the bimolecular reaction mechanism. PMID:5073240

  1. Fatty acid alkyl esters: perspectives for production of alternative biofuels.

    PubMed

    Röttig, Annika; Wenning, Leonie; Bröker, Daniel; Steinbüchel, Alexander

    2010-02-01

    The global economy heads for a severe energy crisis: whereas the energy demand is going to rise, easily accessible sources of crude oil are expected to be depleted in only 10-20 years. Since a serious decline of oil supply and an associated collapse of the economy might be reality very soon, alternative energies and also biofuels that replace fossil fuels must be established. In addition, these alternatives should not further impair the environment and climate. About 90% of the biofuel market is currently captured by bioethanol and biodiesel. Biodiesel is composed of fatty acid alkyl esters (FAAE) and can be synthesized by chemical, enzymatic, or in vivo catalysis mainly from renewable resources. Biodiesel is already established as it is compatible with the existing fuel infrastructure, non-toxic, and has superior combustion characteristics than fossil diesel; and in 2008, the global production was 12.2 million tons. The biotechnological production of FAAE from low cost and abundant feedstocks like biomass will enable an appreciable substitution of petroleum diesel. To overcome high costs for immobilized enzymes, the in vivo synthesis of FAAE using bacteria represents a promising approach. This article points to the potential of different FAAE as alternative biofuels, e.g., by comparing their fuel properties. In addition to conventional production processes, this review presents natural and genetically engineered biological systems capable of in vivo FAAE synthesis.

  2. Diarmed (adamantyl/alkyl) surfactants from nitrilotriacetic acid.

    PubMed

    Trillo, Juan V; Vázquez Tato, José; Jover, Aida; de Frutos, Santiago; Soto, Victor H; Galantini, Luciano; Meijide, Francisco

    2014-11-01

    The compounds presented here constitute a clear example of molecular biomimetics as their design is inspired on the structure and properties of natural phospholipids. Thus novel double-armed surfactants have been obtained in which nitrilotriacetic acid plays the role of glycerol in phospholipids. The hydrophobic arms are linked to the head group through amide bonds (which is also the case of sphingomyelin): (R1NHCOCH2)(R2NHCOCH2)NCH2CO2H (R1 being CH3(CH2)11, CH3(CH2)17, CH3(CH2)7CHCH(CH2)8, and adamantyl, and R2=adamantyl). The dependence of the surface tension with concentration shows the typical profile of surfactants since a breaking point, which corresponds to the critical aggregation concentration (cac), is observed in all cases. The cac of these diarmed derivatives are about 1-3 orders of magnitude lower than those of classical monoalkyl derivatives used as reference compounds. In contrast to conventional surfactants, reversed trends in cac values and molecular areas at the solution-air interface have been observed. This anomalous behavior is tied to the structure of the surfactants and suggests that long and flexible alkyl chains should self-coil previous to the aggregation or adsorption phenomena. Above cac all compounds form large aggregates, globular in shape, which tend to associate forming giant aggregates.

  3. Metal salts of alkyl catechol dithiophosphoric acids and oil compositions containing the salts

    SciTech Connect

    Yamaguchi, E.S.; Liston, T.V.

    1988-03-08

    Metal salts of alkyl catechol esters of dithiophosphoric acid suitable as additives in oil compositions are disclosed in this patent. Oil compositions containing the salts of such esters show improved extreme pressure/anti-wear and anit-oxidant properties.

  4. Comparative Oxidative Stability of Fatty Acid Alkyl Esters by Accelerated Methods

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Several fatty acid alkyl esters were subjected to accelerated methods of oxidation, including EN 14112 (Rancimat method) and pressurized differential scanning calorimetry (PDSC). Structural trends elucidated from both methods that improved oxidative stability included decreasing the number of doubl...

  5. Oligonucleoside alkyl or arylphosphonate derivatives capable of crosslinking with or cleaving nucleic acids

    DOEpatents

    Miller, Paul S.; Ts'o, Paul O.P.

    1999-06-15

    A composition for inactivating a target nucleic acid which comprises an oligonucleoside alkyl or arylphosphonate analogue which is complementary to the sequence of the target nucleic acid and includes a functional group which reacts with the target nucleic acid to render the target nucleic acid inactive or nonfunctional.

  6. Oligonucleoside alkyl or arylphosphonate derivatives capable of crosslinking with or cleaving nucleic acids

    DOEpatents

    Miller, P.S.; Ts'o, P.O.P.

    1999-06-15

    A composition for inactivating a target nucleic acid which comprises an oligonucleoside alkyl or arylphosphonate analogue which is complementary to the sequence of the target nucleic acid is provided. It includes a functional group which reacts with the target nucleic acid to render the target nucleic acid inactive or nonfunctional. 16 figs.

  7. Isolation and identification of products from alkylation of nucleic acids: ethyl- and isopropyl-purines.

    PubMed Central

    Lawley, P D; Orr, D J; Jarman, M

    1975-01-01

    Ethylation and isopropylation of guanine in alkaline solution, or of adenine in formic acid, by alkyl methanesulphonates gave the following products: 1-, N2-, 3-, O6-, 7- and 9-alkylguanines; 1-, 3-, 7- and 9-alkyladenines. The products were identified from their characteristic u.v-absorption spectra, by comparison with either known ethyladenines or with the corresponding known methyladenines, and were also characterized by mass spectrometry. Their chromatographic properties on paper, t.l.c. and various columns were determined. DNA was alkylated in neutral solution with 14C-labelled alkyl methanesulphonates and the ratios of the alkylpurines formed were obtained, and compared for alkylation by methyl, ethyl and isopropyl methanesulphonates and by N-methyl-N-nitrosourea. The extents of alkylation at O-6 of guanine relative to those at N-7 of guanine varied with the reactivity of the methylating agents according to the predictions of Swain & Scott (1953) relating nucleophilicity of the groups alkylated with the substrate constants of the alkylating agents. The relative extents of alkylation at N-3 of adenine did not follow this correlation. PMID:172066

  8. Developmental Toxicity of Perfluoroalkyl Acid Mixtures in CD-1 Mice

    EPA Science Inventory

    Perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS) and perfluorononanoic acid (PFNA) belong to a family of fluoro-organic compounds known as perfluoroalkyl acids (PFAAs). PFAAs have been widely used in industrial and commercial applications, and have been found to be...

  9. Alkylation of phenol with polybutenes in the presence of benzenesulfonic acid

    SciTech Connect

    Belov, P.S.; Gulyaev, I.A.; Korenev, K.D.; Yakovlev, V.B.; Zakupra, V.A.

    1982-09-01

    The purpose of this work is to test benzenesulfonic acid (BSA) as a catalyst in the alkylation of phenol with polyisobutylene (PIB). This material is used as a catalyst in the production of technical C/sub 5/-C/sub 12/ tert-alkylphenol. Finds that the optimal compromise between acceleration of the reaction and the alkylate viscosity increase that limits the reaction rate is achieved at a temperature of about 105 C and a BSA/PIB mole ratio of 0.15. Recommends BSA as an effective replacement for boron fluoride, boron fluoride complexes, and other highly corrosive catalysts used in the alkylation of phenol with polybutenes.

  10. 40 CFR 721.10702 - Polyfluorinated alkyl thio polyacrylic acid-acrylamide (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... acid-acrylamide (generic). 721.10702 Section 721.10702 Protection of Environment ENVIRONMENTAL...-acrylamide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as polyfluorinated alkyl thio polyacrylic acid-acrylamide (PMN P-11-534)...

  11. Alkyl substituent effects on gas-phase acidities - The influence of hybridization.

    NASA Technical Reports Server (NTRS)

    Brauman, J. I.; Blair, L. K.

    1971-01-01

    Exploration of the effect on acidity of alkyl groups bonded to trigonal and digonal carbon. Some results on the relative acidities of toluene and p-xylene, and acetylene and substitute acetylenes, as determined by ion cyclotron resonance (icr) spectroscopy, are described. Some limitations of the CNDO/2 calculation method are discussed.

  12. Process for recovering uranium using an alkyl pyrophosphoric acid and alkaline stripping solution

    SciTech Connect

    Worthington, R.E.; Magdics, A.

    1987-03-24

    A process is described for stripping uranium from a pregnant organic extractant comprising an alkyl pyrophosphoric acid dissolved in a substantially water-immiscible organic diluent. The organic extractant contains tetravalent uranium and an alcohol or phenol modifier in a quantity sufficient to retain substantially all the unhydrolyzed alkyl pyrophosphoric acid in solution in the diluent during stripping. The process comprises adding an oxidizing agent to the organic extractant to and thereby oxidizing the tetravalent uranium to the +6 state in the organic extractant, and contacting the organic extractant containing the uranium in the +6 state with a stripping solution comprising an aqueous solution of an alkali metal or ammonium carbonate, nonsaturated in uranium. The uranium is stripped from, the organic extractant into the stripping solution, and the resulting barren organic extractant containing substantially all of the unhydrolyzed alkyl pyrophosphoric acid dissolved in the diluent is separated from the stripping solution containing the stripped uranium, the barren extractant being suitable for recycle.

  13. Process for recovering uranium using an alkyl pyrophosphoric acid and alkaline stripping solution

    SciTech Connect

    Worthington, R.E.; Magdics, A.

    1987-03-24

    A process is described for stripping uranium for a pregnant organic extractant comprising an alkyl pyrophosphoric acid dissolved in a substantially water-immiscible organic diluent. The organic extractant contains tetravalent uranium and an alcohol or phenol modifier in a quantity sufficient to retain substantially all the unhydrolyzed alkyl pyrophosphoric acid in solution in the diluent during stripping. The process comprises adding an oxidizing agent to the organic extractant and thereby oxidizing the tetravalent uranium to the +6 state in the organic extractant, and contacting the organic extractant containing the uranium in the +6 state with a stripping solution comprising an aqueous solution of an alkali metal or ammonium carbonate or hydroxide thereby stripping uranium from the organic extractant into the stripping solution. The resulting barren organic extractant containing substantially all of the unhydrolyzed alkyl pyrophosphoric acid dissolved in the diluent is separated from the stripping solution containing the stripped uranium, the barren extractant being suitable for recycle.

  14. Enhanced Synthesis of Alkyl Amino Acids in Miller's 1958 H2S Experiment

    NASA Technical Reports Server (NTRS)

    Parker, Eric T.; Cleaves, H. James; Callahan, Michael P.; Dworkin, James P.; Glavin, Daniel P.; Lazcano, Antonio; Bada, Jeffrey L.

    2011-01-01

    Stanley Miller's 1958 H2S-containing experiment, which included a simulated prebiotic atmosphere of methane (CH4), ammonia (NH3), carbon dioxide (CO2), and hydrogen sulfide (H2S) produced several alkyl amino acids, including the alpha-, beta-, and gamma-isomers of aminobutyric acid (ABA) in greater relative yields than had previously been reported from his spark discharge experiments. In the presence of H2S, aspariic and glutamic acids could yield alkyl amino acids via the formation of thioimide intermediates. Radical chemistry initiated by passing H2S through a spark discharge could have also enhanced alkyl amino acid synthesis by generating alkyl radicals that can help form the aldehyde and ketone precursors to these amino acids. We propose mechanisms that may have influenced the synthesis of certain amino acids in localized environments rich in H2S and lightning discharges, similar to conditions near volcanic systems on the early Earth, thus contributing to the prebiotic chemical inventory of the primordial Earth.

  15. Reductive alkylation and sequential reductive alkylation-click chemistry for on-solid-support modification of pyrrolidinyl peptide nucleic acid.

    PubMed

    Ditmangklo, Boonsong; Boonlua, Chalothorn; Suparpprom, Chaturong; Vilaivan, Tirayut

    2013-04-17

    A methodology for the site-specific attachment of fluorophores to the backbone of pyrrolidinyl peptide nucleic acids (PNAs) with an α/β-backbone derived from D-prolyl-(1S,2S)-2-aminocyclopentanecarboxylic acid (acpcPNA) has been developed. The strategy involves a postsynthetic reductive alkylation of the aldehyde-containing labels onto the acpcPNA that was previously modified with (3R,4S)-3-aminopyrrolidine-4-carboxylic acid on the solid support. The reductive alkylation reaction is remarkably efficient and compatible with a range of reactive functional groups including Fmoc-protected amino, azide, and alkynes. This allows further attachment of readily accessible carboxyl-, alkyne-, or azide-containing labels via amide bond formation or Cu-catalyzed azide-alkyne cycloaddition (CuAAC, also known as click chemistry). The label attached in this way does not negatively affect the affinity and specificity of the pairing of the acpcPNA to its DNA target. Applications of this methodology in creating self-reporting pyrene- and thiazole orange-labeled acpcPNA probes that can yield a change in fluorescence in response to the presence of the correct DNA target have also been explored. A strong fluorescence enhancement was observed with thiazole orange-labeled acpcPNA in the presence of DNA. The specificity could be further improved by enzymatic digestion with S1 nuclease, providing a 9- to 60-fold fluorescence enhancement with fully complementary DNA and a less than 3.5-fold enhancement with mismatched DNA targets.

  16. Synthesis of Functionalized Dialkyl Ketones From Carboxylic Acid Derivatives and Alkyl Halides

    PubMed Central

    Wotal, Alexander C.; Weix, Daniel J.

    2012-01-01

    Unsymmetrical dialkyl ketones can be directly prepared by the nickel-catalyzed reductive coupling of carboxylic acid chlorides or (2-pyridyl)thioesters with alkyl iodides or benzylic chlorides. A wide variety of functional groups are tolerated by this process, including common nitrogen protecting groups and C-B bonds. Even hindered ketones flanked by tertiary and secondary centers can be formed. The mechanism is proposed to involve the reaction of a (L)Ni(alkyl)2 intermediate with the carboxylic acid derivative. PMID:22360350

  17. Safety assessment of xylene sulfonic acid, toluene sulfonic acid, and alkyl aryl sulfonate hydrotropes as used in cosmetics.

    PubMed

    Bergfeld, Wilma F; Belsito, Donald V; Klaassen, Curtis D; Hill, Ronald; Liebler, Daniel; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan

    2011-12-01

    Xylene sulfonic acid, toluene sulfonic acid, and alkyl aryl sulfonate hydrotropes used in cosmetics as surfactants, hydrotropes, were reviewed in this safety assessment. The similar structure, properties, functions, and uses of these ingredients enabled grouping them and using the available toxicological data to assess the safety of the entire group. The Cosmetic Ingredient Review Expert Panel reviewed relevant animal and human data related to these ingredients. The panel concluded that xylene sulfonic acid and alkyl aryl sulfonate hydrotropes are safe as cosmetic ingredients in the present practices of use and concentrations as described in this safety assessment, when formulated to be nonirritating.

  18. 40 CFR 721.3130 - Sulfuric acid, mono-C9-11-alkyl esters, sodium salts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Sulfuric acid, mono-C9-11-alkyl esters... Specific Chemical Substances § 721.3130 Sulfuric acid, mono-C9-11-alkyl esters, sodium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as...

  19. 40 CFR 721.3130 - Sulfuric acid, mono-C9-11-alkyl esters, sodium salts.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Sulfuric acid, mono-C9-11-alkyl esters... Specific Chemical Substances § 721.3130 Sulfuric acid, mono-C9-11-alkyl esters, sodium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as...

  20. 40 CFR 721.3130 - Sulfuric acid, mono-C9-11-alkyl esters, sodium salts.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Sulfuric acid, mono-C9-11-alkyl esters... Specific Chemical Substances § 721.3130 Sulfuric acid, mono-C9-11-alkyl esters, sodium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as...

  1. 40 CFR 721.3130 - Sulfuric acid, mono-C9-11-alkyl esters, sodium salts.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Sulfuric acid, mono-C9-11-alkyl esters... Specific Chemical Substances § 721.3130 Sulfuric acid, mono-C9-11-alkyl esters, sodium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as...

  2. 40 CFR 721.3130 - Sulfuric acid, mono-C9-11-alkyl esters, sodium salts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Sulfuric acid, mono-C9-11-alkyl esters... Specific Chemical Substances § 721.3130 Sulfuric acid, mono-C9-11-alkyl esters, sodium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as...

  3. Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases; Part 1: alkyl halide alkylations.

    PubMed

    Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim A

    2013-10-01

    Alkylations of chiral or achiral Ni(II) complexes of glycine Schiff bases constitute a landmark in the development of practical methodology for asymmetric synthesis of α-amino acids. Straightforward, easy preparation as well as high reactivity of these Ni(II) complexes render them ready available and inexpensive glycine equivalents for preparing a wide variety of α-amino acids, in particular on a relatively large scale. In the case of Ni(II) complexes containing benzylproline moiety as a chiral auxiliary, their alkylation proceeds with high thermodynamically controlled diastereoselectivity. Similar type of Ni(II) complexes derived from alanine can also be used for alkylation providing convenient access to quaternary, α,α-disubstituted α-amino acids. Achiral type of Ni(II) complexes can be prepared from picolinic acid or via recently developed modular approach using simple secondary or primary amines. These Ni(II) complexes can be easily mono/bis-alkylated under homogeneous or phase-transfer catalysis conditions. Origin of diastereo-/enantioselectivity in the alkylations reactions, aspects of practicality, generality and limitations of this methodology is critically discussed.

  4. DNA-damaging disinfection byproducts: alkylation mechanism of mutagenic mucohalic acids.

    PubMed

    Gómez-Bombarelli, Rafael; González-Pérez, Marina; Arenas-Valgañón, Jorge; Céspedes-Camacho, Isaac Fabián; Calle, Emilio; Casado, Julio

    2011-10-15

    Hydroxyhalofuranones form a group of genotoxic disinfection byproduct (DBP) of increasing interest. Among them, mucohalic acids (3,4-dihalo-5-hydroxyfuran-2(5H)-one, MXA) are known mutagens that react with nucleotides, affording etheno, oxaloetheno, and halopropenal derivatives. Mucohalic acids have also found use in organic synthesis due to their high functionalization. In this work, the alkylation kinetics of mucochloric and mucobromic acids with model nucleophiles aniline and NBP has been studied experimentally. Also, the alkylation mechanism of nucleosides by MXA has been studied in silico. The results described allow us to reach the following conclusions: (i) based on the kinetic and computational evidence obtained, a reaction mechanism was proposed, in which MXA react directly with amino groups in nucleotides, preferentially attacking the exocyclic amino groups over the endocyclic aromatic nitrogen atoms; (ii) the suggested mechanism is in agreement with both the product distribution observed experimentally and the mutational pattern of MXA; (iii) the limiting step in the alkylation reaction is addition to the carbonyl group, subsequent steps occurring rapidly; and (iv) mucoxyhalic acids, the hydrolysis products of MXA, play no role in the alkylation reaction by MXA.

  5. 40 CFR 721.6475 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... with ethoxylated fatty alcohols. 721.6475 Section 721.6475 Protection of Environment ENVIRONMENTAL... ethoxylated fatty alcohols. (a) Chemical substance and significant new uses subject to reporting. (1) The... generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols (PMN...

  6. 40 CFR 721.6475 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... with ethoxylated fatty alcohols. 721.6475 Section 721.6475 Protection of Environment ENVIRONMENTAL... ethoxylated fatty alcohols. (a) Chemical substance and significant new uses subject to reporting. (1) The... generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols (PMN...

  7. Friedel-crafts alkylation of benzene by normal omega-chloroalkanoic acids and their methyl esters and nitriles

    SciTech Connect

    Zakharkin, L.I.; Anikina, E.V.

    1987-08-20

    In the Friedel-Crafts alkylation of benzene by normal 1-haloalkanes with three or more carbon atoms a mixture of phenylalkanes forms, due to isomerization of the alkyl chain and migration of a hydrogen atoms. Under analogous conditions the alkylation of benzene by omega-chloroalkanoic acids, Cl(CH/sub 2/)/sub n/COOH, and omega-bromoalkanonitriles proceeds with isomerization of the alkyl chain, but beginning only with 6-chlorohexanoic acid and 6-bromohexanonitrile. Such a difference in the behavior of these halogen derivatives has not received a convincing explanation, although the mechanism of Friedel-Crafts alkylation of benzene should be the same in the two cases. For a better understanding of this difference, this work presents a systematic study of benzene alkylation by 4-chlorobutyric, 5-chlorovaleric, 6-chlorohexanoic, and 7-chloroheptanoic acids and their methyl esters and nitriles, and by ..gamma..-butyro- and delta-valerolactones. The catalyst was crystalline AlCl/sub 3/ twice sublimed from Mg. For comparison, alkylation with the respective 1-chloroalkanes was carried out. In the alkylation of benzene by omega-chloroalkanoic acids Cl(CH/sub 2/)/sub n/COOH (where n = 3-6) and their methyl esters and nitriles, in the presence of AlCl/sub 3/, the degree of isomerization of the alkyl chain is less than with the corresponding 1-chloroalkanes, depending on the increase in electron acceptor activity in the sequence HOOC- > CH/sub 3/OCO- > CN-.

  8. An organocatalytic domino Michael-alkylation reaction: highly enantioselective construction of spiro-cyclopentanoneoxindoles and tetronic acid scaffolds.

    PubMed

    Zhou, Jing; Wang, Qi-Lin; Peng, Lin; Tian, Fang; Xu, Xiao-Ying; Wang, Li-Xin

    2014-12-04

    A new organocatalytic asymmetric domino Michael-alkylation reaction of methyleneindolinones and γ-halogenated-β-ketoesters is described. A variety of spiro-cyclopentanoneoxindoles were obtained in high yields (up to 96%), good diastereoselectivities (up to 12 : 1 dr) and excellent enantioselectivities (up to >99% ee) via α-alkylation. Interestingly, O-alkylated products with tetronic acid motifs could be obtained by tuning the N-protecting groups on methyleneindolinones with excellent enantioselectivities (up to >99% ee).

  9. V-shaped crystalline structures of di-n-alkyl esters of phosphoric acid.

    PubMed

    Thünemann, Andreas F; Kurth, Dirk G; Beinhoff, Matthias; Bienert, Ralf; Schulz, Burkhard

    2006-06-20

    We prepared crystals of di-n-alkyl esters of phosphoric acid with chain lengths of n = 10, 12, 14, 16, and 18. These were characterized by single-crystal X-ray analysis and differential scanning calorimetry (DSC). It was found that the alkyl chains are in an extended all-trans conformation and aligned close to perpendicular, forming V-shaped molecules. This is in strong contrast to the typical arrangement of the alkyl chains of phospholipids where the two alkyl chains are arranged parallel in the same direction (e.g., tuning fork configuration in bilayers). Additionally, it was found that the arrangement of the V-shaped molecules of the di-n-alkyl esters in neighboring stacks of the lamellar crystals is antiparallel for short chain lengths (n = 10 and 12) and parallel for the longer (n = 14 and 16). DSC reveals that the melting of the crystals increases systematically with increasing chain lengths from 48 to 82 degrees C. The contribution of each methylene group to the melting enthalpy (70-133 kJ/mol) is independent of the chain length (3.9 kJ per mol CH2).

  10. 40 CFR 721.9220 - Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... amines with a substituted benzenesulfonic acid and sulfuric acid (generic name). 721.9220 Section 721... Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric acid... benzenesulfonic acid and sulfuric acid (PMNs P-89-703, P-89-755, and P-89-756) are subject to reporting under...

  11. 40 CFR 721.9220 - Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... amines with a substituted benzenesulfonic acid and sulfuric acid (generic name). 721.9220 Section 721... Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric acid... benzenesulfonic acid and sulfuric acid (PMNs P-89-703, P-89-755, and P-89-756) are subject to reporting under...

  12. 40 CFR 721.9220 - Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... amines with a substituted benzenesulfonic acid and sulfuric acid (generic name). 721.9220 Section 721... Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric acid... benzenesulfonic acid and sulfuric acid (PMNs P-89-703, P-89-755, and P-89-756) are subject to reporting under...

  13. 40 CFR 721.9220 - Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... amines with a substituted benzenesulfonic acid and sulfuric acid (generic name). 721.9220 Section 721... Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric acid... benzenesulfonic acid and sulfuric acid (PMNs P-89-703, P-89-755, and P-89-756) are subject to reporting under...

  14. 40 CFR 721.9220 - Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... amines with a substituted benzenesulfonic acid and sulfuric acid (generic name). 721.9220 Section 721... Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric acid... benzenesulfonic acid and sulfuric acid (PMNs P-89-703, P-89-755, and P-89-756) are subject to reporting under...

  15. Formulation of ascorbic acid microemulsions with alkyl polyglycosides.

    PubMed

    Pakpayat, N; Nielloud, F; Fortuné, R; Tourne-Peteilh, C; Villarreal, A; Grillo, I; Bataille, B

    2009-06-01

    Ascorbic acid microemulsions for topical application were developed. In this study, microemulsions were prepared using HLD (hydrophilic lipophilic deviation) concept to optimise the formulation. From this optimal formulation, the realisation of dilution ternary diagrams leads to obtain microemulsion zones. In addition, the effects of composition variable on the physicochemical characteristics of each system were investigated. After optimisation of the microemulsion systems, ascorbic acid was loaded in the formulations. Surface tension and small angle neutron scattering were used to characterise the surface properties and the structure of the microemulsions. Bicontinuous structure microemulsions were identified, and the influence of ascorbic acid localisation at the interface leading to modifications of the microemulsion structure was pointed out. The solubilisation of ascorbic acid, the stabilisation and in vitro transdermal penetration "Frantz cells" of ascorbic acid microemulsions were studied. Three different microemulsions were envisaged. The results confirmed that these microemulsion systems present a real interest for formulation and protection of ascorbic acid. Regarding their transcutaneous penetration behaviour, the different microemulsions studied could be useful for different topical applications. A major location of ascorbic acid found in the epidermis where the decomposition of melanin occurred indicates that microemulsion could be considered as a suitable carrier system for application of ascorbic acid as a whitening agent. In addition, a good passage of the drug in the dermis could be interesting for the relative oxygen matrix damage.

  16. 40 CFR 721.10108 - Naphthalenedisulfonic acid, hydrozy-[[[(hydroxyl-disulfo-naphthaleneyl)azo]-alkyl(C=1-5...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...- -alkyl(C=1-5)-(sulfoalkoxy)cyclic]azo]-substituted azo-, metal salt (generic). 721.10108 Section 721.10108 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT... Naphthalenedisulfonic acid, hydrozy- -alkyl(C=1-5)-(sulfoalkoxy)cyclic]azo]-substituted azo-, metal salt (generic)....

  17. 40 CFR 721.10108 - Naphthalenedisulfonic acid, hydrozy-[[[(hydroxyl-disulfo-naphthaleneyl)azo]-alkyl(C=1-5...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...- -alkyl(C=1-5)-(sulfoalkoxy)cyclic]azo]-substituted azo-, metal salt (generic). 721.10108 Section 721.10108 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT... Naphthalenedisulfonic acid, hydrozy- -alkyl(C=1-5)-(sulfoalkoxy)cyclic]azo]-substituted azo-, metal salt (generic)....

  18. 40 CFR 721.10108 - Naphthalenedisulfonic acid, hydrozy-[[[(hydroxyl-disulfo-naphthaleneyl)azo]-alkyl(C=1-5...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...- -alkyl(C=1-5)-(sulfoalkoxy)cyclic]azo]-substituted azo-, metal salt (generic). 721.10108 Section 721.10108 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT... Naphthalenedisulfonic acid, hydrozy- -alkyl(C=1-5)-(sulfoalkoxy)cyclic]azo]-substituted azo-, metal salt (generic)....

  19. Alkyl protocatechuates as novel urinary biomarkers of exposure to p-hydroxybenzoic acid esters (parabens).

    PubMed

    Wang, Lei; Kannan, Kurunthachalam

    2013-09-01

    Human exposure to p-hydroxybenzoic acid esters (parabens) is a concern, owing to adverse health effects of these compounds. Parabens are metabolized and eliminated from the human bodies within a few hours of exposure. In this study, for the first time, methyl- and ethyl-protocatechuates (OH-MeP and OH-EtP) and their parent compounds, methyl- (MeP) and ethyl-parabens (EtP), were determined in urine samples collected from U.S. children and adults. Alkyl protocatechuates were found in almost all urine samples, with median concentrations of 11.8 (OH-MeP) and 2.90ng/mL (OH-EtP) in adults, and 5.43 (OH-MeP) and 0.85ng/mL (OH-EtP) in children. In adults, the concentrations of urinary OH-MeP and OH-EtP were higher than the corresponding concentrations of MeP and EtP. Significant correlation between OH-MeP/OH-EtP and MeP/EtP was observed. This is the first report to document hydroxylation of parabens in humans, and to propose hydroxylated metabolites (i.e., alkyl protocatechuates) as alternative biomarkers of exposure to parabens in human biomonitoring studies. The rates of transformation of parabens between children and adults appeared to be different, as evidenced from the slopes of regression between alkyl protocatechuates and parabens. In addition to alkyl protocatechuates, hydroxybenzoic acid (4-HB) and 3,4-dihydroxybenzoic acid (3,4-DHB) were found at considerable levels in the urine samples. The occurrence of a significant proportion of alkyl protocatechuates and 3,4-DHB suggests the need for inclusion of these derivatives in accurate estimation of human exposure to parabens and in epidemiological studies that associate paraben exposure to health outcomes in populations.

  20. Synthesis of 5-alkylated barbituric acids and 3-alkylated indoles via microwave-assisted three-component reactions in solvent-free conditions using Hantzsch 1,4-dihydropyridines as reducing agents.

    PubMed

    Baruah, Biswajita; Seetham Naidu, P; Borah, Pallabi; Bhuyan, Pulak J

    2012-05-01

    Reaction of barbituric acids with aldehydes and dihydropyridines in one pot under microwave (MW) irradiation in the absence of solvent, affords 55–82% of the 5-benzylated barbituric acids. Use of alkyl nitriles or barbituric acids with indole-3-aldehyde and dihydropyridine (DHP) afforded 3-alkylated indoles in 57–76 % yield. In each case DHPs are converted to pyridines.

  1. Fungicidal Activities of Dihydroferulic Acid Alkyl Ester Analogues

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The natural product dihydroferulic acid (DFA, 1) and the synthesized DFA methyl (4a), ethyl (4b), propyl (4c), hexyl (4d), octyl (4e), and decyl (4f) esters were examined for antifungal activity. Test fungi included Saccharomyces cerevisiae (wild type, and deletion mutants slt2delta and bck1delta), ...

  2. Fungicidal Activities of Dihydroferulic Acid Alkyl Ester Analogs

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The natural product dihydroferulic acid (DFA, 1) and the synthesized DFA methyl (4a), ethyl (4b), propyl (4c), hexyl (4d), octyl (4e), and decyl (4f) esters were examined for antifungal activity. Test fungi included Saccharomyces cerevisiae (wild type, and deletion mutants slt2' and bck1'), Aspergil...

  3. Competing mechanisms for perfluoroalkyl acid accumulation in plants revealed using an Arabidopsis model system.

    PubMed

    Müller, Claudia E; LeFevre, Gregory H; Timofte, Anca E; Hussain, Fatima A; Sattely, Elizabeth S; Luthy, Richard G

    2016-05-01

    Perfluoroalkyl acids (PFAAs) bioaccumulate in plants, presenting a human exposure route if present in irrigation water. Curiously, accumulation of PFAAs in plant tissues is greatest for both the short-chain and long-chain PFAAs, generating a U-shaped relationship with chain length. In the present study, the authors decouple competing mechanisms of PFAA accumulation using a hydroponic model plant system (Arabidopsis thaliana) exposed to a suite of 10 PFAAs to determine uptake, depuration, and translocation kinetics. Rapid saturation of root concentrations occurred for all PFAAs except perfluorobutanoate, the least-sorptive (shortest-chain) PFAA. Shoot concentrations increased continuously, indicating that PFAAs are efficiently transported and accumulate in shoots. Tissue concentrations of PFAAs during depuration rapidly declined in roots but remained constant in shoots, demonstrating irreversibility of the translocation process. Root and shoot concentration factors followed the U-shaped trend with perfluoroalkyl chain length; however, when normalized to dead-tissue sorption, this relationship linearized. The authors therefore introduce a novel term, the "sorption normalized concentration factor," to describe PFAA accumulation in plants; because of their hydrophobicity, sorption is the determining factor for long-chain PFAAs, whereas the shortest-chain PFAAs are most effectively transported in the plant. The present study provides a mechanistic explanation for previously unexplained PFAA accumulation trends in plants and suggests that shorter-chained PFAAs may bioaccumulate more readily in edible portions.

  4. Estrogenic Activity of Perfluoroalkyl Acids in Juvenile Rainbow Trout (Oncorhynchus Mykiss)

    EPA Science Inventory

    The potential estrogenic activity of perfluoroalkyl acids (PFAAs) was determined using separate screening and dose response studies with juvenile rainbow trout (Oncorhynchus mykiss). Results of this study indicate that some PFAAs may act as estrogens in fish.

  5. Ignition Delays of Alkyl Thiophosphites with White and Red Fuming Nitric Acids Within Temperature Range 80 to -105 F

    NASA Technical Reports Server (NTRS)

    Miller, Riley O; Ladanyi, Dezso J

    1953-01-01

    Ignition delays of alkyl thiophosphites were obtained in a modified open-cup apparatus and a small-scale rocket engine apparatus. At -40 F, mixed alkyl thiophosphites gave short delays with white fuming nitric acid containing 2 percent water and red fuming nitric acids of widely varying compositions. At -40 F and higher, triethyl trithiophosphite blended with as much as 40 percent n-heptane gave satisfactory self-igniting properties at temperatures as low as -76 F.

  6. Effects of the addition of dimer acid alkyl esters on the properties of ethyl cellulose.

    PubMed

    Lee, Sangjun; Ko, Kwang-Hwan; Shin, Jihoon; Kim, Nam-Kyun; Kim, Young-Wun; Kim, Joon-Seop

    2015-05-05

    In this study, we synthesized dimer acid (DA) esters, having short to long alkyl chains, (DA-Cn) by the Diels-Alder reaction and subsequent esterification reaction of fatty acids that were prepared by the hydrolysis of waste vegetable oil. It was found that the DA-Cn were thermally more stable than common petroleum-based plasticizer DOP. When the DOP, DA, or DA-Cn with short alkyl chains were added to ethyl cellulose (EC), the optical clarity and SEM images of the samples showed their good miscibility with those additives in a micro-scale. It was also found that the rubbery modulus of the EC decreased with increasing amount of additives; the type of the additives did not affect the rates of the decrease in the rubbery modulus. The main transition temperatures of the EC containing either DA or DA-C1 or DA-C4 decreased with increasing amounts of those additives and were comparable to that of the DOP-containing EC. The above findings suggested that the DA and its esters with short alkyl chains could act as effective plasticizer and, thus, could be used instead of the DOP. In addition, the results obtained from tensile testing and leaching experiments implied that the DA might be better plasticizer than the DA-C1 and DA-C4, at least in some cases, because of hydrogen-bonding with the EC.

  7. Metallaphotoredox-catalysed sp3-sp3 cross-coupling of carboxylic acids with alkyl halides

    NASA Astrophysics Data System (ADS)

    Johnston, Craig P.; Smith, Russell T.; Allmendinger, Simon; MacMillan, David W. C.

    2016-08-01

    In the past 50 years, cross-coupling reactions mediated by transition metals have changed the way in which complex organic molecules are synthesized. The predictable and chemoselective nature of these transformations has led to their widespread adoption across many areas of chemical research. However, the construction of a bond between two sp3-hybridized carbon atoms, a fundamental unit of organic chemistry, remains an important yet elusive objective for engineering cross-coupling reactions. In comparison to related procedures with sp2-hybridized species, the development of methods for sp3-sp3 bond formation via transition metal catalysis has been hampered historically by deleterious side-reactions, such as β-hydride elimination with palladium catalysis or the reluctance of alkyl halides to undergo oxidative addition. To address this issue, nickel-catalysed cross-coupling processes can be used to form sp3-sp3 bonds that utilize organometallic nucleophiles and alkyl electrophiles. In particular, the coupling of alkyl halides with pre-generated organozinc, Grignard and organoborane species has been used to furnish diverse molecular structures. However, the manipulations required to produce these activated structures is inefficient, leading to poor step- and atom-economies. Moreover, the operational difficulties associated with making and using these reactive coupling partners, and preserving them through a synthetic sequence, has hindered their widespread adoption. A generically useful sp3-sp3 coupling technology that uses bench-stable, native organic functional groups, without the need for pre-functionalization or substrate derivatization, would therefore be valuable. Here we demonstrate that the synergistic merger of photoredox and nickel catalysis enables the direct formation of sp3-sp3 bonds using only simple carboxylic acids and alkyl halides as the nucleophilic and electrophilic coupling partners, respectively. This metallaphotoredox protocol is suitable for

  8. Raman Scattering Sensor for Control of the Acid Alkylation Process in Gasoline Production

    SciTech Connect

    Uibel, Rory, H.; Smith, Lee M.; Benner, Robert, E.

    2006-04-19

    Gasoline refineries utilize a process called acid alkylation to increase the octane rating of blended gasoline, and this is the single most expensive process in the refinery. For process efficiency and safety reasons, the sulfuric acid can only be used while it is in the concentration range of 98 to 86 %. The conventional technique to monitor the acid concentration is time consuming and is typically conducted only a few times per day. This results in running higher acid concentrations than they would like to ensure that the process proceeds uninterrupted. Maintaining an excessively high acid concentration costs the refineries millions of dollars each year. Using SBIR funding, Process Instruments Inc. has developed an inline sensor for real time monitoring of acid concentrations in gasoline refinery alkylation units. Real time data was then collected over time from the instrument and its responses were matched up with the laboratory analysis. A model was then developed to correlate the laboratory acid values to the Raman signal that is transmitted back to the instrument from the process stream. The instrument was then used to demonstrate that it could create real-time predictions of the acid concentrations. The results from this test showed that the instrument could accurately predict the acid concentrations to within ~0.15% acid strength, and this level of prediction proved to be similar or better then the laboratory analysis. By utilizing a sensor for process monitoring the most economic acid concentrations can be maintained. A single smaller refinery (50,000 barrels/day) estimates that they should save over $120,000/year, with larger refineries saving considerably more.

  9. Palladium-Catalyzed Synthesis of (Hetero)Aryl Alkyl Sulfones from (Hetero)Aryl Boronic Acids, Unactivated Alkyl Halides, and Potassium Metabisulfite.

    PubMed

    Shavnya, Andre; Hesp, Kevin D; Mascitti, Vincent; Smith, Aaron C

    2015-11-09

    A palladium-catalyzed one-step synthesis of (hetero)aryl alkyl sulfones from (hetero)arylboronic acids, potassium metabisulfite, and unactivated or activated alkylhalides is described. This transformation is of broad scope, occurs under mild conditions, and employs readily available reactants. A stoichiometric experiment has led to the isolation of a catalytically active dimeric palladium sulfinate complex, which was characterized by X-ray diffraction analysis.

  10. Scope and limitations of aliphatic Friedel-Crafts alkylations. Lewis acid catalyzed addition reactions of alkyl chlorides to carbon-carbon double bonds

    SciTech Connect

    Mayr, H.; Striepe, W.

    1983-04-22

    Lewis acid catalyzed addition reactions of alkyl halides with unsaturated hydrocarbons have been studied. 1:1 addition products are formed if the addends dissociate faster than the corresponding products; otherwise, polymerization takes place. For reaction conditions under which these compounds exist mainly undissociated, solvolysis constants of model compounds can be used to predict the outcome of any such addition reactions if systems with considerable steric hindrance are excluded.

  11. 40 CFR 721.3025 - Fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., C12-18 alkyl esters (generic). 721.3025 Section 721.3025 Protection of Environment ENVIRONMENTAL... alkyl esters (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters...

  12. 40 CFR 721.3025 - Fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., C12-18 alkyl esters (generic). 721.3025 Section 721.3025 Protection of Environment ENVIRONMENTAL... alkyl esters (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters...

  13. 40 CFR 721.3025 - Fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., C12-18 alkyl esters (generic). 721.3025 Section 721.3025 Protection of Environment ENVIRONMENTAL... alkyl esters (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters...

  14. Hyaluronic acid alkyl derivative: A novel inhibitor of metalloproteases and hyaluronidases.

    PubMed

    Pavan, Mauro; Galesso, Devis; Secchieri, Cynthia; Guarise, Cristian

    2016-03-01

    Extracellular matrix (ECM) degradation, one of the main features of osteoarthritis, is driven by at least two major classes of enzymes: matrix metalloproteases (MMPs) and hyaluronidases. Among certain glycosaminoglycans, including natural and chemically cross-linked HAs, which are currently used as viscosupplements, the hyaluronic acid (HA) alkyl-amides (Hyadd) were here selected as the strongest MMP and hyaluronidase inhibitors. We used C. histolyticum collagenase (ChC) and bovine testicular hyaluronidase (BTH) as representative models of human MMPs and hyaluronidases, respectively. The role of the alkyl moiety was investigated using HA derivatives with varying alkyl lengths and degrees of derivatization. The selected compound was then screened against 10 different human MMPs in vitro, and the results were validated ex vivo in human synovial fluid. Hyadd-C16, identified as a lead compound, showed the highest inhibition potency against MMP13 and MMP8. The in vitro results were confirmed by the inhibition of human MMP13 (Ki=106.1 μM) and hyaluronidase-2 in the synovial fluid of patients with osteoarthritis. This study demonstrates the unique properties of Hyadd-C16, including its remarkable enzymatic inhibitory activity, which is conferred by the hydrophobic chain, and its high biocompatibility and water solubility of the HA backbone.

  15. Effects of straight alkyl chain, extra hydroxylated alkyl chain and branched chain amino acids on gastric emptying evaluated using a non-invasive breath test in conscious rats

    PubMed Central

    Uchida, Masayuki; Kobayashi, Orie; Iwasawa, Kaori; Shimizu, Kimiko

    2016-01-01

    Aim: Some amino acids been known to influence gastric emptying. Thus we have evaluated the effects of straight alkyl chain, extra hydroxylated alkyl chain and branched chain amino acids on gastric emptying. Materials and Methods: Gastric emptying was evaluated in rats after feeding with Racol (nutrient formulae) containing [1-13C] acetic acid. Using a breath test, the content of 13CO2 in their expired air was measured by infrared analyzers. Rats were orally administered with test amino acids, while control rats were administered orally with distilled water. Results: The expired 13CO2 content in the expired air increased with time, peaked after about 30 min and decreased thereafter. Among the amino acids having an alkyl chain, l-serine, l-alanine and l-glycine, significantly decreased the 13CO2 content and Cmax, and delayed Tmax, suggesting inhibition and delay of gastric emptying. AUC120 min values of l-alanine and l-glycine also decreased significantly. l-Threonine significantly decreased 13CO2 content and delayed Tmax, but had no influence on Cmax and AUC120 min values, suggesting a delay of gastric emptying. l-Isoleucine and l-leucine and l-valine significantly decreased 13CO2 content, suggesting inhibition of the gastric emptying, but Cmax, Tmax and AUC120 min values were not significantly affected. Conclusion: The results show that the amino acids used in the present study had different effects on gastric emptying. Moreover, it was found that inhibition and delay of gastric emptying were clearly classifiable by analyzing the change in 13CO2 content of the expired air and the Cmax, Tmax and AUC120 min values. PMID:27169776

  16. Application of Supercritical Fluids to Solid Acid Catalyst Alkylation and Regeneration

    SciTech Connect

    Lucia M. Petkovic; Daniel M. Ginosar; David N. Thompson; Kyle C. Burch

    2007-05-01

    Supercritical fluid (SCF) regeneration is a promising alternative method for regenerating solid catalysts deactivated by carbonaceous deposits. The unique solvent and transport properties of SCFs such as solvent strength similar to liquids and transport properties similar to gases make them highly suitable for extraction of fouling materials from porous heterogeneous catalysts. A brief review of the research work performed at the Idaho National Laboratory (INL) on the application of supercritical fluids to both isobutane/butene alkylation reaction and solid acid catalyst regeneration is presented in this contribution.

  17. Virucidal effects of bleach activators, sodium alkyl acyloxybenzene sulfonate and acyloxybenzoic acid, against Feline calicivirus.

    PubMed

    Tobe, Seiichi; Hoshi, Marika; Iizuka, Kinue; Tadenuma, Hirohiko; Takaoka, Hiromitsu; Komoriya, Tomoe; Kohno, Hideki

    2012-01-01

    Noroviruses (NVs) are major causative pathogens of gastroenteritis. The disinfection of contaminated clothing during common household washing is desirable. The virucidal effects of 2 bleach activators, sodium alkyl acyloxybenzene sulfonate (OBS) and alkyl acyloxybenzoic acid (OBC), were studied using Feline calicivirus (FCV) as a surrogate for NVs. FCV was added to solutions containing either OBS or OBC and sodium percarbonate at various temperatures and for varying lengths of time. OBS and OBC, which generate long carbon chain peroxy acids, enhanced the virucidal effect of sodium percarbonate (PC). In particular, sodium lauroyloxybenzene sulfonate (OBS-12) and decanoyloxybenzoic acid (OBC-10) showed superior virucidal effects. Although the virucidal effect of 38-200 mg/L OBS-12 was maintained with 2-5% (v/v) horse serum, there was less of an effect with the same concentration of available chlorine. OBS and OBC have been used as ingredients in some laundry products to increase bleaching activity. It is expected that the use of OBS and OBC is also effective for the inactivation of NVs under common household washing conditions.

  18. Perfluoroalkyl acid distribution in various plant compartments of edible crops grown in biosolids-amended soils

    EPA Science Inventory

    Crop uptake of perfluoroalkyl acids (PFAAs) from biosolids-amended soil has been identified as a potential pathway for PFAA entry into the terrestrial food chain. This study compared the uptake of PFAAs in greenhouse-grown radish (Raphanus sativus), celery (Apium graveolens var.d...

  19. Occurrence of perfluoroalkyl acids in environmental waters in Vietnam.

    PubMed

    Duong, Hanh Thi; Kadokami, Kiwao; Shirasaka, Hanako; Hidaka, Rento; Chau, Hong Thi Cam; Kong, Lingxiao; Nguyen, Trung Quang; Nguyen, Thao Thanh

    2015-03-01

    This is the first nationwide study of perfluoroalkyl acids (PFAAs) in environmental waters in Vietnam. Twenty-eight river water and 22 groundwater samples collected in four major cities and 14 river water samples from the Red River were screened to investigate the occurrence and sources of 16 PFAAs. Perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA) were the most prevalent of 11 detected PFAAs with maximum concentrations in urban river water of 5.3, 18 and 0.93ngL(-1), respectively, and in groundwater of 8.2, 4.5 and 0.45ngL(-1), respectively. PFAAs in the Red River water were detected at low levels. PFAA concentrations in river water were higher in the rainy season than in the dry season, possibly due to storm water runoff, a common phenomenon in Southeast Asian countries. The highest concentrations of PFAAs in river water were observed in samples from highly populated and industrialized areas, perhaps sourced from sewage. The PFAA concentrations observed were similar to those in other Southeast Asian countries, but lower than in developed nations. From the composition profiles of PFAAs, industrial products containing PFAAs imported from China and Japan might be one of the major sources of PFAAs in the Vietnamese aquatic environment. According to the health-based values and advisory issued by the United States Environmental Protection Agency (USEPA), the concentrations of detected PFAAs in this study do not pose an immediate health risk to humans and aquatic organisms.

  20. Effects of monovalent cations on the competitive adsorption of perfluoroalkyl acids by kaolinite: experimental studies and modeling.

    PubMed

    Xiao, Feng; Zhang, Xiangru; Penn, Lee; Gulliver, John S; Simcik, Matt F

    2011-12-01

    Our hypothesis that longer-chained perfluoroalkyl acids (PFAAs) outcompete shorter-chained PFAAs during adsorption was tested in this study, wherein the adsorption interactions of six frequently detected PFAAs with kaolinite clay were modeled and examined experimentally using various suspension compositions. Competitive adsorption of PFAAs on the kaolinite surface was observed for the first time, and longer-chained PFAAs outcompeted those with a shorter chain. The electrostatic repulsion between adsorbed PFAA molecules is a primary inhibitory factor in PFAA adsorption. An increase in aqueous sodium or hydrogen ion concentration weakened electrostatic repulsions and changed the adsorption free energy. Therefore, the adsorption of a shorter-chained PFAA with weaker hydrophobicity could occur at high sodium or hydrogen ion concentrations. The experimental and modeling data suggest that the adsorption of shorter-chained PFAAs (≤4 perfluorinated carbons) in freshwater with a typical ionic strength of 10(-2.5) is not thermodynamically favorable. Furthermore, by measuring the electrokinetic potential of kaolinite suspension in the presence of PFAAs, we found that the kaolinite surface became more negatively charged because of the adsorption of PFAAs. This observation indicates that the adsorbed PFAA molecules were within the electrical double layer of the kaolinite surface and that they contributed to the potential at the slipping plane. The possible alignments of adsorbed PFAA molecules on the kaolinite surface were then proposed.

  1. 40 CFR 721.10218 - 2-Propenoic acid, 2-mehtyl-, C12-15-branched and linear alkyl esters, telomers with alkyl 2...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...-branched and linear alkyl esters, telomers with alkyl 2- thio]-2-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated (generic). 721.10218 Section 721.10218...-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated...

  2. 40 CFR 721.10218 - 2-Propenoic acid, 2-mehtyl-, C12-15-branched and linear alkyl esters, telomers with alkyl 2...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...-branched and linear alkyl esters, telomers with alkyl 2- thio]-2-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated (generic). 721.10218 Section 721.10218...-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated...

  3. 40 CFR 721.10218 - 2-Propenoic acid, 2-mehtyl-, C12-15-branched and linear alkyl esters, telomers with alkyl 2...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-branched and linear alkyl esters, telomers with alkyl 2- thio]-2-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated (generic). 721.10218 Section 721.10218...-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated...

  4. 40 CFR 721.10218 - 2-Propenoic acid, 2-mehtyl-, C12-15-branched and linear alkyl esters, telomers with alkyl 2...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-branched and linear alkyl esters, telomers with alkyl 2- thio]-2-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated (generic). 721.10218 Section 721.10218...-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated...

  5. Induction of mitochondrial fusion by cysteine-alkylators ethacrynic acid and N-ethylmaleimide.

    PubMed

    Bowes, Timothy J; Gupta, Radhey S

    2005-03-01

    Mitochondrial fusion and fission are important aspects of eukaryotic cell function that permit the adoption of varied mitochondrial morphologies depending upon cellular physiology. We previously observed that ethacrynic acid (EA) induced mitochondrial fusion in cultured BSC-1 and CHO/wt cells. However, the mechanism responsible for it was not clear since EA has a number of known cellular effects including glutathione (GSH) depletion and alkylation of cysteine residues. To gain insight, we have tested the effects of a variety of compounds on EA induced cellular toxicity and mitochondrial fusion. N-acetyl cysteine (NAC), a GSH precursor, was found to abrogate both the toxic and fusion-inductive effects, whereas diethylmaleate (dEM), a GSH depletor, potentiated both these effects in a dose-dependent manner. However, treatment with dEM alone, which depleted GSH to the same degree as EA, did not induce mitochondrial fusion. These results indicate that although detoxification of EA via formation of GSH conjugates is dependant upon GSH levels, the depletion of GSH by EA is not responsible for its effect on mitochondrial fusion. Dihydro-EA (DH-EA), a saturated EA analogue, lacked EA's toxicity and effect on fusion, indicating that the alpha,beta-unsaturated ketone is central to its observed effects. N-ethylmaleimide (NEM), another well-known cysteine-alkylator, also induced mitochondrial fusion at near toxic concentrations. These data suggests that cysteine-alkylation is the causative factor for fusion and toxicity. In live BSC-1 cells, EA induced fusion of mitochondria occurred very rapidly (<20 min), which suggests that it is inducing fusion by modifying certain critical cysteine residue(s) in proteins involved in the process.

  6. Determining a Robust D-Optimal Design for Testing for Departure from Additivity in a Mixture of Four Perfluoroalkyl Acids.

    EPA Science Inventory

    Our objective is to determine an optimal experimental design for a mixture of perfluoroalkyl acids (PFAAs) that is robust to the assumption of additivity. PFAAs are widely used in consumer products and industrial applications. The presence and persistence of PFAAs, especially in ...

  7. Microbial biodegradation of aromatic alkanoic naphthenic acids is affected by the degree of alkyl side chain branching

    PubMed Central

    Johnson, Richard J; Smith, Ben E; Sutton, Paul A; McGenity, Terry J; Rowland, Steven J; Whitby, Corinne

    2011-01-01

    Naphthenic acids (NAs) occur naturally in oil sands and enter the environment through natural and anthropogenic processes. NAs comprise toxic carboxylic acids that are difficult to degrade. Information on NA biodegradation mechanisms is limited, and there are no studies on alkyl branched aromatic alkanoic acid biodegradation, despite their contribution to NA toxicity and recalcitrance. Increased alkyl side chain branching has been proposed to explain NA recalcitrance. Using soil enrichments, we examined the biodegradation of four aromatic alkanoic acid isomers that differed in alkyl side chain branching: (4′-n-butylphenyl)-4-butanoic acid (n-BPBA, least branched); (4′-iso-butylphenyl)-4-butanoic acid (iso-BPBA); (4′-sec-butylphenyl)-4-butanoic acid (sec-BPBA) and (4′-tert-butylphenyl)-4-butanoic acid (tert-BPBA, most branched). n-BPBA was completely metabolized within 49 days. Mass spectral analysis confirmed that the more branched isomers iso-, sec- and tert-BPBA were transformed to their butylphenylethanoic acid (BPEA) counterparts at 14 days. The BPEA metabolites were generally less toxic than BPBAs as determined by Microtox assay. n-BPEA was further transformed to a diacid, showing that carboxylation of the alkyl side chain occurred. In each case, biodegradation of the carboxyl side chain proceeded through beta-oxidation, which depended on the degree of alkyl side chain branching, and a BPBA degradation pathway is proposed. Comparison of 16S rRNA gene sequences at days 0 and 49 showed an increase and high abundance at day 49 of Pseudomonas (sec-BPBA), Burkholderia (n-, iso-, tert-BPBA) and Sphingomonas (n-, sec-BPBA). PMID:20962873

  8. Microbial biodegradation of aromatic alkanoic naphthenic acids is affected by the degree of alkyl side chain branching.

    PubMed

    Johnson, Richard J; Smith, Ben E; Sutton, Paul A; McGenity, Terry J; Rowland, Steven J; Whitby, Corinne

    2011-03-01

    Naphthenic acids (NAs) occur naturally in oil sands and enter the environment through natural and anthropogenic processes. NAs comprise toxic carboxylic acids that are difficult to degrade. Information on NA biodegradation mechanisms is limited, and there are no studies on alkyl branched aromatic alkanoic acid biodegradation, despite their contribution to NA toxicity and recalcitrance. Increased alkyl side chain branching has been proposed to explain NA recalcitrance. Using soil enrichments, we examined the biodegradation of four aromatic alkanoic acid isomers that differed in alkyl side chain branching: (4'-n-butylphenyl)-4-butanoic acid (n-BPBA, least branched); (4'-iso-butylphenyl)-4-butanoic acid (iso-BPBA); (4'-sec-butylphenyl)-4-butanoic acid (sec-BPBA) and (4'-tert-butylphenyl)-4-butanoic acid (tert-BPBA, most branched). n-BPBA was completely metabolized within 49 days. Mass spectral analysis confirmed that the more branched isomers iso-, sec- and tert-BPBA were transformed to their butylphenylethanoic acid (BPEA) counterparts at 14 days. The BPEA metabolites were generally less toxic than BPBAs as determined by Microtox assay. n-BPEA was further transformed to a diacid, showing that carboxylation of the alkyl side chain occurred. In each case, biodegradation of the carboxyl side chain proceeded through beta-oxidation, which depended on the degree of alkyl side chain branching, and a BPBA degradation pathway is proposed. Comparison of 16S rRNA gene sequences at days 0 and 49 showed an increase and high abundance at day 49 of Pseudomonas (sec-BPBA), Burkholderia (n-, iso-, tert-BPBA) and Sphingomonas (n-, sec-BPBA).

  9. Interaction of model aryl- and alkyl-boronic acids and 1,2-diols in aqueous solution.

    PubMed

    Marinaro, William A; Prankerd, Richard; Kinnari, Kaisa; Stella, Valentino J

    2015-04-01

    The goal of this work was to quantitate ester formation between alkyl and aryl boronic acids and vicinal-diols or 1,2-diols in aqueous solution. As used here, 1,2-diols includes polyols with one or more 1,2-diol pairs. Multiple techniques were used including apparent pKa shifts of the boronic acids using UV spectrophotometry (for aryl acids) and titration (for aryl and alkyl acids). Isothermal microcalorimetry was also used, with all reactions being enthalpically favored. For all the acids and 1,2-diols and the conditions studied, evidence only supported 1:1 ester formation. All the esters formed were found to be significantly more acidic, as Lewis acids, by 3-3.5 pKa units than the corresponding nonesterified boronic acid. The equilibrium constants for ester formation increased with increasing number of 1,2-diol pairs but stereochemistry may also play a role as sorbitol with five possible 1,2-diol pairs and five isomers (taking into account the stereochemistry of the alcohol groups) was twice as efficient at ester formation compared with mannitol, also with five possible 1,2-diol pairs but only three isomers. Alkyl boronic acids formed esters to a greater extent than aryl acids. Although some quantitative differences were seen between the various techniques used, rank ordering of the structure/reactivity was consistent. Formulation implications of ester formation between boronic acids and 1,2-diols are discussed.

  10. δ-Aminolevulinic acid dehydrase activity in the blood of men working with lead alkyls

    PubMed Central

    Millar, J. A.; Thompson, G. G.; Goldberg, A.; Barry, P. S. I.; Lowe, E. H.

    1972-01-01

    Millar, J. A., Thompson, G. G., Goldberg, A., Barry, P. S. I., and Lowe, E. H. (1972).Brit. J. industr. Med.,29, 317-320. δ-Aminolevulinic acid dehydrase activity in the blood of men working with lead alkyls. The activity of erythrocyte ALA1-dehydrase is inhibited in vivo at blood lead (Pb2+) levels within the upper range of normal (20-40 μg/100 ml) and in vitro at lead concentrations greater than 10-7 M. In view of the high sensitivity of the enzyme to Pb2+, the levels of enzyme activity in the blood of men occupationally exposed to lead alkyls, particularly tetraethyllead, were measured. It was found that the enzyme activity in an exposed group of men was significantly less (P<0·001) than in a control group, the respective mean values being 220 and 677 units of enzyme activity. Tetraethyllead is metabolized in the body via triethyllead and diethyllead ions. As the latter compound possesses properties similar to Pb2+, it was synthesized in the laboratory and its effect on ALA-dehydrase was studied. Diethyllead ion was found to inhibit ALA-dehydrase activity at concentrations greater than 5 x 10-5 M, although the degree of inhibition was less than that obtained with Pb2+. These results suggest that exposure to tetraethyllead can cause a decrease in erythrocyte ALA-dehydrase activity. PMID:5044603

  11. Fatty acid alkyl esters presence in olive oil vs. organoleptic assessment.

    PubMed

    Gómez-Coca, R B; Moreda, W; Pérez-Camino, M C

    2012-12-01

    The scientific work on the authenticity and quality of olive oil is an ever-growing area. Olive oil genuineness is not only valuable for the producers, but also for the consumers who expect an actual correspondence between the products they purchase and the information on the packaging labels. Sometimes oil's rejection by consumers is just a matter of taste, sometimes is a more objective question. Low quality olive oils with weak organoleptic defects are the targets of illegal blends that can be detected by determining the content of fatty acid alkyl esters (FAAEs). In this line we have established a relationship between the FAAEs concentration of olive oils and their sensory classification. Besides, a connection between the presence of large quantities of FAAEs and fermentative organoleptic defects has been proven.

  12. Transition metal ion-assisted photochemical generation of alkyl halides and hydrocarbons from carboxylic acids

    SciTech Connect

    Carraher, Jack; Pestovsky, Oleg; Bakac, Andreja

    2012-03-14

    Near-UV photolysis of aqueous solutions of propionic acid and aqueous Fe3+ in the absence of oxygen generates a mixture of hydrocarbons (ethane, ethylene and butane), carbon dioxide, and Fe2+. The reaction becomes mildly catalytic (about five turnovers) in the presence of oxygen which converts a portion of alkyl radicals to oxidizing intermediates that reoxidize Fe2+. The photochemistry in the presence of halide ions (X− = Cl−, Br−) generates ethyl halides via halogen atom abstraction from FeXn3−n by ethyl radicals. Near-quantitative yields of C2H5X are obtained at ≥0.05 M X−. Competition experiments with Co(NH3)5Br2+ provided kinetic data for the reaction of ethyl radicals with FeCl2+ (k = (4.0 ± 0.5) × 106 M−1 s−1) and with FeBr2+ (k = (3.0 ± 0.5) × 107 M−1 s−1). Photochemical decarboxylation of propionic acid in the presence of Cu2+ generates ethylene and Cu+. Longer-chain acids also yield alpha olefins as exclusive products. These reactions become catalytic under constant purge with oxygen which plays a dual role. It reoxidizes Cu+ to Cu2+, and removes gaseous olefins to prevent accumulation of Cu+(olefin) complexes and depletion of Cu2+. The results underscore the profound effect that the choice of metal ions, the medium, and reaction conditions exert on the photochemistry of carboxylic acids.

  13. Asymmetric PTC C-alkylation catalyzed by chiral derivatives of tartaric acid and aminophenols. Synthesis Of (R)- and (S)-alpha-methyl amino acids

    PubMed

    Belokon; Kochetkov; Churkina; Ikonnikov; Chesnokov; Larionov; Singh; Parmar; Vyskocil; Kagan

    2000-10-20

    A new type of efficient chiral catalyst has been elaborated for asymmetric C-alkylation of CH acids under PTC conditions. Sodium alkoxides formed from chiral derivatives of tartaric acid and aminophenols (TADDOL's 2a-e and NOBIN's 3a-h) can be used as chiral catalysts in the enantioselective alkylation, as exemplified by the reaction of Schiff's bases 1a-e derived from alanine esters and benzaldehydes with active alkyl halides. Acid-catalyzed hydrolysis of the products formed in the reaction afforded (R)-alpha-methylphenylalanine, (R)-alpha-naphthylmethylalanine, and (R)-alpha-allylalanine in 61-93% yields and with ee 69-93%. The procedure could be successfully scaled up to 6 g of substrate 1b. When (S,S)-TADDOL or (R)-NOBIN are used, the (S)-amino acids are formed. A mechanism rationalizing the observed features of the reaction has been suggested.

  14. CHEMISTRY OF FOG WATER IN CALIFORNIA'S CENTRAL VALLEY: 2. PHOTOCHEMICAL TRANSFORMATIONS OF AMINO ACIDS AND ALKYL AMINES. (R825433)

    EPA Science Inventory

    Although amino compounds are seemingly ubiquitous in atmospheric particles and deposition, little is known of their fate in the troposphere. We report here on the fate of 21 amino acids and alkyl amines in fog waters from Davis, California, illuminated with simulated sunlight ...

  15. Stereoselective Alkylation of the Vinylketene Silyl N,O-Acetal and Its Application to the Synthesis of Mycocerosic Acid.

    PubMed

    Nakamura, Tatsuya; Kubota, Kei; Ieki, Takanori; Hosokawa, Seijiro

    2016-01-04

    Stereoselective alkylation of the vinylketene silyl N,O-acetal possessing a chiral auxiliary has been achieved by using activated alkyl halides including allyl iodides, benzyl iodides, and propargyl iodide with Ag(I) ion in the presence of BF3·OEt2. The reaction proceeded to give reduced polyketides in high stereoselectivity. The synthesis of mycocerosic acid, a component of the cell envelope of Mycobacterium tuberculosis, has been accomplished by this methodology. During the synthetic studies, 2-methylbenzimidazole was found to be a bulky proton source which worked in the presence of liquid ammonia.

  16. DDQ-promoted dehydrogenation from natural rigid polycyclic acids or flexible alkyl acids to generate lactones by a radical ion mechanism.

    PubMed

    Ding, Ye; Huang, Zhangjian; Yin, Jian; Lai, Yisheng; Zhang, Shibo; Zhang, Zhiguo; Fang, Lei; Peng, Sixun; Zhang, Yihua

    2011-09-07

    A novel and facile DDQ-mediated dehydrogenation from natural rigid polycyclic acids or flexible alkyl acids to generate lactones is described. The formation of lactones proceeds by a radical ion mechanism, which has been established by DPPH˙-mediated chemical identification, ESR spectroscopy and an enol intermediate trapping.

  17. Alkylation of nucleic acids by DNA-targeted 4-anilinoquinolinium aniline mustards: kinetic studies.

    PubMed

    O'Connor, C J; Denny, W A; Fan, J Y

    1991-01-01

    The rate of constant for hydrolysis of a series of 4-substituted aniline mustards Ar-X-pC6H4-N(CH2CH2Cl)2, where Ar is 4-anilinoquinolinium and X = O, CH2, CONH and CO, have been measured in water and 0.02 M imidazole buffer at 37 degrees C and in 50% aqueous acetone at 66 degrees C. The equilibrium binding constants of the compounds and their hydrolysis products to nucleic acids of differing base composition have been determined at varying ionic strengths, and the results are consistent with the compounds binding as expected in the DNA minor groove. The alkylating reactivity of the mustards towards these nucleic acids has been measured in water at 37 degrees C and in 0.01 M HEPES buffer over a range of temperatures from 25 degrees C to 60 degrees C. Evaluation of the thermodynamic parameters for these kinetic and equilibrium studies suggests that the interaction with nucleic acids is via an internal SN2 mechanism involving an aziridinium ion.

  18. Antioxidant activity of ferulic acid alkyl esters in a heterophasic system: a mechanistic insight.

    PubMed

    Anselmi, Cecilia; Centini, Marisanna; Granata, Paola; Sega, Alessandro; Buonocore, Anna; Bernini, Andrea; Facino, Roberto Maffei

    2004-10-20

    The antioxidant activity of some esters of ferulic acid with the linear fatty alcohols C7, C8 (branched and linear), C9, C11, C12, C13, C15, C16, and C18 has been studied in homogeneous and heterogeneous phases. Whereas in homogeneous phase all of the alkyl ferulates possessed similar radical-scavenging abilities, in rat liver microsomes they showed striking differences, the more effective being C12 (7) (IC50 = 11.03 M), linear C8 (3) (IC50 = 12.40 microM), C13 (8) (IC50 = 18.60 microM), and C9 (5) (IC50 = 19.74 microM), followed by C7 (2), C15 (9), C11 (6), branched C8 (4), C16 (10), and C18 (11) (ferulic acid was the less active, IC50 = 243.84 microM). All of the molecules showed similar partition coefficients in an octanol-buffer system. Three-dimensional studies (NMR in solution, modeling in vacuo) indicate that this behavior might be due to a different anchorage of the molecules with the ester side chain to the microsomal phospholipid bilayer and to a consequent different orientation/positioning of the scavenging phenoxy group outside the membrane surface against the flux of oxy radicals.

  19. 40 CFR 721.10442 - 1,2-Benzenedicarboxylic acid, di-C6-14-branched and linear alkyl esters.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-branched and linear alkyl esters. 721.10442 Section 721.10442 Protection of Environment ENVIRONMENTAL...-branched and linear alkyl esters. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as 1,2-benzenedicarboxylic acid, di-C6-14-branched and linear...

  20. 40 CFR 721.10442 - 1,2-Benzenedicarboxylic acid, di-C6-14-branched and linear alkyl esters.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-branched and linear alkyl esters. 721.10442 Section 721.10442 Protection of Environment ENVIRONMENTAL...-branched and linear alkyl esters. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as 1,2-benzenedicarboxylic acid, di-C6-14-branched and linear...

  1. 40 CFR 721.10441 - 1,2-Benzenedicarboxylic acid, di-C7-14-branched and linear alkyl esters.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-branched and linear alkyl esters. 721.10441 Section 721.10441 Protection of Environment ENVIRONMENTAL...-branched and linear alkyl esters. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as 1,2-benzenedicarboxylic acid, di-C7-14-branched and linear...

  2. 40 CFR 721.10441 - 1,2-Benzenedicarboxylic acid, di-C7-14-branched and linear alkyl esters.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-branched and linear alkyl esters. 721.10441 Section 721.10441 Protection of Environment ENVIRONMENTAL...-branched and linear alkyl esters. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as 1,2-benzenedicarboxylic acid, di-C7-14-branched and linear...

  3. Surface active molecules: preparation and properties of long chain n-acyl-l-alpha-amino-omega-guanidine alkyl acid derivatives.

    PubMed

    Infante, R; Dominguez, J G; Erra, P; Julia, R; Prats, M

    1984-12-01

    Synopsis A new route for the synthesis of long chain N(alpha)-acyl-l-alpha-amino-omega-guamdine alkyl acid derivatives, with cationic or amphoteric character has been established. The general formula of these compounds is shown below. A physico-chemical and antimicrobial study of these products as a function of the alkyl ester or sodium salt (R), the straight chain length of the fatty acid residue (x) and the number of carbons between the omega-guanidine and omega-carboxyl group (n) has been investigated. The water solubility, surface tension, critical micelle concentration (c.m.c.) and minimum inhibitory concentration (MIC) against Gram-positive and Gram-negative bacteria (including Pseudomonas) has been determined. Dicyclohexylcarbodiimide has been used to condense fatty acids and alpha-amino-omega-guanidine alkyl acids. In these conditions protection of the omega-guanidine group is not necessary. The main characteristic of this synthetic procedure is the use of very mild experimental conditions (temperature, pH) to form the amide linkage which leads to pure optical compounds in high yield in the absence of electrolytes. The results show that some structural modifications, particularly the protection of the carboxyl group, promote variations of the surfactant and antimicrobial properties. Only those molecules with the blocked carboxyl group (cationic molecules, where R = Me, Et or Pr) showed a good surfactant and antimicrobial activity. When the carboxyl group was unprotected (amphoteric molecules, where R = Na(+)) the resulting compounds were inactive.

  4. Elevated levels of perfluoroalkyl acids in family members of occupationally exposed workers: the importance of dust transfer

    PubMed Central

    Fu, Jianjie; Gao, Yan; Wang, Thanh; Liang, Yong; Zhang, Aiqian; Wang, Yawei; Jiang, Guibin

    2015-01-01

    The exposure pathways of perfluoroalkyl acids (PFAAs) to humans are still not clear because of the complex living environment, and few studies have simultaneously investigated the bioaccumulative behaviour of different PFAAs in humans. In this study, serum, dust, duplicate diet, and other matrices were collected around a manufacturing plant in China, and homologous series of PFAAs were analysed. PFAA levels in dust and serum of local residents in this area were considerably higher than those in non-polluted area. Although dietary intake was the major exposure pathway in the present study, dust ingestion played an important role in this case. Serum PFAAs in local residents was significantly correlated with dust PFAAs levels in their living or working microenvironment. Serum PFAAs and dust PFAAs were significantly higher in family members of occupational workers (FM) than in ordinary residents (OR) (p < 0.01). After a careful analysis of the PFAAs exposure pathway, a potential pathway in addition to direct dust ingestion was suggested: PFAAs might transferred from occupational worker's clothes to dinners via cooking processes. The bioaccumulative potential of PFHxS and PFOS were higher than other PFAAs, which suggested a substantial difference between the bioaccumulative ability of perfluorinated sulfonic acids and perfluorinated carboxylic acids. PMID:25791573

  5. Elevated levels of perfluoroalkyl acids in family members of occupationally exposed workers: the importance of dust transfer

    NASA Astrophysics Data System (ADS)

    Fu, Jianjie; Gao, Yan; Wang, Thanh; Liang, Yong; Zhang, Aiqian; Wang, Yawei; Jiang, Guibin

    2015-03-01

    The exposure pathways of perfluoroalkyl acids (PFAAs) to humans are still not clear because of the complex living environment, and few studies have simultaneously investigated the bioaccumulative behaviour of different PFAAs in humans. In this study, serum, dust, duplicate diet, and other matrices were collected around a manufacturing plant in China, and homologous series of PFAAs were analysed. PFAA levels in dust and serum of local residents in this area were considerably higher than those in non-polluted area. Although dietary intake was the major exposure pathway in the present study, dust ingestion played an important role in this case. Serum PFAAs in local residents was significantly correlated with dust PFAAs levels in their living or working microenvironment. Serum PFAAs and dust PFAAs were significantly higher in family members of occupational workers (FM) than in ordinary residents (OR) (p < 0.01). After a careful analysis of the PFAAs exposure pathway, a potential pathway in addition to direct dust ingestion was suggested: PFAAs might transferred from occupational worker's clothes to dinners via cooking processes. The bioaccumulative potential of PFHxS and PFOS were higher than other PFAAs, which suggested a substantial difference between the bioaccumulative ability of perfluorinated sulfonic acids and perfluorinated carboxylic acids.

  6. Concentration effects in the nucleophilic reactions of tertiary amines in aqueous solutions: Alkylation of amines with chloroacetic acid

    NASA Astrophysics Data System (ADS)

    Kazantsev, O. A.; Baruta, D. S.; Shirshin, K. V.; Sivokhin, A. P.; Kamorin, D. M.

    2011-03-01

    In alkylations of tertiary amines with chloroacetic acid in aqueous solutions, an increase in the initial concentrations of reagents to a certain level led to an abrupt increase in the initial rates and conversions attained during the control time. Viscosimetric and refractometric data showed that association with reagents occurred in these systems. The structures of associates that determine the character of the concentration effects of the Menschutkin reaction in water were suggested.

  7. Sulfotanone, a new alkyl sulfonic acid derivative from Streptomyces sp. IFM 11694 with TRAIL resistance-overcoming activity.

    PubMed

    Abdelfattah, Mohamed S; Ishikawa, Naoki; Karmakar, Utpal K; Ishibashi, Masami

    2016-04-01

    One new alkyl sulfonic acid derivative, sulfotanone (1), and the known panosialin wA (2) were isolated from the methanolic extract of mycelium of Streptomyces sp. 11694. The structure of the new compound (1) was established by a combination of spectroscopic techniques, including HRESIMS, IR, 1D and 2D NMR measurements. Compound 1 (40 µM) in combination with TRAIL showed synergistic activity in sensitizing TRAIL-resistance in human gastric adenocarcinoma cell lines.

  8. 40 CFR 721.5375 - Ni-tro-thio-phene-car-boxy-lic acid, ethyl es-ter, bis-[[[[(sub-sti-tut-ed)] amino]-alkyl-phenyl...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-boxy-lic acid, ethyl es-ter, bis- amino]-alkyl-phenyl]-az-o] (ge-ner-ic name). (a) Chemical substance...-lic acid, ethyl ester, bis- -amino]-alkyl-phenyl]-azo] (PMN P-87-304) is subject to reporting under... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Ni-tro-thio-phene-car-boxy-lic...

  9. 40 CFR 721.5375 - Ni-tro-thio-phene-car-boxy-lic acid, ethyl es-ter, bis-[[[[(sub-sti-tut-ed)] amino]-alkyl-phenyl...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...-boxy-lic acid, ethyl es-ter, bis- amino]-alkyl-phenyl]-az-o] (ge-ner-ic name). (a) Chemical substance...-lic acid, ethyl ester, bis- -amino]-alkyl-phenyl]-azo] (PMN P-87-304) is subject to reporting under... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Ni-tro-thio-phene-car-boxy-lic...

  10. Syn-Selective Synthesis of β-Branched α-Amino Acids by Alkylation of Glycine-Derived Imines with Secondary Sulfonates.

    PubMed

    Lou, Sha; McKenna, Grace M; Tymonko, Steven A; Ramirez, Antonio; Benkovics, Tamas; Conlon, David A; González-Bobes, Francisco

    2015-10-16

    A syn-selective synthesis of β-branched α-amino acids has been developed based on the alkylation of glycine imine esters with secondary sulfonates. The potassium counterion for the enolate, the solvent, and the leaving group on the electrophile were key levers to maximize the diasteroselectivity of the alkylation. The optimized conditions enabled a straightforward preparation of a number of β-branched α-amino acids that can be challenging to obtain.

  11. 40 CFR 721.5375 - Ni-tro-thio-phene-car-boxy-lic acid, ethyl es-ter, bis-[[[[(sub-sti-tut-ed)] amino]-alkyl-phenyl...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...-boxy-lic acid, ethyl es-ter, bis- amino]-alkyl-phenyl]-az-o] (ge-ner-ic name). (a) Chemical substance...-lic acid, ethyl ester, bis- -amino]-alkyl-phenyl]-azo] (PMN P-87-304) is subject to reporting under... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Ni-tro-thio-phene-car-boxy-lic...

  12. 40 CFR 721.5375 - Ni-tro-thio-phene-car-boxy-lic acid, ethyl es-ter, bis-[[[[(sub-sti-tut-ed)] amino]-alkyl-phenyl...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-boxy-lic acid, ethyl es-ter, bis- amino]-alkyl-phenyl]-az-o] (ge-ner-ic name). (a) Chemical substance...-lic acid, ethyl ester, bis- -amino]-alkyl-phenyl]-azo] (PMN P-87-304) is subject to reporting under... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Ni-tro-thio-phene-car-boxy-lic...

  13. 40 CFR 721.5375 - Ni-tro-thio-phene-car-boxy-lic acid, ethyl es-ter, bis-[[[[(sub-sti-tut-ed)] amino]-alkyl-phenyl...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...-boxy-lic acid, ethyl es-ter, bis- amino]-alkyl-phenyl]-az-o] (ge-ner-ic name). (a) Chemical substance...-lic acid, ethyl ester, bis- -amino]-alkyl-phenyl]-azo] (PMN P-87-304) is subject to reporting under... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Ni-tro-thio-phene-car-boxy-lic...

  14. Method of making alkyl esters

    DOEpatents

    Elliott, Brian

    2010-09-14

    Methods of making alkyl esters are described herein. The methods are capable of using raw, unprocessed, low-cost feedstocks and waste grease. Generally, the method involves converting a glyceride source to a fatty acid composition and esterifying the fatty acid composition to make alkyl esters. In an embodiment, a method of making alkyl esters comprises providing a glyceride source. The method further comprises converting the glyceride source to a fatty acid composition comprising free fatty acids and less than about 1% glyceride by mass. Moreover, the method comprises esterifying the fatty acid composition in the presence of a solid acid catalyst at a temperature ranging firm about 70.degree. C. to about 120.degree. C. to produce alkyl esters, such that at least 85% of the free fatty acids are converted to alkyl esters. The method also incorporates the use of packed bed reactors for glyceride conversion and/or fatty acid esterification to make alkyl esters.

  15. Are perfluoroalkyl acids in waste water treatment plant effluents the result of primary emissions from the technosphere or of environmental recirculation?

    PubMed

    Filipovic, Marko; Berger, Urs

    2015-06-01

    Wastewater treatment plants (WWTP) have been suggested to be one of the major pathways of perfluoroalkyl acids (PFAAs) from the technosphere to the aquatic environment. The origin of PFAAs in WWTP influents is either from current primary emissions or a result of recirculation of PFAAs that have been residing and transported in the environment for several years or decades. Environmental recirculation can then occur when PFAAs from the environment enter the wastewater stream in, e.g., tap water. In this study 13 PFAAs and perfluorooctane sulfonamide were analyzed in tap water as well as WWTP influent, effluent and sludge from three Swedish cities: Bromma (in the metropolitan area of Stockholm), Bollebygd and Umeå. A mass balance of the WWTPs was assembled for each PFAA. Positive mass balances were observed for PFHxA and PFOA in all WWTPs, indicating the presence of precursor compounds in the technosphere. With regard to environmental recirculation, tap water was an important source of PFAAs to the Bromma WWTP influent, contributing >40% for each quantified sulfonic acid and up to 30% for the carboxylic acids. The PFAAs in tap water from Bollebygd and Umeå did not contribute significantly to the PFAA load in the WWTP influents. Our results show that in order to estimate current primary emissions from the technosphere, it may be necessary to correct the PFAA emission rates in WWTP effluents for PFAAs present in tap water, especially in the case of elevated levels in tap water.

  16. Quinolone antimicrobial agents. 1. Versatile new synthesis of 1-alkyl-1,4-dihydro-4-oxo-3-quinolinecarboxylic acids.

    PubMed

    Mitscher, L A; Gracey, H E; Clark, G W; Suzuki, T

    1978-05-01

    A flexible reaction sequence has been developed which starts with readily available anthranilic acids or isatoic anhydrides and leads regiospecifically to 1-alkyl-1,4-dihydro-4-oxo-3-quinolinecarboxylic acids after reaction with 1,3-dicarbonyl compounds. The sequence is superior to earlier published methods by allowing electron-releasing and -withdrawing groups in any position on the aro;atic ring, by allowing convenient substitution at C2, and better overall yield. A number of new and known antimicrobial agents were prepared and tested in vitro, demonstrating, inter alia, that substitution of the H at C2 abolished antibacterial activity.

  17. The role of alkyl chain length of monothiol-terminated alkyl carboxylic acid in the synthesis, characterization, and application of gelatin-g-poly(N-isopropylacrylamide) carriers for antiglaucoma drug delivery.

    PubMed

    Luo, Li-Jyuan; Lai, Jui-Yang

    2017-02-01

    To improve ocular bioavailability and extend pharmacological response, this study aims to investigate the role of alkyl chain length of monothiol-terminated alkyl carboxylic acids in the synthesis, characterization, and application of gelatin-g-poly(N-isopropylacrylamide) (GN) biodegradable in situ gelling carriers for antiglaucoma drug delivery. In the presence of mercaptoacetic acid (MAA), mercaptopropionic acid (MPA), mercaptobutyric acid (MBA), or mercaptohexanoic acid (MHA) as a chain transfer agent, the carboxylic end-capped poly(N-isopropylacrylamide) samples were prepared by free radical polymerization technique. Our results showed that with increasing alkyl chain length, the hydrophobicity of thermo-responsive polymer segments significantly increased, mainly due to an increase in CH stretching frequencies. In addition, the greater hydrophobic association favored the decrease in both phase transition temperature and weight loss of GN copolymers, thereby accelerating their temperature-triggered gelation process and retarding the degradation progress under physiological conditions. The benefits from these features allowed the pilocarpine carriers to increase drug payload and extend drug release. Irrespective of carbon number of monothiol-terminated alkyl carboxylic acid, the synthesized GN materials exhibited high tolerance to corneal endothelial cells without any evidence of inhibited proliferation, viability loss, inflammatory stimulation, and functional abnormality, indicating good biocompatibility. Results of clinical observations and histological examinations demonstrated that the therapeutic efficacies in treating glaucomatous damage are in response to in vivo drug release profiles from various intracamerally injected GN carriers. The research findings suggest the influence of alkyl chain length of chain transfer agent-mediated polymer hydrophobicity and degradability on pharmacological bioavailability and action of pilocarpine in a glaucomatous rabbit

  18. Selective Alkylation of C-Rich Bulge Motifs in Nucleic Acids by Quinone Methide Derivatives.

    PubMed

    Lönnberg, Tuomas; Hutchinson, Mark; Rokita, Steven

    2015-09-07

    A quinone methide precursor featuring a bis-cyclen anchoring moiety has been synthesized and its capacity to alkylate oligonucleotide targets quantified in the presence and absence of divalent metal ions (Zn(2+) , Ni(2+) and Cd(2+) ). The oligonucleotides were designed for testing the sequence and secondary structure specificity of the reaction. Gel electrophoretic analysis revealed predominant alkylation of C-rich bulges, regardless of the presence of divalent metal ions or even the bis-cyclen anchor. This C-selectivity appears to be an intrinsic property of the quinone methide electrophile as reflected by its reaction with an equimolar mixture of the 2'-deoxynucleosides. Only dA-N1 and dC-N3 alkylation products were detected initially and only the dC adduct persisted for detection under conditions of the gel electrophoretic analysis.

  19. Enantioselective Alkylation of Amino Acid Derivatives Promoted by Cyclic Peptoids under Phase-Transfer Conditions.

    PubMed

    Schettini, Rosaria; De Riccardis, Francesco; Della Sala, Giorgio; Izzo, Irene

    2016-03-18

    The effects of substituents and cavity size on catalytic efficiency of proline-rich cyclopeptoids under phase-transfer conditions were studied. High affinity constants (Ka) for the sodium and potassium cations, comparable to those reported for crown ethers, were observed for an alternated N-benzylglycine/L-proline hexameric cyclopeptoid. This compound was found to catalyze the alkylation of N-(diphenylmethylene)glycine cumyl ester in values of enantioselectivities comparable with those reported for the Cinchona alkaloid ammonium salts derivatives (83-96% ee), and with lower catalyst loading (1-2.5% mol), in the presence of a broad range of benzyl, allyl and alkyl halides.

  20. Targeted synthesis of silicomolybdic acid (Keggin acid) inside mesoporous silica hollow spheres for Friedel-Crafts alkylation.

    PubMed

    Dou, Jian; Zeng, Hua Chun

    2012-10-03

    Herein we report an inside-out preinstallation-infusion-hydration method for targeted synthesis of Keggin heteropoly acids (silicomolybdic acid, H(4)SiMo(12)O(40)) within mesoporous silica (SiO(2)) hollow spheres. In this process, discrete molybdenum dioxide (MoO(2)) nanoparticles with diameter size ranging from 25 to 60 nm were first prepared by a one-pot hydrothermal route in water/ethanol mixed solvents at 180 °C, which were then used as cores to grow the shell of supramolecular templated silica with tetraethyl orthosilicate (TEOS) and hexadecyltrimethyl- ammonium chloride (CTACl) in alkaline solution. By thermal treatment of as-synthesized MoO(2)@SiO(2) core-shell spheres, the organic template was burned off and mesoporous shell was formed (BET specific surface area was as high as 872 m(2)/g). Meanwhile, the encapsulated MoO(2) was oxidized to Mo(6+) and infused to the mesoporous silica shells, forming heptamolybdate species (Mo(7)O(24)(6-)) uniformly dispersed on the mesopore surfaces of silica, while generating void space at the center of spheres. After hydration with water, H(4)SiMo(12)O(40) was formed by reaction between the surface Mo(7)O(24)(6-) and silica species in the presence of water. The prepared H(4)SiMo(12)O(40) @mSiO(2) hollow spheres were tested for Friedel-Crafts alkylation of toluene by benzyl alcohol. The H(4)SiMo(12)O(40)@mSiO(2) catalysts fabricated via this novel route exhibited excellent catalytic activity toward benzylation of toluene, which was approximately 2.6 times as high as that of commercial Amberlyst-15 catalyst. In addition, the H(4)SiMo(12)O(40)@mSiO(2) catalyst was very robust and could be reused after regeneration.

  1. A surprising substituent effect provides a superior boronic acid catalyst for mild and metal-free direct Friedel-Crafts alkylations and prenylations of neutral arenes.

    PubMed

    Ricardo, Carolynne L; Mo, Xiaobin; McCubbin, J Adam; Hall, Dennis G

    2015-03-09

    The development of more general and efficient catalytic processes for Friedel-Crafts alkylations is an important objective of interest toward the production of pharmaceuticals and commodity chemicals. Herein, 2,3,4,5-tetrafluorophenylboronic acid was identified as a potent air- and moisture-tolerant metal-free catalyst that significantly improves the scope of direct Friedel-Crafts alkylations of a variety of slightly activated and neutral arenes, including polyarenes, with allylic and benzylic alcohols. This method also provides a simple alternative for the direct installation of prenyl units commonly found in naturally occurring arenes. Alkylations with benzylic alcohols occur under exceptionally mild conditions.

  2. Heterogeneous catalysis by solid superacids--14. Perfluorinated resinsulfonic acid (nafion-h) catalyzed Friedel-crafts alkylation of toluene and phenol with alkyl chloroformates and oxalates

    SciTech Connect

    Olah, G.A.; Meidar, D.; Malhotra, R.; Olah, J.A.; Narang, S.C.

    1980-01-01

    Product distributions obtained in the alkylation of toluene with methyl, ethyl, and isopropyl chloroformate and dimethyl oxalate and of phenol with methyl and ethyl chloroformate and dimethyl- and diethyloxalate.

  3. Intra- and intermolecular alkylation of N,O-acetals and π-activated alcohols catalyzed by in situ generated acid.

    PubMed

    Hamon, Mélanie; Dickinson, Niall; Devineau, Alice; Bolien, David; Tranchant, Marie-José; Taillier, Catherine; Jabin, Ivan; Harrowven, David C; Whitby, Richard J; Ganesan, A; Dalla, Vincent

    2014-03-07

    Intramolecular and intermolecular alkylations of carbocation precursors of limited ionization ability, principally N,O-acetals, without the use of an exogenous reagent have been developed. The reactions are carried out in 1,1,2,2-tetrachloroethane (TCE) and take advantage of the ability of this solvent to continuously release small amounts of HCl by thermolytic elimination. A study of the reaction led to several improved protocols such as (1) preheated TCE, (2) microwave-assisted reactions, and (3) flow or sealed-tube conditions, which allow significant reaction rate enhancements and made possible some challenging reactions such as the α-amidoalkylation of ketones. Studies using flow chemistry confirmed not only that very low concentrations of HCl generated from the solvent were responsible for the reactivity but also that TCE had additional beneficial properties in comparison to other chlorinated solvents such as dichloroethane. The method can easily be extended to the alkylation using proelectrophiles such as π-activated alcohols, which are normally unreactive toward HCl catalysis. This work represents the first successful use of HCl, the simplest strong Brønsted acid, as an efficient alkylation catalyst.

  4. Enantioselective sp(3) C-H alkylation of γ-butyrolactam by a chiral Ir(I) catalyst for the synthesis of 4-substituted γ-amino acids.

    PubMed

    Tahara, Yu-ki; Michino, Masamichi; Ito, Mamoru; Kanyiva, Kyalo Stephen; Shibata, Takanori

    2015-12-04

    Ir-catalyzed sp(3) C-H alkylation of γ-butyrolactam with alkenes was used for the highly enantioselective synthesis of 5-substituted γ-lactams, which were readily converted into chiral 4-substituted γ-amino acids. A broad scope of alkenes was amenable as coupling partners, and the alkylated product using acrylate could be transformed into the key intermediate of pyrrolam A synthesis.

  5. Developmental Toxicity

    EPA Science Inventory

    This chapter provides an overview the developmental toxicity resulting from exposure to perfluorinated alkyl acids (PFAAs). The majority of studies of PFAA-induced developmental toxicity have examined effects of perfluorooctane sulfonate (PFOS) or perfluorooctanoic acid (PFOA) a...

  6. Comparative Pharmacokinetics of Perfluorononanoic acid in Rats and Mice.

    EPA Science Inventory

    Perfluorononanoic acid (pFNA), a member of the perfluoroalkyl acids (PFAAs) is found at low concentrations in the environment, but detectable in humans and wildlife. Previous studies have examined the pharmacokinetics (PK) of shorter carbon-chain PFAAs, such as perfluorobutyric a...

  7. *Comparative pharmacokinetics of perfluorononanoic acid in rats and mice

    EPA Science Inventory

    Perfluorononanoic acid (PFNA), a member of the perfluoroalkyl acids (PFAAs) is found at low concentrations in the environment, but detectable in humans and wildlife. Previous studies have examined the pharmacokinetics (PK) of shorter carbon-chain PFAAs, such as perfluorobutyric a...

  8. Comparative Pharmacokinetics of Perfluorononanoic acid in Rats and Mice*.

    EPA Science Inventory

    Perfluorononanoic acid (PFNA), a member of the perfluoroalkyl acids (PFAAs) is found at low concentrations in the environment, but is also detectable in humans and wildlife. Previous studies have examined the pharmacokinetics (PK) of lower carbon-chain PFAAs, such as perfluorobut...

  9. Perfluorooctanoic acid and environmental risks

    EPA Science Inventory

    Perfluorooctanoic acid (PFOA) is a member of the perfluoroalkyl acids (PFAA) family of chemicals, which consist of a carbon backbone typically four to fourteen carbons in length and a charged functional moiety.

  10. N-Chlorosuccinimide-mediated oxidative chlorination of thiols to Nα-protected amino alkyl sulfonyl azides and their utility in the synthesis of sulfonyl triazole acids.

    PubMed

    Sharnabai, K M; Krishnamurthy, M; Sagar, N R; Santhosh, L; Vommina, Sureshbabu V

    2016-11-30

    An efficient oxidative chlorination of thiols to Nα-protected amino alkyl sulfonyl azides is delineated. The reaction involves in situ generation of sulfonyl chloride employing N-chlorosuccinimide and tetrabutylammonium chloride-water in acetonitrile, followed by the reaction with sodium azide. The protocol is simple, straight forward, mild and high yielding. Amino acids with simple as well as bifunctional side chains were used to obtain Nα-protected amino alkyl sulfonyl azides. Further, sulfonyl azides were utilized to synthesize unnatural amino acids via Cu(OAc)2.H2O/2-amino phenol catalyzed Click reaction with propiolic acid.

  11. Lewis Acid Catalyzed Friedel-Crafts Alkylation of Alkenes with Trifluoropyruvates.

    PubMed

    Xiang, Bin; Xu, Teng-Fei; Wu, Liang; Liu, Ren-Rong; Gao, Jian-Rong; Jia, Yi-Xia

    2016-05-06

    A Friedel-Crafts alkylation reaction of styrenes with trifluoropyruvates has been developed, which delivered allylic alcohols in excellent yields (up to 98%) using the Ni(ClO4)2·6H2O/bipyridine complex as a catalyst. The asymmetric reaction was catalyzed by the chiral Cu(OTf)2/bisoxazoline complex to afford the corresponding chiral allylic alcohols bearing trifluoromethylated quaternary stereogenic centers in moderate enantioselectivities (up to 75% ee).

  12. Water-mediated recognition of simple alkyl chains by heart-type fatty-acid-binding protein.

    PubMed

    Matsuoka, Shigeru; Sugiyama, Shigeru; Matsuoka, Daisuke; Hirose, Mika; Lethu, Sébastien; Ano, Hikaru; Hara, Toshiaki; Ichihara, Osamu; Kimura, S Roy; Murakami, Satoshi; Ishida, Hanako; Mizohata, Eiichi; Inoue, Tsuyoshi; Murata, Michio

    2015-01-26

    Long-chain fatty acids (FAs) with low water solubility require fatty-acid-binding proteins (FABPs) to transport them from cytoplasm to the mitochondria for energy production. However, the precise mechanism by which these proteins recognize the various lengths of simple alkyl chains of FAs with similar high affinity remains unknown. To address this question, we employed a newly developed calorimetric method for comprehensively evaluating the affinity of FAs, sub-Angstrom X-ray crystallography to accurately determine their 3D structure, and energy calculations of the coexisting water molecules using the computer program WaterMap. Our results clearly showed that the heart-type FABP (FABP3) preferentially incorporates a U-shaped FA of C10-C18 using a lipid-compatible water cluster, and excludes longer FAs using a chain-length-limiting water cluster. These mechanisms could help us gain a general understanding of how proteins recognize diverse lipids with different chain lengths.

  13. Regioselective, borinic acid-catalyzed monoacylation, sulfonylation and alkylation of diols and carbohydrates: expansion of substrate scope and mechanistic studies.

    PubMed

    Lee, Doris; Williamson, Caitlin L; Chan, Lina; Taylor, Mark S

    2012-05-16

    Synthetic and mechanistic aspects of the diarylborinic acid-catalyzed regioselective monofunctionalization of 1,2- and 1,3-diols are presented. Diarylborinic acid catalysis is shown to be an efficient and general method for monotosylation of pyranoside derivatives bearing three secondary hydroxyl groups (7 examples, 88% average yield). In addition, the scope of the selective acylation, sulfonylation, and alkylation is extended to 1,2- and 1,3-diols not derived from carbohydrates (28 examples); the efficiency, generality, and operational simplicity of this method are competitive with those of state-of-the-art protocols including the broadly applied organotin-catalyzed or -mediated reactions. Mechanistic details of the organoboron-catalyzed processes are explored using competition experiments, kinetics, and catalyst structure-activity relationships. These experiments are consistent with a mechanism in which a tetracoordinate borinate complex reacts with the electrophilic species in the turnover-limiting step of the catalytic cycle.

  14. Determination of methyl-, 2-hydroxyethyl- and 2-cyanoethylmercapturic acids as biomarkers of exposure to alkylating agents in cigarette smoke.

    PubMed

    Scherer, Gerhard; Urban, Michael; Hagedorn, Heinz-Werner; Serafin, Richard; Feng, Shixia; Kapur, Sunil; Muhammad, Raheema; Jin, Yan; Sarkar, Mohamadi; Roethig, Hans-Juergen

    2010-10-01

    Alkylating agents occur in the environment and are formed endogenously. Tobacco smoke contains a variety of alkylating agents or precursors including, among others, N-nitrosodimethylamine (NDMA), 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), acrylonitrile and ethylene oxide. We developed and validated a method for the simultaneous determination of methylmercapturic acid (MMA, biomarker for methylating agents such as NDMA and NNK), 2-hydroxyethylmercapturic acid (HEMA, biomarker for ethylene oxide) and 2-cyanoethylmercapturic acid (CEMA, biomarker for acrylonitrile) in human urine using deuterated internal standards of each compound. The method involves liquid/liquid extraction of the urine sample, solid phase extraction on anion exchange cartridges, derivatization with pentafluorobenzyl bromide (PFBBr), liquid/liquid extraction of the reaction mixture and LC-MS/MS analysis with positive electrospray ionization. The method was linear in the ranges of 5.00-600, 1.00-50.0 and 1.50-900 ng/ml for MMA, HEMA and CEMA, respectively. The method was applied to two clinical studies in adult smokers of conventional cigarettes who either continued smoking conventional cigarettes, were switched to test cigarettes consisting of either an electrically heated cigarette smoking system (EHCSS) or having a highly activated carbon granule filter that were shown to have reduced exposure to specific smoke constituents, or stopped smoking. Urinary excretion of MMA was found to be unaffected by switching to the test cigarettes or stop smoking. Urinary HEMA excretion decreased by 46 to 54% after switching to test cigarettes and by approximately 74% when stopping smoking. Urinary CEMA excretion decreased by 74-77% when switching to test cigarettes and by approximately 90% when stopping smoking. This validated method for urinary alkylmercapturic acids is suitable to distinguish differences in exposure not only between smokers and nonsmokers but also between smoking of conventional and

  15. Nitrated Fatty Acids Reverse Cigarette Smoke-Induced Alveolar Macrophage Activation and Inhibit Protease Activity via Electrophilic S-Alkylation.

    PubMed

    Reddy, Aravind T; Lakshmi, Sowmya P; Muchumarri, Ramamohan R; Reddy, Raju C

    2016-01-01

    Nitrated fatty acids (NFAs), endogenous products of nonenzymatic reactions of NO-derived reactive nitrogen species with unsaturated fatty acids, exhibit substantial anti-inflammatory activities. They are both reversible electrophiles and peroxisome proliferator-activated receptor γ (PPARγ) agonists, but the physiological implications of their electrophilic activity are poorly understood. We tested their effects on inflammatory and emphysema-related biomarkers in alveolar macrophages (AMs) of smoke-exposed mice. NFA (10-nitro-oleic acid or 12-nitrolinoleic acid) treatment downregulated expression and activity of the inflammatory transcription factor NF-κB while upregulating those of PPARγ. It also downregulated production of inflammatory cytokines and chemokines and of the protease cathepsin S (Cat S), a key mediator of emphysematous septal destruction. Cat S downregulation was accompanied by decreased AM elastolytic activity, a major mechanism of septal destruction. NFAs downregulated both Cat S expression and activity in AMs of wild-type mice, but only inhibited its activity in AMs of PPARγ knockout mice, pointing to a PPARγ-independent mechanism of enzyme inhibition. We hypothesized that this mechanism was electrophilic S-alkylation of target Cat S cysteines, and found that NFAs bind directly to Cat S following treatment of intact AMs and, as suggested by in silico modeling and calculation of relevant parameters, elicit S-alkylation of Cys25 when incubated with purified Cat S. These results demonstrate that NFAs' electrophilic activity, in addition to their role as PPARγ agonists, underlies their protective effects in chronic obstructive pulmonary disease (COPD) and support their therapeutic potential in this disease.

  16. Application of Pre-Column Labeling Liquid Chromatography for Canine Plasma-Free Amino Acid Analysis

    PubMed Central

    Azuma, Kazuo; Hirao, Yoshiko; Hayakawa, Yoshihiro; Murahata, Yusuke; Osaki, Tomohiro; Tsuka, Takeshi; Imagawa, Tomohiro; Okamoto, Yoshiharu; Ito, Norihiko

    2016-01-01

    Plasma-free amino acid (PFAA) levels are a useful metric for diagnosing cancer and providing a prognosis. However, the use of analysis of PFAA levels has been limited in the veterinary medicine field. We addressed the application of liquid chromatography (LC) using a pre-column labeling technique for analysis of canine PFAA levels. This method significantly shortened the analysis time relative to conventional methods. No diurnal fluctuations were detected at 9:00 AM in most PFAA levels, and food intake increased the levels of some PFAAs, including valine, leucine, tyrosine, phenylalanine, and proline. These results indicate that LC with pre-column labeling is useful for measuring canine PFAA levels, for which time of day and interval after food intake must be taken into consideration. PMID:26771650

  17. Extraction of manganese by alkyl monocarboxylic acid in a mixed extractant from a leaching solution of spent lithium-ion battery ternary cathodic material

    NASA Astrophysics Data System (ADS)

    Joo, Sung-Ho; Shin, Dongju; Oh, ChangHyun; Wang, Jei-Pil; Shin, Shun Myung

    2016-02-01

    We investigate the separation of manganese by an antagonistic effect from a leaching solution of ternary cathodic material of spent lithium-ion batteries that contain 11,400 mg L-1 Co, 11,700 mg L-1 Mn, 12,200 mg L-1 Ni, and 5300 mg L-1 Li using a mixture of alkyl monocarboxylic acid and di-(2-ethylhexyl)phosphoric acid extractants. pH isotherm, distribution coefficient, separation factor, McCabe-Thiele diagram, selective scrubbing, and countercurrent extraction tests are carried out to prove an antagonistic effect and to recover manganese using alkyl monocarboxylic in the mixed extractant. Slope analysis is used to determine the extraction mechanism between a mixture of extractants and valuable metals. An increasing concentration of alkyl monocarboxylic acid in the mixture of extractants results in a decrease in distribution coefficient of cobalt and manganese, however, the separation factor value (β(Mn/Co)) increases at pH 4.5. This is caused by slope analysis where alkyl monocarboxylic acid disrupts the extraction mechanism between di-(2-ethylhexyl)phosphoric acid and cobalt. Finally, continuous countercurrent extraction in a mini-plant test demonstrate the feasibility of manganese recovery from cobalt, nickel, and lithium.

  18. 40 CFR 721.3025 - Fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Fatty acids C12-18, C18 unsaturated... Significant New Uses for Specific Chemical Substances § 721.3025 Fatty acids C12-18, C18 unsaturated, C12-18... chemical substance identified generically as fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters...

  19. 40 CFR 721.3025 - Fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Fatty acids C12-18, C18 unsaturated... Significant New Uses for Specific Chemical Substances § 721.3025 Fatty acids C12-18, C18 unsaturated, C12-18... chemical substance identified generically as fatty acids C12-18, C18 unsaturated, C12-18 alkyl esters...

  20. Fast and selective sugar conversion to alkyl lactate and lactic acid with bifunctional carbon-silica catalysts.

    PubMed

    de Clippel, Filip; Dusselier, Michiel; Van Rompaey, Ruben; Vanelderen, Pieter; Dijkmans, Jan; Makshina, Ekaterina; Giebeler, Lars; Oswald, Steffen; Baron, Gino V; Denayer, Joeri F M; Pescarmona, Paolo P; Jacobs, Pierre A; Sels, Bert F

    2012-06-20

    A novel catalyst design for the conversion of mono- and disaccharides to lactic acid and its alkyl esters was developed. The design uses a mesoporous silica, here represented by MCM-41, which is filled with a polyaromatic to graphite-like carbon network. The particular structure of the carbon-silica composite allows the accommodation of a broad variety of catalytically active functions, useful to attain cascade reactions, in a readily tunable pore texture. The significance of a joint action of Lewis and weak Brønsted acid sites was studied here to realize fast and selective sugar conversion. Lewis acidity is provided by grafting the silica component with Sn(IV), while weak Brønsted acidity originates from oxygen-containing functional groups in the carbon part. The weak Brønsted acid content was varied by changing the amount of carbon loading, the pyrolysis temperature, and the post-treatment procedure. As both catalytic functions can be tuned independently, their individual role and optimal balance can be searched for. It was thus demonstrated for the first time that the presence of weak Brønsted acid sites is crucial in accelerating the rate-determining (dehydration) reaction, that is, the first step in the reaction network from triose to lactate. Composite catalysts with well-balanced Lewis/Brønsted acidity are able to convert the trioses, glyceraldehyde and dihydroxyacetone, quantitatively into ethyl lactate in ethanol with an order of magnitude higher reaction rate when compared to the Sn grafted MCM-41 reference catalyst. Interestingly, the ability to tailor the pore architecture further allows the synthesis of a variety of amphiphilic alkyl lactates from trioses and long chain alcohols in moderate to high yields. Finally, direct lactate formation from hexoses, glucose and fructose, and disaccharides composed thereof, sucrose, was also attempted. For instance, conversion of sucrose with the bifunctional composite catalyst yields 45% methyl lactate in

  1. TOWARD A RISK ASSESSMENT OF PERFLUOROALKYL ACIDS

    EPA Science Inventory

    Perfluoroalkyl acids (PFAA) such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS),and fluorotelomer alcoholsare surfactants that have wide applications in industrial and consumer products. Various fluorotelomer alcohols are known to be metabolized to perfluo...

  2. Fluoride exposure from hydrofluoric acid in a motor gasoline alkylation unit

    SciTech Connect

    Brown, M.G.

    1985-11-01

    To assess the possible health risks associated with occupational exposure to gaseous fluoride, air and biological monitoring surveys were carried out at a motor gasoline alkylation unit within an oil refinery. Pre- and post-shift urinary fluoride measurements were obtained from 27 male operators and maintenance workers attached to the plant; personal fluoride-in-air monitoring was carried out simultaneously for 23 of these men. All readings were below NIOSH recommendations and Australia exposure standards. Significant exposure identified by changes in urine level during the shift could be demonstrated only in sub-groups of workers whose jobs involved higher routine exposures. No significant correlation between air levels and changes in urinary fluoride during the shift could be demonstrated. This survey indicates that the workers in this plant are not at risk of chronic fluorosis.

  3. Morphology Tailoring of Sulfonic Acid Functionalized Organosilica Nanohybrids for the Synthesis of Biomass-Derived Alkyl Levulinates.

    PubMed

    An, Sai; Song, Daiyu; Lu, Bo; Yang, Xia; Guo, Yi-Hang

    2015-07-20

    Morphology evolution of sulfonic acid functionalized organosilica nanohybrids (Si(Et)Si-Pr/ArSO3 H) with a 1D tubular structure (inner diameter of ca. 5 nm), a 2D hexagonal mesostructure (pore diameter of ca. 5 nm), and a 3D hollow spherical structure (shell thickness of 2-3 nm and inner diameter of ca. 15 nm) was successfully realized through P123-templated sol-gel cocondensation strategies and fine-tuning of the acidity followed by aging or a hydrothermal treatment. The Si(Et)Si-Pr/ArSO3 H nanohybrids were applied in synthesis of alkyl levulinates from the esterification of levulinic acid and ethanolysis of furfural alcohol. Hollow spherical Si(Et)Si-Pr/ArSO3 H and hexagonal mesoporous analogues exhibited the highest and lowest catalytic activity, respectively, among three types of nanohybrids; additionally, the activity was influenced by the -SO3 H loading. The activity differences are explained in terms of different Brønsted acid and textural properties, reactant/product diffusion, and mass transfer rate, as well as accessibility of -SO3 H sites to the reactant molecules. The reusability of the nanohybrids was also evaluated.

  4. Asymmetric direct α-alkylation of 2-oxindoles with Michler's hydrol catalyzed by bis-cinchona alkaloid-Brønsted acid via an SN1-type pathway.

    PubMed

    Zhang, Tao; Qiao, Zhen; Wang, Yan; Zhong, Nengjun; Liu, Li; Wang, Dong; Chen, Yong-Jun

    2013-02-25

    An enantioselective direct α-alkylation of 2-oxindoles with Michler's hydrol via an S(N)1-type pathway in the non-covalent activation mode using the bis-cinchona alkaloid and Brønsted acid as a co-catalyst was developed and good to high yields and enantioselectivities were obtained.

  5. Lewis acid-catalyzed Friedel-Crafts alkylations of 3-hydroxy-2-oxindole: an efficient approach to the core structure of azonazine.

    PubMed

    Ghosh, Santanu; Kinthada, Lakshmana K; Bhunia, Subhajit; Bisai, Alakesh

    2012-10-18

    A Lewis acid catalyzed Friedel-Crafts reaction of electron rich aromatics with 3-alkyl-3-hydroxy-2-oxindole (5) has been developed. The methodology provides a straightforward access to the core of azonazine (2) sharing an all-carbon quaternary stereocenter at the tetracyclic ring junction.

  6. Enantioselective Friedel-Crafts alkylation of indole derivatives catalyzed by new Yb(OTf)3-pyridylalkylamine complexes as chiral Lewis acids.

    PubMed

    Grach, Guillaume; Dinut, Aurelia; Marque, Sylvain; Marrot, Jérôme; Gil, Richard; Prim, Damien

    2011-01-21

    New Yb(OTf)(3)-pyridylalkylamine complexes have been employed as chiral Lewis acids in the enantioselective Friedel-Crafts alkylation of indole derivatives with trifluoropyruvates. The influence of the substituents as well as the configuration of the ligands have been studied and allowed us to reach enantiomeric excesses up to 83%.

  7. General approach for the stereocontrolled construction of the beta-lactam ring in amino acid-derived 4-alkyl-4-carboxy-2-azetidinones.

    PubMed

    Gerona-Navarro, Guillermo; García-López, M Teresa; González-Muñiz, Rosario

    2002-05-31

    The first general approach toward the asymmetric synthesis of 4-alkyl-4-carboxy-2-azetidinones derived from amino acids is described. The stereoselective construction of the beta-lactam ring was achieved through base-mediated intramolecular cyclization of the corresponding N(alpha)-chloroacetyl derivatives bearing (+)- or (-)-10-(N,N-dicyclohexylsulfamoyl)isoborneol as chiral auxiliary (ee up to 82%).

  8. Parameters affecting the formation of perfluoroalkyl acids during wastewater treatment.

    PubMed

    Guerra, P; Kim, M; Kinsman, L; Ng, T; Alaee, M; Smyth, S A

    2014-05-15

    This study examined the fate and behaviour of perfluoroalkyl acids (PFAAs) in liquid and solid samples from five different wastewater treatment types: facultative and aerated lagoons, chemically assisted primary treatment, secondary aerobic biological treatment, and advanced biological nutrient removal treatment. To the best of our knowledge, this is the largest data set from a single study available in the literature to date for PFAAs monitoring study in wastewater treatment. Perfluorooctanoic acid (PFOA) was the predominant PFAA in wastewater with levels from 2.2 to 150ng/L (influent) and 1.9 to 140ng/L (effluent). Perfluorooctanesulfonic acid (PFOS) was the predominant compound in primary sludge, waste biological sludge, and treated biosolids with concentrations from 6.4 to 2900ng/g dry weight (dw), 9.7 to 8200ng/gdw, and 2.1 to 17,000ng/gdw, respectively. PFAAs were formed during wastewater treatment and it was dependant on both process temperature and treatment type; with higher rates of formation in biological wastewater treatment plants (WWTPs) operating at longer hydraulic retention times and higher temperatures. PFAA removal by sorption was influenced by different sorption tendencies; median log values of the solid-liquid distribution coefficient estimated from wastewater biological sludge and final effluent were: PFOS (3.73)>PFDA (3.68)>PFNA (3.25)>PFOA (2.49)>PFHxA (1.93). Mass balances confirmed the formation of PFAAs, low PFAA removal by sorption, and high PFAA levels in effluents.

  9. Sulfuric acid functional zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts for alkylation of phenol with tert-butyl alcohol

    SciTech Connect

    Jiang, Tingshun Cheng, Jinlian; Liu, Wangping; Fu, Lie; Zhou, Xuping; Zhao, Qian; Yin, Hengbo

    2014-10-15

    Several zirconium (or aluminum) incorporated mesoporous MCM-48 solid acid catalysts (SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48) were prepared by the impregnation method and their physicochemical properties were characterized by means of XRD, FT-IR, TEM, NH{sub 3}-TPD and N{sub 2} physical adsorption. Also, the catalytic activities of these solid acid catalysts were evaluated by the alkylation of phenol with tert-butyl alcohol. The effect of weight hour space velocity (WHSV), reaction time and reaction temperature on catalytic properties was also studied. The results show that the SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48 still have good mesoporous structure and long range ordering. Compared with the Zr (or Al)–MCM-48 samples, SO{sub 4}{sup 2−}/Zr-MCM-48 and SO{sub 4}{sup 2−}/Al-MCM-48 solid acid catalysts have strong acidity and exhibit high activities in alkylation reaction of phenol with tert-butyl alcohol. The SO{sub 4}{sup 2−}/Zr-MCM-48-25 (molar ratio of Si/Zr=0.04) catalyst was found to be the most promising and gave the highest phenol conversion among all catalysts. A maximum phenol conversion of 91.6% with 4-tert-butyl phenol (4-TBP) selectivity of 81.8% was achieved when the molar ratio of tert-butyl alcohol:phenol is 2:1, reaction time is 2 h, the WHSV is 2 h{sup −1} and the reaction temperature is 140 °C. - Highlights: • Sulfuric acid functional mesoporous solid acid catalysts were prepared via impregnation method. • The alkylation of phenol with tert-butyl alcohol was carried out over these solid acid catalysts. • The catalytic activity of SO{sub 4}{sup 2−}/Zr-MCM-48-25 catalyst is much higher than that of the others. • A maximum phenol conversion of 91.6% was achieved under optimum reaction conditions for SO{sub 4}{sup 2−}/Zr-MCM-48-25.

  10. Hydrogen-Bond Directed Regioselective Pd-Catalyzed Asymmetric Allylic Alkylation: The Construction of Chiral α-Amino Acids with Vicinal Tertiary and Quaternary Stereocenters.

    PubMed

    Wei, Xuan; Liu, Delong; An, Qianjin; Zhang, Wanbin

    2015-12-04

    A Pd-catalyzed asymmetric allylic alkylation of azlactones with 4-arylvinyl-1,3-dioxolan-2-ones was developed, providing "branched" chiral α-amino acids with vicinal tertiary and quaternary stereocenters, in high yields and with excellent selectivities. Mechanistic studies revealed that the formation of a hydrogen bond between the Pd-allylic complex and azlactone isomer is responsible for the excellent regioselectivities. This asymmetric alkylation can be carried out on a gram scale without a loss of catalytic efficiency, and the resulting product can be further transformed to a chiral azetidine in two simple steps.

  11. Molecular design of boronic acid-functionalized squarylium cyanine dyes for multiple discriminant analysis of sialic acid in biological samples: selectivity toward monosaccharides controlled by different alkyl side chain lengths.

    PubMed

    Ouchi, Kazuki; Colyer, Christa L; Sebaiy, Mahmoud; Zhou, Jin; Maeda, Takeshi; Nakazumi, Hiroyuki; Shibukawa, Masami; Saito, Shingo

    2015-02-03

    We designed a new series of boronic acid-functionalized squarylium cyanine dyes (SQ-BA) with different lengths of alkyl chain residues, suitable for multiple discriminant analysis (MDA) of sialic acid (Neu5Ac) in biological samples. The SQ-BA dyes form aggregates based on hydrophobic interactions, which result in quenched fluorescence in aqueous solutions. When the boronic acid binds with saccharides, the fluorescence intensity increases as a result of dissociation to the emissive monomeric complex. We inferred that different dye aggregate structures (H-aggregates and J-aggregates) were induced depending on the alkyl chain length, so that monosaccharides would be recognized in different ways (especially, multipoint interaction with J-aggregates). A distinctive emission enhancement of SQ-BA dyes with shorter-alkyl-chains in the presence of Neu5Ac was observed (2.4-fold fluorescence enhancement; with formation constant 10(1.7) M(-1)), with no such enhancement for SQ-BA dyes with longer-alkyl-chain. In addition, various enhancement factors for other monosaccharides were observed depending on the alkyl chain length. Detailed thermodynamic and NMR studies of the SQ-BA complexes revealed the unique recognition mechanism: the dye aggregate with a shorter-alkyl-chain causes the slipped parallel structure and forms a stable 2:1 complex with Neu5Ac, as distinct from longer-alkyl-chain dyes, which form a 1:1 monomeric complex. MDA using the four SQ-BA dyes was performed for human urine samples, resulting in the successful discrimination between normal and abnormal Neu5Ac levels characteristic of disease. Thus, we successfully controlled various responses to similar monosaccharides with a novel approach that chemically modified not the boronic acid moiety itself but the length of the alkyl chain residue attached to the dye in order to generate specificity.

  12. 40 CFR 721.7785 - Substituted alkyl aminomethylene polyphosphonic acid, salt (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... polyphosphonic acid, salt (generic). 721.7785 Section 721.7785 Protection of Environment ENVIRONMENTAL PROTECTION... acid, salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted alkylamino methylene polyphosphonic acid,...

  13. 40 CFR 721.7785 - Substituted alkyl aminomethylene polyphosphonic acid, salt (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... polyphosphonic acid, salt (generic). 721.7785 Section 721.7785 Protection of Environment ENVIRONMENTAL PROTECTION... acid, salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted alkylamino methylene polyphosphonic acid,...

  14. 40 CFR 721.7785 - Substituted alkyl aminomethylene polyphosphonic acid, salt (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... polyphosphonic acid, salt (generic). 721.7785 Section 721.7785 Protection of Environment ENVIRONMENTAL PROTECTION... acid, salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted alkylamino methylene polyphosphonic acid,...

  15. 40 CFR 721.7785 - Substituted alkyl aminomethylene polyphosphonic acid, salt (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... polyphosphonic acid, salt (generic). 721.7785 Section 721.7785 Protection of Environment ENVIRONMENTAL PROTECTION... acid, salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted alkylamino methylene polyphosphonic acid,...

  16. 40 CFR 721.7785 - Substituted alkyl aminomethylene polyphosphonic acid, salt (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... polyphosphonic acid, salt (generic). 721.7785 Section 721.7785 Protection of Environment ENVIRONMENTAL PROTECTION... acid, salt (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a substituted alkylamino methylene polyphosphonic acid,...

  17. 40 CFR 721.9460 - Tall oil fatty acids, reaction products with polyamines, alkyl substituted.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Tall oil fatty acids, reaction... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9460 Tall oil fatty acids, reaction... reporting. (1) The chemical substance identified generically as tall oil fatty acids, reaction products...

  18. 40 CFR 721.9460 - Tall oil fatty acids, reaction products with polyamines, alkyl substituted.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Tall oil fatty acids, reaction... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9460 Tall oil fatty acids, reaction... reporting. (1) The chemical substance identified generically as tall oil fatty acids, reaction products...

  19. 40 CFR 721.9460 - Tall oil fatty acids, reaction products with polyamines, alkyl substituted.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Tall oil fatty acids, reaction... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9460 Tall oil fatty acids, reaction... reporting. (1) The chemical substance identified generically as tall oil fatty acids, reaction products...

  20. 40 CFR 721.9460 - Tall oil fatty acids, reaction products with polyamines, alkyl substituted.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Tall oil fatty acids, reaction... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9460 Tall oil fatty acids, reaction... reporting. (1) The chemical substance identified generically as tall oil fatty acids, reaction products...

  1. 40 CFR 721.9460 - Tall oil fatty acids, reaction products with polyamines, alkyl substituted.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Tall oil fatty acids, reaction... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.9460 Tall oil fatty acids, reaction... reporting. (1) The chemical substance identified generically as tall oil fatty acids, reaction products...

  2. Outlook for the U. S. alkylation industry

    SciTech Connect

    Felten, J.R.; Bradshaw, T.; McCarthy, K. )

    1994-01-01

    Alkylation has long been recognized in the refining industry as one of the best options to convert refinery olefins into valuable, clean, high octane blending components. In fact, refinery alkylation is a preferred source of blending stocks for reformulated gasoline. However, the hydrofluoric acid (HF) alkylation process and, to a lesser extent, the sulfuric acid (SA) process have come under increasing pressure in the US due to safety and environmental concerns. This paper examines the current outlook for the US alkylation industry including: key trends and driving forces in the industry, the impact of environmental issues on both HF and SA alkylation, US alkylation supply/demand forecast including the outlook for oxygenates, how US refines will respond to the increased demand and restricted supply for alkylates, and the outlook for new solid acid alkylation (SAC) technology.

  3. Enhanced production of short-chain fatty acid from food waste stimulated by alkyl polyglycosides and its mechanism.

    PubMed

    Zhao, Jianwei; Yang, Qi; Li, Xiaoming; Wang, Dongbo; Luo, Kun; Zhong, Yu; Xu, Qiuxiang; Zeng, Guangming

    2015-12-01

    Short-chain fatty acids (SCFAs) are the valuable products derived from the anaerobic fermentation of organic solid waste. However, SCFAs yield was limited by the worse solubilization and hydrolysis of particulate organic matter, and rapid consumption of organic acid by methanogens. In this study, an efficient and green strategy, i.e. adding biosurfactant alkyl polyglycosides (APG) into anaerobic fermentation system, was applied to enhance SCFAs production from food waste. Experimental results showed that APG not only greatly improved SCFAs production but also shortened the fermentation time for the maximum SCFAs accumulation. The SCFAs yield at optimal APG dosage 0.2g/g TS (total solid) reached 37.2g/L, which was 3.1-fold of that in blank. Meanwhile, the time to accumulate the maximum SCFAs in the presence of APG was shortened from day 14 to day 6. The activities of key enzymes such as hydrolytic and acid-forming enzymes were greatly promoted due to the presence of APG. These results demonstrated that the enhanced mechanism of SCFAs production should be attributed to the acceleration of solubilization and hydrolysis, enhancement of acidification and inhibition of methanogenesis by APG.

  4. Ruthenium-catalyzed alkylation of indoles with tertiary amines by oxidation of a sp3 C-H bond and Lewis acid catalysis.

    PubMed

    Wang, Ming-Zhong; Zhou, Cong-Ying; Wong, Man-Kin; Che, Chi-Ming

    2010-05-17

    Ruthenium porphyrins (particularly [Ru(2,6-Cl(2)tpp)CO]; tpp=tetraphenylporphinato) and RuCl(3) can act as oxidation and/or Lewis acid catalysts for direct C-3 alkylation of indoles, giving the desired products in high yields (up to 82% based on 60-95% substrate conversions). These ruthenium compounds catalyze oxidative coupling reactions of a wide variety of anilines and indoles bearing electron-withdrawing or electron-donating substituents with high regioselectivity when using tBuOOH as an oxidant, resulting in the alkylation of N-arylindoles to 3-{[(N-aryl-N-alkyl)amino]methyl}indoles (yield: up to 82%, conversion: up to 95%) and the alkylation of N-alkyl or N-H indoles to 3-[p-(dialkylamino)benzyl]indoles (yield: up to 73%, conversion: up to 92%). A tentative reaction mechanism involving two pathways is proposed: an iminium ion intermediate may be generated by oxidation of an sp(3) C-H bond of the alkylated aniline by an oxoruthenium species; this iminium ion could then either be trapped by an N-arylindole (pathway A) or converted to formaldehyde, allowing a subsequent three-component coupling reaction of the in situ generated formaldehyde with an N-alkylindole and an aniline in the presence of a Lewis acid catalyst (pathway B). The results of deuterium-labeling experiments are consistent with the alkylation of N-alkylindoles via pathway B. The relative reaction rates of [Ru(2,6-Cl(2)tpp)CO]-catalyzed oxidative coupling reactions of 4-X-substituted N,N-dimethylanilines with N-phenylindole (using tBuOOH as oxidant), determined through competition experiments, correlate linearly with the substituent constants sigma (R(2)=0.989), giving a rho value of -1.09. This rho value and the magnitudes of the intra- and intermolecular deuterium isotope effects (k(H)/k(D)) suggest that electron transfer most likely occurs during the initial stage of the oxidation of 4-X-substituted N,N-dimethylanilines. Ruthenium-catalyzed three-component reaction of N-alkyl/N-H indoles

  5. Perfluoroalkyl acid uptake in lettuce (Lactuca sativa) and strawberry (Fragaria ananassa) irrigated with reclaimed water.

    PubMed

    Blaine, Andrea C; Rich, Courtney D; Sedlacko, Erin M; Hyland, Katherine C; Stushnoff, Cecil; Dickenson, Eric R V; Higgins, Christopher P

    2014-12-16

    Using reclaimed water to irrigate food crops presents an exposure pathway for persistent organic contaminants such as perfluoroalkyl acids (PFAAs) to enter the human food chain. This greenhouse study used reclaimed water augmented with varying concentrations (0.2-40 μg/L) of PFAAs, including perfluorocarboxylates (C3F7COO(-) to C8F17COO(-)) and perfluorosulfonates (C4F9SO2O(-), C6F13SO2O(-), C8F17SO2O(-)), to investigate potential uptake and concentration-response trends in lettuce (Lactuca sativa) and strawberry (Fragaria ananassa). In addition, studies were conducted to evaluate the role of soil organic carbon concentrations on plant uptake of PFAAs. PFAA concentrations in lettuce leaves and strawberry fruit were measured for each aqueous PFAA concentration applied. PFAA plant concentrations increased linearly with the aqueous concentration for all PFAAs, with PFCAs bioaccumulating to a greater degree than PFSAs in the edible portions of the tested plants. Chain-length-dependency trends were evident in both lettuce shoot and strawberry fruit, with decreasing concentrations associated with increasing chain length. Perfluorobutanoate (PFBA) and perfluoropentanoate (PFPeA), both short-chain PFAAs (<8 carbon chain length), accumulated the most compared with other PFAAs tested in the edible parts of both lettuce and strawberry. PFAA concentrations in strawberry root and shoot were also measured at selected PFAA aqueous concentrations (0.4, 4, and 40 μg/L). Short-chain perfluorocarboxylates were the dominant fraction in the strawberry fruit and shoot compartments, whereas a more even distribution of all PFAAs appeared in the root compartment. Lettuce grown in soils with varying organic carbon contents (0.4%, 2%, 6%) was used to assess the impact of organic carbon sorption on PFAA bioaccumulation. The lettuce grown in soil with the 6% organic carbon content had the lowest bioaccumulation of PFAAs. Bioaccumulation factors for lettuce were correlated to carbon chain

  6. Perfluoroalkyl acids in the serum and milk of breastfeeding North Carolina women

    EPA Science Inventory

    Perfluoroalkyl acids (PFAAs) comprise a group of man-made persistent environmental compounds. They are widely used in consumer products such as food packaging material, non-stick cookware and cleaning agents, and have been detected in drinking water. Certain PFAAs tend to bioaccu...

  7. PRENATAL AND POSTNATAL EFFECTS IN RATS OF PERFLUORONONANOIC ACID EXPOSURE IN UTERO

    EPA Science Inventory

    In recent years, our understanding of the developmental toxicity of perfluoroalkyl acids (PFAAs) has focused on the C8 compounds. Ubiquitous environmental contaminants, PFAA’s are utilized as surfactants in a variety of industrial applications. Although several PFAAs have been ex...

  8. Uptake of perfluoroalkyl acids into edible crops via land applied biosolids: Field and greenhouse studies

    EPA Science Inventory

    The presence of perfluoroalkyl acids (PFAAs) in biosolids destined for use in agriculture has raised concerns about their potential to enter the terrestrial food chain via bioaccumulation in edible plants. Uptake of PFAAs by greenhouse lettuce ( Lactuca sativa) and tomato (Lycope...

  9. Concentrations of volatile 4-alkyl-branched fatty acids in sheep and goat milk and dairy products.

    PubMed

    Kaffarnik, Stefanie; Kayademir, Yasemin; Heid, Carolina; Vetter, Walter

    2014-11-01

    Goat and sheep milk and dairy products thereof are characterized by a strong and unique flavor. In this context, the volatile minor fatty acid 4-ethyloctanoic acid plays a prominent role along with 4-methyloctanoic acid when both are present in free form. Using a novel GC/MS method in the selected ion-monitoring mode, previously developed for sheep subcutaneous adipose tissue, we were able to analyze the total concentrations of these flavor-relevant minor fatty acids as methyl esters in goat and sheep milk as well as in their products. Differences between the concentrations and ratios of 4-methyloctanoic acid and 4-ethyloctanoic acid in goat milk (n = 4), goat cheese (n = 4), sheep milk (n = 2), and sheep cheese (n = 4) were observed. Goat milk and cheese resulted in higher concentrations for both fatty acids (190 to 480 μg/g milk fat) and smaller 4-Me-8:0 to 4-Et-8:0 ratios (1.4 to 2.7) compared to sheep milk and cheese (78 to 220 μg/g milk fat; 4-Me-8:0 to 4-Et-8:0 ratio: 15 to 42). In all samples, the concentration of 4-Me-8:0 exceeded the one of 4-Et-8:0. However, due to its lower flavor threshold value the contribution of 4-Et-8:0 to the flavor was generally >76%. The calculated flavor values were >1400 for goat milk and cheeses and >200 for sheep milk and cheeses. In goat milk and its products, only a proportion of <0.1% 4-alkyl-branched fatty acids present in free form in the goat milk and <0.5% in the sheep samples would be sufficient to generate the characteristic goaty flavor. Parameters that promote or prevent the release of 4-Me-8:0, and especially 4-Et-8:0, will be decisive for the flavor in the resulting dairy product.

  10. Developmental Toxicity of Perfluorinated Phosphonic Acids in Mice

    EPA Science Inventory

    Perfluorinated phosphonic acids (PFPAs) are a third member of the perfluoroalkyl acid (PFAA) family, and are structurally similar to the perfluoroalkyl sulfonates and perfluoroalkyl carboxylates. PFPAs are used primarily as a surfactant defoaming agent in pesticide production. Re...

  11. Toxicogenomic profiling of perfluorononanoic acid in wild-type and PPARa-null mice

    EPA Science Inventory

    Perfluorononanoic acid (PFNA) is a ubiquitous environmental contaminant and a developmental toxicant in laboratory animals. Like other perfluoroalkyl acids (PFAAs) such as perfluorooctane sulfonate (PFOA) and perfluoroalkyl acid (PFOS), PFNA is a known activator ofperoxisome prol...

  12. [EFfect of quinazolone-alkyl-carboxylic acid derivatives on the transmembrane Ca2+ ion flux mediated by AMPA receptors].

    PubMed

    Szárics, Eva; LaszTóczi, Bálint; Nyikos, Lajos; Barabás, Péter; Kovács, Ilona; Skuban, Nina; Nagy, Péter I; Kökösi, József; Takácsné, Novák Krisztina; Kardos, Julianna

    2002-01-01

    The excitatory neurotransmitter, Glu, plays a crucial role in many sensory and motor functions as well as in brain development, learning and memory and it is also involved in the pathogenesis of a number of neurological disorders, including epilepsy, Alzheimer's and Parkinson's diseases. Therefore, the study of Glu receptors (GluRs) is of therapeutical importance. We showed here by fluorescence monitoring of transmembrane Ca2+ ion fluxes in response to (S)-alpha-amino-3-hidroxi-5-metil-4-izoxazol propionic acid ((S)-AMPA) on the time scale of 0.00004-10 s that Ca2+ ion influx proceeds through faster and slower desensitizing receptors. Pharmacological isolation of the slower and faster desensitizing AMPA receptor was possible by fluorescence monitoring of Ca2+ ion translocation in response to (S)-AMPA in the presence and absence of various 2-methyl-4-oxo-3H-quinazoline-3-alkyl-carboxilic acid derivatives (Qxs): the acetic acid Q1 inhibits the slower desensitizing receptor response specifically, while the acetyl-piperidine Q5 is a more potent inhibitor of the faster desensitizing receptor response. In addition, spontaneous interictal activity, as induced by high [K+] conditions in hippocampal slices, was reduced significantly by Q5, suggesting a possible anticonvulsant property of Q5. Substitutions of Qxs into the GluR2 S1S2 binding core were consistent with their effect by causing variable degree of S1S2 bridging interaction as one of the main determinants of AMPA receptor agonist activity. The exploitation of differences between similar receptors will be important in the development and use of drugs with high pharmacological specificity.

  13. Stabilization of alkylated azacrown ether by fatty acid at the air-water interface.

    PubMed

    Zarbakhsh, Ali; Campana, Mario; Webster, John R P; Wojciechowski, Kamil

    2010-12-07

    The adsorbed amount of partially deuterated dihexadecyl-diaza-18-crown-6 ether (d-ACE16) in the presence of different chain length fatty acids as a function of surface pressure was determined by neutron reflectometry technique. The highest adsorbed amount of the azacrown ether was observed for the mixture of ACE16 with hexadecanoic (palmitic) acid, pointing to the importance of chain length matching between the two species for optimum stabilization of the mixed monolayer. The contrast variation technique was used to estimate the contribution to the total adsorbed amount from stearic acid and ACE16. It was found that the mixed Langmuir monolayer is stable against dissolution up to a surface pressure of 20 mN m(-1). Above this pressure, however, the spread and adsorbed amounts start to deviate, indicative of partial dissolution into the aqueous subphase. The consequences of this behavior for the transport of metal ions through the interfaces of permeation liquid membranes (PLMs) are discussed.

  14. A national discharge load of perfluoroalkyl acids derived from industrial wastewater treatment plants in Korea.

    PubMed

    Kim, Hee-Young; Seok, Hyun-Woo; Kwon, Hye-Ok; Choi, Sung-Deuk; Seok, Kwang-Seol; Oh, Jeong Eun

    2016-09-01

    Levels of 11 perfluoroalkyl acids (PFAAs), including perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), were measured in wastewater (influent and effluent) and sludge samples collected from 25 industrial wastewater treatment plants (I-WWTPs) in five industrial sectors (chemicals, electronics, metals, paper, and textiles) in South Korea. The highest ∑11PFAAs concentrations were detected in the influent and effluent from the paper (median: 411ng/L) and textile (median: 106ng/L) industries, and PFOA and PFOS were the predominant PFAAs (49-66%) in wastewater. Exceptionally high levels of PFAAs were detected in the sludge associated with the electronics (median: 91.0ng/g) and chemical (median: 81.5ng/g) industries with PFOS being the predominant PFAA. The discharge loads of 11 PFAAs from I-WWTP were calculated that total discharge loads for the five industries were 0.146ton/yr. The textile industry had the highest discharge load with 0.055ton/yr (PFOA: 0.039ton/yr, PFOS: 0.010ton/yr). Municipal wastewater contributed more to the overall discharge of PFAAs (0.489ton/yr) due to the very small industrial wastewater discharge compared to municipal wastewater discharge, but the contribution of PFAAs from I-WWTPs cannot be ignored.

  15. Spatiotemporal distribution and potential sources of perfluoroalkyl acids in Huangpu River, Shanghai, China.

    PubMed

    Sun, Zhuyu; Zhang, Chaojie; Yan, Hong; Han, Changlai; Chen, Ling; Meng, Xiangzhou; Zhou, Qi

    2017-05-01

    Perfluoroalkyl acids (PFAAs) have been found to be ubiquitously disseminated in the environment due to their widespread use in recent decades. In this study, the occurrence and spatiotemporal distribution of PFAAs in the surface water of Huangpu River, Shanghai, China were investigated from 2012 to 2014. The total concentration of 14 PFAAsPFAAs) ranged from 39.8 to 596.2 ng L(-1), with a mean value of 226.3 ng L(-1). Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) were dominant, with their mean concentrations of 139.6 and 46.5 ng L(-1), respectively. The concentration of ΣPFAAs increased greatly downstream especially in the lower reach of an industrial and urbanized area. Samples collected in different seasons were used to analyze the seasonal variation. The results showed that higher concentration of ΣPFAAs occurred in the wet season, especially downstream. Therefore, industrial discharges, municipal wastewater and surface runoff were identified as major potential sources. The annual discharge load of ΣPFAAs from Huangpu River to Yangtze River was estimated to be 2263.4 kg yr(-1). The hazard assessment suggested that the contamination of PFAAs in Huangpu River could pose risks to the aquatic environment and drinking water safety, which should draw more attention.

  16. Alkyl polyglucose enhancing propionic acid enriched short-chain fatty acids production during anaerobic treatment of waste activated sludge and mechanisms.

    PubMed

    Luo, Jingyang; Feng, Leiyu; Chen, Yinguang; Sun, Han; Shen, Qiuting; Li, Xiang; Chen, Hong

    2015-04-15

    Adding alkyl polyglucose (APG) into an anaerobic treatment system of waste activated sludge (WAS) was reported to remarkably improve the production of short-chain fatty acids (SCFAs), especially propionic acid via simultaneously accelerating solubilization and hydrolysis, enhancing acidification, inhibiting methanogenesis and balancing carbon to nitrogen (C/N) ratio of substrate. Not only the production of SCFAs, especially propionic acid, was significantly improved by APG, but also the feasible operation time was shortened. The SCFAs yield at 0.3 g APG per gram of total suspended solids (TSS) within 4 d was 2988 ± 60 mg chemical oxygen demand (COD) per liter, much higher than that those from sole WAS or sole WAS plus sole APG. The corresponding yield of propionic acid was 1312 ± 25 mg COD/L, 7.9-fold of sole WAS. Mechanism investigation showed that during anaerobic treatment of WAS in the presence of APG both the solubilization and hydrolysis were accelerated and the acidification was enhanced, while the methanogenesis was inhibited. Moreover, the activities of key enzymes involved in WAS hydrolysis and acidification were improved through the adjustment of C/N ratio of substrates with APG. The abundance of microorganisms responsible for organic compounds hydrolysis and SCFAs production was also observed to be greatly enhanced with APG via 454 high-throughput pyrosequencing analysis.

  17. Perfluoroalkyl acids in the water cycle from a freshwater river basin to coastal waters in eastern China.

    PubMed

    Zhu, Xiaobin; Jin, Ling; Yang, Jingping; Wu, Jianfeng; Zhang, Beibei; Zhang, Xiaowei; Yu, Nanyang; Wei, Si; Wu, Jichun; Yu, Hongxia

    2017-02-01

    The distribution of perfluoroalkyl acids (PFAAs), one class of persistent organic pollutants, in groundwater, especially in confined aquifers remains poorly understood. In this study, we investigated the occurrence of 12 PFAAs through a water cycle from the Huai River Basin to the Yellow Sea, including confined aquifers, unconfined aquifers, rivers, and coastal waters. We found the ubiquity of PFAAs in all types of samples, including those from confined aquifers (2.7-6.8 ng/L). Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) were the major PFAAs in all samples, accounting for an average of 49.1% (0.8-84.8%) and 33.3% (6.3-92.2%) of total PFAAs, respectively. Comparing the concentration of PFOA with that of PFOS, we found a higher concentration of PFOA in rivers and a higher concentration of PFOS in confined aquifers. Short-chain perfluoropentanoic acid accounted for an average of 10.3% (1.9-24.6%) of total PFAAs in rivers and coastal waters. Branched isomers of both PFOA and PFOS were detected in most samples (36/42 and 39/42, respectively). One-way analysis of variance indicated a significant difference in the profiles of PFAAs among the different types of water samples. Principal component analysis suggested that rainwater and recent uses of PFAAs could be the major sources of PFAAs in confined aquifers, while recent and current uses of PFAAs could be the major source of PFAAs in unconfined aquifers, rivers and coastal waters. The risk quotients of PFOA and PFOS in groundwater and rivers were 2-3 orders of magnitude lower than unity, indicating no immediate risks via drinking water consumption.

  18. Chiral phosphoric acid catalyzed highly enantioselective Friedel-Crafts alkylation reaction of C3-substituted indoles to β,γ-unsaturated α-ketimino esters.

    PubMed

    Bi, Bo; Lou, Qin-Xin; Ding, Yu-Yang; Chen, Sheng-Wei; Zhang, Sha-Sha; Hu, Wen-Hui; Zhao, Jun-Ling

    2015-02-06

    A highly enantioselective C2 Friedel-Crafts alkylation reaction of 3-substituted indoles to β,γ-unsaturated α-ketimino esters has been developed. This reaction was efficiently catalyzed by a chiral phosphoric acid catalyst. The corresponding C2-substituted indole derivatives, bearing an α-ketimino ester motif, were obtained in moderate to high yields (up to 93%) and with high enantioselectivities (up to >99% ee).

  19. Electrochemical method for producing a biodiesel mixture comprising fatty acid alkyl esters and glycerol

    DOEpatents

    Lin, YuPo J; St. Martin, Edward J

    2013-08-13

    The present invention relates to an integrated method and system for the simultaneous production of biodiesel from free fatty acids (via esterification) and from triglycerides (via transesterification) within the same reaction chamber. More specifically, one preferred embodiment of the invention relates to a method and system for the production of biodiesel using an electrodeionization stack, wherein an ion exchange resin matrix acts as a heterogeneous catalyst for simultaneous esterification and transesterification reactions between a feedstock and a lower alcohol to produce biodiesel, wherein the feedstock contains significant levels of free fatty acid. In addition, because of the use of a heterogeneous catalyst, the glycerol and biodiesel have much lower salt concentrations than raw biodiesel produced by conventional transesterification processes. The present invention makes it much easier to purify glycerol and biodiesel.

  20. Accumulation potentials of perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs) in maize (Zea mays).

    PubMed

    Krippner, Johanna; Falk, Sandy; Brunn, Hubertus; Georgii, Sebastian; Schubert, Sven; Stahl, Thorsten

    2015-04-15

    Uptake of perfluoroalkyl acids (PFAAs) by maize represents a potential source of exposure for humans, either directly or indirectly via feed for animals raised for human consumption. The aim of the following study was, therefore, to determine the accumulation potential of perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs) in maize (Zea mays). Two different concentrations of PFAAs were applied as aqueous solution to the soil to attain target concentrations of 0.25 mg or 1.00 mg of PFAA per kg of soil. Maize was grown in pots, and after harvesting, PFAA concentrations were measured in the straw and kernels of maize. PFCA and PFSA concentrations of straw decreased significantly with increasing chain length. In maize kernels, only PFCAs with a chain length ≤ C8 as well as perfluorobutanesulfonic acid (PFBS) were detected. The highest soil-to-plant transfer for both straw and kernels was determined for short-chained PFCAs and PFSAs.

  1. Polyimides with pendant alkyl groups

    NASA Technical Reports Server (NTRS)

    Jensen, B. J.; Young, P. R.

    1982-01-01

    The effect on selected polyimide properties when pendant alkyl groups were attached to the polymer backbone was investigated. A series of polymers were prepared using benzophenone tetracarboxylic acid dianhydride (BTDA) and seven different p-alkyl-m,p'-diaminobenzophenone monomers. The alkyl groups varied in length from C(1) (methyl) to C(9) (nonyl). The polyimide prepared from BTDA and m,p'-diaminobenzophenone was included as a control. All polymers were characterized by various chromatographic, spectroscopic, thermal, and mechanical techniques. Increasing the length of the pendant alkyl group resulted in a systematic decrease in glass transition temperature (Tg) for vacuum cured films. A 70 C decrease in Tg to 193 C was observed for the nonyl polymer compared to the Tg for the control. A corresponding systematic increase in Tg indicative of crosslinking, was observed for air cured films. Thermogravimetric analysis revealed a slight sacrifice in thermal stability with increasing alkyl length. No improvement in film toughness was observed.

  2. Current Understanding of Perfluoroalkyl Acid Toxicology ...

    EPA Pesticide Factsheets

    The perfluoroalkyl acids (PFAAs) are a family of organic chemicals consisting of a perfluorinated carbon backbone (4-14 carbons in length) and an anionic head group (sulfonate, carboxylate or phosphonate). These compounds have excellent surface-tension reducing properties and have numerous industrial and consumer applications. However, they are chemically stable, persistent in the environment, ubiquitously distributed, and present in humans and wildlife. Two issues must be considered regarding PFAA toxicology: pharmacokinetics and potency of the chemicals. The rates of PFAA clearance and their body burden accumulation are dependent on carbon-chain length and animal species. In general, the serum half-life of PFAAs increases with chain length in both rodents and humans, but the estimates in humans are markedly higher than those in laboratory animals. Recent studies with laboratory animal models have indicated a number of toxic effects of PFAAs, including tumor induction, hepatotoxicity, developmental toxicity, immunotoxicity, neurotoxicity and endocrine disruption. The modes of PFAA actions are not well understood, but are thought to involve, in part, activation of nuclear receptor signals (such as peroxisome proliferator-activated receptor-a, PPARa). Based on PPARa activation, potency of PFAAs increases with carbon-chain length, carboxylates are stronger than sulfonates, and mouse receptor is more reactive than human receptor. Adverse effects of perfluorophospho

  3. Perfluoroalkyl acid distribution in various plant compartments ...

    EPA Pesticide Factsheets

    Crop uptake of perfluoroalkyl acids (PFAAs) from biosolids-amended soil has been identified as a potential pathway for PFAA entry into the terrestrial food chain. This study compared the uptake of PFAAs in greenhouse-grown radish (Raphanus sativus), celery (Apium graveolens var.dulce), tomato (Lycopersicon lycopersicum), and sugar snap pea (Pisum sativum var. macrocarpon) from an industrially impacted biosolids-amended soil, a municipal biosolids­ amended soil, and a control soil. Individual concentrations of PFAAs, on a dry weight basis, in mature, edible portions of crops grown in soil amended with PFAA industrially impacted biosolids were highest for perfluorooctanoate (PFOA; 67 ng/g) in radish root, perfluorobutanoate (PFBA;232 ng/g) in celery shoot, and PFBA (150 ng/g) in pea fruit. Comparatively, PFAA concentrations in edible compartments of crops grown in the municipal biosolids-amended soil and in the control soil were less than 25 ng/g. Bioaccumulation factors (BAFs) were calculated for the root, shoot, and fruit compartments (as applicable) of all crops grown in the industrially impacted soil. BAFs were highest for PFBA in the shoots of all crops, as well as in the fruit compartment of pea. Root­ soil concentration factors (RCFs) for tomato and pea were independent of PFAA chain length, while radish and celery RCFs showed a slight decrease with increasing chain length. Shoot-soil concentration factors (SCFs) for all crops showed a decrease with incre

  4. Footprints of Urban Micro-Pollution in Protected Areas: Investigating the Longitudinal Distribution of Perfluoroalkyl Acids in Wildlife Preserves

    PubMed Central

    Rodriguez-Jorquera, Ignacio A.; Silva-Sanchez, Cecilia; Strynar, Mark; Denslow, Nancy D.; Toor, Gurpal S.

    2016-01-01

    Current approaches to protect biodiversity by establishing protected areas usually gloss over water pollution as a threat. Our objective was to determine the longitudinal and seasonal distribution of perfluoroalkyl acids (PFAAs) in water column and sediments from a wastewater dominated stream that enters preservation areas. Water samples were collected along the longitudinal section (six sites, 1000 m away from each other) of the stream during the dry and wet seasons. Sediments were collected from three sites along the stream from three depths. Water and sediments were analyzed for PFAAs using high performance liquid chromatography-tandem mass spectrometry. Eleven PFAAs with 5 to 14 carbon atoms were detected in the water column at all sampling points, with a minor reduction at the last point suggesting a dilution effect. The most detected PFAAs was PFOS, followed by perfluorooctanoic acid (PFOA), and perfluorohexanoic acid (PFHxA). Seasonal differences in PFAAs concentrations suggested contribution of stormwater runoff during the wet season. All analyzed PFAAs in sediments were under the limit of quantification, likely due to the high proportion of sand and low organic matter. However, high concentrations of PFAAs were detected in the water column inside the protected areas, which includes PFOS in concentrations considered not safe for avian wildlife. Water samples appear to be more relevant than sediments to determine PFAAs micro-pollution in water bodies with sandy sediments. Inclusion of a management plans on micro-pollution research, monitoring, and mitigation is recommended for protected areas. PMID:26909512

  5. Footprints of Urban Micro-Pollution in Protected Areas: Investigating the Longitudinal Distribution of Perfluoroalkyl Acids in Wildlife Preserves.

    PubMed

    Rodriguez-Jorquera, Ignacio A; Silva-Sanchez, Cecilia; Strynar, Mark; Denslow, Nancy D; Toor, Gurpal S

    2016-01-01

    Current approaches to protect biodiversity by establishing protected areas usually gloss over water pollution as a threat. Our objective was to determine the longitudinal and seasonal distribution of perfluoroalkyl acids (PFAAs) in water column and sediments from a wastewater dominated stream that enters preservation areas. Water samples were collected along the longitudinal section (six sites, 1000 m away from each other) of the stream during the dry and wet seasons. Sediments were collected from three sites along the stream from three depths. Water and sediments were analyzed for PFAAs using high performance liquid chromatography-tandem mass spectrometry. Eleven PFAAs with 5 to 14 carbon atoms were detected in the water column at all sampling points, with a minor reduction at the last point suggesting a dilution effect. The most detected PFAAs was PFOS, followed by perfluorooctanoic acid (PFOA), and perfluorohexanoic acid (PFHxA). Seasonal differences in PFAAs concentrations suggested contribution of stormwater runoff during the wet season. All analyzed PFAAs in sediments were under the limit of quantification, likely due to the high proportion of sand and low organic matter. However, high concentrations of PFAAs were detected in the water column inside the protected areas, which includes PFOS in concentrations considered not safe for avian wildlife. Water samples appear to be more relevant than sediments to determine PFAAs micro-pollution in water bodies with sandy sediments. Inclusion of a management plans on micro-pollution research, monitoring, and mitigation is recommended for protected areas.

  6. Lipase-catalyzed enantioselective synthesis of (R,R)-lactide from alkyl lactate to produce PDLA (poly D-lactic acid) and stereocomplex PLA (poly lactic acid).

    PubMed

    Jeon, Byoung Wook; Lee, Jumin; Kim, Hyun Sook; Cho, Dae Haeng; Lee, Hyuk; Chang, Rakwoo; Kim, Yong Hwan

    2013-10-20

    R-lactide, a pivotal monomer for the production of poly (D-lactic acid) (PDLA) or stereocomplex poly (lactic acid) (PLA) was synthesized from alkyl (R)-lactate through a lipase-catalyzed reaction without racemization. From among several types of lipase, only lipase B from Candida antarctica (Novozym 435; CAL-B) was effective in the reaction that synthesized (R,R)-lactide. Enantiopure (R,R)-lactide, which consisted of over 99% enantiomeric excess, was synthesized from methyl (R)-lactate through CAL-B catalysis. Removal of the methanol by-product was critical to obtain a high level of lactide conversion. The (R,R)-lactide yield was 56% in a reaction containing 100 mg of Novozym 435, 10 mM methyl (R)-lactate and 1500 mg of molecular sieve 5A in methyl tert-butyl ether (MTBE). The important monomer (R,R)-lactide that is required for the production of the widely recognized bio-plastic PDLA and the PLA stereocomplex can be obtained using this novel synthetic method.

  7. Occurrence and transport of 17 perfluoroalkyl acids in 12 coastal rivers in south Bohai coastal region of China with concentrated fluoropolymer facilities.

    PubMed

    Wang, Pei; Lu, Yonglong; Wang, Tieyu; Fu, Yaning; Zhu, Zhaoyun; Liu, Shijie; Xie, Shuangwei; Xiao, Yang; Giesy, John P

    2014-07-01

    Perfluoroalkyl acids (PFAAs) are emerging contaminants that have raised great concern in recent years. While PFAAs manufacturing becomes regulated in developed countries, production has been partly shifted to China. Eight fluoropolymer manufacturing facilities located in the South Bohai coastal region, one of the most populated areas of China, have been used to manufacture PFAA-related substances since 2001. The environmental consequence of the intensive production of PFAAs in this region remains largely unknown. We analyzed 17 PFAAs in twelve coastal rivers of this region, and found staggeringly high concentrations of perfluorooctanoic acid (PFOA) ranging from 0.96 to 4534.41 ng/L. The highest concentration was observed in the Xiaoqing River which received effluents from certain fluoropolymer facilities. Principal component analysis indicated similar sources of several perfluoroalkyl carboxylic acids (PFCAs) in all rivers, which indicated that atmospheric transport, wastewater treatment and surface runoff also acted as important supplements to direct discharge to surface water.

  8. Effects of Perfluorinated Phosphonic Acid Exposure during pregnancy in the mouse

    EPA Science Inventory

    Perfluorinated phosphonic acids (PFPAs) are a member of the perfluoroalkyl acid (PFAA) family, and are structurally similar to the perfluoroalkyl sulfonates and perfluoroalkyl carboxylates. These chemicals have recently been detected in the environment, particularly in surface wa...

  9. Preliminary assessment of developmental toxicity of Perfluorinated Phosphonic Acid in mice

    EPA Science Inventory

    Perfluorinated phosphonic acids (PFPAs) are a third member of the perfluoroalkyl acid (PFAA) family, and are structurally similar to the perfluoroalkyl sulfonates and perfluoroalkyl carboxylates. These emerging chemicals have recently been detected in the environment, particularl...

  10. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    DOEpatents

    Ginosar, Daniel M.; Petkovic, Lucia

    2009-09-22

    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  11. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    DOEpatents

    Ginosar, Daniel M.; Petkovic, Lucia M.

    2010-12-28

    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  12. Nanofiltration and granular activated carbon treatment of perfluoroalkyl acids.

    PubMed

    Appleman, Timothy D; Dickenson, Eric R V; Bellona, Christopher; Higgins, Christopher P

    2013-09-15

    Perfluoroalkyl acids (PFAAs) are of concern because of their persistence in the environment and the potential toxicological effects on humans exposed to PFAAs through a variety of possible exposure routes, including contaminated drinking water. This study evaluated the efficacy of nanofiltration (NF) and granular activated carbon (GAC) adsorption in removing a suite of PFAAs from water. Virgin flat-sheet NF membranes (NF270, Dow/Filmtec) were tested at permeate fluxes of 17-75 Lm(-2)h(-1) using deionized (DI) water and artificial groundwater. The effects of membrane fouling by humic acid on PFAA rejection were also tested under constant permeate flux conditions. Both virgin and fouled NF270 membranes demonstrated >93% removal for all PFAAs under all conditions tested. GAC efficacy was tested using rapid small-scale columns packed with Calgon Filtrasorb300 (F300) carbon and DI water with and without dissolved organic matter (DOM). DOM effects were also evaluated with F600 and Siemens AquaCarb1240C. The F300 GAC had <20% breakthrough of all PFAAs in DI water for up to 125,000 bed volumes (BVs). When DOM was present, >20% breakthrough of all PFAAs by 10,000 BVs was observed for all carbons.

  13. Perfluoroalkyl acids and related chemistries Toxicokinetics and modes of action

    EPA Science Inventory

    The perfluoroalkyl acid salts (both carboxylates and sulfonates, hereafter designated as PFAAs) and their derivatives are important chemicals that have numerous consumer and industrial applications. However, recent discoveries that some of these compounds have global distribution...

  14. Synergistic effects of perfluoroalkyl acids mixtures with J-shaped concentration-responses on viability of a human liver cell line.

    PubMed

    Hu, Jiayue; Li, Juan; Wang, Jianshe; Zhang, Aiqian; Dai, Jiayin

    2014-02-01

    Some perfluoroalkyl acids (PFAAs) are highly persistent and bioaccumulative, resulting in their broad coexisting distribution in humans and the environment. Our aim was to investigate the individual and joint effects of PFAAs on cellular viability of a human liver cell line (HL-7702) using the MTT assay. Equipartition ray design and equivalent-effect concentration ratio (EECR) mixtures were used to investigate the binary and multiple effects of PFAAs, respectively. All tested PFAAs mixtures and the individuals (except perfluorododecanoic acid (PFDoDA) and perfluorotetradecanoic acid (PFTeDA)) showed obvious non-monotonic J-shaped concentration-response curves (CRC) on HL-7702. The inhibitory effect of individual PFAAs increased with the elongation of the carbon chain and was dominated by their molecular volume. The three binary mixtures (PFOA/S, PFHxA/S and PFBA/S) showed that synergistic effects occurred under effective inhibitory concentrations (IC) of IC0, IC10, and IC50 in mixtures, while for IC-20 the synergistic effect only occurred under higher PFSA proportion in mixtures. Furthermore, EECR mixtures of the nine individual PFAAs with J-shaped CRC also showed synergistic effects. However, mixtures of the eleven individual PFAAs including those with S-shaped CRC resulted in partial addition effects on HL-7702. Our results indicated that the individual stimulatory responses of HL-7702 to PFAA may produce adverse effects in mixtures at relevant dose levels.

  15. Preparation and evaluation of poly(alkyl methacrylate-co-methacrylic acid-co-ethylene dimethacrylate) monolithic columns for separating polar small molecules by capillary liquid chromatography.

    PubMed

    Lin, Shu-Ling; Wu, Yu-Ru; Lin, Tzuen-Yeuan; Fuh, Ming-Ren

    2015-04-29

    In this study, methacrylic acid (MAA) was incorporated with alkyl methacrylates to increase the hydrophilicity of the synthesized ethylene dimethacrylate-based (EDMA-based) monoliths for separating polar small molecules by capillary LC analysis. Different alkyl methacrylate-MAA ratios were investigated to prepare a series of 30% alkyl methacrylate-MAA-EDMA monoliths in fused-silica capillaries (250-μm i.d.). The porosity, permeability, and column efficiency of the synthesized MAA-incorporated monolithic columns were characterized. A mixture of phenol derivatives is employed to evaluate the applicability of using the prepared monolithic columns for separating small molecules. Fast separation of six phenol derivatives was achieved in 5 min with gradient elution using the selected poly(lauryl methacrylate-co-MAA-co-EDMA) monolithic column. In addition, the effect of acetonitrile content in mobile phase on retention factor and plate height as well as the plate height-flow velocity curves were also investigated to further examine the performance of the selected poly(lauryl methacrylate-co-MAA-co-EDMA) monolithic column. Moreover, the applicability of prepared polymer-based monolithic column for potential food safety applications was also demonstrated by analyzing five aflatoxins and three phenicol antibiotics using the selected poly(lauryl methacrylate-co-MAA-co-EDMA) monolithic column.

  16. Activation of mouse and human peroxisome proliferator-activated receptor alpha by perfluoroalkyl acids of different functional groups and chain lengths.

    PubMed

    Wolf, Cynthia J; Takacs, Margy L; Schmid, Judith E; Lau, Christopher; Abbott, Barbara D

    2008-11-01

    Perfluoroalkyl acids (PFAAs) are surfactants used in consumer products and persist in the environment. Some PFAAs elicit adverse effects on rodent development and survival. PFAAs can activate peroxisome proliferator-activated receptor alpha (PPARalpha) and may act via PPARalpha to produce some of their effects. This study evaluated the ability of numerous PFAAs to induce mouse and human PPARalpha activity in a transiently transfected COS-1 cell assay. COS-1 cells were transfected with either a mouse or human PPARalpha receptor-luciferase reporter plasmid. After 24 h, cells were exposed to either negative controls (water or dimethyl sulfoxide, 0.1%); positive control (WY-14643, PPARalpha agonist); perfluorooctanoic acid or perfluorononanoic acid at 0.5-100 microM; perfluorobutanoic acid, perfluorohexanoic acid, perfluorohexane sulfonate, or perfluorodecanoic acid (PFDA) at 5-100 microM; or perfluorobutane sulfonate or perfluorooctane sulfonate at 1-250 microM. After 24 h of exposure, luciferase activity from the plasmid was measured. Each PFAA activated both mouse and human PPARalpha in a concentration-dependent fashion, except PFDA with human PPARalpha. Activation of PPARalpha by PFAA carboxylates was positively correlated with carbon chain length, up to C9. PPARalpha activity was higher in response to carboxylates compared to sulfonates. Activation of mouse PPARalpha was generally higher compared to that of human PPARalpha. We conclude that, in general, (1) PFAAs of increasing carbon backbone chain lengths induce increasing activity of the mouse and human PPARalpha with a few exceptions, (2) PFAA carboxylates are stronger activators of mouse and human PPARalpha than PFAA sulfonates, and (3) in most cases, the mouse PPARalpha appears to be more sensitive to PFAAs than the human PPARalpha in this model.

  17. Perfluoroalkyl acids: recent research highlights | Science ...

    EPA Pesticide Factsheets

    Perfluorinated compounds are organic chemicals in which all hydrogen molecules of the carbon-chain are substituted by fluorine molecules. Generally, there are two types of perfluorinated compounds, the perfluoroalkanes that are primarily used clinically for oxygenation and respiratory ventilation, and the perfluoroalkyl acids (PFAAs). Environmentally relevant PFAAs are a family of about 30 chemicals that consist of a carbon backbone typically 4-14 molecules in length and a charged functional group composed of either sulfonates, carboxylates or phosphonates (and to a lesser extent, phosphinates). While many (>100) derivatives ofPFAAs (such as alcohols, amides, esters and acids) are used for industrial and consumer applications, they can be degraded or metabolized to PFAAs as end-stage products. Thus, PFAAs, rather than their intermediates or derivatives, have drawn the most public attention and research interest. The most widely known PFAAs are the eight-carbon (C8) sulfonate (perfluorooctane sulfonate, PFOS) and carboxylate (perfluorooctanoic acid, PFOA), although the C4 (perfluorobutane) and C6 (perfluorohexane) sulfonates, as well as the C4, C6 and C9 (perfluorononanoic) carboxylates have also been used in commerce. The perfluoroalkyl phosphonates (PFPAs) are fairly new entities for this class ofchemicals. They are typically used as leveling and wetting agents, and defoaming additives in the production of pesticides. They were considered biologically inert by

  18. N-Acyl Amino Acid Ligands for Ruthenium(II)-Catalyzed meta-C-H tert-Alkylation with Removable Auxiliaries.

    PubMed

    Li, Jie; Warratz, Svenja; Zell, Daniel; De Sarkar, Suman; Ishikawa, Eloisa Eriko; Ackermann, Lutz

    2015-11-04

    Acylated amino acid ligands enabled ruthenium(II)-catalyzed C-H functionalizations with excellent levels of meta-selectivity. The outstanding catalytic activity of the ruthenium(II) complexes derived from monoprotected amino acids (MPAA) set the stage for the first ruthenium-catalyzed meta-functionalizations with removable directing groups. Thereby, meta-alkylated anilines could be accessed, which are difficult to prepare by other means of direct aniline functionalizations. The robust nature of the versatile ruthenium(II)-MPAA was reflected by challenging remote C-H transformations with tertiary alkyl halides on aniline derivatives as well as on pyridyl-, pyrimidyl-, and pyrazolyl-substituted arenes. Detailed mechanistic studies provided strong support for an initial reversible C-H ruthenation, followed by a SET-type C-Hal activation through homolytic bond cleavage. Kinetic analyses confirmed this hypothesis through an unusual second-order dependence of the reaction rate on the ruthenium catalyst concentration. Overall, this report highlights the exceptional catalytic activity of ruthenium complexes derived from acylated amino acids, which should prove instrumental for C-H activation chemistry beyond remote functionalization.

  19. Spatial distribution and importance of potential perfluoroalkyl acid precursors in urban rivers and sewage treatment plant effluent--case study of Tama River, Japan.

    PubMed

    Ye, Feng; Tokumura, Masahiro; Islam, Md Saiful; Zushi, Yasuyuki; Oh, Jungkeun; Masunaga, Shigeki

    2014-12-15

    Production and use of perfluorooctane sulfonate (PFOS) is regulated worldwide. However, numerous potential precursors that eventually decompose into PFOS and other perfluoroalkyl acids (PFAAs) such as perfluorooctanoic acid (PFOA) are still being used and have not been studied in detail. Therefore, knowledge about the levels and sources of the precursors is essential. We investigated the total concentration of potential PFAA precursors in the Tama River, which is one of the major rivers flowing into the Tokyo Bay, by converting all the perfluorinated carboxylic acid (PFCA) and perfluoroalkyl sulfonic acid (PFSA) precursors into PFCAs by chemical oxidation. The importance of controlling PFAA precursors was determined by calculating the ratios of PFCAs formed by oxidation to the PFAAs originally present (ΣΔ[PFCAC4-C12]/Σ[PFAAs]before oxidation) (average = 0.28 and 0.69 for main and tributary branch rivers, respectively). Higher total concentrations of Δ[PFCAs] were found in sewage treatment plant (STP) effluents. However, the ratios found in the effluents were lower (average = 0.21) than those found in the river water samples, which implies the decomposition of some precursors into PFAAs during the treatment process. On the other hand, higher ratios were observed in the upstream water samples and the existence of emission sources other than the STP effluents was indicated. This study showed that although the treatment process converting a part of the PFAA precursors into PFAAs, STPs were important sources of precursors to the Tama River. To reduce the levels of PFAAs in the aquatic environment, it is necessary to reduce the emission of the PFAA precursors as well.

  20. The AlkB Family of Fe(II)/α-Ketoglutarate-dependent Dioxygenases: Repairing Nucleic Acid Alkylation Damage and Beyond.

    PubMed

    Fedeles, Bogdan I; Singh, Vipender; Delaney, James C; Li, Deyu; Essigmann, John M

    2015-08-21

    The AlkB family of Fe(II)- and α-ketoglutarate-dependent dioxygenases is a class of ubiquitous direct reversal DNA repair enzymes that remove alkyl adducts from nucleobases by oxidative dealkylation. The prototypical and homonymous family member is an Escherichia coli "adaptive response" protein that protects the bacterial genome against alkylation damage. AlkB has a wide variety of substrates, including monoalkyl and exocyclic bridged adducts. Nine mammalian AlkB homologs exist (ALKBH1-8, FTO), but only a subset functions as DNA/RNA repair enzymes. This minireview presents an overview of the AlkB proteins including recent data on homologs, structural features, substrate specificities, and experimental strategies for studying DNA repair by AlkB family proteins.

  1. The AlkB Family of Fe(II)/α-Ketoglutarate-dependent Dioxygenases: Repairing Nucleic Acid Alkylation Damage and Beyond*

    PubMed Central

    Fedeles, Bogdan I.; Singh, Vipender; Delaney, James C.; Li, Deyu; Essigmann, John M.

    2015-01-01

    The AlkB family of Fe(II)- and α-ketoglutarate-dependent dioxygenases is a class of ubiquitous direct reversal DNA repair enzymes that remove alkyl adducts from nucleobases by oxidative dealkylation. The prototypical and homonymous family member is an Escherichia coli “adaptive response” protein that protects the bacterial genome against alkylation damage. AlkB has a wide variety of substrates, including monoalkyl and exocyclic bridged adducts. Nine mammalian AlkB homologs exist (ALKBH1–8, FTO), but only a subset functions as DNA/RNA repair enzymes. This minireview presents an overview of the AlkB proteins including recent data on homologs, structural features, substrate specificities, and experimental strategies for studying DNA repair by AlkB family proteins. PMID:26152727

  2. Acid-catalyzed ortho-alkylation of anilines with styrenes: an improved route to chiral anilines with bulky substituents.

    PubMed

    Cherian, Anna E; Domski, Gregory J; Rose, Jeffrey M; Lobkovsky, Emil B; Coates, Geoffrey W

    2005-11-10

    [reaction: see text] Reaction of para-substituted anilines with styrene derivatives at elevated temperatures, when catalyzed by CF3SO3H, results in highly chemoselective ortho-alkylation of the aniline. When R = H, dialkylation can be achieved by varying the ratio of styrene to aniline. Several different substituted anilines and styrenes were examined, and good yields (42-87%) were obtained, except in the case where electron-withdrawing substituents are present on the styrene.

  3. Impact of treatment processes on the removal of perfluoroalkyl acids from the drinking water production chain.

    PubMed

    Eschauzier, Christian; Beerendonk, Erwin; Scholte-Veenendaal, Petra; De Voogt, Pim

    2012-02-07

    The behavior of polyfluoralkyl acids (PFAAs) from intake (raw source water) to finished drinking water was assessed by taking samples from influent and effluent of the several treatment steps used in a drinking water production chain. These consisted of intake, coagulation, rapid sand filtration, dune passage, aeration, rapid sand filtration, ozonation, pellet softening, granular activated carbon (GAC) filtration, slow sand filtration, and finished drinking water. In the intake water taken from the Lek canal (a tributary of the river Rhine), the most abundant PFAA were PFBA (perfluorobutanoic acid), PFBS (perfluorobutane sulfonate), PFOS (perfluorooctane sulfonate), and PFOA (perfluorooctanoic acid). During treatment, longer chain PFAA such as PFNA (perfluorononanoic acid) and PFOS were readily removed by the GAC treatment step and their GAC effluent concentrations were reduced to levels below the limits of quantitation (LOQ) (0.23 and 0.24 ng/L for PFOS and PFNA, respectively). However, more hydrophilic shorter chain PFAA (especially PFBA and PFBS) were not removed by GAC and their concentrations remained constant through treatment. A decreasing removal capacity of the GAC was observed with increasing carbon loading and with decreasing carbon chain length of the PFAAs. This study shows that none of the treatment steps, including softening processes, are effective for PFAA removal, except for GAC filtration. GAC can effectively remove certain PFAA from the drinking water cycle.The enrichment of branched PFOS and PFOA isomers relative to non branched isomers during GAC filtration was observed during treatment. The finished water contained 26 and 19 ng/L of PFBA and PFBS. Other PFAAs were present in concentrations below 4.2 ng/L The concentrations of PFAA observed in finished waters are no reason for concern for human health as margins to existing guidelines are sufficiently large.

  4. Identification of protein tyrosine phosphatase SHP-2 as a new target of perfluoroalkyl acids in HepG2 cells.

    PubMed

    Yang, Yu; Lv, Qi-Yan; Guo, Liang-Hong; Wan, Bin; Ren, Xiao-Min; Shi, Ya-Li; Cai, Ya-Qi

    2016-08-29

    Perfluoroalkyl acids (PFAAs) are widespread environmental contaminants which have been detected in humans and linked to adverse health effects. Previous toxicological studies mostly focused on nuclear receptor-mediated pathways and did not support the observed toxic effects. In this study, we aimed to investigate the molecular mechanisms of PFAA toxicities by identifying their biological targets in cells. Using a novel electrochemical biosensor, 16 PFAAs were evaluated for inhibition of protein tyrosine phosphatase SHP-2 activity. Their potency increased with PFAA chain length, with perfluorooctadecanoic acid (PFODA) showing the strongest inhibition. Three selected PFAAs, 25 μM perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid, and PFODA, also inhibited SHP-2 activity in HepG2 cells and increased paxillin phosphorylation level. PFOA was detected in the immunoprecipitated SHP-2 from the cells exposed to 250 μM PFOA, providing unequivocal evidence for the direct binding of PFOA with SHP-2 in the cell. Molecular docking rationalized the formation of PFAA/SHP-2 complex and chain length-dependent inhibition potency. Our results have established SHP-2 as a new cellular target of PFAAs.

  5. Toxicology of Perfluoroalkyl Acids*

    EPA Science Inventory

    The perfluoroalkyl acids (PFAAs) are a family of organic chemicals consisting of a perfluorinated carbon backbone (4-12 in length) and an acidic functional moiety (carboxylate or sulfonate). These compounds are chemically stable, have excellent surface-tension reducing properties...

  6. Perfluoroalkyl acids in aqueous samples from Germany and Kenya.

    PubMed

    Shafique, Umer; Schulze, Stefanie; Slawik, Christian; Böhme, Alexander; Paschke, Albrecht; Schüürmann, Gerrit

    2016-06-22

    Continuous monitoring of chemicals in the environment is important to control their fate and to protect human health, flora, and fauna. Perfluoroalkyl acids (PFAAs) have been detected frequently in different environmental compartments during the last 15 years and have drawn much attention because of their environmental persistence, omnipresence, and bioaccumulation potential. Water is an important source of their transport. In the present study, distributions of PFAAs in river water, wastewater treatment plant (WWTP) effluent, and tap water from eastern part of Germany and western part of Kenya were investigated. Eleven perfluorocarboxylic acids (PFCAs) and five perfluorosulfonic acids (PFSAs) were analyzed using liquid chromatography/tandem mass spectrometry. Sum of mean concentrations of eight PFAAs detected in drinking tap water from Leipzig was 11.5 ng L(-1), dominated by perfluorooctanoic acid (PFOA, 6.2 ng L(-1)). Sums of mean riverine concentrations of PFAAs detected in Pleiße/White Elster, Saale, and Elbe (Germany) were 24.8, 54.3, and 26.8 ng L(-1), respectively. Annual flux of PFAAs from River Saale was estimated to be 164 ± 23 kg a(-1). The effluent of WWTP in Halle was found to contain four times higher levels of PFAAs than river water and was dominated by perfluorobutane sulfonate (PFBS) with 32 times higher concentration than the riverine level. It advocates that WWTPs are the point source of contaminating water bodies with PFAAs, and short-chain PFAAs are substituting long-chain homologues. Sums of mean riverine concentrations of PFAAs in Sosiani (Kenya) in samples from sparsely populated and densely populated areas were 58.8 and 109.4 ng L(-1), respectively, indicating that population directly affected the emissions of PFAAs to surface waters. The discussion includes thorough review and comparison of recently published literature reporting occurrence of PFAAs in aqueous matrices. Graphical abstract Perfluoroalkyl acids in aqueous

  7. Use of short chain alkyl imidazolium ionic liquids for on-line stacking and sweeping of methotrexate, flinic acid and folic acid: their application to biological fluids.

    PubMed

    Abd El-Hady, Deia; Albishri, Hassan M; Rengarajan, Rajesh; Wätzig, Hermann

    2014-07-01

    Methotrexate (MTX) is widely used for the treatment of many types of cancer. Folinic acid (FNA) and folic acid (FA) were usually simultaneously supplemented with MTX to reduce the side effects of a folate deficiency. This study, for the first time, included on-line sample preconcentration by stacking and sweeping techniques under reduced or enhanced electric conductivity in the sample region using short chain alkyl imidazolium ionic liquids (ILs) as micelle forming agents for analyte focusing. Both analyte focusing by micelle collapse (AFMC) and sweeping-MEKC had been investigated for the comparison of their effectiveness to examine simultaneously MTX, FNA and FA in plasma and urine under physiological conditions. In sweeping-MEKC, the sample solution without micelles was hydrodynamically injected as a long plug into a fused-silica capillary pre-filled with phosphate buffer containing 3.0 mol/L of 1-butyl-3-methylimidazolium bromide (BMIMBr). Using AFMC, the analytes were prepared in BMIMBr micellar matrix and hydrodynamically injected into the phosphate buffer without IL micelles. The conductivity ratio between BGE and sample (γ, BGE/sample) was optimized to be 3.0 in sweeping-MEKC and 0.33 in AFMC resulting the adequate separation of analytes within 4.0 min. To reduce the possibility of BMIMBr adsorption, an appropriate rinsing protocol was used. The limits of detection were calculated as 0.1 ng/mL MTX, 0.05 ng/mL FNA and 0.05 ng/mL FA by sweeping-MEKC and 0.5 ng/mL MTX, 0.3 ng/mL FNA and 0.3 ng/mL FA by AFMC. The accuracy was tested by recovery in plasma and urine matrices giving values ranging between 90 and 110%. Both stacking and sweeping by BMIMBr could be successfully used for the rapid, selective and sensitive determination of pharmaceuticals in complex matrices due to its fascinating properties, including high conductivity, good thermal stability and ability to form different types of interactions by electrostatic, hydrophobic, hydrogen bonding and

  8. Uptake of perfluoroalkyl acids into edible crops via land ...

    EPA Pesticide Factsheets

    The presence of perfluoroalkyl acids (PFAAs) in biosolids destined for use in agriculture has raised concerns about their potential to enter the terrestrial food chain via bioaccumulation in edible plants. Uptake of PFAAs by greenhouse lettuce ( Lactuca sativa) and tomato (Lycopersicon lycopersicum ) grown in an industrially impacted biosolids-amended soil, a municipal biosolids-amended soil, and a control soil was measured. Bioaccumulation factors (BAFs) were calculated for the edible portions of both lettuce and tomato. Dry weight concentrations observed in lettuce grown in a soil amended (biosolids:soil dry weight ratio of 1:10) with PFAA industrially contaminated biosolids were up to 266 and 236 ng/g for perfluorobutanoic acid (PFBA) and perfluoropentanoic acid (PFPeA), respectively, and reached 56 and 211 ng/g for PFBA and PFPeA in tomato, respectively. BAFs for many PFAAs were well above unity, with PFBA having the highest BAF in lettuce (56.8) and PFPeA the highest in tomato (17.1). In addition, the BAFs for PFAAs in greenhouse lettuce decreased approximately 0.3 log units per CF2 group. A limited-scale field study was conducted to verify greenhouse findings. The greatest accumulation was seen for PFBA and PFPeA in both field-grown lettuce and tomato; BAFs for PFBA were highest in both crops. PFAA levels measured in lettuce and tomato grown in field soil amended with only a single application of biosolids (at an agronomic rate for nitrogen) were predomina

  9. Variation in perfluoroalkyl acids in the American alligator (Alligator mississippiensis) at Merritt Island National Wildlife Refuge.

    PubMed

    Bangma, Jacqueline T; Reiner, Jessica L; Jones, Martin; Lowers, Russell H; Nilsen, Frances; Rainwater, Thomas R; Somerville, Stephen; Guillette, Louis J; Bowden, John A

    2017-01-01

    This study aimed to quantify concentrations of fifteen perfluoroalkyl acids (PFAAs) in the plasma of American alligators (Alligator mississippiensis) inhabiting wetlands surrounding the Kennedy Space Center (KSC) in Florida, USA located at Merritt Island National Wildlife Refuge (MINWR). Approximately 10 male and 10 female alligators (ntotal = 229) were sampled each month during 2008 and 2009 to determine if seasonal or spatial trends existed with PFAA burden. PFOS represented the highest plasma burden (median 185 ng/g) and PFHxS the second highest (median 7.96 ng/g). While no significant seasonal trends were observed, unique spatial trends emerged. Many of the measured PFAAs co-varied strongly together and similar trends were observed for PFOS, PFDA, PFUnA, and PFDoA, as well as for PFOA, PFHxS, PFNA, PFTriA, and PFTA, suggesting more than one source of PFAAs at MINWR. Higher concentrations of PFOS and the PFAAs that co-varied with PFOS were collected from animals around sites that included the Shuttle Landing Facility (SLF) fire house and the Neil Armstrong Operations and Checkout (O&C) retention pond, while higher concentrations of PFOA and the PFAA that co-varied with PFOA were sampled from animals near the gun range and the old fire training facility. Sex-based differences and snout-vent length (SVL) correlations with PFAA burden were also investigated.

  10. Short term exposure to perluoroalkyl acids causes increase of hepatic lipid and triglyceride in conjunction with liver hypertrophy

    EPA Science Inventory

    ABSTRACT BODY: Persistent presence of perfluoroalkyl acids (PFAAs) in the environment is due to extensive use of industrial and consumer products. These chemicals activate peroxisome proliferatoractivated receptor-alpha (PPARa) in liver and after lipid metabolism. The current stu...

  11. Gas chromatography with tandem differential mobility spectrometry of fatty acid alkyl esters and the selective detection of methyl linolenate in biodiesels by dual-stage ion filtering.

    PubMed

    Pasupuleti, D; Pierce, K; Eiceman, G A

    2015-11-20

    Alkyl esters of fatty acids (FAAEs) with carbon numbers from 8 to 20 formed protonated monomers and proton bound dimers through atmospheric pressure chemical ionization reactions and these gas ions were characterized for their field dependent mobility coefficients using differential mobility spectrometry (DMS). Separation of ion peaks with a vapor modifier was achieved for ions with masses of 317-1033 Da though the differences in these coefficients and the resolution of ion peaks decreased proportionally with increased ion mass. Differences in dispersion curves were sufficient to isolate ions from specific FAAEs in the effluent of a gas chromatograph by dual stage ion filtering using a tandem DMS detector. Methyl linolenate was isolated from nearby eluting methyl oleate, methyl stearate and methyl linoleate within analysis times of 10s without measureable complications from charge suppression in the ion source or leakage in filtering of ions with close proximity of dispersion behavior.

  12. Efficient conversion of furfuryl alcohol into alkyl levulinates catalyzed by an organic-inorganic hybrid solid acid catalyst.

    PubMed

    Zhang, Zehui; Dong, Kun; Zhao, Zongbao Kent

    2011-01-17

    A clean, facile, and environment-friendly catalytic method has been developed for the conversion of furfuryl alcohol into alkyl levulinates making use of the novel solid catalyst methylimidazolebutylsulfate phosphotungstate ([MIMBS]₃PW₁₂O₄₀). The solid catalyst is an organic-inorganic hybrid material, which consists of an organic cation and an inorganic anion. A study for optimizing the reaction conditions such as the reaction time, the temperature and the catalyst loading has been performed. Under optimal conditions, a high n-butyl levulinate yield of up to 93 % is obtained. Furthermore, the kinetics of the reaction pathways and the mechanism for the alcoholysis of furfuryl alcohol are discussed. This method is environmentally benign and economical for the conversion of biomass-based derivatives into fine chemicals.

  13. Methods of making alkyl esters

    DOEpatents

    Elliott, Brian

    2010-08-03

    A method comprising contacting an alcohol, a feed comprising one or more glycerides and equal to or greater than 2 wt % of one or more free fatty acids, and a solid acid catalyst, a nanostructured polymer catalyst, or a sulfated zirconia catalyst in one or more reactors, and recovering from the one or more reactors an effluent comprising equal to or greater than about 75 wt % alkyl ester and equal to or less than about 5 wt % glyceride.

  14. Influences of humic acid on the bioavailability of phenanthrene and alkyl phenanthrenes to early life stages of marine medaka (Oryzias melastigma).

    PubMed

    Liu, Yangzhi; Yang, Chenghu; Cheng, Pakkin; He, Xiaojing; Zhu, Yaxian; Zhang, Yong

    2016-03-01

    The influences of humic acid (HA) on the environmental behavior and bioavailability of parent polycyclic aromatic hydrocarbons (PAHs) and alkyl PAHs were investigated and compared using the early life stages of marine medaka (Oryzias melastigma, O. melastigma). It was demonstrated that the binding affinity of parent phenanthrene (PHE) with HA was smaller than that of 3-methyl phenanthrene (3-MP) and 9-ethyl phenanthrene (9-EP). Furthermore, the bioaccumulation of the three PAHs and the levels of lipid peroxidation (LPO) were calculated to study the changes in bioavailability of PAHs in presence of HA. The results indicated that the addition of HA significantly decreased the bioaccumulation and toxicity of PAHs by decreasing free PAHs concentrations. The bioavailable fractions of HA-bound PAHs in bioaccumulation (α) and toxicity (β) were evaluated, indicating that the HA-bound 3-MP and 9-EP show higher bioavailability in bioaccumulation and lower bioavailability in toxicity relative to those of PHE. The β/α values were less than 1 for all PAH treatment groups containing HA, suggesting that the fraction of HA-bound PAHs contributing to bioaccumulation was higher than that of HA-bound PAHs inducing toxic effect. In addition, we proposed that the free PAHs generated by desorption from HA in the cell were toxic by showing that the β/α ratio values are correlated with the log KOW values (p = 0.007 and R(2) = 0.8355). Thus, oil spill risk assessments should consider both alkyl PAHs and the factors that influence the bioavailability and toxicity of PAHs in the natural aquatic environments.

  15. Perfluoroalkyl acid distribution in various plant compartments of edible crops grown in biosolids-amended soils.

    PubMed

    Blaine, Andrea C; Rich, Courtney D; Sedlacko, Erin M; Hundal, Lakhwinder S; Kumar, Kuldip; Lau, Christopher; Mills, Marc A; Harris, Kimberly M; Higgins, Christopher P

    2014-07-15

    Crop uptake of perfluoroalkyl acids (PFAAs) from biosolids-amended soil has been identified as a potential pathway for PFAA entry into the terrestrial food chain. This study compared the uptake of PFAAs in greenhouse-grown radish (Raphanus sativus), celery (Apium graveolens var. dulce), tomato (Lycopersicon lycopersicum), and sugar snap pea (Pisum sativum var. macrocarpon) from an industrially impacted biosolids-amended soil, a municipal biosolids-amended soil, and a control soil. Individual concentrations of PFAAs, on a dry weight basis, in mature, edible portions of crops grown in soil amended with PFAA industrially impacted biosolids were highest for perfluorooctanoate (PFOA; 67 ng/g) in radish root, perfluorobutanoate (PFBA; 232 ng/g) in celery shoot, and PFBA (150 ng/g) in pea fruit. Comparatively, PFAA concentrations in edible compartments of crops grown in the municipal biosolids-amended soil and in the control soil were less than 25 ng/g. Bioaccumulation factors (BAFs) were calculated for the root, shoot, and fruit compartments (as applicable) of all crops grown in the industrially impacted soil. BAFs were highest for PFBA in the shoots of all crops, as well as in the fruit compartment of pea. Root-soil concentration factors (RCFs) for tomato and pea were independent of PFAA chain length, while radish and celery RCFs showed a slight decrease with increasing chain length. Shoot-soil concentration factors (SCFs) for all crops showed a decrease with increasing chain length (0.11 to 0.36 log decrease per CF2 group). The biggest decrease (0.54-0.58 log decrease per CF2 group) was seen in fruit-soil concentration factors (FCFs). Crop anatomy and PFAA properties were utilized to explain data trends. In general, fruit crops were found to accumulate fewer long-chain PFAAs than shoot or root crops presumably due to an increasing number of biological barriers as the contaminant is transported throughout the plant (roots to shoots to fruits). These data were

  16. Uptake of perfluoroalkyl acids in the leaves of coniferous and deciduous broad-leaved trees.

    PubMed

    Zhang, Huanhuan; Liu, Wei; He, Xin; Wang, Yu; Zhang, Qian

    2015-07-01

    Analytical methods for determining perfluoroalkyl acids (PFAAs) in leaves were developed to quantify a suite of analytes in both coniferous and deciduous broad-leaved trees. Sodium hydroxide-methanol and solid-phase extraction was selected as the extracting and cleanup strategy for PFAA analysis. Ten perfluorocarboxylic acids (PFCAs) and 4 perfluorosulfonic acids (PFSAs) were monitored in 7 kinds of leaves grown in the urban areas of Dalian, China. The results show that coniferous tree leaves take up more PFAAs than broad-leaved tree leaves, with the highest amount of 150 ng/g in pine needles. Leaf PFCA levels were much higher than PFSAs level. Short carbon-chain PFCAs with 3 to 6 perfluorinated carbons account for approximately 40% to 80% of the total leaf PFAAs, where uptake decreased with increasing carbon chain length. Temporal observation of leaf PFAAs revealed no significant variation of concentrations in the leaves over a weekly interval and the absence of significant seasonal change in pine needles and sophora. The present study provides some evidence for the accumulation of PFAAs in leaves, which is valuable for understanding their environmental behavior and the development of alternative bioindicator.

  17. Aerobic biotransformation of alkyl branched aromatic alkanoic naphthenic acids via two different pathways by a new isolate of Mycobacterium.

    PubMed

    Johnson, Richard J; West, Charles E; Swaih, Aisha M; Folwell, Ben D; Smith, Ben E; Rowland, Steven J; Whitby, Corinne

    2012-04-01

    Naphthenic acids (NAs) are complex mixtures of carboxylic acids found in weathered crude oils and oil sands, and are toxic, corrosive and persistent. However, little is known about the microorganisms and mechanisms involved in NA degradation. We isolated a sediment bacterium (designated strain IS2.3), with 100% 16S rRNA gene sequence identity to Mycobacterium aurum, which degraded synthetic NAs (4'-n-butylphenyl)-4-butanoic acid (n-BPBA) and (4'-t-butylphenyl)-4-butanoic acid (t-BPBA). n-BPBA was readily oxidized with almost complete degradation (96.8% ± 0.3) compared with t-BPBA (77.8% ± 3.7 degraded) by day 49. Cell counts increased fourfold by day 14 but decreased after day 14 for both n- and t-BPBA. At day 14, (4'-butylphenyl)ethanoic acid (BPEA) metabolites were detected. Additional metabolites produced during t-BPBA degradation were identified by mass spectrometry of derivatives as (4'-carboxy-t-butylphenyl)-4-butanoic acid and (4'-carboxy-t-butylphenyl)ethanoic acid; suggesting that strain IS2.3 used omega oxidation of t-BPEA to oxidize the tert-butyl side-chain to produce (4'-carboxy-t-butylphenyl)ethanoic acid, as the primary route for biodegradation. However, strain IS2.3 also produced this metabolite through initial omega oxidation of the tert-butyl side-chain of t-BPBA, followed by beta-oxidation of the alkanoic acid side-chain. In conclusion, an isolate belonging to the genus Mycobacterium degraded highly branched aromatic NAs via two different pathways.

  18. Regioselectivity of Birch reductive alkylation of biaryls.

    PubMed

    Lebeuf, Raphaël; Robert, Frédéric; Landais, Yannick

    2005-10-13

    [reaction: see text] The regioselectivity of the Birch reductive alkylation of polysubstituted biaryls has been investigated. Results indicate that regioselectivity is affected by the electronic nature of substituents on both aromatic rings. The electron-rich 3,5-dimethoxyphenyl moiety is selectively reduced and then alkylated, while phenols and aniline are not dearomatized under these conditions. Biaryls possessing a phenol moiety are alkylated on the second ring, providing that the acidic proton has been removed prior to the Li/NH3 reduction.

  19. Nitro-fatty acid reaction with glutathione and cysteine. Kinetic analysis of thiol alkylation by a Michael addition reaction.

    PubMed

    Baker, Laura M S; Baker, Paul R S; Golin-Bisello, Franca; Schopfer, Francisco J; Fink, Mitchell; Woodcock, Steven R; Branchaud, Bruce P; Radi, Rafael; Freeman, Bruce A

    2007-10-19

    Fatty acid nitration by nitric oxide-derived species yields electrophilic products that adduct protein thiols, inducing changes in protein function and distribution. Nitro-fatty acid adducts of protein and reduced glutathione (GSH) are detected in healthy human blood. Kinetic and mass spectrometric analyses reveal that nitroalkene derivatives of oleic acid (OA-NO2) and linoleic acid (LNO2) rapidly react with GSH and Cys via Michael addition reaction. Rates of OA-NO2 and LNO2 reaction with GSH, determined via stopped flow spectrophotometry, displayed second-order rate constants of 183 M(-1)S(-1) and 355 M(-1)S(-1), respectively, at pH 7.4 and 37 degrees C. These reaction rates are significantly greater than those for GSH reaction with hydrogen peroxide and non-nitrated electrophilic fatty acids including 8-iso-prostaglandin A2 and 15-deoxy-Delta(12,14)-prostaglandin J2. Increasing reaction pH from 7.4 to 8.9 enhanced apparent second-order rate constants for the thiol reaction with OA-NO2 and LNO2, showing dependence on the thiolate anion of GSH for reactivity. Rates of nitroalkene reaction with thiols decreased as the pKa of target thiols increased. Increasing concentrations of the detergent octyl-beta-d-glucopyranoside decreased rates of nitroalkene reaction with GSH, indicating that the organization of nitro-fatty acids into micellar or membrane structures can limit Michael reactivity with more polar nucleophilic targets. In aggregate, these results reveal that the reversible adduction of thiols by nitro-fatty acids is a mechanism for reversible post-translational regulation of protein function by nitro-fatty acids.

  20. Cytotoxicity of copper(II)-complexes with some S-alkyl derivatives of thiosalicylic acid. Crystal structure of the binuclear copper(II)-complex with S-ethyl derivative of thiosalicylic acid

    NASA Astrophysics Data System (ADS)

    Nikolić, Miloš V.; Mijajlović, Marina Ž.; Jevtić, Verica V.; Ratković, Zoran R.; Novaković, Slađana B.; Bogdanović, Goran A.; Milovanović, Jelena; Arsenijević, Aleksandar; Stojanović, Bojana; Trifunović, Srećko R.; Radić, Gordana P.

    2016-07-01

    The spectroscopically predicted structure of the obtained copper(II)-complex with S-ethyl derivative of thiosalicylic acid was confirmed by X-ray structural study and compared to previously reported crystal structure of the Cu complex with S-methyl derivative. Single crystals suitable for X-ray measurements were obtained by slow crystallization from a water solution. Cytotoxic effects of S-alkyl (R = benzyl (L1), methyl (L2), ethyl (L3), propyl (L4) and butyl (L5)) derivatives of thiosalicylic acid and the corresponding binuclear copper(II)-complexes on murine colon carcinoma cell lines, CT26 and CT26.CL25 and human colon carcinoma cell line HCT-116 were reported here. The analysis of cancer cell viability showed that all the tested complexes had low cytotoxic effect on murine colon carcinoma cell lines, but several times higher cytotoxicity on normal human colon carcinoma cells.

  1. Determination of relative acidities of some alpha, omega-bis(3-alkyl(aryl)-4,5-dihydro-1H-1,2,4-triazol-5-on-4-yl) alkanes.

    PubMed

    Karaböcek, S; Dalman, O; Nohut, S; Tüfekçi, M; Sancak, K; Güner, S

    1998-07-01

    The solutions of nine alpha, omega-bis(3-alkyl(aryl)-4,5-dihydro-1H-1,2,4-triazol-5-on-4-yl) alkanes were titrated with tetrabutylammoniumhydroxide (TBAH) in methanol, using potentiometric methods. The half neutralization potentials values were found for all cases. Potentiometric titration curves of compounds in methanol with 0.03 M TBAH are similar to those of weak acids obtained in aqueous media with strong bases. Methanol is found to be a suitable medium for the weakly acidic compounds titrated since they are poorly dissolved in other organic solvents. A comparison among the compounds having the same alkyl chains between the two ring systems has shown that basicity increases and acidity decreases as the size of alkyl chains increases. However, the compound with a substituted phenyl group was found to be the most acidic one among the examined compounds indicating that phenyl group donates ring electrons less effectively to the system. This can be attributed to the stability of the benzene ring.

  2. Nanostructured alkyl carboxylic acid-based restricted access solvents: Application to the combined microextraction and cleanup of polycyclic aromatic hydrocarbons in mosses.

    PubMed

    Caballero-Casero, N; Çabuk, H; Martínez-Sagarra, G; Devesa, J A; Rubio, S

    2015-08-26

    Alkyl carboxylic acid-based nanostructured solvents, synthesized in mixtures of tetrahydrofuran (THF) and water through self-assembly and coacervation, were proved to behave as restricted access liquids. Both physical and chemical mechanisms were found responsible for exclusion of macromolecules such as proteins and polysaccharides. The potential of these solvents for extracting small molecules from complex solid samples, without interference from large biomolecules, was here evaluated. For this purpose, they were applied to the extraction of 14 priority polycyclic aromatic hydrocarbons (PAHs) from mosses prior to their separation by liquid chromatography and fluorescence detection (LC-FLD). Sample treatment involved the vortex shaking of 200 mg of moss with 200 μL of decanoic acid-based solvent for 5 min, subsequent centrifugation for 8 min and analysis of the extract by LC-FLD using external calibration. Proteins precipitated during extraction because of both the decrease of the dielectric constant of the solution caused by THF and the formation of macromolecular complexes with decanoic acid. Polysaccharides were not solubilized in the aqueous cavities of the solvent because of their size exclusion. In-house method validation was performed according to the recommendations of the European Commission Decision 202/657/EC. Method detection and quantification limits for the different PAHs were in the ranges 0.04-0.24 and 0.14-0.80 μg kg(-1), respectively. The method was applied to the determination of different moss species collected in both polluted and unpolluted sites in the South of Spain. Recoveries were within the range 71-110%. The results obtained show that solvents with restricted access properties have the potential to expand the scope of application of restricted access materials to areas other than biological fluids because of their suitability to combine analyte isolation and sample cleanup of solid samples in a single step.

  3. Alkyl sulfonic acide hydrazides: Synthesis, characterization, computational studies and anticancer, antibacterial, anticarbonic anhydrase II (hCA II) activities

    NASA Astrophysics Data System (ADS)

    O. Ozdemir, Ummuhan; İlbiz, Firdevs; Balaban Gunduzalp, Ayla; Ozbek, Neslihan; Karagoz Genç, Zuhal; Hamurcu, Fatma; Tekin, Suat

    2015-11-01

    Methane sulfonic acide hydrazide, CH3SO2NHNH2 (1), ethane sulfonic acide hydrazide, CH3CH2SO2NHNH2 (2), propane sulfonic acide hydrazide, CH3CH2CH2SO2NHNH2 (3) and butane sulfonic acide hydrazide, CH3CH2CH2CH2SO2NHNH2 (4) have been synthesized as homologous series and characterized by using elemental analysis, spectrophotometric methods (1H-13C NMR, FT-IR, LC-MS). In order to gain insight into the structure of the compounds, we have performed computational studies by using 6-311G(d, p) functional in which B3LYP functional were implemented. The geometry of the sulfonic acide hydrazides were optimized at the DFT method with Gaussian 09 program package. A conformational analysis of compounds were performed by using NMR theoretical calculations with DFT/B3LYP/6-311++G(2d, 2p) level of theory by applying the (GIAO) approach. The anticancer activities of these compounds on MCF-7 human breast cancer cell line investigated by comparing IC50 values. The antibacterial activities of synthesized compounds were studied against Gram positive bacteria; Staphylococcus aureus ATCC 6538, Bacillus subtilis ATCC 6633, Bacillus cereus NRRL-B-3711, Enterococcus faecalis ATCC 29212 and Gram negative bacteria; Escherichia coli ATCC 11230, Pseudomonas aeruginosa ATCC 15442, Klebsiella pneumonia ATCC 70063 by using the disc diffusion method. The inhibition activities of these compounds on carbonic anhydrase II enzyme (hCA II) have been investigated by comparing IC50 and Ki values. The biological activity screening shows that butane sulfonic acide hydrazide (4) has more activity than the others against tested breast cancer cell lines MCF-7, Gram negative/Gram positive bacteria and carbonic anhydrase II (hCA II) isoenzyme.

  4. Estimation of alkane-water logP for neutral, acidic, and basic compounds using an alkylated polystyrene-divinylbenzene high-performance liquid chromatography column.

    PubMed

    Jensen, Derek A; Gary, Ronald K

    2015-10-23

    Reliable HPLC methods are available to estimate octanol-water partition coefficients, but there is no comparable method for alkane-water partition coefficients that is accurate and applicable across a broad span of logP(alk). This study describes a high-throughput method for determining HPLC-logP(alk), a chromatographic parameter closely related to logP(alk), using an alkylated polystyrene-divinylbenzene column and fast acetonitrile gradient. A structurally diverse set of neutral, acidic, and basic compounds was analyzed under ionization-suppressing pH conditions. In this chromatographic system, the relationship between gradient retention time and isocratic logk was essentially linear. Thus, gradient retention time could be used as the sole input needed to determine an apparent logP(alk)by HPLC. HPLC-logP(alk) showed linear correlation (R(2)>0.96, n=59) with reference logP(alk) values from shake-flask measurements over 8 orders of magnitude, ranging from -2.3 to +5.7. Linear solvation energy relationship (LSER) analysis revealed that the relative contributions of intermolecular forces effecting retention in the fast gradient system or its corresponding isocratic variant were highly similar to those governing partition in bulk alkane-water.

  5. Synthesis, biological evaluation, and structure-activity relationships for 5-[(E)-2-arylethenyl]-3-isoxazolecarboxylic acid alkyl ester derivatives as valuable antitubercular chemotypes.

    PubMed

    Pieroni, Marco; Lilienkampf, Annamaria; Wan, Baojie; Wang, Yuehong; Franzblau, Scott G; Kozikowski, Alan P

    2009-10-22

    Tuberculosis (TB), mostly caused by Mycobacterium tuberculosis (Mtb), is one of the leading causes of death from infectious disease worldwide. Its coinfection with HIV and the emergence of multidrug-resistant TB (MDR-TB) and extensively drug-resistant TB (XDR-TB) strains have further worsened the TB pandemic. Despite its global impact, TB is considered a neglected disease and no new anti-TB therapeutics have been introduced over the last four decades. The nonreplicating persistent form of TB (NRP-TB) is responsible for the length of the treatment and is the putative cause of treatment failure. Therefore, new anti-TB agents, which are active against both the replicating form of Mtb (R-TB) and NRP-TB, are urgently needed. Herein, we report the synthesis and structure-activity relationships (SAR) of a series of 5-[(E)-2-arylethenyl]-3-isoxazolecarboxylic acid alkyl esters as potent anti-TB agents. Several compounds had submicromolar minimum inhibitory concentrations (MIC) against R-TB and were active against NRP-TB in the low micromolar range, thus representing attractive lead compounds for the possible development of new anti-TB agents.

  6. Use of dynamic simulation to assess the behaviour of linear alkyl benzene sulfonates and their biodegradation intermediates (sulfophenylcarboxylic acids) in estuaries

    NASA Astrophysics Data System (ADS)

    García-Luque, E.; González-Mazo, E.; Forja, J. M.; Gómez-Parra, A.

    2009-02-01

    Dynamic laboratory simulation of processes affecting chemical species in their transit through estuaries is a very useful tool to characterize these littoral systems. To date, laboratory studies concerning biodegradation and sorption (onto suspended particulate matter) of LAS in an estuary are scarce. For this reason, a dynamic automated estuarine simulator has been employed to carry out different experiments in order to assess the biodegradability of linear alkyl benzene sulfonates (LAS) and their biodegradation intermediates (sulfophenylcarboxylic acids, SPCs) using environmentally representative LAS concentrations in estuaries by a continuous injection of LAS into the system. During the experiments, a great affinity of LAS for the solid phase has been found, as well as an increased adsorption in line with increased chain length. On the other hand, the presence of SPCs with chain length between 6 and 13 carbon atoms was detected. Accumulation and persistence of medium chain length SPCs (C 6-C 8) along the experiments show that their degradation constitutes the limiting step for the process of LAS mineralization. In the final zone of the simulated estuarine system, the levels of SPCs were below the limits of detection. Thus, the disappearance of SPCs indicated that LAS biodegradation had been completed along the estuary. Similar results have been described for different Iberian littoral ecosystems. Therefore, the simulator employed in this research appears to be a useful tool to anticipate the behaviour of a xenobiotic chemical in its transit through littoral systems with different salinity gradients.

  7. Cyclic phosphatidic acid inhibits alkyl-glycerophosphate-induced downregulation of histone deacetylase 2 expression and suppresses the inflammatory response in human coronary artery endothelial cells.

    PubMed

    Tsukahara, Tamotsu; Haniu, Hisao; Matsuda, Yoshikazu

    2014-01-01

    Activation of the endothelium by alkyl-glycerophosphate (AGP) has been implicated in the development of atherosclerosis. Our previous study suggested that cyclic phosphatidic acid (cPA) inhibits arterial wall remodeling in a rat model in vivo. However, the mechanisms through which specific target genes are regulated during this process remain unclear. Here, we examined whether cPA inhibited AGP-induced expression of class I histone deacetylases (HDACs, namely HDAC1, HDAC2, HDAC3, and HDAC8), which may affect subsequent transcriptional activity of target genes. Our experimental results showed that human coronary artery endothelial cells (HCAECs) expressed high levels of HDAC2 and low levels HDAC1, HDAC3, and HDAC8. Moreover, AGP treatment induced downregulation of HDAC2 expression in HCAECs. However, cotreatment with cPA inhibited this downregulation of HDAC2 expression. Interestingly, treatment with AGP increased the expression and secretion of endogenous interleukin (IL)-6 and IL-8; however, this effect was inhibited when HCAECs were cotreated with cPA or the synthetic peroxisome proliferator-activator receptor gamma (PPARγ) antagonist T0070907. Thus, our data suggested that cPA may have beneficial effects in inflammation-related cardiovascular disease by controlling HDAC2 regulation.

  8. Searches for new alkylation catalysts, processes forge ahead

    SciTech Connect

    Rhodes, A.

    1994-08-22

    As a result of the hazardous properties of hydrofluoric acid (HF), HF alkylation has been the subject of much recent controversy. The safety and environmental requirements associated with the HF alkylation processes continue to drive industry to develop new alkylation technologies. In fact, several major process licensors are well on their ways to bringing these new technologies to market. The new alkylation processes under development center around new, less-harmful catalysts. Although this work is progressing rapidly, an update of the status of some of these new processes will keep refiners abreast of the new options they may soon have for building new alkylation units or retrofitting existing ones. The process development and economics are described for a Topsoe/Kellogg fixed bed alkylation process and the Kerr-McGee homogeneous alkylation technology process.

  9. Advanced asymmetric synthesis of (1R,2S)-1-amino-2-vinylcyclopropanecarboxylic acid by alkylation/cyclization of newly designed axially chiral Ni(II) complex of glycine Schiff base.

    PubMed

    Kawashima, Aki; Shu, Shuangjie; Takeda, Ryosuke; Kawamura, Akie; Sato, Tatsunori; Moriwaki, Hiroki; Wang, Jiang; Izawa, Kunisuke; Aceña, José Luis; Soloshonok, Vadim A; Liu, Hong

    2016-04-01

    Asymmetric synthesis of (1R,2S)-1-amino-2-vinylcyclopropanecarboxylic acid (vinyl-ACCA) is in extremely high demand due to the pharmaceutical importance of this tailor-made, sterically constrained α-amino acid. Here we report the development of an advanced procedure for preparation of the target amino acid via two-step SN2 and SN2' alkylation of novel axially chiral nucleophilic glycine equivalent. Excellent yields and diastereoselectivity coupled with reliable and easy scalability render this method of immediate use for practical synthesis of (1R,2S)-vinyl-ACCA.

  10. LATE POISONING WITH CHLOROFORM AND OTHER ALKYL HALIDES IN RELATIONSHIP TO THE HALOGEN ACIDS FORMED BY THEIR CHEMICAL DISSOCIATION

    PubMed Central

    Graham, Evarts A.

    1915-01-01

    The central lobular necrosis in the liver, which has been regarded by some writers as characteristic of late chloroform poisoning, has been produced experimentally with a number of other drugs. It is, therefore, in no sense peculiar to chloroform poisoning. Substances which have been shown to produce a morphological picture indistinguishable from that of late chloroform poisoning are: (a) dichlor- and tetrachlormethane, (b) tribrom- and triiodomethane, (c) monochlor-, monobrom-, and monoiodoethane, also the dibromethane; that is, in general, the halogen substituted aliphatic hydrocarbons containing one or two carbon atoms. Presumably similar results might be obtained with the higher members of the same series. The mechanism by which chloroform produces its characteristic tissue changes must accordingly be considered as a group reaction. Outside the body the similarities between the chemical behavior of different members of this group have been correlated by Nef on the basis of the type of dissociation which these substances undergo and the differences in their behavior on the basis of the differences of the degree to which such dissociations occur. According to the work of Nef, the group of substances under discussion has the property of dissociating to yield a halogen acid and an unsaturated alkylidene rest. Thus with chloroform the type of dissociation may be expressed thus: See PDF for Equation In this paper the view is developed that the changes characteristic of late poisonings with the above named group, namely edema, multiple hemorrhages, fat infiltration, and necrosis are ascribable (1) to acids and (2) to the fact that the amount of acid formed parallels the chemical dissociability of the drug outside of the body. Favoring the view that acid is responsible for the changes are the following observations. 1. All the characteristic features of late chloroform poisoning have been produced merely by the administration of hydrochloric acid, except, however, for

  11. Electrocatalytic activities of cathode electrodes for water electrolysis using tetra-alkyl-ammonium-sulfonic acid ionic liquid as electrolyte

    NASA Astrophysics Data System (ADS)

    Fiegenbaum, Fernanda; de Souza, Michèle O.; Becker, Márcia R.; Martini, Emilse M. A.; de Souza, Roberto F.

    2015-04-01

    The hydrogen evolution reaction (HER) performed with platinum (Pt), nickel (Ni), stainless steel 304 (SS) or glassy carbon (GC) cathodes in 0.1 M 3-triethylammonium-propanesulfonic acid tetrafluoroborate (TEA-PS.BF4) solution is studied using quasi-potentiostatic and impedance spectroscopy techniques. The objective is to compare the catalytic effect on the cathode using different materials to obtain hydrogen by water electrolysis. Furthermore, the catalytic effect of the ionic liquid (IL) on the cathode compared with that of a hydrochloric acid (HCl) solution with same pH value (0.8) is reported. A low activation energy (Ea) of 8.7 kJ mol-1 is found for the glassy carbon cathode. Tafel plots obtained with TEA-PS.BF4 IL suggest the formation of an electroactive layer of IL on the cathode, which may be responsible for the catalytically enhanced performance observed.

  12. Alkylation of isobutane with light olefins: Yields of alkylates for different olefins

    SciTech Connect

    Albright, L.F.; Kranz, K.E.; Masters, K.R.

    1993-12-01

    For alkylation of isobutane with C{sub 3}-C{sub 5} olefins using sulfuric acid as the catalyst, the yields of alkylates with different olefins are compared as the operating conditions are changed. The results of recent pilot plant experiments with propylene, C{sub 4} olefins, and C{sub 5} olefins permit such comparisons. The yields expressed as weight of alkylate produced per 100 wt of olefin consumed varied from about 201:100 to 220:100. Weight ratios of the isobutane consumed per olefin consumed vary from about 101:100 to 120:100. differences of yield values are explained by the changes in the overall chemistry. The procedure employed to calculate yields with good accuracy is based on the analysis of the alkylate and the amount of conjunct polymers produced. Based on literature data, yields are also reported for alkylations using HF as the catalyst.

  13. Effects of alkyl polyglycoside, a nonionic surfactant, and forage-to-concentrate ratio on rumen fermentation, amino acid composition of rumen content, bacteria and plasma in goats.

    PubMed

    Zeng, Bo; Tan, Zhiliang; Tang, Shaoxun; Han, Xuefeng; Tan, Chuanyan; Zhong, Rongzhen; Hea, Zhixiong; Arigbede, Oluwasanmi Moses

    2011-06-01

    In the present study, the effects of different forage-to-concentrate ratios (F:C) and an alkyl polyglycoside (APG) supplementation on parameters of rumen and blood metabolism were investigated in goats. A 2 x 2 factorial experiment was arranged within a 4 x 4 Latin square design (four 22-day periods), using four wether goats equipped with permanent ruminal cannulas. The experimental diets included two F:C levels (40:60 vs. 60:40), and two APG supplementation levels (None or 13 ml APG daily per animal). Rumen contents and blood samples were collected at the end of each period. Dietary F:C alteration affected plasma urea and influenced the proportions of leucine, histidine, arginine, glycine, proline, alanine, valine, phenylalanine, cysteine and tyrosine in rumen content, and the proportions of methionine, threonine and proline in solid-associated bacteria (SAB) significantly. Dietary APG decreased the proportions of valine and phenylalanine in rumen content, and the histidine content of liquid-associated bacteria. The interaction between dietary F:C and APG was significant for the proportions of glycine and alanine in rumen content, and the proportions of lysine and threonine in SAB. The proportion of lysine was greater, but the proportion of threonine was less in SAB for goats fed high F:C diet without APG supplementation. The proportions of plasma free amino acids and glucose concentration were not affected by experimental treatments. These results indicated that dietary APG addition affected the amino acid composition of the rumen content and ruminal bacteria, but this depended on the dietary F:C ratio. It is necessary to validate the effectiveness of dietary APG supplementation in further studies with more animals.

  14. The Alkylation of Nucleic Acids of Rat and Mouse In Vivo by the Carcinogen 1,2-Dimethylhydrazine

    PubMed Central

    Hawks, A.; Magee, P. N.

    1974-01-01

    1,2-Dimethylhydrazine, in contrast to 1-methylhydrazine, is a potent carcinogen for the colon in rats and mice. 1,2-[14C]Dimethylhydrazine was administered to rats and mice in doses which are carcinogenic following a single dose in the former species, or carcinogenic on repeated administration in the latter species, and the rate of 14CO2 exhalation was measured. Exhalation of 14CO2 was also studied after administration of single doses of 1-[14C]methylhydrazine to mice. Incorporation of radioactivity into the nucleic acids of a variety of organs was found at a time after injection (about 6 h) when 14CO2 production from both compounds was virtually complete. Methylation of nucleic acids of liver and colon, as indicated by the formation of 7-methylguanine, was observed after treatment with 1,2-dimethylhydrazine and to a smaller extent by a factor of about 10 after treatment with 1-methylhydrazine. Less than 1% of a single dose of 1,2-[14C]dimethylhydrazine was excreted in the bile of rats as determined by chemical and radioactivity assays. The similarities of the biological and biochemical actions of 1,2-dimethylhydrazine with those of some nitroso compounds and of cycasin (methylazoxymethanol glucoside) are emphasized. PMID:4469196

  15. Quantifying diffuse and point inputs of perfluoroalkyl acids in a nonindustrial river catchment.

    PubMed

    Müller, Claudia E; Spiess, Nora; Gerecke, Andreas C; Scheringer, Martin; Hungerbühler, Konrad

    2011-12-01

    Recently, the role of diffuse inputs of perfluoroalkyl acids (PFAAs) into surface waters has been investigated. It has been observed that river loads increased during rain and that street runoff contained considerable loads of PFAAs. This study aims at quantifying these diffuse inputs and identifying the initial sources in a small nonindustrial river catchment. The river was sampled in three distinct subcatchments (rural, urban, and wastewater treatment plant) at high temporal resolution during two rain events and samples were analyzed for perfluorocarboxylates and perfluorosulfonates. Additionally, rain, stormwater runoff, wastewater effluent, and drinking water were sampled. PFAA concentrations in river water were all low (e.g., < 10 ng/L for perfluorooctanoate, PFOA), but increased during rainfall. PFAA concentrations and water discharge data were integrated into a mass balance assessment that shows that 30-60% of PFAA loads can be attributed to diffuse inputs. Rain contributed 10-50% of the overall loads, mobilization of dry deposition and outdoor release of PFAA from products with 20-60%. We estimated that within a year 2.5-5 g of PFOA originating from rain and surface runoff are emitted into this small catchment (6 km(2), 12,500 persons).

  16. Electrochemical treatment of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) in groundwater impacted by aqueous film forming foams (AFFFs).

    PubMed

    Schaefer, Charles E; Andaya, Christina; Urtiaga, Ana; McKenzie, Erica R; Higgins, Christopher P

    2015-09-15

    Laboratory experiments were performed to evaluate the use of electrochemical treatment for the decomposition of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), as well as other perfluoroalkyl acids (PFAAs), in aqueous film forming foam (AFFF)-impacted groundwater collected from a former firefighter training area and PFAA-spiked synthetic groundwater. Using a commercially-produced Ti/RuO2 anode in a divided electrochemical cell, PFOA and PFOS decomposition was evaluated as a function of current density (0-20 mA/cm(2)). Decomposition of both PFOA and PFOS increased with increasing current density, although the decomposition of PFOS did not increase as the current density was increased above 2.5 mA/cm(2). At a current density of 10 mA/cm(2), the first-order rate constants, normalized for current density and treatment volume, for electrochemical treatment of both PFOA and PFOS were 46 × 10(-5) and 70 × 10(-5) [(min(-1)) (mA/cm(2))(-1) (L)], respectively. Defluorination was confirmed for both PFOA and PFOS, with 58% and 98% recovery as fluoride, respectively (based upon the mass of PFOA and PFOS degraded). Treatment of other PFAAs present in the groundwater also was observed, with shorter chain PFAAs generally being more recalcitrant. Results highlight the potential for electrochemical treatment of PFAAs, particularly PFOA and PFOS, in AFFF-impacted groundwater.

  17. From chain collapse to new structures: spectroscopic properties of poly(3-thiophene acetic acid) upon binding by alkyl trimethylammonium bromide surfactants.

    PubMed

    Franco, I Echavarri; Lorchat, P; Lamps, J-P; Schmutz, M; Schröder, A; Catala, J-M; Combet, J; Schosseler, F

    2012-03-13

    The binding of cationic surfactants with varying alkyl chain length to a regiorandom conjugated polyanion, poly(3-thiophene acetic acid) (PTAA), is studied in an aqueous buffer by using absorption and emission spectroscopies, photon correlation spectroscopy, isothermal titration calorimetry, and cryogenic transmission electron microscopy. We study the mixed solutions as a function of composition ratio R of surfactant molecules to monomer units molar concentrations, at low polymer concentration and in a very wide composition range (10(-6) < R < 10(2)) below the critical micellar concentration. Upon surfactant binding, the molecularly dispersed chains first collapse progressively and then form new structures as the mixed aggregates get enriched in surfactant. The collapse leads to a strong decrease of the conjugation length and to a blue shift of the absorption spectra by 30 to 50 nm. The new structures are responsible for a new intense emission band at about 600 nm, red-shifted by nearly 130 nm from the initial emission maximum of the polymer (~472 nm). As the surfactant tail becomes shorter, the blue shift of the absorption spectra and the intensity raise of the new emission are delayed to larger composition ratios while their variations become smoother functions of the surfactant concentration. These particular spectroscopic properties of PTAA seem related to its unique combination of a strongly hydrophobic backbone, a large ratio of contour length to persistence length, and an overall good aqueous solubility. Our results show that such features are well suited to design a colorimetric biosensor at small composition ratio, and a fluorescent biomarker at large composition ratio.

  18. [Molluscacide activity of a mixture of 6-n-alkyl salicylic acids (anacardic acid) and 2 of its complexes with copper (II) and lead (II)].

    PubMed

    Mendes, N M; de Oliveira, A B; Guimarães, J E; Pereira, J P; Katz, N

    1990-01-01

    The molluscicide activity of hexanic extract from Anacardium occidentale L. (cashew) nut shell, of copper (II) complex, of lead (II) complex and anacardic acid has been compared in the laboratory in an attempt to obtain better stability than anacardic acid. This was obtained from the hexanic extract of the cashew nut shell by precipitation with lead (II) hydroxide or cupric sulfate plus sodium hydroxide or (II) cupric hydroxide followed by treatment of lead (II) complex with a diluted solution of sulfuric acid. Ten products of the mixture obtained were tested on adults snails of Biomphalaria glabrata at 1 to 10 ppm. The most active products were copper (II) complex, obtained by cupric sulfate plus sodium hydroxide, and anacardic acid (sodium hydroxide) which presented activity at 4 ppm. The anacardic acid's lead content was above the limits accepted by the United States standards.

  19. PREPARATION OF ALKYL PYROPHOSPHATE EXTRACTANTS

    DOEpatents

    Levine, C.A.; Skiens, W.E.; Moore, G.R.

    1960-08-01

    A process for providing superior solvent extractants for metal recovery processes is given wherein the extractant comprises an alkyl pyrophosphoric acid ester dissolved in an organic solvent diluent. Finely divided solid P/sub 2/O/ sub 5/ is slurried in an organic solvent-diluent selected from organic solvents such as kerosene, benzene, chlorobenzene, toluene, etc. An alcohol selected from the higher alcohols having 4 to 17 carbon atoms. e.g.. hexanol-1. heptanol-3, octanol-1. 2.6-dimethyl-heptanol-4, and decanol-1, is rapidly added to the P/sub 2/O/sub 5/ slurry in the amount of about 2 moles of alcohol to 1 mole of P/sub 2/ O/sub 5/. The temperature is maintained below about 110 deg C during the course of the P/sub 2/O/sub 5/-alcohol reaction. An alkyl pyrophosphate extractant compound is formed as a consequence of the reaction process. The alkyl pyrophosphate solvent-diluent extractant phase is useful in solvent extraction metal recovery processes.

  20. Two di-alkyl-ammonium salts of 2-amino-4-nitro-benzoic acid: crystal structures and Hirshfeld surface analysis.

    PubMed

    Wardell, James L; Jotani, Mukesh M; Tiekink, Edward R T

    2016-12-01

    The crystal structures of two ammonium salts of 2-amino-4-nitro-benzoic acid are described, namely di-methyl-aza-nium 2-amino-4-nitro-benzoate, C2H8N(+)·C7H5N2O4(-), (I), and di-butyl-aza-nium 2-amino-4-nitro-benzoate, C8H20N(+)·C7H5N2O4(-), (II). The asymmetric unit of (I) comprises a single cation and a single anion. In the anion, small twists are noted for the carboxyl-ate and nitro groups from the ring to which they are connected, as indicated by the dihedral angles of 11.45 (13) and 3.71 (15)°, respectively; the dihedral angle between the substituents is 7.9 (2)°. The asymmetric unit of (II) comprises two independent pairs of cations and anions. In the cations, different conformations are noted in the side chains in that three chains have an all-trans [(+)-anti-periplanar] conformation, while one has a distinctive kink resulting in a (+)-synclinal conformation. The anions, again, exhibit twists with the dihedral angles between the carboxyl-ate and nitro groups and the ring being 12.73 (6) and 4.30 (10)°, respectively, for the first anion and 8.1 (4) and 12.6 (3)°, respectively, for the second. The difference between anions in (I) and (II) is that in the anions of (II), the terminal groups are conrotatory, forming dihedral angles of 17.02 (8) and 19.0 (5)°, respectively. In each independent anion of (I) and (II), an intra-molecular amino-N-H⋯O(carboxyl-ate) hydrogen bond is formed. In the crystal of (I), anions are linked into a jagged supra-molecular chain by charge-assisted amine-N-H⋯O(carboxyl-ate) hydrogen bonds and these are connected into layers via charge-assisted ammonium-N-H⋯O(carboxyl-ate) hydrogen bonds. The resulting layers stack along the a axis, being connected by nitro-N-O⋯π(arene) and methyl-C-H⋯O(nitro) inter-actions. In the crystal of (II), the anions are connected into four-ion aggregates by charge-assisted amino-N-H⋯O(carboxyl-ate) hydrogen bonding. The formation of ammonium

  1. Concentrations and patterns of perfluoroalkyl acids in Georgia, USA surface waters near and distant to a major use source

    USGS Publications Warehouse

    Konwick, B.J.; Tomy, G.T.; Ismail, N.; Peterson, J.T.; Fauver, R.J.; Higginbotham, D.; Fisk, A.T.

    2008-01-01

    Perfluoroalkyl acids (PFAAs) are widespread contaminants emanating from, among other sources, the production/degradation of fluorinated chemicals used in surface repellant applications, such as carpet manufacturing. The goal of the present study was to assess the concentrations of PFAAs, including perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUA), and perfluorooctane sulfonamide (PFOSA), in surface waters both near a wastewater land application system (LAS) in Dalton (GA, USA), home to North America's largest carpet manufacturing site, and distant to this location (Altamaha River, GA, USA) to understand the fate of PFAAs in freshwater. Levels of PFAAs were high in the Conasauga River (GA, USA) downstream of the LAS (PFOA, 253-1,150 ng/L; PFOS, 192-318 ng/L; PFNA, 202-369 ng/L; PFDA, 30.1-113 ng/L; PFUA, 58.0-99.2 ng/L; PFOSA, 162-283 ng/L) and in streams and ponds in Dalton (PFOA, 49.9-299 ng/L; PFOS, 15.8-120 ng/L), and were among the highest measured at a nonspill or directrelease location. Perfluoroalkyl acids in the Altamaha River were much lower (PFOA, 3.0-3.1 ng/L; PFOS, 2.6-2.7 ng/L), but were a source of PFAAs to Georgia's estuaries. A preliminary hazard assessment indicated that concentrations of PFOS at two sites in the Conasauga River exceeded the threshold effect predicted for birds consuming aquatic organisms that are exposed continuously to the PFOS levels at these sites. Assuming that toxicity for all PFAAs quantified is equal to that of PFOS, the sum total PFAAs at two sites within the Conasauga River exceeded PFOS thresholds for aquatic and avian species, warranting additional research. ?? 2008 SETAC Printed in the USA.

  2. A comparison of the solvation thermodynamics of amino acid analogues in water, 1-octanol and 1-n-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids by molecular simulation

    NASA Astrophysics Data System (ADS)

    Paluch, Andrew S.; Vitter, Cameron A.; Shah, Jindal K.; Maginn, Edward J.

    2012-11-01

    A computational approach is developed to quantitatively study the solvation thermodynamics of amino acid analogues in ionic liquids via molecular simulation. The solvation thermodynamics of amino acid analogues in ionic liquids is important for an understanding of protein-ionic liquid interactions, shedding insight into the structure and solubility of proteins, and the activity of enzymes in ionic liquids. This information is additionally key to developing novel extraction processes. As a result of the challenge of quantitatively describing the solvation behavior of ionic liquids, a key outcome of the present study is the development of a "hydrophobicity" scale to quantitatively describe the amino acid analogues. The scale allows one to separate the results of both the hydrophobic and hydrophillic analogues, simplifying an understanding of the observed trends. Equipped with the proposed hydrophobicity scale, one needs only perform conventional solvation free energy calculations of the amino acid analogues in the ionic liquids of interest. The necessary simulation tools are available in most open-source simulation software, facilitating the adoption of this approach by the simulation community at large. We have studied the case of varying the cation alkyl-chain length of a 1-n-alkyl-3-methylimidazolium cation paired with the bis(trifluoromethylsulfonyl)imide anion. The findings suggest that a judicious selection of both the cation and anion could potentially lead to a solvent for which the amino acid analogues have an affinity far greater than that for both water and a non-polar reference solvent.

  3. Bioaccumulation of perfluoroalkyl acids including the isomers of perfluorooctane sulfonate in carp (Cyprinus carpio) in a sediment/water microcosm.

    PubMed

    Fang, Shuhong; Zhang, Yifeng; Zhao, Shuyan; Qiang, Liwen; Chen, Meng; Zhu, Lingyan

    2016-12-01

    Carp (Cyprinus carpio) were exposed to perfluoroalkyl acids (PFAAs) including perfluorooctane sulfonate (PFOS) isomers in an artificially contaminated sediment/water microcosm. The uptake constant of PFAAs increased with increasing carbon chain length, whereas the elimination coefficient displayed the opposite trend, suggesting that carbon chain length plays an important role in the bioaccumulation of PFAAs. When the contribution of suspended particulate matter was taken into account, the bioaccumulation factors (BAFs) became lower (3.61-600 L/kg) compared with BAFs derived from only considering the absorption from free PFAAs in water (3.85-97000 L/kg). The results indicate that suspended particulate matter in water constitutes an important source of exposure for aquatic organisms to long-chain PFAAs. Linear (n-)PFOS was preferentially accumulated compared with branched isomers in carp. Among the branched isomers, 1m-PFOS displayed the greatest bioaccumulation, whereas m2 -PFOS had the lowest. Linear PFOS displayed greater partitioning ability from blood to other tissues over branched PFOS (br-PFOS) isomers, leading to a relatively lower n-PFOS proportion in blood. In summary, suspended particulate matter made a contribution to the accumulation of long-chain PFAAs in aquatic organisms, and n-PFOS was preferentially accumulated compared with br-PFOS isomers. Environ Toxicol Chem 2016;35:3005-3013. © 2016 SETAC.

  4. Effect of GABA on oxidative stress in the skeletal muscles and plasma free amino acids in mice fed high-fat diet.

    PubMed

    Xie, Z X; Xia, S F; Qiao, Y; Shi, Y H; Le, G W

    2015-06-01

    Increased levels of plasma free amino acids (pFAAs) can disturb the blood glucose levels in patients with obesity, diabetes mellitus and metabolic syndrome (MS) and are associated with enhanced protein oxidation. Oxidation of proteins, especially in the muscles, can promote protein degradation and elevate the levels of pFAAs. Gamma-aminobutyric acid (GABA), a food additive, can reduce high-fat diet (HFD)-induced hyperglycaemia; however, the mechanisms remain unclear. The aim of this study was to evaluate the effects of GABA on protein oxidation and pFAAs changes. One hundred male C57BL/6 mice were randomly divided into five groups that were fed with control diet, HFD and HFD supplied with 0.2%, 0.12% and 0.06% GABA in drinking water for 20 weeks respectively. HFD feeding led to muscular oxidative stress, protein oxidation, pFAA disorders, hyperglycaemia and augmented plasma GABA levels. Treatment with GABA restored normally fasting blood glucose level and dose-dependently inhibited body weight gains, muscular oxidation and protein degradation. While medium and low doses of GABA mitigated HFD-induced pFAA disorders, the high dose of GABA deteriorated the pFAA disorders. Medium dose of GABA increased the levels of GABA, but high dose of GABA reduced the levels of plasma GABA and increased the activity of succinic semialdehyde dehydrogenase in the liver. Therefore, treatment with GABA mitigated HFD-induced hyperglycaemia probably by repairing HFD-induced muscular oxidative stress and pFAA disorders in mice. Our data also suggest that an optimal dose of GABA is crucial for the prevention of excess GABA-related decrease in the levels of pFAA and GABA as well as obesity.

  5. Current Understanding of Perfluoroalkyl Acid Toxicology

    EPA Science Inventory

    The perfluoroalkyl acids (PFAAs) are a family of organic chemicals consisting of a perfluorinated carbon backbone (4-14 carbons in length) and an anionic head group (sulfonate, carboxylate or phosphonate). These compounds have excellent surface-tension reducing properties and hav...

  6. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1993-01-05

    Aromatic compounds are alkylated in a combination reactor/distillation column comprising a vessel suitable for operating between 70 C and 500 C and from 0.5 to 20 atmospheres pressure; an inert distillation packing in the lower one-third of said vessel; solid acidic catalytic material such as zeolites or an acidic cation exchange resin supported in the middle one-third of said vessel; and inert distillation packing in the upper one-third of said vessel. A benzene inlet is located near the upper end of the vessel; an olefin inlet is juxtaposed with said solid acidic catalytic material; a bottoms outlet is positioned near the bottom of said vessel for removing said cumene and ethyl benzene; and an overhead outlet is placed at the top of said vessel for removing any unreacted benzene and olefin.

  7. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1993-01-01

    Aromatic compounds are alkylated in a combination reactor/distillation column comprising a vessel suitable for operating between 70.degree. C. and 500.degree. C. and from 0.5 to 20 atmospheres pressure; an inert distillation packing in the lower one-third of said vessel; solid acidic catalytic material such as zeolites or an acidic cation exchange resin supported in the middle one-third of said vessel; and inert distillation packing in the upper one-third of said vessel. A benzene inlet is located near the upper end of the vessel; an olefin inlet is juxtaposed with said solid acidic catalytic material; a bottoms outlet is positioned near the bottom of said vessel for removing said cumene and ethyl benzene; and an overhead outlet is placed at the top of said vessel for removing any unreacted benzene and olefin.

  8. Evaluating the additivity of perfluoroalkyl acids in binary combinations on peroxisome proliferator-activated receptor-α activation.

    PubMed

    Wolf, Cynthia J; Rider, Cynthia V; Lau, Christopher; Abbott, Barbara D

    2014-02-28

    Perfluoroalkyl acids (PFAAs) are found globally in the environment, detected in humans and wildlife, and are typically present as mixtures of PFAA congeners. Mechanistic studies have found that responses to PFAAs are mediated in part by PPARα. Our previous studies showed that individual PFAAs activate PPARα transfected into COS-1 cells. The goal of the current study was to determine if binary combinations of perfluorooctanoic acid (PFOA) and another PFAA act in an additive fashion to activate PPARα in the mouse one-hybrid in vitro model. COS-1 cells were transiently transfected with mouse PPARα luciferase reporter construct and exposed to either vehicle control (0.1% DMSO or water), PPARα agonist (WY14643, 10 μM), PFOA at 1-128μM, perfluorononanoic acid (PFNA) at 1-128 μM, perfluorohexanoic acid (PFHxA) at 8-1024 μM, perfluorooctane sulfonate (PFOS) at 4-384 μM or perfluorohexane sulfonate (PFHxS) at 8-2048 μM to generate sigmoidal concentration-response curves. In addition, cells were exposed to binary combinations of PFOA+either PFNA, PFHxA, PFOS or PFHxS in an 8×8 factorial design. The concentration-response data for individual chemicals were fit to sigmoidal curves and analyzed with nonlinear regression to generate EC₅₀s and Hillslopes, which were used in response-addition and concentration-addition models to calculate predicted responses for mixtures in the same plate. All PFOA+PFAA combinations produced concentration-response curves that were closely aligned with the predicted curves for both response addition and concentration addition at low concentrations. However, at higher concentrations of all chemicals, the observed response curves deviated from the predicted models of additivity. We conclude that binary combinations of PFAAs behave additively at the lower concentration ranges in activating PPARα in this in vitro system.

  9. DISRUPTION OF THYROID HORMONE HOMEOSTASIS BY PERFLUROALKYL ACIDS

    EPA Science Inventory

    Perfluoroalkyl acids (PFAA) are man-made chemicals found ubiquitously in humans and wildlife; the major representatives of these are those with an 8-carbon chain (C-8, perfluorooctane sulfonate, PFOS and perfluorooctanoic acid, PFOA). Presently, we have investigated the effects o...

  10. Covalent triazine-based framework: A promising adsorbent for removal of perfluoroalkyl acids from aqueous solution.

    PubMed

    Wang, Bingyu; Lee, Linda S; Wei, Chenhui; Fu, Heyun; Zheng, Shourong; Xu, Zhaoyi; Zhu, Dongqiang

    2016-09-01

    Perfluoroalkyl acids (PFAAs) are highly stable, persistent, and ubiquitous in the environment with significant concerns growing with regards to both human and ecosystem health. Due to the high stability to both biological and chemical attack, the only currently feasible approach for their removal from water is adsorbent technology. The main objective of this study was to assess a covalent triazine-based framework (CTF) adsorbent for removal from aqueous solutions of perfluoro C4, C6, and C8 carboxylates and sulfonates including the two C8s most commonly monitored, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). Adsorption affinity and capacity were quantified and compared to three commonly used sorbents: pulverized microporous activated carbon, single-walled carbon nanotubes, and Amberlite IRA-400 anion-exchange resin. CTF adsorbent exhibited pronouncedly higher adsorption affinity and capacity of PFAAs than other test sorbents. The remarkably strong adsorption to CTF can be attributed to the favored electrostatic interaction between the protonated triazine groups on the inner wall of the hydrophobic CTF pore and the negatively charged head groups of the PFAAs intercalated between the CTF layers. The homogeneous, nanosized pores (1.2 nm) of CTF hindered adsorption of a large-sized dissolved humic acid, thus minimizing the suppression of PFAA adsorption. Additionally, regeneration of CTF was easily accomplished by simply raising pH > 11, which inhibited the electrostatic adsorptive interaction of PFAAs.

  11. Iron-Catalyzed C-H Alkylation of Heterocyclic C-H Bonds.

    PubMed

    Babu, Kaki Raveendra; Zhu, Nengbo; Bao, Hongli

    2017-01-06

    An efficient, iron-catalyzed C-H alkylation of benzothiazoles by using alkyl diacyl peroxides and alkyl tert-butyl peresters which are readily accessible from carboxylic acids to synthesize 2-alkylbenzothiazoles is developed. This reaction is environmentally benign and compatible with a broad range of functional groups. Various primary, secondary, and tertiary alkyl groups can be efficiently incorporated into diverse benzothiazoles. The effectiveness of this method is illustrated by late-stage functionalization of biologically active heterocycles.

  12. Transition metal-free decarboxylative alkylation reactions.

    PubMed

    Liu, Ping; Zhang, Guanghui; Sun, Peipei

    2016-11-22

    This review summarizes advances in the decarboxylative alkylation of carboxylic acids and their derivatives under transition metal-free conditions in recent years. Unlike most transition metal-catalyzed decarboxylative coupling reactions which tend to undergo catalytic cycles, the mechanisms of reactions under metal-free conditions are usually diverse and even ambiguous in some cases. This article offers an overview of reaction types and their corresponding mechanisms, highlights some of the advantages and limitations, and focuses on introducing UV and visible light-induced, organocatalyst and peroxide promoted radical processes for decarboxylative alkylation and the formation of C-C bonds.

  13. Alkyl ferulates in wound healing potato tubers.

    PubMed

    Bernards, M A; Lewis, N G

    1992-10-01

    Seven ferulic acid esters of 1-alkanols ranging in carbon length from C16 to C28 were synthesized and an HPLC protocol for their separation developed. Extracts prepared from wound healing potato (Solanum tuberosum) tubers and analysed by HPLC indicated that alkyl ferulate esters begin to accumulate 3-7 days after wound treatment. Of the nine esters identified by EIMS, (including two esters of odd chain length alkanols) hexadecyl and octadecyl ferulates were predominant. Alkyl ferulate esters were restricted to the wound periderm.

  14. Mitsunobu alkylation of cancerostatic 5-fluorouridine with (2E)-10-hydroxydec-2-enoic acid, a fatty acid from royal jelly with multiple biological activities.

    PubMed

    Ottenhaus, Vanessa; Rosemeyer, Helmut

    2015-09-01

    5-Fluorouridine (1) - a nucleoside antimetabolite with strong cancerostatic properties - was protected i) at the 2'- and 3'-OH groups with a heptan-4-ylidene residue and ii) at the 5'-OH group with a (4-methoxyphenyl)(diphenyl)methyl residue. This fully protected compound, 3, was submitted to a Mitsunobu reaction with the N-hydroxysuccinimide (NHS) ester, 5, of (2E)-10-hydroxydec-2-enoic acid (4) which gave nucleolipid 6. The latter was detritylated with Cl2 CHCOOH to yield the co-drug 7 as NHS ester.

  15. Synthesis Of Alkyl Hydroperoxides Via Alkylation Of gem-Dihydroperoxides

    PubMed Central

    Kyasa, ShivaKumar; Puffer, Benjamin W.

    2013-01-01

    Two-fold alkylation of 1,1-dihydroperoxides, followed by hydrolysis of the resulting bisperoxyacetals, provides a convenient method for synthesis of primary and secondary alkyl hydroperoxides. PMID:23469994

  16. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.

    1989-07-18

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 fig.

  17. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1994-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  18. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1993-09-07

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a molecular sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene to about the mid point of the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 figures.

  19. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.

    1989-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  20. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1993-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene to about the mid point of the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  1. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1994-06-14

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a molecular sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 fig.

  2. Ligand-promoted alkylation of C(sp3)-H and C(sp2)-H bonds.

    PubMed

    Zhu, Ru-Yi; He, Jian; Wang, Xiao-Chen; Yu, Jin-Quan

    2014-09-24

    9-Methylacridine was identified as a generally effective ligand to promote a Pd(II)-catalyzed C(sp(3))-H and C(sp(2))-H alkylation of simple amides with various alkyl iodides. This alkylation reaction was applied to the preparation of unnatural amino acids and geometrically controlled tri- and tetrasubstituted acrylic acids.

  3. Perfluoroalkyl acids in selected wastewater treatment plants and their discharge load within the Lake Victoria basin in Kenya.

    PubMed

    Chirikona, Florah; Filipovic, Marko; Ooko, Seline; Orata, Francis

    2015-05-01

    A major ecological challenge facing Lake Victoria basin is the influx of chemical contaminants from domestic, hospital, and industrial effluents. Determined levels of perfluoroalkyl acids (PFAAs) in wastewater and sludge from selected wastewater treatment plants (WWTPs) in Kenya are presented and their daily discharge loads calculated for the first time within the Lake Victoria basin. Samples were extracted and separated using solid-phase extraction and ultra-performance liquid chromatography (UPLC)-MS/MS or LC-MS/MS methodology. All sewage sludge and wastewater samples obtained from the WWTPs contained detectable levels of PFAAs in picogram per gram dry weight (d.w.) and in nanogram per liter, respectively. There was variability in distribution of PFAAs in domestic, hospital, and industrial waste with domestic WWPTs observed to contain higher levels. Almost all PFAA homologues of chain length C-6 and above were detected in samples analyzed, with long-chain PFAAs (C-8 and above chain length) being dominant. The discharge from hospital contributes significantly to the amounts of PFAAs released to the municipal water systems and the lake catchment. Using the average output of wastewater from the five WWTPs, a mass load of 1013 mg day(-1) PFAAs per day discharged has been calculated, with the highest discharge obtained at Kisumu City (656 mg day(-1)). The concentration range of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in wastewater was 1.3-28 and 0.9-9.8 ng L(-1) and in sludge samples were 117-673 and 98-683 pg g(-1), respectively.

  4. Low-risk gasoline alkylation process using a homogeneous liquid phase catalyst

    SciTech Connect

    Nelson, S.R.; Nelson, L.G.

    1996-12-31

    Kerr-McGee`s interest in finding additional applications for its ROSES technology has led to a promising new alkylation process for the production of gasoline. The technology is timely due to its inherent environmental safety. The Homogeneous Alkylation Technology (HAT{trademark}) process uses a soluble alkylaluminum chloride-based catalyst at less than 1 percent of the acid concentrations used in conventional alkylation processes. The patented process greatly reduces the environmental risks associated with accidental acid releases from HF and sulfuric acid alkylation units. In addition, the process is projected to operate at lower cost than sulfuric acid alkylation and is a retrofit option for existing HF and sulfuric-acid alkylation units. Kerr-McGee has entered into a relationship with a major U.S. refiner to carry on the development of the HAT process. A gallon-per-day-scale pilot unit has been constructed for use in developing the process. 1 fig., 1 tab.

  5. Mass balance of perfluoroalkyl acids in the Baltic Sea.

    PubMed

    Filipovic, Marko; Berger, Urs; McLachlan, Michael S

    2013-05-07

    A mass balance was assembled for perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), perfluorodecanoic acid (PFDA), and perfluorooctanesulfonic acid (PFOS) in the Baltic Sea. Inputs (from riverine discharge, atmospheric deposition, coastal wastewater discharges, and the North Sea) and outputs (to sediment burial, transformation of the chemical, and the North Sea), as well as the inventory in the Baltic Sea, were estimated from recently published monitoring data. Formation of the chemicals in the water column from precursors was not considered. River inflow and atmospheric deposition were the dominant inputs, while wastewater treatment plant (WWTP) effluents made a minor contribution (<5%). A mass balance of the Oder River watershed was assembled to explore the sources of the perfluoroalkyl acids (PFAAs) in the river inflow. It indicated that WWTP effluents made only a moderate contribution to riverine discharge (21% for PFOA, 6% for PFOS), while atmospheric deposition to the watershed was 1-2 orders of magnitude greater than WWTP discharges. The input to the Baltic Sea exceeded the output for all four PFAAs, suggesting that inputs were higher during 2005-2010 than during the previous 20 years despite efforts to reduce emissions of PFAAs. One possible explanation is the retention and delayed release of PFAAs from atmospheric deposition in the soils and groundwater of the watershed.

  6. Polyimide characterization studies - Effect of pendant alkyl groups

    NASA Technical Reports Server (NTRS)

    Jensen, B. J.; Young, P. R.

    1984-01-01

    The effect on selected polyimide properties when pendant alkyl groups were attached to the polymer backbone was investigated. A series of polymers were prepared using benzophenone tetracarboxylic acid dianhydride (BTDA) and seven different p-alkyl-m,p'-diaminobenzophenone monomers. The alkyl groups varied in length from C(1) (methyl) to C(9) (nonyl). The polyimide prepared from BTDA and m,p'-diaminobenzophenone was included as a control. All polymers were characterized by various chromatographic, spectroscopic, thermal, and mechanical techniques. Increasing the length of the pendant alkyl group resulted in a systematic decrease in glass transition temperature (Tg) for vacuum cured films. A 70 C decrease in Tg to 193 C was observed for the nonyl polymer compared to the Tg for the control. A corresponding systematic increase in Tg indicative of crosslinking, was observed for air cured films. Thermogravimetric analysis revealed a slight sacrifice in thermal stability with increasing alkyl length. No improvement in film toughness was observed.

  7. Spectroscopic and structural characterization of the charge-transfer interaction of N,N'-bis-alkyl derivatives of 1,4,6,8-naphthalenediimide with chloranilic and picric acids

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; Ahmed, Hamdy A.; Grabchev, Ivo; El-Zayat, Lamia A.

    2008-09-01

    Charge-transfer (CT) complexes formed from the reactions of two N,N'-bis-alkyl derivatives of 1,4,6,8-naphthalenediimide such as N, N'-bis[2-hydroxyethyl)]-1,4,6,8-naphthalenediimide (BHENDI) and N, N'-bis-[2- N, N-dimethylaminoethyl)]-1,4,6,8-naphthalenediimide (BDMAENDI) with chloranilic acid (CLA) and piciric acid (PA) as π-acceptors, have been studied spectrophotometrically in methanol and chloroform, respectively at 25 °C. The photometric titration curves for the reactions indicated that the data obtained refer to 1:1 charge-transfer complexes of [(BHENDI)(CLA)], [(BDMAENDI)(CLA)], [(BHENDI)(PA)] and [(BDMAENDI)(PA)] were formed. Benesi-Hildebrand and its modification methods were applied to the determination of association constant ( K), molar extinction coefficient ( ɛ). The solid CT complexes have been synthesized and characterization by different spectral methods.

  8. Molecular requisites for drug binding to muscle CLC-1 and renal CLC-K channel revealed by the use of phenoxy-alkyl derivatives of 2-(p-chlorophenoxy)propionic acid.

    PubMed

    Liantonio, Antonella; Accardi, Alessio; Carbonara, Giuseppe; Fracchiolla, Giuseppe; Loiodice, Fulvio; Tortorella, Paolo; Traverso, Sonia; Guida, Patrizia; Pierno, Sabata; De Luca, Annamaria; Camerino, Diana Conte; Pusch, Michael

    2002-08-01

    CLC channels are a gene family of Cl(-) channels that serve a variety of functions, several of which are involved in genetic diseases. Few specific ligands of CLC channels are known that could be useful as pharmacological tools or potential drugs. We synthesized various derivatives of 2-(p-chlorophenoxy)propionic acid, the S(-)-enantiomer of which is a specific blocker of the muscle channel CLC-1. In particular, compounds with different alkyl or phenoxy-alkyl groups on the chiral center, isosteres of the oxygen in the aryloxy moiety, or bioisosteres of the carboxy function were prepared. We found that compounds containing a phenoxy and a phenoxy-alkyl group on the chiral center (bis-phenoxy derivatives) specifically inhibited renal CLC-K channels from the extracellular side with an affinity in the 150-microM range and with almost no effect on other CLC channels when applied from the outside. Surprisingly, the same substances inhibited CLC-1 from the intracellular side in a voltage-dependent manner with an apparent K(D) of <5 microM at -140 mV, thus being the most potent blockers of a CLC channel known so far. Although the chlorine atom in para- position of the second phenoxy group was essential for inhibition of CLC-K channels from the outside, it could be substituted by a methoxy group without changing the potency of block for CLC-1 from the inside. These newly identified substances provide powerful tools for studying the structure-function relationship and the physiological role of CLC channels and may represent a starting point for the development of useful drugs targeting CLC-K channels.

  9. Congener-specific numbering systems for the environmentally relevant C4 through C8 perfluorinated homologue groups of alkyl sulfonates, carboxylates, telomer alcohols, olefins, and acids, and their derivatives.

    PubMed

    Rayne, Sierra; Forest, Kaya; Friesen, Ken J

    2008-10-01

    We introduce a congener-specific numbering system for the C4 through C8 perfluorinated homologue groups of alkyl sulfonates, carboxylates, telomer alcohols, olefins, and acids, and their derivatives. Increasing length of the carbon chain beyond C3 leads to a corresponding rapid increase in the number of potential isomers (C4 = 4, C5 = 8, C6 = 17, C7 = 39, and C8 = 89 congeners). There is a need for clear and unambiguous chemical shorthand to ensure accuracy and consistency in the future perfluorinated alkyl substance (PFA) literature, and to correct previous misconceptions that may have restricted research efforts into developing full-congener PFA analysis. If adopted by the research community, introduction of a numbering system at this relatively early stage of investigations into the congener-specific analysis, environmental behavior, and toxicology of PFAs would not require an arduous and difficult reassignment of historical structures and naming conventions presented in the prior art. Many PFA congeners are chiral, necessitating a consideration of their enantiospecific environmental behavior and toxicology.

  10. EVALUATION OF PERFLUOROALKYL ACID ACTIVITY USING PRIMARY MOUSE AND HUMAN HEPATOCYTES

    EPA Science Inventory

    While perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) have been studied at length, less is know about the biological activity of other environmental perfluoroalkyl acids (pFAAs). Using a transient transfection assay developed in COS-l cells, our group has previ...

  11. Evaluation of Perfluoroalkyl Acid Activity Using Primary Mouse and Human Hepatocytes.

    EPA Science Inventory

    While perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) have been studied at length, less is known about the biological activity of other perfluoroalkyl acids (PFAAs) in the environment. Using a transient transfection assay developed in COS-1 cells, our group h...

  12. ALKYL PYROPHOSPHATE METAL SOLVENT EXTRACTANTS AND PROCESS

    DOEpatents

    Long, R.L.

    1958-09-30

    A process is presented for the recovery of uranium from aqueous mineral acidic solutions by solvent extraction. The extractant is a synmmetrical dialkyl pyrophosphate in which the alkyl substituents have a chain length of from 4 to 17 carbon atoms. Mentioned as a preferred extractant is dioctyl pyrophosphate. The uranium is precipitated irom the organic extractant phase with an agent such as HF, fluoride salts. alcohol, or ammonia.

  13. Effect of olive storage conditions on Chemlali olive oil quality and the effective role of fatty acids alkyl esters in checking olive oils authenticity.

    PubMed

    Jabeur, Hazem; Zribi, Akram; Abdelhedi, Ridha; Bouaziz, Mohamed

    2015-02-15

    The present paper accounts for the study of the storage of Chemlali olive fruits at two conditions of limited aerobiosis: in closed plastic bags and in open perforated plastic boxes for different periods before oil extraction. The ultimate objective is to investigate the effect of the container type of the postharvest fruit storage on the deterioration of the olive oil quality. The results have shown that the oil quality of Chemlali olives deteriorated more rapidly during fruit storage in closed plastic bags than in perforated plastic boxes. Therefore, the use of perforated plastic boxes is recommended for keeping the olives for longer periods of storage. The repeated measures analysis of variance of all parameters analyzed indicated that the olive oil quality is mainly affected by the olives storage conditions (containers type and storage periods). Finally, blends of extra-virgin olive oil and mildly deodorized low-quality olive oils can be detected by their alkyl esters concentrations.

  14. 40 CFR 721.10679 - Carboxylic acid, substituted alkylstannylene ester, reaction products with inorganic acid tetra...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... alkylstannylene ester, reaction products with inorganic acid tetra alkyl ester (generic). 721.10679 Section 721... Carboxylic acid, substituted alkylstannylene ester, reaction products with inorganic acid tetra alkyl ester... identified generically as carboxylic acid, substituted alkylstannylene ester, reaction products...

  15. 76 FR 6335 - Sodium and Potassium Salts of N-alkyl (C8

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-02-04

    ... AGENCY 40 CFR Part 180 Sodium and Potassium Salts of N-alkyl (C 8 - C 18 )-beta-iminodipropionic acid... residues of sodium and potassium salts of N-alkyl (C 8 -C 18 )-beta-iminodipropionic acid where the C 8 -C.... EPA previously published a final rule to establish a tolerance exemption for sodium salts of SSNA...

  16. Formation of furan fatty alkyl esters from their bis-epoxide fatty esters

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Reactions of epoxidized alkyl soyate with four different alcohols: ethanol, isopropyl alcohol, 2-ethylhexanol, and benzyl alcohol were investigated in the presence of Bronsted acid catalyst. Products not reported in prior studies of similar reactions were found. These were furan fatty acid alkyl est...

  17. PERFLUOROPHOSPHONIC ACID ACTIVATES PEROXISOME PROUFERATOR-ACTIVATED RECEPTOR-ALPHA BUT NOT CONSTITUTIVE ANDROSTANE RECEPTOR IN THE MURINE LIVER

    EPA Science Inventory

    Masurf FS-780 is a commercial perfluoro-chemical mixture that contains C612-perfluoroalkylphosphonic acid (PFPA) derivatives. PFPAs have received recent attention as a previously under recognized subclass of perfluoroalkyl acids (PFAAs) that are found in the environment. The curr...

  18. 40 CFR 721.2140 - Carbo-poly-cycli-col azo-alkyl-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt. 721.2140 Section 721.2140 Protection of Environment...-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt. (a) Chemical substance and significant new uses...-mino-al-kyl-car-bo-mon-o-cyc-lic ester, halogen acid salt (PMN P-88-1682) is subject to reporting...

  19. 40 CFR 721.2140 - Carbo-poly-cycli-col azo-alkyl-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt. 721.2140 Section 721.2140 Protection of Environment...-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt. (a) Chemical substance and significant new uses...-mino-al-kyl-car-bo-mon-o-cyc-lic ester, halogen acid salt (PMN P-88-1682) is subject to reporting...

  20. 40 CFR 721.2140 - Carbo-poly-cycli-col azo-alkyl-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt. 721.2140 Section 721.2140 Protection of Environment...-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt. (a) Chemical substance and significant new uses...-mino-al-kyl-car-bo-mon-o-cyc-lic ester, halogen acid salt (PMN P-88-1682) is subject to reporting...

  1. 40 CFR 721.2140 - Carbo-poly-cycli-col azo-alkyl-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt. 721.2140 Section 721.2140 Protection of Environment...-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt. (a) Chemical substance and significant new uses...-mino-al-kyl-car-bo-mon-o-cyc-lic ester, halogen acid salt (PMN P-88-1682) is subject to reporting...

  2. 40 CFR 721.2140 - Carbo-poly-cycli-col azo-alkyl-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt. 721.2140 Section 721.2140 Protection of Environment...-aminoalkyl-carbo-mono-cyclic ester, halogen acid salt. (a) Chemical substance and significant new uses...-mino-al-kyl-car-bo-mon-o-cyc-lic ester, halogen acid salt (PMN P-88-1682) is subject to reporting...

  3. Formation of carboxylic acids from alcohols and olefins in zeolite H-ZSM-5 under mild conditions via trapping of alkyl carbenium ions with carbon monoxide: An in situ {sup 13}C solid state NMR study

    SciTech Connect

    Stepanov, A.G.; Luzgin, M.V.; Romannikov, V.N.; Sidelnikov, V.N.; Zamaraev K.I.

    1996-12-01

    Using in situ {sup 13}C solid state MAS NMR (for some reagents in combination with ex situ GC-MS), it is shown that butyl alcohols and olefins (ethene, isobutene, octene-1) undergo carbonylation to form carboxylic acids (the Koch reaction) with high conversion on zeolite H-ZSM-5 at 296-373 K. The reactions proceed without application of pressurized conditions, just upon coadsorption of CO and alcohols or CO, H{sub 2}O, and olefins on zeolite. The observed Koch reaction under mild conditions provides strong evidence for the formation of alkyl carbenium ions from alcohols and olefins on the zeolites as crucial reaction intermediates. Of the family of carbenium ions, CO reacts selectively with tertiary cations to produce tertiary carboxylic acids, unless the carbonylated molecule is too large for more bulky tertiary moieties to be accommodated and carbonylated in the narrow pores of H-ZSM05. Thus, t-BuOH, i-BuOH, and isobutene produce trimethylacetic acid with high selectivity and conversion, while ethene transforms selectively into 2-methyl-2-ethyl butyric acid. Reaction of octene-1 molecules with CO and H{sub 2}O results in acids of the C{sub 8}H{sub 17}COOH and C{sub 16}H{sub 33}COOH families with predominantly linear hydrocarbon chains. The data obtained may open up new possibilities in using solid acids in organic synthesis as carbonylation catalysts under mild conditions i.e., low temperature and normal atmospheric pressure. 55 refs., 8 figs.

  4. Influence of contaminated drinking water on perfluoroalkyl acid levels in human serum--A case study from Uppsala, Sweden.

    PubMed

    Gyllenhammar, Irina; Berger, Urs; Sundström, Maria; McCleaf, Philip; Eurén, Karin; Eriksson, Sara; Ahlgren, Sven; Lignell, Sanna; Aune, Marie; Kotova, Natalia; Glynn, Anders

    2015-07-01

    In 2012 a contamination of drinking water with perfluoroalkyl acids (PFAAs) was uncovered in the City of Uppsala, Sweden. The aim of the present study was to determine how these substances have been distributed from the contamination source through the groundwater to the drinking water and how the drinking water exposure has influenced the levels of PFAAs in humans over time. The results show that PFAA levels in groundwater measured 2012-2014 decreased downstream from the point source, although high ΣPFAA levels (>100ng/L) were still found several kilometers from the point source in the Uppsala aquifer. The usage of aqueous film forming fire-fighting foams (AFFF) at a military airport in the north of the city is probably an important contamination source. Computer simulation of the distribution of PFAA-contaminated drinking water throughout the City using a hydraulic model of the pipeline network suggested that consumers in the western and southern parts of Uppsala have received most of the contaminated drinking water. PFAA levels in blood serum from 297 young women from Uppsala County, Sweden, sampled during 1996-1999 and 2008-2011 were analyzed. Significantly higher concentrations of perfluorobutane sulfonic acid (PFBS) and perfluorohexane sulfonic acid (PFHxS) were found among women who lived in districts modeled to have received contaminated drinking water compared to unaffected districts both in 1996-1999 and 2008-2011, indicating that the contamination was already present in the late 1990s. Isomer-specific analysis of PFHxS in serum showed that women in districts with contaminated drinking water also had an increased percentage of branched isomers. Our results further indicate that exposure via contaminated drinking water was the driving factor behind the earlier reported increasing temporal trends of PFBS and PFHxS in blood serum from young women in Uppsala.

  5. Safety assessment of alkyl benzoates as used in cosmetics.

    PubMed

    'Becker, Lillian C; Bergfeld, Wilma F; Belsito, Donald V; Hill, Ronald A; Klaassen, Curtis D; Liebler, Daniel; Marks, James G; Shank, Ronald C; Slaga, Thomas J; Snyder, Paul W; Andersen, F Alan

    2012-01-01

    The functions of alkyl benzoates in cosmetics include fragrance ingredients, skin-conditioning agents--emollient, skin-conditioning agents--miscellaneous, preservatives, solvents, and plasticizers. The Cosmetic Ingredient Review Expert Panel reviewed the relevant animal and human data and noted gaps in the available safety data for some of the alkyl benzoates. Similar structure activity relationships, biologic functions, and cosmetic product usage allowed the available data of many of the alkyl benzoates to be extended to the entire group. Carcinogenicity data were not available, but available data indicated that these alkyl benzoate cosmetic ingredients are not genotoxic. Also benzoic acid and tested component alcohols were not reproductive or developmental toxicants, are not genotoxic in almost all assays, and are not carcinogenic. These ingredients were determined to be safe in the present practices of use and concentration.

  6. Regeneration of a deactivated USY alkylation catalyst using supercritical isobutane

    SciTech Connect

    Daniel M. Ginosar; David N. Ghompson; Kyle C. Burch

    2005-01-01

    Off-line, in-situ alkylation activity recovery from a completely deactivated solid acid catalyst was examined in a continuous-flow reaction system employing supercritical isobutane. A USY zeolite catalyst was initially deactivated during the liquid phase alkylation of butene with isobutane in a single-pass reactor and then varying amounts of alkylation activity were recovered by passing supercritical isobutane over the catalyst bed at different reactivation conditions. Temperature, pressure and regeneration time were found to play important roles in the supercritical isobutane regeneration process when applied to a completely deactivated USY zeolite alkylation catalyst. Manipulation of the variables that influence solvent strength, diffusivity, surface desorption, hydride transfer rates, and coke aging, strongly influence regeneration effectiveness.

  7. Toxicokinetics of seven perfluoroalkyl sulfonic and carboxylic acids in pigs fed a contaminated diet.

    PubMed

    Numata, Jorge; Kowalczyk, Janine; Adolphs, Julian; Ehlers, Susan; Schafft, Helmut; Fuerst, Peter; Müller-Graf, Christine; Lahrssen-Wiederholt, Monika; Greiner, Matthias

    2014-07-16

    The transfer of a mixture of perfluoroalkyl acids (PFAAs) from contaminated feed into the edible tissues of 24 fattening pigs was investigated. Four perfluoroalkyl sulfonic (PFSAs) and three perfluoroalkyl carboxylic acids (PFCAs) were quantifiable in feed, plasma, edible tissues, and urine. As percentages of unexcreted PFAA, the substances accumulated in plasma (up to 51%), fat, and muscle tissues (collectively, meat 40-49%), liver (under 7%), and kidney (under 2%) for most substances. An exception was perfluorooctanesulfonic acid (PFOS), with lower affinity for plasma (23%) and higher for liver (35%). A toxicokinetic model is developed to quantify the absorption, distribution, and excretion of PFAAs and to calculate elimination half-lives. Perfluorohexanoic acid (PFHxA), a PFCA, had the shortest half-life at 4.1 days. PFSAs are eliminated more slowly (e.g., half-life of 634 days for PFOS). PFAAs in pigs exhibit longer elimination half-lives than in most organisms reported in the literature, but still shorter than in humans.

  8. Bioaccumulation of perfluoroalkyl acids by earthworms (Eisenia fetida) exposed to contaminated soils.

    PubMed

    Rich, Courtney D; Blaine, Andrea C; Hundal, Lakhwinder; Higgins, Christopher P

    2015-01-20

    The presence of perfluoroalkyl acids (PFAAs) in biosolids-amended and aqueous film-forming foam (AFFF)-impacted soils results in two potential pathways for movement of these environmental contaminants into terrestrial foodwebs. Uptake of PFAAs by earthworms (Eisenia fetida) exposed to unspiked soils with varying levels of PFAAs (a control soil, an industrially impacted biosolids-amended soil, a municipal biosolids-amended soil, and two AFFF-impacted soils) was measured. Standard 28 day exposure experiments were conducted in each soil, and measurements taken at additional time points in the municipal soil were used to model the kinetics of uptake. Uptake and elimination rates and modeling suggested that steady state bioaccumulation was reached within 28 days of exposure for all PFAAs. The highest concentrations in the earthworms were for perfluorooctane sulfonate (PFOS) in the AFFF-impacted Soil A (2160 ng/g) and perfluorododecanoate (PFDoA) in the industrially impacted soil (737 ng/g). Wet-weight (ww) and organic carbon (OC)-based biota soil accumulation factors (BSAFs) for the earthworms were calculated after 28 days of exposure for all five soils. The highest BSAF in the industrially impacted soil was for PFDoA (0.42 goc/gww,worm). Bioaccumulation factors (BAFs, dry-weight-basis, dw) were also calculated at 28 days for each of the soils. With the exception of the control soil and perfluorodecanoate (PFDA) in the industrially impacted soil, all BAF values were above unity, with the highest being for perfluorohexanesulfonate (PFHxS) in the AFFF-impacted Soil A (139 gdw,soil/gdw,worm). BSAFs and BAFs increased with increasing chain length for the perfluorocarboxylates (PFCAs) and decreased with increasing chain length for the perfluoroalkyl sulfonates (PFSAs). The results indicate that PFAA bioaccumulation into earthworms depends on soil concentrations, soil characteristics, analyte, and duration of exposure, and that accumulation into earthworms may be a potential

  9. Contribution of diffuse inputs to the aqueous mass load of perfluoroalkyl acids in river and stream catchments in Korea.

    PubMed

    Kim, Seung-Kyu; Li, Dong-Hao; Shoeib, Mahiba; Zoh, Kyung-Duk

    2014-02-01

    Recent studies disagree regarding the contributions of point versus non-point sources to the aqueous mass loads of perfluoroalkyl acids (PFAAs). This study investigated the longitudinal change in PFAA mass load from upstream to downstream stations along rivers and/or streams to assess the relative contributions of point versus nonpoint inputs. With concentrations 10 to 100 times higher than running water, point sources such as wastewater treatment plants (WWTPs) effluent and airport ditch-outlet (ADO) water were separated from neighboring upstream and downstream running waters using principal component analysis. Source waters were characterized by certain predominant components [e.g., perfluorobutylsulfonate (PFBS) and perfluorooctanoic acid (PFOA) in WWTP effluent and perfluorohexylsulfonate (PFHxS) and perfluorooctylsulfonate (PFOS) in ADO water], which were minor components of running water. From a mass balance assessment of PFAA mass load, certain compounds such as PFOA and PFBS dominated the contribution of point sources to the mass load in the running water at downstream stations or in small catchment basins with high levels of industrial activity. Most of the mass load in the investigated catchments was attributable to upstream running water with a minor influence from industrial, commercial, and domestic human activities. Furthermore, the negative relationship of per capita emission factors (hereafter, EFs) with population density and a lower contribution of PFAA from WWTPs (~30% on average) compared to the running water-derived mass load at the national level indicated that diffuse inputs were more important contributors to aqueous PFAA contamination in each catchment basin as well as the entire watershed of the country (Korea). Volatile precursor compounds, which are readily dispersed to neighboring basins and transformed to PFAAs in the ambient environment, can be an important source of these diffuse inputs and will become more significant over time.

  10. Synergistic interplay of a non-heme iron catalyst and amino acid coligands in H2 O2 activation for asymmetric epoxidation of α-alkyl-substituted styrenes.

    PubMed

    Cussó, Olaf; Ribas, Xavi; Lloret-Fillol, Julio; Costas, Miquel

    2015-02-23

    Highly enantioselective epoxidation of α-substituted styrenes with aqueous H2 O2 is described by using a chiral iron complex as the catalyst and N-protected amino acids (AAs) as coligands. The amino acids synergistically cooperate with the iron center in promoting an efficient activation of H2 O2 to catalyze epoxidation of this challenging class of substrates with good yields and stereoselectivities (up to 97%ee) in short reaction times.

  11. A new procedure for N1-alkylation of imidazolidin-4-ones and its NMR characterization

    NASA Astrophysics Data System (ADS)

    Vale, Nuno; Figueiredo, Patrícia

    2016-12-01

    N1-unsubstituted imidazolidin-4-ones of primaquine (PQ) can be stabilized by N1-alkylation under basic conditions. Here we report the development, with our conditions, of peptidomimetic derivatives of PQ with L-amino acid and alkyl derivatives. The new derivatives represent potential new therapeutics for use against protozoan parasites, through enzymatic protection of aminopeptidases.

  12. Human placental transfer of perfluoroalkyl acid precursors: Levels and profiles in paired maternal and cord serum.

    PubMed

    Yang, Lin; Wang, Zhen; Shi, Yu; Li, Jingguang; Wang, Yuxin; Zhao, Yunfeng; Wu, Yongning; Cai, Zongwei

    2016-02-01

    Perfluoroalkyl acids (PFAAs) precursors, the indirect source of PFAA exposure, have been observed in environmental and human samples. However, the maternal-fetal transfer of these chemicals has not been well examined. In this study, 50 paired maternal and cord serum samples collected in Jiangsu province of China were analyzed for fifteen PFAA precursors. Among the detected PFAAs, 6:2 fluorotelomer sulfonate (6:2 FTS), N-methyl- and N-ethyl-perfluorooctanesulfonamidoacetates had comparable detection rate in both maternal and cord sera, while the mean concentrations and detection rates of 8:2 FTS and perfluorooctane sulfonamide (PFOSA) were higher in maternal sera compared to cord sera (Mann-Whitney U test, P < 0.05). Analysis of variance and least significant difference tests showed that the youngest maternal age group (21-24 years old) had the highest concentration of 6:2 FTS in cord sera. Maternal serum PFOSA was found significantly correlated with the cord serum perfluorooctanesulfonate (PFOS) (Spearman test, r = 0.361, P = 0.010), indicating that maternal serum PFOSA might be an indirect source of PFOS in fetuses. The obtained results suggested the potential prenatal exposure and human placental transfer of perfluoroalkyl acid precursors.

  13. Polymethylated DOTA ligands. 1. Synthesis of rigidified ligands and studies on the effects of alkyl substitution on acid-base properties and conformational mobility.

    PubMed

    Ranganathan, Ramachandran S; Pillai, Radhakrishna K; Raju, Natarajan; Fan, Helen; Nguyen, Hanh; Tweedle, Michael F; Desreux, Jean F; Jacques, Vincent

    2002-12-16

    This work describes the synthesis and the conformational properties of new polymethylated macrocyclic ligands of potential interest for magnetic resonance imaging. M4cyclen, (2S,5S,8S,11S)-2,5,8,11-tetramethyl-1,4,7,10-tetraazacyclododecane, was obtained by cyclotetramerization of (2S)-1-benzyl-2-methylaziridine followed by catalytic hydrogenation. The ligands M4DOTA, [(2S,5S,8S,11S)-4,7,10-tris-carboxymethyl-2,5,8,11-tetramethyl- 1,4,7,10-tetraazacyclododecan-1-yl]acetic acid, and M4DOTMA, (R)-2-[(2S,5S,8S,11S)-4,7,10-tris-((R)-1-carboxyethyl)-2,5,8,11-tetramethyl-1,4,7,10-tetraazacyclododecan-1-yl]propionic acid, were prepared by carboxyalkylation of M4cyclen in the presence of Na(2)CO(3). The triacetic ligand M4DO3A, [(2S,5S,8S,11S)-4,7-bis-carboxymethyl-2,5,8,11-tetramethyl-1,4,7,10-tetraazacyclododecan-1-yl]acetic acid, was obtained in good yields without traces of M4DOTA if NaHCO(3) was the acid scavenger when adding the carboxylic arms. In the same conditions, cyclen yielded M4DOTA in 82% yield. The difference between the reactivity of cyclen and M4cyclen is assigned to the high basicity of the substituted tetraamine as estimated by NMR titration. The one- and two-dimensional (1)H and (13)C NMR spectra of M4DOTA and M4DOTMA in the H(4)L or H(6)L(2+) forms are interpreted as arising from a slow exchange between two elongated geometries in which the methyl substituents are in one of the two possible equatorial-like positions, either close to or away from the carboxylic arms. The axial-like positions are sterically too crowded and cannot be occupied by the methyl groups. An elongated conformation is also adopted by DOTMA, (R)-2-[4,7,10-tris-((R)-carboxyethyl)-1,4,7,10-tetraazacyclododecan-1-yl]propionic acid, in the H(6)L(2+) form. The rigidification of the polymethylated ligands allows a detailed NMR analysis that cannot be carried out on the parent unsubstituted ligand DOTA.

  14. Mild Catalytic methods for Alkyl-Alkyl Bond Formation

    SciTech Connect

    Vicic, David A

    2009-08-10

    Overview of Research Goals and Accomplishments for the Period 07/01/06 – 06/30/07: Our overall research goal is to transform the rapidly emerging synthetic chemistry involving alkyl-alkyl cross-couplings into more of a mechanism-based field so that that new, rationally-designed catalysts can be performed under energy efficient conditions. Our specific objectives for the previous year were 1) to obtain a proper electronic description of an active catalyst for alkyl-alkyl cross-coupling reactions and 2) to determine the effect of ligand structure on the rate, scope, selectivity, and functional group compatibility of C(sp3)-C(sp3) cross-coupling catalysis. We have completed both of these initial objectives and established a firm base for further studies. The specific significant achievements of the current grant period include: 1) we have performed magnetic and computational studies on (terpyridine)NiMe, an active catalyst for alkyl-alkyl cross couplings, and have discovered that the unpaired electron resides heavily on the terpyridine ligand and that the proper electronic description of this nickel complex is a Ni(II)-methyl cation bound to a reduced terpyridine ligand; 2) we have for the first time shown that alkyl halide reduction by terpyridyl nickel catalysts is substantially ligand based; 3) we have shown by isotopic labeling studies that the active catalyst (terpyridine)NiMe is not produced via a mechanism that involves the formation of methyl radicals when (TMEDA)NiMe2 is used as the catalyst precursor; 4) we have performed an extensive ligand survey for the alkyl-alkyl cross-coupling reactions and have found that electronic factors only moderately influence reactivity in the terpyridine-based catalysis and that the most dramatic effects arise from steric and solubility factors; 5) we have found that the use of bis(dialkylphosphino)methanes as ligands for nickel does not produce active catalysts for cross-coupling but rather leads to bridging hydride

  15. Synthetic resin-bound truncated Candida antarctica lipase B for production of fatty acid alkyl esters by transesterification of corn and soybean oils with ethanol or butanol.

    PubMed

    Hughes, Stephen R; Moser, Bryan R; Robinson, Samantha; Cox, Elby J; Harmsen, Amanda J; Friesen, Jon A; Bischoff, Kenneth M; Jones, Marjorie A; Pinkelman, Rebecca; Bang, Sookie S; Tasaki, Ken; Doll, Kenneth M; Qureshi, Nasib; Liu, Siqing; Saha, Badal C; Jackson, John S; Cotta, Michael A; Rich, Joseph O; Caimi, Paolo

    2012-05-31

    A gene encoding a synthetic truncated Candida antarctica lipase B (CALB) was generated via automated PCR and expressed in Saccharomyces cerevisiae. Western blot analysis detected five truncated CALB variants, suggesting multiple translation starts from the six in-frame ATG codons. The longest open reading frame, which corresponds to amino acids 35-317 of the mature lipase, appeared to be expressed in the greatest amount. The truncated CALB was immobilized on Sepabeads® EC-EP resin and used to produce ethyl and butyl esters from crude corn oil and refined soybean oil. The yield of ethyl esters was 4-fold greater from corn oil than from soybean oil and was 36% and 50% higher, respectively, when compared to a commercially available lipase resin (Novozym 435) using the same substrates. A 5:1 (v/v) ratio of ethanol to corn oil produced 3.7-fold and 8.4-fold greater yields than ratios of 15:1 and 30:1, respectively. With corn oil, butyl ester production was 56% higher than ethyl ester production. Addition of an ionic catalytic resin step prior to the CALB resin increased yields of ethyl esters from corn oil by 53% compared to CALB resin followed by ionic resin. The results suggest resin-bound truncated CALB has potential application in biodiesel production using biocatalysts.

  16. PROCESS OF RECOVERING ZIRCONIUM VALUES FROM HAFNIUM VALUES BY SOLVENT EXTRACTION WITH AN ALKYL PHOSPHATE

    DOEpatents

    Peppard, D.F.

    1960-02-01

    A process of separating hafnium nitrate from zirconium nitrate contained in a nitric acid solution by selectively. extracting the zirconium nitrate with a water-immiscible alkyl phosphate is reported.

  17. In situ EPR studies of reaction pathways in Titania photocatalyst-promoted alkylation of alkenes.

    PubMed

    Rhydderch, Shona; Howe, Russell F

    2015-03-03

    In situ EPR spectroscopy at cryogenic temperatures has been used to observe and identify paramagnetic species produced when titania is irradiated in the presence of reactants used in the photocatalytic alkylation of maleimide with t-butyl carboxylic acid or phenoxyacetic acid. It is shown that maleimide acts as an acceptor of conduction band electrons. Valence band holes oxidise t-butyl carboxylic acid to the t-butyl radical and phenoxyacetic acid to the phenoxyacetic acid radical cation. In the presence of maleimide, the phenoxymethyl radical is formed from phenoxyacetic acid. The relevance of these observations to the mechanisms of titania photocatalyst-promoted alkylation of alkenes is discussed.

  18. Materials performance in HF-alkylation units

    SciTech Connect

    Forsen, O.; Aromaa, J.; Somervuori, M.; Tavi, M.

    1995-11-01

    Materials selection in HF-alkylation units is mostly based on long time experience. The most widely used material in the Station units is standard carbon steel, because it is capable to form a thick protective FeF{sub 2} layer in concentrated or anhydrous hydrofluoric acid. The corrosion resistance decreases, when the acid is dilute (less than 64% HF) or the temperature is above 160F (70 C). The composition and metallurgical state are also suspected to affect the corrosion resistance of carbon steel. The effect of composition appears more complicated than believed, especially the A-106 specification on the total amount of Cr+Ni+Cu+Mo+V < 1% should be studied more closely from the corrosion point of view. Laboratory tests showed that the uniform corrosion rate may be 100 times higher in galvanic contact of two dissimilar steels. The effect of galvanic contacts can neither be excluded in the process equipment corrosion cases.

  19. Screening for perfluoroalkyl acids in consumer products, building materials and wastes.

    PubMed

    Bečanová, Jitka; Melymuk, Lisa; Vojta, Šimon; Komprdová, Klára; Klánová, Jana

    2016-12-01

    Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are a large group of important chemical compounds with unique and useful physico-chemical properties, widely produced and used in many applications. However, due to the toxicity, bioaccumulation and long-range transport potential of certain PFASs, they are of significant concern to scientists and policy makers. To assess human exposure to PFASs, it is necessary to understand the concentrations of these emerging contaminants in our environment, and particularly environments where urban population spend most of their time, i.e. buildings and vehicles. A total of 126 samples of building materials, consumer products, car interior materials and wastes were therefore analyzed for their content of key PFASs - 15 perfluoroalkyl acids (PFAAs). At least one of the target PFAAs was detected in 88% of all samples. The highest concentration of Σ15PFAAs was found in textile materials (77.61 μg kg(-1)), as expected, since specific PFAAs are known to be used for textile treatment during processing. Surprisingly, PFAAs were also detected in all analyzed composite wood building materials, which were dominated by perfluoroalkyl carboxylic acids with 5-8 carbons in the chain (Σ4PFCAs up to 32.9 μg kg(-1)). These materials are currently widely used for building refurbishment, and this is the first study to find evidence of the presence of specific PFASs in composite wood materials. Thus, in addition to consumer products treated with PFASs, materials used in the construction of houses, schools and office buildings may also play an important role in human exposure to PFASs.

  20. Total synthesis of alkyl citrate natural products.

    PubMed

    Rizzacasa, Mark A; Sturgess, Dayna

    2014-03-07

    This review highlights the synthesis of members of the alkyl citrate family of natural products. The focus is on the stereoselective construction of the alkyl citrate moiety common to these compounds.

  1. Two di­alkyl­ammonium salts of 2-amino-4-nitro­benzoic acid: crystal structures and Hirshfeld surface analysis

    PubMed Central

    Wardell, James L.; Jotani, Mukesh M.; Tiekink, Edward R. T.

    2016-01-01

    The crystal structures of two ammonium salts of 2-amino-4-nitro­benzoic acid are described, namely di­methyl­aza­nium 2-amino-4-nitro­benzoate, C2H8N+·C7H5N2O4 −, (I), and di­butyl­aza­nium 2-amino-4-nitro­benzoate, C8H20N+·C7H5N2O4 −, (II). The asymmetric unit of (I) comprises a single cation and a single anion. In the anion, small twists are noted for the carboxyl­ate and nitro groups from the ring to which they are connected, as indicated by the dihedral angles of 11.45 (13) and 3.71 (15)°, respectively; the dihedral angle between the substituents is 7.9 (2)°. The asymmetric unit of (II) comprises two independent pairs of cations and anions. In the cations, different conformations are noted in the side chains in that three chains have an all-trans [(+)-anti­periplanar] conformation, while one has a distinctive kink resulting in a (+)-synclinal conformation. The anions, again, exhibit twists with the dihedral angles between the carboxyl­ate and nitro groups and the ring being 12.73 (6) and 4.30 (10)°, respectively, for the first anion and 8.1 (4) and 12.6 (3)°, respectively, for the second. The difference between anions in (I) and (II) is that in the anions of (II), the terminal groups are conrotatory, forming dihedral angles of 17.02 (8) and 19.0 (5)°, respectively. In each independent anion of (I) and (II), an intra­molecular amino-N—H⋯O(carboxyl­ate) hydrogen bond is formed. In the crystal of (I), anions are linked into a jagged supra­molecular chain by charge-assisted amine-N—H⋯O(carboxyl­ate) hydrogen bonds and these are connected into layers via charge-assisted ammonium-N—H⋯O(carboxyl­ate) hydrogen bonds. The resulting layers stack along the a axis, being connected by nitro-N—O⋯π(arene) and methyl-C—H⋯O(nitro) inter­actions. In the crystal of (II), the anions are connected into four-ion aggregates by charge-assisted amino-N—H⋯O(carboxyl­ate) hydrogen bonding. The formation of ammonium

  2. Alkylating potential of styrene oxide: reactions and factors involved in the alkylation process.

    PubMed

    González-Pérez, Marina; Gómez-Bombarelli, Rafael; Pérez-Prior, M Teresa; Arenas-Valgañón, Jorge; García-Santos, M Pilar; Calle, Emilio; Casado, Julio

    2014-10-20

    The chemical reactivity of styrene-7,8-oxide (SO), an alkylating agent with high affinity for the guanine–N7 position and a probable carcinogen for humans, with 4-(p-nitrobenzyl)pyridine (NBP), a trap for alkylating agents with nucleophilic characteristics similar to those of DNA bases, was investigated kinetically in water/dioxane media. UV–vis spectrophotometry and ultrafast liquid chromatography were used to monitor the reactions involved. It was found that in the alkylation process four reactions occur simultaneously: (a) the formation of a β-NBP–SO adduct through an SN2 mechanism; (b) the acid-catalyzed formation of the stable α-NBP–SO adduct through an SN2′ mechanism; (c) the base-catalyzed hydrolysis of the β-adduct, and (d) the acid-catalyzed hydrolysis of SO. At 37.5 °C and pH = 7.0 (in 7:3 water/dioxane medium), the values of the respective reaction rate constants were as follows: kalkβ = (2.1 ± 0.3) × 10–4 M–1 s–1, kalkα = (1.0 ± 0.1) × 10–4 M–1 s–1, khydAD = (3.06 ± 0.09) × 10–6 s–1, and khyd = (4.2 ± 0.9) × 10–6 s–1. These values show that, in order to determine the alkylating potential of SO, none of the four reactions involved can be neglected. Temperature and pH were found to exert a strong influence on the values of some parameters that may be useful to investigate possible chemicobiological correlations (e.g., in the pH 5.81–7.69 range, the fraction of total adducts formed increased from 24% to 90% of the initial SO, whereas the adduct lifetime of the unstable β-adduct, which gives an idea of the permanence of the adduct over time, decreased from 32358 to 13313 min). A consequence of these results is that the conclusions drawn in studies addressing alkylation reactions at temperatures and/or pH far from those of biological conditions should be considered with some reserve.

  3. Efficient asymmetric synthesis of novel gastrin receptor antagonist AG-041R via highly stereoselective alkylation of oxindole enolates.

    PubMed

    Emura, Takashi; Esaki, Toru; Tachibana, Kazutaka; Shimizu, Makoto

    2006-10-27

    An efficient method for asymmetric synthesis of the potent Gastrin/CCK-B receptor antagonist AG-041R was developed. Core oxindole stereochemistry was established by asymmetric alkylation of oxindole enolates with bromoacetic acid esters, using l-menthol as a chiral auxiliary. The key alkylation reaction of the oxindole enolates generated tetrasubstituted chiral intermediates with high diastereoselectivity. The stereoselective alkylation reactions are described in detail.

  4. Chichibabin-type direct alkylation of pyridyl alcohols with alkyl lithium reagents.

    PubMed

    Jeffrey, Jenna L; Sarpong, Richmond

    2012-11-02

    Direct C(6) alkylation of pyridyl alcohols can be achieved following an initial deprotonation of the hydroxy group. This transformation, which is believed to occur by a Chichibabin-type alkylation, avoids lateral deprotonation prior to pyridine ring alkylation and gives increased regioselectivity for C(6) over C(4) alkylation.

  5. Refiners discuss HF alkylation process and issues

    SciTech Connect

    Not Available

    1992-04-06

    Safety and oxygenate operations made HF alkylation a hot topic of discussion at the most recent National Petroleum Refiners Association annual question and answer session on refining and petrochemical technology. This paper provides answers to a variety of questions regarding the mechanical, process, and safety aspects of the HF alkylation process. Among the issues discussed were mitigation techniques, removal of oxygenates from alkylation unit feed, and amylene alkylation.

  6. 40 CFR 721.9892 - Alkylated urea.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkylated urea. 721.9892 Section 721... Alkylated urea. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an alkylated urea (PMN P-93-1649) is subject to reporting under...

  7. Radioiodination of Aryl-Alkyl Cyclic Sulfates

    PubMed Central

    Mushti, Chandra; Papisov, Mikhail I.

    2015-01-01

    Among the currently available positron emitters suitable for Positron Emission Tomography (PET), 124I has the longest physical half-life (4.2 days). The long half-life and well-investigated behavior of iodine in vivo makes 124I very attractive for pharmacological studies. In this communication, we describe a simple yet effective method for the synthesis of novel 124I labeled compounds intended for PET imaging of arylsulfatase activity in vivo. Arylsulfatases have important biological functions, and genetic deficiencies of such functions require pharmacological replacement, the efficacy of which must be properly and non-invasively evaluated. These enzymes, even though their natural substrates are mostly of aliphatic nature, hydrolyze phenolic sulfates to phenol and sulfuric acid. The availability of [124I]iodinated substrates is expected to provide a PET-based method for measuring their activity in vivo. The currently available methods of synthesis of iodinated arylsulfates usually require either introducing of a protected sulfate ester early in the synthesis or introduction of sulfate group at the end of synthesis in a separate step. The described method gives the desired product in one step from an aryl-alkyl cyclic sulfate. When treated with iodide, the source cyclic sulfate opens with substitution of iodide at the alkyl center and gives the desired arylsulfate monoester. PMID:23135631

  8. Microbial degradation of n-alkyl tetrahydrothiophenes found in petroleum.

    PubMed Central

    Fedorak, P M; Payzant, J D; Montgomery, D S; Westlake, D W

    1988-01-01

    Although n-alkyl-substituted tetrahydrothiophenes are found in nonbiodegraded petroleums, they are not found in petroleums which have undergone biodegradation in their reservoirs. These observations suggested that this group of compounds with alkyl chain lengths from approximately C10 to at least C30 is biodegradable. Two of these sulfides, 2-n-dodecyltetrahydrothiophene (DTHT) and 2-n-undecyltetrahydrothiophene, were synthesized, and their biodegradabilities were tested by using five gram-positive, n-alkane-degrading bacterial isolates. The alkyl side chains of these compounds were oxidized, and the major intermediates found in 2-n-undecyltetrahydrothiophene- and DTHT-metabolizing cultures were 2-tetrahydrothiophenecarboxylic acid (THTC) and 2-tetrahydrothiopheneacetic acid (THTA), respectively. Four n-alkane-degrading fungi were also shown to degrade DTHT, yielding both THTA and THTC. Quantitation of tetrahydrothiophene ring-containing products in 28-day-old bacterial and fungal cultures suggested that THTC and THTA were metabolized further to unidentified products. In addition, two of the bacterial isolates were shown to degrade a mixture of n-alkyl tetrahydrothiophenes isolated from Bellshill Lake crude oil. PMID:3389816

  9. Determination of Selected Perfluorinated Alkyl Acids in ...

    EPA Pesticide Factsheets

    The 1996 amendments to the Safe Drinking Water Act (SDWA) required EPA to establish a Contaminant Candidate List (CCL), that contains a list of drinking water contaminants that the Agency will consider for future regulation. EPA must make a regulatory determination on a minimum of five contaminants every five years. The first CCL was published in 1998, and updates were anticipated every five years thereafter. One of the key pieces of information that must be available in order to make a regulatory determination is nationwide occurrence data for the chemical contaminants under consideration. Historically, EPA has collected the necessary occurrence data under its Unregulated Contaminant Monitoring Regulations (UCMR). Under the UCMR, monitoring is conducted at selected drinking water utilities for specific contaminants of interest. The chemical analyses are usually performed by the utilities or by commercial laboratories. To meet the requirements of monitoring under the UCMR program, the analytical methods developed should be specific, sensitive, and practical enough for application in commercial laboratories. This task will focus on the development of analytical methods for chemicals identified on future CCLs or emerging contaminants not yet listed on the CCL. These methods will be used for the collection of occurrence data under future UCMRs. The objective of this research effort is to develop analytical methods to be used to measure the occurrence of

  10. Favourable effects of eicosapentaenoic acid on the late step of the cell division in a piezophilic bacterium, Shewanella violacea DSS12, at high-hydrostatic pressures.

    PubMed

    Kawamoto, Jun; Sato, Takako; Nakasone, Kaoru; Kato, Chiaki; Mihara, Hisaaki; Esaki, Nobuyoshi; Kurihara, Tatsuo

    2011-08-01

    Shewanella violacea DSS12, a deep-sea bacterium, produces eicosapentaenoic acid (EPA) as a component of membrane phospholipids. Although various isolates from the deep sea, such as Photobacterium profundum SS9, Colwellia psychrerythraea 34H and various Shewanella strains, produce EPA- or docosahexaenoic acid-containing phospholipids, the physiological role of these polyunsaturated fatty acids remains unclear. In this article, we illustrate the physiological importance of EPA for high-pressure adaptation in strain DSS12 with the help of an EPA-deficient mutant (DSS12(pfaA)). DSS12(pfaA) showed significant growth retardation at 30 MPa, but not at 0.1 MPa. We also found that DSS12(pfaA) grown at 30 MPa forms filamentous cells. When an EPA-containing phospholipid (sn-1-oleoly-sn-2-eicosapentaenoyl phosphatidylethanolamine) was supplemented, the growth retardation and the morphological defect of DSS12(pfaA) were suppressed, indicating that the externally added EPA-containing phospholipid compensated for the loss of endogenous EPA. In contrast, the addition of an oleic acid-containing phospholipid (sn-1,2-dioleoyl phosphatidylethanolamine) did not affect the growth and the morphology of the cells. Immunofluorescent microscopic analysis with anti-FtsZ antibody revealed a number of Z-rings and separated nucleoids in DSS12(pfaA) grown at 30 MPa. These results demonstrate the physiological importance of EPA for the later step of Z-ring formation of S. violacea DSS12 under high-pressure conditions.

  11. Bifunctional alkylating agent-induced p53 and nonclassical nuclear factor kappaB responses and cell death are altered by caffeic acid phenethyl ester: a potential role for antioxidant/electrophilic response-element signaling.

    PubMed

    Minsavage, Gary D; Dillman, James F

    2007-04-01

    Bifunctional alkylating agents (BFA) such as mechlorethamine (nitrogen mustard) and bis-(2-chloroethyl) sulfide (sulfur mustard; SM) covalently modify DNA and protein. The roles of nuclear factor kappaB (NF-kappaB) and p53, transcription factors involved in inflammatory and cell death signaling, were examined in normal human epidermal keratinocytes (NHEK) and immortalized HaCaT keratinocytes, a p53-mutated cell line, to delineate molecular mechanisms of action of BFA. NHEK and HaCaT cells exhibited classical NF-kappaB signaling as degradation of inhibitor protein of NF-kappaBalpha (IkappaBalpha) occurred within 5 min after exposure to tumor necrosis factor-alpha. However, exposure to BFA induced nonclassical NF-kappaB signaling as loss of IkappaBalpha was not observed until 2 or 6 h in NHEK or HaCaT cells, respectively. Exposure of an NF-kappaB reporter gene-expressing HaCaT cell line to 12.5, 50, or 100 muM SM activated the reporter gene within 9 h. Pretreatment with caffeic acid phenethyl ester (CAPE), a known inhibitor of NF-kappaB signaling, significantly decreased BFA-induced reporter gene activity. A 1.5-h pretreatment or 30-min postexposure treatment with CAPE prevented BFA-induced loss of membrane integrity by 24 h in HaCaT cells but not in NHEK. CAPE disrupted BFA-induced phosphorylation of p53 and p90 ribosomal S6 kinase (p90RSK) in both cell lines. CAPE also increased nuclear factor E2-related factor 2 and decreased aryl hydrocarbon receptor protein expression, both of which are involved in antioxidant/electrophilic response element (ARE/EpRE) signaling. Thus, disruption of p53/p90RSK-mediated NF-kappaB signaling and activation of ARE/EpRE pathways may be effective strategies to delineate mechanisms of action of BFA-induced inflammation and cell death signaling in immortalized versus normal skin systems.

  12. Microminipigs as a new experimental animal model for toxicological studies: comparative pharmacokinetics of perfluoroalkyl acids.

    PubMed

    Guruge, Keerthi S; Noguchi, Michiko; Yoshioka, Koji; Yamazaki, Eriko; Taniyasu, Sachi; Yoshioka, Miyako; Yamanaka, Noriko; Ikezawa, Mitsutaka; Tanimura, Nobuhiko; Sato, Masumi; Yamashita, Nobuyoshi; Kawaguchi, Hiroaki

    2016-01-01

    In this study, we evaluated the efficacy of a novel minipig strain, the Microminipig (MMPig), as an animal model for studying the pharmacokinetics of a mixture of 10 perfluoroalkyl acids (PFAAs). After a single oral dose was given, we found that the blood depuration of PFAAs (blood t1/2), which we calculated using first-order elimination curves, ranged from 1.6 to 86.6 days. Among the five body compartments analyzed, the liver was the greatest site of accumulation of perfluorooctanesulfonate and longer chain perfluorinated carboxylates such as perfluorodecanoic acid, perfluoroundecanoic acid and perfluorododecanoic acid. We observed an increasing accumulation trend of perfluorinated carboxylates in the organs associated with the fluorinated carbon chain length. The perfluorononanoic acid burden was the highest among the treated compounds 21 days after a single exposure, as 29% of the given perfluorononanoic acid dose was accumulated in the tissues. The persistence of PFAAs in edible pig tissues even after 21 days post-exposure raises concerns about the safety of swine products. This was the first study to use MMPigs to elucidate the pharmacokinetics of a group of environmental pollutants. We found that MMPigs could be excellent experimental animals for toxicological studies due to their easy handling, cost efficacy for target compounds and ease of waste treatment.

  13. Brominated flame retardants and perfluoroalkyl acids in groundwater, tile drainage, soil, and crop grain following a high application of municipal biosolids to a field.

    PubMed

    Gottschall, N; Topp, E; Edwards, M; Payne, M; Kleywegt, S; Lapen, D R

    2017-01-01

    Dewatered municipal biosolids (DMB) were applied at a rate of 22Mgdwha(-1) to an agricultural field in fall 2008. Concentrations of polybrominated diphenyl ethers (PBDEs; BDE-47, -99, -100, -153, -154, -183, -197, -207, -209), other brominated flame retardants (BFRs; HBB, PBEB, DBDPE, BTBPE) and perfluoroalkyl acids (PFAAs; PFHxS, PFOS, PFDS, PFOSA, PFHpA, PFOA, PFNA, PFDA, PFUnA, PFDoA, PFTA) were monitored in tile drainage, groundwater (2m, 4m and 6m depth), soil cores (0-0.3m) pre- and post-application, DMB aggregates incorporated into the soil post-application, and in wheat (Triticum spp.) planted post-application. Several compounds were detected in soil and water pre-application and on a reference field plot. PBDEs, other BFRs and PFAAs were detected in tile drainage and 2m groundwater throughout the post-application study period; a few PBDEs were also detected sporadically at lower depths in groundwater. Some of these compounds had not been detected pre-application, while some exceeded reference field plot/pre-application levels (some significantly (p<0.05) in tile drainage); both cases indicating biosolid-based water contamination. In DMB aggregates, several PBDE congeners were found to have dissipated exponentially, with reductions >90% in many of them within 1year post-application. Exponential dissipation of other BFRs and PFAAs in DMB aggregates were not significant. No PBDEs, other BFRs, or PFAAs were detected in wheat grain.

  14. Bimetallic oxidative addition involving radical intermediates in nickel-catalyzed alkyl-alkyl Kumada coupling reactions.

    PubMed

    Breitenfeld, Jan; Ruiz, Jesus; Wodrich, Matthew D; Hu, Xile

    2013-08-14

    Many nickel-based catalysts have been reported for cross-coupling reactions of nonactivated alkyl halides. The mechanistic understanding of these reactions is still primitive. Here we report a mechanistic study of alkyl-alkyl Kumada coupling catalyzed by a preformed nickel(II) pincer complex ([(N2N)Ni-Cl]). The coupling proceeds through a radical process, involving two nickel centers for the oxidative addition of alkyl halide. The catalysis is second-order in Grignard reagent, first-order in catalyst, and zero-order in alkyl halide. A transient species, [(N2N)Ni-alkyl(2)](alkyl(2)-MgCl), is identified as the key intermediate responsible for the activation of alkyl halide, the formation of which is the turnover-determining step of the catalysis.

  15. Reactions of Tributylstannyl Anioniods with Alkyl Bromides.

    DTIC Science & Technology

    1981-09-28

    g (12 mmol) of cesium tert-butoxide was added to the reaction vessel before the addition of n-butyllithium. Alkylation of Tributylstannyl Anionoids...Dry reaction vessels were purged with argon. The desired alkyl halide (1.0 mmol unless noted) and any desired additive were added to the reaction ...OFFICE OF NAVAL RESEARCH Contract N00014-79-C-0584 Task No. NR 053-714 TECHNICAL REPORT No. 2 Reactions of Tributylstannyl Anionoids with Alkyl

  16. Alkylation of benzene or toluene with MeOH or C{sub 2}H{sub 4} over ZSM-5 or {beta} zeolite: Effect of the zeolite pore openings and of the hydrocarbons involved on the mechanism of alkylation

    SciTech Connect

    Smirniotis, P.G.; Ruckenstein, E.

    1995-05-01

    A comparative study of the alkylation of benzene or toluene with MeOH or C{sub 2}H{sub 4} over a medium (ZSM-5) and a large pore ({beta}) zeolite of comparable acidities was carried out. It was observed that the reaction temperature in combination with the structure of the zeolite plays an important role in the reactions that take place. The maximum yield of either the primary or secondary alkylation products may occur at an intermediate temperature, which is lower over {beta} zeolite. Due to its pore structure, {beta} zeolite favors secondary alkylation reactions and also disproportionation reactions of the generated alkylaromatics to a higher extent than ZSM-5 does. MeOH generates both primary and secondary alkylation products, while C{sub 2}H{sub 4} favors oligomerization reactions, primary alkylation reactions, and particularly, disproportionation reactions. Toluene is more reactive than benzene. The aromatic/alkylating agent molar ratio plays an important role in the relative importance of the reactions that take place. The size of the pores of the zeolite in combination with the sizes of the aromatic hydrocarbons and the alkylating agents employed determines whether the alkylation occurs via a Langmuir-Henshelwood (LH) or Rideal-Eley (RE) mechanism. When a LH mechanism occurs, the alkylation rate passes through a maximum with respect to the concentration of the aromatic hydrocarbon employed; no such maximum occurs for the RE mechanism.

  17. Antibacterial, antibiofilm and antioxidant screening of copper(II)-complexes with some S-alkyl derivatives of thiosalicylic acid. Crystal structure of the binuclear copper(II)-complex with S-propyl derivative of thiosalicylic acid

    NASA Astrophysics Data System (ADS)

    Bukonjić, Andriana M.; Tomović, Dušan Lj.; Nikolić, Miloš V.; Mijajlović, Marina Ž.; Jevtić, Verica V.; Ratković, Zoran R.; Novaković, Slađana B.; Bogdanović, Goran A.; Radojević, Ivana D.; Maksimović, Jovana Z.; Vasić, Sava M.; Čomić, Ljiljana R.; Trifunović, Srećko R.; Radić, Gordana P.

    2017-01-01

    The spectroscopically predicted structure of the obtained copper(II)-complex with S-propyl derivative of thiosalicylic acid was confirmed by X-ray structural study. The binuclear copper(II)-complex with S-propyl derivative of thiosalicylic acid crystallized in two polymorphic forms with main structural difference in the orientation of phenyl rings relative to corresponding carboxylate groups. The antibacterial activity was tested determining the minimum inhibitory concentration (MIC) and the minimum bactericidal concentration (MBC) by using microdilution method. The influence on bacterial biofilm formation was determined by tissue culture plate method. In general, the copper(II)-complexes manifested a selective and moderate activity. The most sensitive bacteria to the effects of Cu(II)-complexes was a clinical isolate of Pseudomonas aeruginosa. For this bacteria MIC and biofilm inhibitory concentration (BIC) values for all tested complexes were in the range or better than the positive control, doxycycline. Also, for the established biofilm of clinical isolate Staphylococcus aureus, BIC values for the copper(II)-complex with S-ethyl derivative of thiosalicylic acid,[Cu2(S-et-thiosal)4(H2O)2] (C3) and copper(II)-complex with S-butyl derivative of thiosalicylic acid, [Cu2(S-bu-thiosal)4(H2O)2] (C5) were in range or better than the positive control. All the complexes acted better against Gram-positive bacteria (Staphylococcus aureus and Staphylococcus aureus ATCC 25923) than Gram-negative bacteria (Proteus mirabilis ATCC 12453, Pseudomonas aeruginosa, and P. aeruginosa ATCC 27855). The complexes showed weak antioxidative properties tested by two methods (1,1-diphenyl-2-picrylhydrazyl (DPPH) and reducing power assay).

  18. High levels, partitioning and fish consumption based water guidelines of perfluoroalkyl acids downstream of a former firefighting training facility in Canada.

    PubMed

    Bhavsar, Satyendra P; Fowler, Craig; Day, Sarah; Petro, Steve; Gandhi, Nilima; Gewurtz, Sarah B; Hao, Chunyan; Zhao, Xiaoming; Drouillard, Ken G; Morse, Dave

    2016-09-01

    High levels of perfluoroalkyl acids (PFAAs), especially perfluorooctane sulfonic acid (PFOS), have been observed at locations in/around/downstream of the sites where PFOS-based firefighting foam was used repeatedly for a prolonged period. In this study, we conducted a detailed investigation of PFAA contamination in the Lake Niapenco area in Ontario, Canada, where among the highest ever reported levels of PFOS were recently measured in amphipods, fish and snapping turtle plasma. Levels and distribution of PFAAs in water, sediment and fish samples collected from the area varied widely. An upstream pond beside a former firefighting training area (FFTA) was confirmed as the source of PFAAs even 20years after the last use of the foam at the FFTA. Recent PFOS concentration in water (~60ng/L) at Lake Niapenco, about 14km downstream of the pond, was still 3-7× higher than the background levels. For PFOS, Log KD ranged 1.3-2.5 (mean±SE: 1.7±0.1), Log BAFs ranged 2.4-4.7 (3.4±0.05), and Log BSAFs ranged 0.7-2.9 (1.7±0.05). Some fish species-specific differences in BAF and BSAF were observed. At Log BAF of 4.7, fish PFOS levels at Lake Niapenco could reach 15,000ng/g, 100× greater than a "do not eat" advisory benchmark, without exceeding the current drinking water guideline of 300ng/L. A fish consumption based water guideline was estimated at 1-15ng/L, which is likely applicable worldwide given that the Log BAFs observed in this study were comparable to those previously reported in the literature. It appears that PFAA in the downstream waters increased between 2011 and 2015; however, further monitoring is required to confirm this trend.

  19. Catalytic enantioselective synthesis of naturally occurring butenolides via hetero-allylic alkylation and ring closing metathesis.

    PubMed

    Mao, Bin; Geurts, Koen; Fañanás-Mastral, Martín; van Zijl, Anthoni W; Fletcher, Stephen P; Minnaard, Adriaan J; Feringa, Ben L

    2011-03-04

    An efficient catalytic asymmetric synthesis of chiral γ-butenolides was developed based on the hetero-allylic asymmetric alkylation (h-AAA) in combination with ring closing metathesis (RCM). The synthetic potential of the h-AAA-RCM protocol was illustrated with the facile synthesis of (-)-whiskey lactone, (-)-cognac lactone, (-)-nephrosteranic acid, and (-)-roccellaric acid.

  20. Formation of furan fatty alkyl esters from their bis-epoxide fatty esters

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Reactions of epoxidized alkyl soyate with four different alcohols: ethanol, isopropyl alcohol, 2-ethylhexanol, benzyl alcohol, in the presence of Bronsted acid catalyst, were investigated. Products that were not reported in prior studies of similar reactions were found. These were furan fatty acid a...

  1. S-alkylation of soft scorpionates.

    PubMed

    Rajasekharan-Nair, Rajeev; Moore, Dean; Chalmers, Kirsten; Wallace, Dawn; Diamond, Louise M; Darby, Lisa; Armstrong, David R; Reglinski, John; Spicer, Mark D

    2013-02-11

    The alkylation reactions of soft scorpionates are reported. The hydrotris(S-alkyl-methimazolyl)borate dications (alkyl = methyl, allyl, benzyl), which were prepared by the reaction of Tm(Me) anion and primary alkyl halides, have been isolated and structurally characterised. The reaction is, however, not universally successful. DFT analysis of these alkylation reactions (C=S versus B-H alkylation) indicates that the observed outcome is driven by kinetic factors. Extending the study to incorporate alternative imine thiones (mercaptobenzothiazole, bz; thiazoline, tz) led to the structural characterisation of di[aquo-μ-aquohydrotris(mercaptobenzothiazolyl)boratosodium], which contains sodium atoms in the κ(3)-S,S,S coordination mode. Alkylation of Na[Tbz] and Na[tzTtz] leads to decomposition resulting in the formation of the simple S-alkylated heterocycles. The analysis of the species involved in these reactions shows an inherent weakness in the B-N bond in soft scorpionates, which has implications for their use in more advanced chemistry.

  2. Occupational asthma due to alkyl cyanoacrylate

    SciTech Connect

    Nakazawa, T. )

    1990-08-01

    A case of bronchial asthma induced by occupational exposure to alkyl cyanoacrylate, an adhesive, occurred in an assembly operation. Provocative exposure testing induced immediate and delayed asthmatic responses. Alkyl cyanoacrylate seemed to act as an allergen or as an irritant, resulting in the development of asthma.

  3. Analysis of plasma free amino acid profiles in canine brain tumors

    PubMed Central

    Utsugi, Shinichi; Azuma, Kazuo; Osaki, Tomohiro; Murahata, Yusuke; Tsuka, Takeshi; Ito, Norihiko; Imagawa, Tomohiro; Okamoto, Yoshiharu

    2017-01-01

    Canine brain tumors are best diagnosed using magnetic resonance imaging (MRI). However, opportunities of MRI examination are restricted due to its limited availability in veterinary facilities; thus, numerous canine brain tumors are diagnosed at an advanced stage. Therefore, development of a noninvasive diagnostic biomarker is required for the early detection of brain tumors. In the present study, plasma free amino acid (PFAA) profiles between dogs with and without brain tumors were compared. A total of 12 dogs with brain tumors, diagnosed based on clinical signs, and on the results of intracranial MRI and/or pathological examination were evaluated. In addition, eight dogs diagnosed with idiopathic epilepsy and 16 healthy dogs were also included. A liquid chromatography system with automated pre-column derivatization functionality was used to measure the levels of 20 amino acids. As a result, the levels of three amino acids (alanine, proline and isoleucine) were increased significantly (1.6-, 1.5- and 1.6-fold, respectively) in the plasma of dogs with brain tumors as compared with the levels in control dogs (all P<0.05). Thus, the PFAA levels of dogs with brain tumors differed from those of healthy dogs. The present study demonstrated that analysis of PFAA levels of dogs with brain tumors may serve as a useful biomarker for the early detection of canine brain tumors. PMID:28357072

  4. A General Alkyl-Alkyl Cross-Coupling Enabled by Redox-Active Esters and Alkylzinc Reagents

    PubMed Central

    Qin, Tian; Cornella, Josep; Li, Chao; Malins, Lara R.; Edwards, Jacob T.; Kawamura, Shuhei; Maxwell, Brad D.; Eastgate, Martin D.; Baran, Phil S.

    2016-01-01

    Alkyl carboxylic acids are ubiquitous in all facets of chemical science, from natural products to polymers and represent an ideal starting material with which to forge new connections. This study demonstrates how the same activating principles used for decades to make simple C–N (amide) bonds from carboxylic acids with loss of water can be employed to make C–C bonds through coupling with dialkylzinc reagents and loss of carbon dioxide. This disconnection strategy benefits from the use of a simple, inexpensive nickel catalyst and exhibits a remarkably broad scope across a range of substrates (>70 examples). PMID:27103669

  5. Environmental Occurrence of Perfluoroalkyl Acids and Novel Fluorotelomer Surfactants in the Freshwater Fish Catostomus commersonii and Sediments Following Firefighting Foam Deployment at the Lac-Mégantic Railway Accident.

    PubMed

    Munoz, Gabriel; Desrosiers, Mélanie; Duy, Sung Vo; Labadie, Pierre; Budzinski, Hélène; Liu, Jinxia; Sauvé, Sébastien

    2017-02-07

    On July 6th 2013, an unmanned train laden with almost 8 million liters of crude oil careened off the rails downtown Lac-Mégantic (Québec, Canada). In the aftermath of the derailment accident, the emergency response entailed the deployment of 33 000 L of aqueous film forming foam (AFFF) concentrate that contained proprietary fluorosurfactants. The present study examines the environmental occurrence of perfluoroalkyl acids (PFAAs) and newly identified per and polyfluoroalkyl substances (PFASs) in the benthic fish white sucker (Catostomus commersonii) and sediments from Lake Mégantic and Chaudière River. In sediments, PFAAs displayed relatively low concentrations (∑PFAAs = 0.06-0.5 ng g(-1) dw) while the sum of fluorotelomer-based PFASs was in the range < LOD-6.2 ng g(-1) dw. Notably, fluorotelomer sulfonamide betaines (8:2-FTAB and 10:2-FTAB), fluorotelomer betaines (9:3-FTB, 11:3-FTB and 9:1:2 FTB) and 6:2 fluorotelomer sulfonate (6:2-FTSA) were ubiquitously identified in the sediment samples surveyed. Levels of PFAAs remained moderate in fish muscle (e.g.

  6. Structure-activity relationships for perfluoroalkane-induced in vitro interference with rat liver mitochondrial respiration.

    PubMed

    Wallace, K B; Kissling, G E; Melnick, R L; Blystone, C R

    2013-10-09

    Perfluorinated alkyl acids (PFAAs) represent a broad class of commercial products designed primarily for the coatings industry. However, detection of residues globally in a variety of species led to the discontinuation of production in the U.S. Although PFAAs cause activation of the PPARα and CAR nuclear receptors, interference with mitochondrial bioenergetics has been implicated as an alternative mechanism of cytotoxicity. Although the mechanisms by which the eight carbon chain PFAAs interfere with mitochondrial bioenergetics are fairly well described, the activities of the more highly substituted or shorter chain PFAAs are far less well characterized. The current investigation was designed to explore structure-activity relationships by which PFAAs interfere with mitochondrial respiration in vitro. Freshly isolated rat liver mitochondria were incubated with one of 16 different PFAAs, including perfluorinated carboxylic, acetic, and sulfonic acids, sulfonamides and sulfamido acetates, and alcohols. The effect on mitochondrial respiration was measured at five concentrations and dose-response curves were generated to describe the effects on state 3 and 4 respiration and respiratory control. With the exception of PFOS, all PFAAs at sufficiently high concentrations (>20μM) stimulated state 4 and inhibited state 3 respiration. Stimulation of state 4 respiration was most pronounced for the carboxylic acids and the sulfonamides, which supports prior evidence that the perfluorinated carboxylic and acetic acids induce the mitochondrial permeability transition, whereas the sulfonamides are protonophoric uncouplers of oxidative phosphorylation. In both cases, potency increased with increasing carbon number, with a prominent inflection point between the six and eight carbon congeners. The results provide a foundation for classifying PFAAs according to specific modes of mitochondrial activity and, in combination with toxicokinetic considerations, establishing structure

  7. Molecular mechanisms in alkylation mutagenesis. Induced reversion of bacteriophage T4rII AP72 by ethyl methanesulphonate in relation to extent and mode of ethylation of purines in bacteriophage deoxyribonucleic acid.

    PubMed Central

    Lawley, P D; Martin, C N

    1975-01-01

    Survival and reversion to T4r+ of bacteriophage T4rII AP72 after treatment with ethyl methanesulphonate at 37 degrees or 45 degrees C were studied in relation to the extent and mode of alkylation of purines in DNA of ethylated bacteriophage. A single-burst technique was used for reversion assay. Survival was lower at 45 degrees C than at 37 degrees C at a given extent of ethylation of bacteriophage DNA, confirming that events subsequent to ethylation, probably depurinations, are the main cause of decreased survival. Reversion was positively correlated (approximately linearly except at low extents at 37 degrees C) with ethylation of bacteriophage DNA, showing that ethylation itself causes mutation. Following the concept that reversion results from G-C leads to A-T transition at a single site (Krieg, 1963a,b) and the suggestion that O6-alkylation of guanine generates the miscoding base (Loveless, 1969), it was calculated that about one-third of induced O6-ethylguanines at this site would miscode to induce mutation. PMID:172067

  8. Microbial Degradation and Assimilation of n-Alkyl-Substituted Cycloparaffins1

    PubMed Central

    Beam, H. W.; Perry, J. J.

    1974-01-01

    Studies were conducted on the oxidation and assimilation of n-alkyl-substituted cycloalkane substrates by several hydrocarbon-utilizing microorganisms. These microorganisms utilized heptadecylcyclohexane and dodecylcyclohexane as the sole source of carbon and energy. Neither methylcyclohexane nor ethylcyclohexane was utilized as a growth substrate by any organisms tested. Gas-liquid chromatographic analyses of fatty acids present in cells after growth on dodecylcyclohexane confirm direct incorporation of both alpha- and beta-oxidation products. Growth patterns of these organisms on n-alkyl-substituted cyclohexane fatty acids of varying chain lengths suggest a greater probability of ring cleavage when the side chain contains an odd number of carbons. PMID:4597441

  9. Synthesis and antitumor activity of 10-alkyl-10-deazaminopterins. A convenient synthesis of 10-deazaminopterin.

    PubMed

    DeGraw, J I; Brown, V H; Tagawa, H; Kisliuk, R L; Gaumont, Y; Sirotnak, F M

    1982-10-01

    Requirements for large-scale synthesis of the potent antitumor drug 10-deazaminopterin have led to development of a facile synthesis of this compound and its 10-alkyl analogues. The lithium diisopropyl amide generated dianions of appropriate p-alkylbenzoic acids were alkylated with 3-methoxyallyl chloride. The resulting 4-(p-carboxyphenyl)-1-methoxy-1-butenes were brominated at pH 7-8 to afford the 2-bromo-4-(p-carboxyphenyl)butyraldehydes. Condensation with 2,4,5,6-tetraminopyrimidine and subsequent in situ oxidation of the resulting dihydropteridines yielded crystalline 10-alkyl-10-deaza-4-amino-4-deoxypteroic acids. The pteroic acids were coupled with diethyl glutamate via the mixed anhydride method, followed by saponification at room temperature, to give the target 10-deazaminopterins. The 10-alkyl compounds were approximately equipotent to 10-deazaminopterin as growth inhibitors of folate-dependent bacteria. Their abilities to inhibit Lactobacillus casei and L1210 derived dihydrofolate reductases were also similar. Transport properties in vitro were suggestive of an improved therapeutic index for the 10-alkyl analogues. Against L1210 in mice, the percent increase in life span at the LD10 dosage was +151% (methotrexate), +178% (10-deazaminopterin), +235% (10-methyl analogue), and +211% (10-ethyl analogue). 10,10-Dimethyl-10-deazaminopterin was less effective at an equimolar dosage, but the ILS at the maximum dose tested (72 mg/kg) was +135%. It was far less toxic than the other analogues possibly because of enhanced clearance.

  10. Synthesis of new kojic acid based unnatural α-amino acid derivatives.

    PubMed

    Balakrishna, C; Payili, Nagaraju; Yennam, Satyanarayana; Devi, P Uma; Behera, Manoranjan

    2015-11-01

    An efficient method for the preparation of kojic acid based α-amino acid derivatives by alkylation of glycinate schiff base with bromokojic acids have been described. Using this method, mono as well as di alkylated kojic acid-amino acid conjugates have been prepared. This is the first synthesis of C-linked kojic acid-amino acid conjugate where kojic acid is directly linked to amino acid through a C-C bond.

  11. Alterations of primary fatty acid amides in serum of patients with severe mental illness.

    PubMed

    Schwarz, Emanuel; Whitfield, Phil; Nahnsen, Sven; Wang, Lan; Major, Hilary; Leweke, F Markus; Koethe, Dagmar; Lio, Pietro; Bahn, Sabine

    2011-01-01

    Cannabis consumption is a well known risk factor for the onset of schizophrenia and evidence accumulates that the endocannabinoid system may play a central role in the disease etiology. Using a clinical bioinformatics approach, we have previously found primary fatty acid amides, which are linked to the endocannabinoid system, to be elevated in drug naive schizophrenia and affective disorder. Here, we provide a detailed description of these findings and expand the investigation by analyzing serum from 74 patients after short term treatment with antipsychotic medication using a liquid chromatography-mass spectrometry (LC-MS) metabolomics approach. We show that primary fatty acid amide (pFAA) levels normalize after treatment with typical but not after treatment with atypical antipsychotic medication. Also, the comparison of pFAA levels in schizophrenia patients to those of sleep deprived healthy volunteers suggests that pFAA abnormalities were not related to changes in the sleep architecture of patients with mental illness. Our findings support the involvement of the endocannabinoid system in the pathology of schizophrenia.

  12. Thermodynamic Interactions between Polystyrene and Long-Chain Poly(n-Alkyl Acrylates) Derived from Plant Oils.

    PubMed

    Wang, Shu; Robertson, Megan L

    2015-06-10

    Vegetable oils and their fatty acids are promising sources for the derivation of polymers. Long-chain poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) are readily derived from fatty acids through conversion of the carboxylic acid end-group to an acrylate or methacrylate group. The resulting polymers contain long alkyl side-chains with around 10-22 carbon atoms. Regardless of the monomer source, the presence of alkyl side-chains in poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) provides a convenient mechanism for tuning their physical properties. The development of structured multicomponent materials, including block copolymers and blends, containing poly(n-alkyl acrylates) and poly(n-alkyl methacrylates) requires knowledge of the thermodynamic interactions governing their self-assembly, typically described by the Flory-Huggins interaction parameter χ. We have investigated the χ parameter between polystyrene and long-chain poly(n-alkyl acrylate) homopolymers and copolymers: specifically we have included poly(stearyl acrylate), poly(lauryl acrylate), and their random copolymers. Lauryl and stearyl acrylate were chosen as model alkyl acrylates derived from vegetable oils and have alkyl side-chain lengths of 12 and 18 carbon atoms, respectively. Polystyrene is included in this study as a model petroleum-sourced polymer, which has wide applicability in commercially relevant multicomponent polymeric materials. Two independent methods were employed to measure the χ parameter: cloud point measurements on binary blends and characterization of the order-disorder transition of triblock copolymers, which were in relatively good agreement with one another. The χ parameter was found to be independent of the alkyl side-chain length (n) for large values of n (i.e., n > 10). This behavior is in stark contrast to the n-dependence of the χ parameter predicted from solubility parameter theory. Our study complements prior work investigating the interactions between

  13. Perfluoroalkyl acids and their precursors in indoor air sampled in children's bedrooms.

    PubMed

    Winkens, Kerstin; Koponen, Jani; Schuster, Jasmin; Shoeib, Mahiba; Vestergren, Robin; Berger, Urs; Karvonen, Anne M; Pekkanen, Juha; Kiviranta, Hannu; Cousins, Ian T

    2017-03-01

    The contamination levels and patterns of perfluoroalkyl acids (PFAAs) and their precursors in indoor air of children's bedrooms in Finland, Northern Europe, were investigated. Our study is among the most comprehensive indoor air monitoring studies (n = 57) and to our knowledge the first one to analyse air in children's bedrooms for PFASs (17 PFAAs and 9 precursors, including two acrylates, 6:2 FTAC and 6:2 FTMAC). The most frequently detected compound was 8:2 fluorotelomer alcohol (8:2 FTOH) with the highest median concentration (3570 pg/m(3)). FTOH concentrations were generally similar to previous studies, indicating that in 2014/2015 the impact of the industrial transition had been minor on FTOH levels in indoor air. However, in contrast to earlier studies (with one exception), median concentrations of 6:2 FTOH were higher than 10:2 FTOH. The C8 PFAAs are still the most abundant acids, even though they have now been phased out by major manufacturers. The mean concentrations of FOSE/As, especially MeFOSE (89.9 pg/m(3)), were at least an order of magnitude lower compared to previous studies. Collectively the comparison of FTOHs, PFAAs and FOSE/FOSAs with previous studies indicates that indoor air levels of PFASs display a time lag to changes in production of several years. This is the first indoor air study investigating 6:2 FTMAC, which was frequently detected (58%) and displayed some of the highest maximum concentrations (13 000 pg/m(3)). There were several statistically significant correlations between particular house and room characteristics and PFAS concentrations, most interestingly higher EtFOSE air concentrations in rooms with plastic floors compared to wood or laminate.

  14. Partitioning behavior of an acid-cleavable, 1,3-dioxolane alkyl ethoxylate, surfactant in single and binary surfactant mixtures for 2- and 3-phase microemulsion systems according to ethoxylate head group size.

    PubMed

    Gomez del Rio, Javier; Hayes, Douglas G; Urban, Volker S

    2010-12-15

    Partition coefficients for a pH-degradable 1,3-dioxolane alkyl ethoxylate surfactant, 4-CH(3)O (CH(2)CH(2)O)(5.6)-CH(2), 2,2-(CH(2))(12)CH(3), 2-(CH(2)) CH(3), 1,3-dioxolane or "cyclic ketal" surfactant, CK-2,13-E(5.6,ave), between isooctane- and water-rich phases of 2- and 3-phase microemulsion systems (K(n)) were determined as functions of the ethoxylate size, n, and temperature for the neat surfactant and its binary surfactant mixtures, to understand the partitioning of alkyl ethoxylates possessing a broad distribution of ethoxylate size and to determine conditions required for formation of 3-phase microemulsion systems at an optimal temperature where phase separation occurs rapidly, important for protein purification via proteins' selective partitioning to the middle phase, driven by affinity to the second surfactant of the binary mixture. A semi-empirical thermodynamic mathematical model described the partitioning data well, provided optimal temperature values consistent with phase diagrams and theory, and demonstrated that the tail region of CK-2,13-E(5.6,ave) is more polar than the hydrophobes of fatty alcohol ethoxylates. The addition of Aerosol-OT (AOT) removed the temperature sensitivity of CK-2,13-E(5.6,ave)s partitioning, producing 3-phase microemulsion systems between 20 °C and 40 °C. Analysis of the bottom phases of the 2- and 3-phase microemulsion systems formed by CK-2,13-E(5.6,ave) via small-angle neutron scattering demonstrated the presence of spherical, monodisperse oil-in-water microemulsions.

  15. Partitioning behavior of an acid-cleavable, 1,3-dioxolane alkyl ethoxylate, surfactant in single and binary surfactant mixtures for 2- and 3-phase microemulsion systems according to ethoxylate head group size

    SciTech Connect

    Gomez Del Rio, Javier A; Hayes, Douglas G; Urban, Volker S

    2010-01-01

    Partition coefficients for a pH-degradable 1,3-dioxolane alkyl ethoxylate surfactant, 4-CH{sub 3}O (CH{sub 2}CH{sub 2}O){sub 5.6}-CH{sub 2}, 2,2-(CH{sub 2}){sub 12}CH{sub 3}, 2-(CH{sub 2}) CH{sub 3}, 1,3-dioxolane or ''cyclic ketal'' surfactant, CK-2,13-E{sub 5.6,ave}, between isooctane- and water-rich phases of 2- and 3-phase microemulsion systems (K{sub n}) were determined as functions of the ethoxylate size, n, and temperature for the neat surfactant and its binary surfactant mixtures, to understand the partitioning of alkyl ethoxylates possessing a broad distribution of ethoxylate size and to determine conditions required for formation of 3-phase microemulsion systems at an optimal temperature where phase separation occurs rapidly, important for protein purification via proteins selective partitioning to the middle phase, driven by affinity to the second surfactant of the binary mixture. A semi-empirical thermodynamic mathematical model described the partitioning data well, provided optimal temperature values consistent with phase diagrams and theory, and demonstrated that the tail region of CK-2,13-E{sub 5.6,ave} is more polar than the hydrophobes of fatty alcohol ethoxylates. The addition of Aerosol-OT (AOT) removed the temperature sensitivity of CK-2,13-E{sub 5.6,ave}s partitioning, producing 3-phase microemulsion systems between 20 C and 40 C. Analysis of the bottom phases of the 2- and 3-phase microemulsion systems formed by CK-2,13-E{sub 5.6,ave} via small-angle neutron scattering demonstrated the presence of spherical, monodisperse oil-in-water microemulsions.

  16. 21 CFR 176.120 - Alkyl ketene dimers.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Alkyl ketene dimers. 176.120 Section 176.120 Food... Use Only as Components of Paper and Paperboard § 176.120 Alkyl ketene dimers. Alkyl ketene dimers may... section. (a) The alkyl ketene dimers are manufactured by the dehydrohalogenation of the acyl...

  17. 21 CFR 176.120 - Alkyl ketene dimers.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Alkyl ketene dimers. 176.120 Section 176.120 Food... Use Only as Components of Paper and Paperboard § 176.120 Alkyl ketene dimers. Alkyl ketene dimers may... section. (a) The alkyl ketene dimers are manufactured by the dehydrohalogenation of the acyl...

  18. Ruthenium-catalyzed meta/ortho-selective C-H alkylation of azoarenes using alkyl bromides.

    PubMed

    Li, Gang; Ma, Xingxing; Jia, Chunqi; Han, Qingqing; Wang, Ya; Wang, Junjie; Yu, Liuyang; Yang, Suling

    2017-01-19

    meta/ortho-Selective CAr-H (di)alkylation reactions of azoarenes have been achieved via [Ru(p-cymene)Cl2]2 catalyzed ortho-metalation using various types of alkyl bromides. Particularly, dual meta-alkylation of azoarene and reduction offer an attractive strategy for the synthesis of meta-alkylanilines, which are difficult to access via traditional aniline functionalization methods.

  19. Methods and Mechanisms for Cross-Electrophile Coupling of Csp2 Halides with Alkyl Electrophiles

    PubMed Central

    2016-01-01

    halides to form diarylmethanes. Arylnickel(II) intermediates can insert carbon monoxide to form acylnickel(II) intermediates that react with alkyl halides to form ketones, demonstrating the connection between the mechanisms of reactions of aryl halides and acid chlorides with alkyl halides. The low reactivity of epoxides with nickel can be overcome by the use of either titanium or iodide cocatalysis to facilitate radical generation and this can also be extended to enantioselective arylation of meso-epoxides. The high reactivity of benzyl bromide with nickel, which leads to the formation of bibenzyl in attempted reactions with bromobenzene, can be overcome by using a benzyl mesylate along with cobalt phthalocyanine cocatalysis to convert the mesylate into an alkyl radical. PMID:26011466

  20. Synthesis of acid addition salt of delta-aminolevulinic acid from 5-bromo levulinic acid esters

    DOEpatents

    Moens, Luc

    2003-06-24

    A process of preparing an acid addition salt of delta-aminolevulinc acid comprising: a) dissolving a lower alkyl 5-bromolevulinate and hexamethylenetetramine in a solvent selected from the group consisting of water, ethyl acetate, chloroform, acetone, ethanol, tetrahydrofuran and acetonitrile, to form a quaternary ammonium salt of the lower alkyl 5-bromolevulinate; and b) hydrolyzing the quaternary ammonium salt with an inorganic acid to form an acid addition salt of delta-aminolevulinic acid.

  1. Estrogen-like activity of perfluoroalkyl acids in vivo and interaction with human and rainbow trout estrogen receptors in vitro.

    PubMed

    Benninghoff, Abby D; Bisson, William H; Koch, Daniel C; Ehresman, David J; Kolluri, Siva K; Williams, David E

    2011-03-01

    The objectives of this study were to determine the structural characteristics of perfluoroalkyl acids (PFAAs) that confer estrogen-like activity in vivo using juvenile rainbow trout (Oncorhynchus mykiss) as an animal model and to determine whether these chemicals interact directly with the estrogen receptor (ER) using in vitro and in silico species comparison approaches. Perfluorooctanoic (PFOA), perfluorononanoic (PFNA), perfluorodecanoic (PFDA), and perfluoroundecanoic (PFUnDA) acids were all potent inducers of the estrogen-responsive biomarker protein vitellogenin (Vtg) in vivo, although at fairly high dietary exposures. A structure-activity relationship for PFAAs was observed, where eight to ten fluorinated carbons and a carboxylic acid end group were optimal for maximal Vtg induction. These in vivo findings were corroborated by in vitro mechanistic assays for trout and human ER. All PFAAs tested weakly bound to trout liver ER with half maximal inhibitory concentration (IC(50)) values of 15.2-289 μM. Additionally, PFOA, PFNA, PFDA, PFUnDA, and perlfuorooctane sulfonate (PFOS) significantly enhanced human ERα-dependent transcriptional activation at concentrations ranging from 10-1000 nM. Finally, we employed an in silico computational model based upon the crystal structure for the human ERα ligand-binding domain complexed with E2 to structurally investigate binding of these putative ligands to human, mouse, and trout ERα. PFOA, PFNA, PFDA, and PFOS all efficiently docked with ERα from different species and formed a hydrogen bond at residue Arg394/398/407 (human/mouse/trout) in a manner similar to the environmental estrogens bisphenol A and nonylphenol. Overall, these data support the contention that several PFAAs are weak environmental xenoestrogens of potential concern.

  2. Estrogen-Like Activity of Perfluoroalkyl Acids In Vivo and Interaction with Human and Rainbow Trout Estrogen Receptors In Vitro

    PubMed Central

    Benninghoff, Abby D.; Bisson, William H.; Koch, Daniel C.; Ehresman, David J.; Kolluri, Siva K.; Williams, David E.

    2011-01-01

    The objectives of this study were to determine the structural characteristics of perfluoroalkyl acids (PFAAs) that confer estrogen-like activity in vivo using juvenile rainbow trout (Oncorhynchus mykiss) as an animal model and to determine whether these chemicals interact directly with the estrogen receptor (ER) using in vitro and in silico species comparison approaches. Perfluorooctanoic (PFOA), perfluorononanoic (PFNA), perfluorodecanoic (PFDA), and perfluoroundecanoic (PFUnDA) acids were all potent inducers of the estrogen-responsive biomarker protein vitellogenin (Vtg) in vivo, although at fairly high dietary exposures. A structure-activity relationship for PFAAs was observed, where eight to ten fluorinated carbons and a carboxylic acid end group were optimal for maximal Vtg induction. These in vivo findings were corroborated by in vitro mechanistic assays for trout and human ER. All PFAAs tested weakly bound to trout liver ER with half maximal inhibitory concentration (IC50) values of 15.2–289μM. Additionally, PFOA, PFNA, PFDA, PFUnDA, and perlfuorooctane sulfonate (PFOS) significantly enhanced human ERα-dependent transcriptional activation at concentrations ranging from 10–1000nM. Finally, we employed an in silico computational model based upon the crystal structure for the human ERα ligand-binding domain complexed with E2 to structurally investigate binding of these putative ligands to human, mouse, and trout ERα. PFOA, PFNA, PFDA, and PFOS all efficiently docked with ERα from different species and formed a hydrogen bond at residue Arg394/398/407 (human/mouse/trout) in a manner similar to the environmental estrogens bisphenol A and nonylphenol. Overall, these data support the contention that several PFAAs are weak environmental xenoestrogens of potential concern. PMID:21163906

  3. N-Alkylation by Hydrogen Autotransfer Reactions.

    PubMed

    Ma, Xiantao; Su, Chenliang; Xu, Qing

    2016-06-01

    Owing to the importance of amine/amide derivatives in all fields of chemistry, and also the green and environmentally benign features of using alcohols as alkylating reagents, the relatively high atom economic dehydrative N-alkylation reactions of amines/amides with alcohols through hydrogen autotransfer processes have received much attention and have developed rapidly in recent decades. Various efficient homogeneous and heterogeneous transition metal catalysts, nano materials, electrochemical methods, biomimetic methods, asymmetric N-alkylation reactions, aerobic oxidative methods, and even certain transition metal-free, catalyst-free, or autocatalyzed methods, have also been developed in recent years. With a brief introduction to the background and developments in this area of research, this chapter focuses mainly on recent progress and technical and conceptual advances contributing to the development of this research in the last decade. In addition to mainstream research on homogeneous and heterogeneous transition metal-catalyzed reactions, possible mechanistic routes for hydrogen transfer and alcohol activation, which are key processes in N-alkylation reactions but seldom discussed in the past, the recent reports on computational mechanistic studies of the N-alkylation reactions, and the newly emerged N-alkylation methods based on novel alcohol activation protocols such as air-promoted reactions and transition metal-free methods, are also reviewed in this chapter. Problems and bottlenecks that remained to be solved in the field, and promising new research that deserves greater future attention and effort, are also reviewed and discussed.

  4. Concentrations of perfluoroalkyl compounds in the serum and milk of lactating North Carolina women

    EPA Science Inventory

    Perfluoroalkyl acids (PFAAs) and their derivatives are ubiquitous environmental contaminants that have been detected in a multitude of terrestrial and aquatic organisms. Some PFAAs bind the human estrogen receptors in vitro. Further, some PFAAs induce estrogen responsive genes a...

  5. Enantioselective Friedel-Crafts Alkylation Reactions of 3-Substituted Indoles with Electron-Deficient Alkenes.

    PubMed

    Weng, Jian-Quan; Fan, Ren-Jie; Deng, Qiao-Man; Liu, Ren-Rong; Gao, Jian-Rong; Jia, Yi-Xia

    2016-04-01

    Highly enantioselective Friedel-Crafts C2-alkylation reactions of 3-substituted indoles with α,β-unsaturated esters and nitroalkenes were developed using chiral Lewis acids as catalysts, which afforded chiral indole derivatives bearing C2-benzylic stereogenic centers in good to excellent yields (up to 99%) and enantioselectivities (up to 96% ee).

  6. Promotion of Hepatocarcinogenesis by Perfluoroalkyl Acids in Rainbow Trout

    PubMed Central

    Benninghoff, Abby D.; Orner, Gayle A.; Buchner, Clarissa H.; Hendricks, Jerry D.; Duffy, Aaron M.; Williams, David E.

    2012-01-01

    Previously, we reported that perfluorooctanoic acid (PFOA) promotes liver cancer in a manner similar to that of 17β-estradiol (E2) in rainbow trout. Also, other perfluoroalkyl acids (PFAAs) are weakly estrogenic in trout and bind the trout liver estrogen receptor. The primary objective of this study was to determine whether multiple PFAAs enhance hepatic tumorigenesis in trout, an animal model that represents human insensitivity to peroxisome proliferation. A two-stage chemical carcinogenesis model was employed in trout to evaluate PFOA, perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluorooctane sulfonate (PFOS), and 8:2 fluorotelomer alcohol (8:2FtOH) as complete carcinogens or promoters of aflatoxin B1 (AFB1)- and/or N-methyl-N′-nitro-N-nitrosoguanidine (MNNG)-induced liver cancer. A custom trout DNA microarray was used to assess hepatic transcriptional response to these dietary treatments in comparison with E2 and the classic peroxisome proliferator, clofibrate (CLOF). Incidence, multiplicity, and size of liver tumors in trout fed diets containing E2, PFOA, PFNA, and PFDA were significantly higher compared with AFB1-initiated animals fed control diet, whereas PFOS caused a minor increase in liver tumor incidence. E2 and PFOA also enhanced MNNG-initiated hepatocarcinogenesis. Pearson correlation analyses, unsupervised hierarchical clustering, and principal components analyses showed that the hepatic gene expression profiles for E2 and PFOA, PFNA, PFDA, and PFOS were overall highly similar, though distinct patterns of gene expression were evident for each treatment, particularly for PFNA. Overall, these data suggest that multiple PFAAs can promote liver cancer and that the mechanism of promotion may be similar to that of E2. PMID:21984479

  7. Promotion of hepatocarcinogenesis by perfluoroalkyl acids in rainbow trout.

    PubMed

    Benninghoff, Abby D; Orner, Gayle A; Buchner, Clarissa H; Hendricks, Jerry D; Duffy, Aaron M; Williams, David E

    2012-01-01

    Previously, we reported that perfluorooctanoic acid (PFOA) promotes liver cancer in a manner similar to that of 17β-estradiol (E2) in rainbow trout. Also, other perfluoroalkyl acids (PFAAs) are weakly estrogenic in trout and bind the trout liver estrogen receptor. The primary objective of this study was to determine whether multiple PFAAs enhance hepatic tumorigenesis in trout, an animal model that represents human insensitivity to peroxisome proliferation. A two-stage chemical carcinogenesis model was employed in trout to evaluate PFOA, perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluorooctane sulfonate (PFOS), and 8:2 fluorotelomer alcohol (8:2FtOH) as complete carcinogens or promoters of aflatoxin B(1) (AFB(1))- and/or N-methyl-N'-nitro-N-nitrosoguanidine (MNNG)-induced liver cancer. A custom trout DNA microarray was used to assess hepatic transcriptional response to these dietary treatments in comparison with E2 and the classic peroxisome proliferator, clofibrate (CLOF). Incidence, multiplicity, and size of liver tumors in trout fed diets containing E2, PFOA, PFNA, and PFDA were significantly higher compared with AFB(1)-initiated animals fed control diet, whereas PFOS caused a minor increase in liver tumor incidence. E2 and PFOA also enhanced MNNG-initiated hepatocarcinogenesis. Pearson correlation analyses, unsupervised hierarchical clustering, and principal components analyses showed that the hepatic gene expression profiles for E2 and PFOA, PFNA, PFDA, and PFOS were overall highly similar, though distinct patterns of gene expression were evident for each treatment, particularly for PFNA. Overall, these data suggest that multiple PFAAs can promote liver cancer and that the mechanism of promotion may be similar to that of E2.

  8. Palladium-Catalyzed Arylation of Alkyl Sulfenate Anions.

    PubMed

    Jia, Tiezheng; Zhang, Mengnan; Jiang, Hui; Wang, Carol Y; Walsh, Patrick J

    2015-11-04

    A unique palladium-catalyzed arylation of alkyl sulfenate anions is introduced that affords aryl alkyl sulfoxides in high yields. Due to the base sensitivity of the starting sulfoxides, sulfenate anion intermediates, and alkyl aryl sulfoxide products, the use of a mild method to generate alkyl sulfenate anions was crucial to the success of this process. Thus, a fluoride triggered elimination strategy was employed with alkyl 2-(trimethylsilyl)ethyl sulfoxides to liberate the requisite alkyl sulfenate anion intermediates. In the presence of palladium catalysts with bulky monodentate phosphines (SPhos and Cy-CarPhos) and aryl bromides or chlorides, alkyl sulfenate anions were readily arylated. Moreover, the thermal fragmentation and the base promoted elimination of alkyl sulfoxides was overridden. The alkyl sulfenate anion arylation exhibited excellent chemoselectivity in the presence of functional groups, such as anilines and phenols, which are also known to undergo palladium catalyzed arylation reactions.

  9. Neighbor-directed histidine N(τ) alkylation. A route to imidazolium-containing phosphopeptide macrocycles

    SciTech Connect

    Qian, Wen-Jian; Park, Jung-Eun; Grant, Robert; Lai, Christopher C.; Kelley, James A.; Yaffe, Michael B.; Lee, Kyung S.; Burke, Terrence R.

    2015-07-07

    Our recently discovered, selective, on-resin route to N(τ)-alkylated imidazolium-containing histidine residues affords new strategies for peptide mimetic design. In this, we demonstrate the use of this chemistry to prepare a series of macrocyclic phosphopeptides, in which imidazolium groups serve as ring-forming junctions. These cationic moieties subsequently serve to charge-mask the phosphoamino acid group that directed their formation. Furthermore, neighbor-directed histidine N(τ)-alkylation opens the door to new families of phosphopeptidomimetics for use in a range of chemical biology contexts.

  10. Neighbor-directed histidine N (τ)-alkylation: A route to imidazolium-containing phosphopeptide macrocycles.

    PubMed

    Qian, Wen-Jian; Park, Jung-Eun; Grant, Robert; Lai, Christopher C; Kelley, James A; Yaffe, Michael B; Lee, Kyung S; Burke, Terrence R

    2015-11-01

    Our recently discovered, selective, on-resin route to N(τ)-alkylated imidazolium-containing histidine residues affords new strategies for peptide mimetic design. In this, we demonstrate the use of this chemistry to prepare a series of macrocyclic phosphopeptides, in which imidazolium groups serve as ring-forming junctions. Interestingly, these cationic moieties subsequently serve to charge-mask the phosphoamino acid group that directed their formation. Neighbor-directed histidine N(τ)-alkylation opens the door to new families of phosphopeptidomimetics for use in a range of chemical biology contexts.

  11. Multidimensional Self-Assembled Structures of Alkylated Cellulose Oligomers Synthesized via in Vitro Enzymatic Reactions.

    PubMed

    Yataka, Yusuke; Sawada, Toshiki; Serizawa, Takeshi

    2016-10-04

    The self-assembly of biomolecules into highly ordered nano-to-macroscale structures is essential in the construction of biological tissues and organs. A variety of biomolecular assemblies composed of nucleic acids, peptides, and lipids have been used as molecular building units for self-assembled materials. However, crystalline polysaccharides have rarely been utilized in self-assembled materials. In this study, we describe multidimensional self-assembled structures of alkylated cellulose oligomers synthesized via in vitro enzymatic reactions. We found that the alkyl chain length drastically affected the assembled morphologies and allomorphs of cellulose moieties. The modulation of the intermolecular interactions of cellulose oligomers by alkyl substituents was highly effective at controlling their assembly into multidimensional structures. This study proposes a new potential of crystalline oligosaccharides for structural components of molecular assemblies with controlled morphologies and crystal structures.

  12. Chiral Alkyl Halides: Underexplored Motifs in Medicine

    PubMed Central

    Gál, Bálint; Bucher, Cyril; Burns, Noah Z.

    2016-01-01

    While alkyl halides are valuable intermediates in synthetic organic chemistry, their use as bioactive motifs in drug discovery and medicinal chemistry is rare in comparison. This is likely attributable to the common misconception that these compounds are merely non-specific alkylators in biological systems. A number of chlorinated compounds in the pharmaceutical and food industries, as well as a growing number of halogenated marine natural products showing unique bioactivity, illustrate the role that chiral alkyl halides can play in drug discovery. Through a series of case studies, we demonstrate in this review that these motifs can indeed be stable under physiological conditions, and that halogenation can enhance bioactivity through both steric and electronic effects. Our hope is that, by placing such compounds in the minds of the chemical community, they may gain more traction in drug discovery and inspire more synthetic chemists to develop methods for selective halogenation. PMID:27827902

  13. Degradation of Alkyl Benzene Sulfonate by Pseudomonas Species1

    PubMed Central

    Horvath, R. S.; Koft, B. W.

    1972-01-01

    Pseudomonas sp. HK-1 showed a direct relation between the concentration of alkyl benzene sulfonate (ABS) supplied and cell yields. Since growth on ABS alone did not occur, it was necessary to correlate the total energy obtained by the cells to the ABS concentration when glucose was supplied in a limiting concentration. Several types of metabolic attack in addition to the sulfonate removal were noted: (i) side-chain utilization as indicated by the production of tertiarybutyl alcohol and isopropanol and (ii) ring metabolism as indicated by the presence of phenol, catechol, mandelic acid, benzyl alcohol, and benzoic acid in spent growth media. Utilization of ABS was greatly enhanced by the presence of phenol. This enhancement suggests co-metabolism and that limited concentrations of phenolic products derived from ABS must be accumulated to get active metabolism of the ABS molecule. PMID:5017680

  14. Nucleotide sequence of alkyl-dihydroxyacetonephosphate synthase cDNA from Dictyostelium discoideum.

    PubMed

    de Vet, E C; van den Bosch, H

    1998-11-27

    The nucleotide sequence is reported of alkyl-dihydroxyacetonephosphate synthase cDNA from the cellular slime mold Dictyostelium discoideum. The open reading frame encodes a protein of 611 amino acids which shows a 33% amino acid identity to the human enzyme. This D. discoideum homolog carries a variant of the peroxisomal targeting signal type 1 at its C-terminus (PKL). Expression of the cDNA in Escherichia coli yielded an enzymatically active protein.

  15. Auxiliary-assisted palladium-catalyzed arylation and alkylation of sp2 and sp3 carbon-hydrogen bonds.

    PubMed

    Shabashov, Dmitry; Daugulis, Olafs

    2010-03-24

    We have developed a method for auxiliary-directed, palladium-catalyzed beta-arylation and alkylation of sp(3) and sp(2) C-H bonds in carboxylic acid derivatives. The method employs a carboxylic acid 2-methylthioaniline- or 8-aminoquinoline amide substrate, aryl or alkyl iodide coupling partner, palladium acetate catalyst, and an inorganic base. By employing 2-methylthioaniline auxiliary, selective monoarylation of primary sp(3) C-H bonds can be achieved. If arylation of secondary sp(3) C-H bonds is desired, 8-aminoquinoline auxiliary may be used. For alkylation of sp(3) and sp(2) C-H bonds, 8-aminoquinoline auxiliary affords the best results. Some functional group tolerance is observed and amino- and hydroxy-acid derivatives can be functionalized. Preliminary mechanistic studies have been performed. A palladacycle intermediate has been isolated, characterized by X-ray crystallography, and its reactions have been studied.

  16. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject...

  17. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327)...

  18. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject...

  19. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327)...

  20. IONIC LIQUID-CATALYZED ALKYLATION OF ISOBUTANE WITH 2-BUTENE

    EPA Science Inventory

    A detailed study of the alkylation of isobutane with 2-butene in ionic liquid media has been conducted using 1-alkyl-3-methylimidazolium halides?aluminum chloride encompassing various alkyl groups (butyl-, hexyl-, and octyl-) and halides (Cl, Br, and I) on its cations and anions,...

  1. 40 CFR 721.2825 - Alkyl ester (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl ester (generic name). 721.2825... Substances § 721.2825 Alkyl ester (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance alkyl ester (PMN P-84-968) is subject to reporting under this...

  2. 40 CFR 721.2825 - Alkyl ester (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkyl ester (generic name). 721.2825... Substances § 721.2825 Alkyl ester (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance alkyl ester (PMN P-84-968) is subject to reporting under this...

  3. 40 CFR 721.2825 - Alkyl ester (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl ester (generic name). 721.2825... Substances § 721.2825 Alkyl ester (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance alkyl ester (PMN P-84-968) is subject to reporting under this...

  4. 40 CFR 721.2825 - Alkyl ester (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkyl ester (generic name). 721.2825... Substances § 721.2825 Alkyl ester (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance alkyl ester (PMN P-84-968) is subject to reporting under this...

  5. 40 CFR 721.2825 - Alkyl ester (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkyl ester (generic name). 721.2825... Substances § 721.2825 Alkyl ester (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance alkyl ester (PMN P-84-968) is subject to reporting under this...

  6. 40 CFR 721.10233 - Linear alkyl epoxide (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Linear alkyl epoxide (generic). 721... Substances § 721.10233 Linear alkyl epoxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as linear alkyl epoxide (PMN...

  7. 40 CFR 721.10233 - Linear alkyl epoxide (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Linear alkyl epoxide (generic). 721... Substances § 721.10233 Linear alkyl epoxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as linear alkyl epoxide (PMN...

  8. 40 CFR 721.10233 - Linear alkyl epoxide (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Linear alkyl epoxide (generic). 721... Substances § 721.10233 Linear alkyl epoxide (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as linear alkyl epoxide (PMN...

  9. 40 CFR 721.4136 - Alkyl heteropolycyclic-aniline (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl heteropolycyclic-aniline... Specific Chemical Substances § 721.4136 Alkyl heteropolycyclic-aniline (generic). (a) Chemical substance... alkyl heteropolycyclic-aniline (PMN P-00-0067) is subject to reporting under this section for...

  10. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  11. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  12. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  13. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  14. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  15. 40 CFR 721.10699 - Polyfluorinated alkyl thio acrylamide (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Polyfluorinated alkyl thio acrylamide... Specific Chemical Substances § 721.10699 Polyfluorinated alkyl thio acrylamide (generic). (a) Chemical... as polyfluorinated alkyl thio acrylamide (PMN P-11-529) is subject to reporting under this...

  16. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327)...

  17. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject...

  18. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327)...

  19. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject...

  20. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject...

  1. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327)...

  2. Copper-catalyzed radical carbooxygenation: alkylation and alkoxylation of styrenes.

    PubMed

    Liao, Zhixiong; Yi, Hong; Li, Zheng; Fan, Chao; Zhang, Xu; Liu, Jie; Deng, Zixin; Lei, Aiwen

    2015-01-01

    A simple copper-catalyzed direct radical carbooxygenation of styrenes is developed utilizing alkyl bromides as radical resources. This catalytic radical difunctionalization accomplishes both alkylation and alkoxylation of styrenes in one pot. A broad range of styrenes and alcohols are well tolerated in this transformation. The EPR experiment shows that alkyl halides could oxidize Cu(I) to Cu(II) in this transformation.

  3. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  4. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  5. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  6. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  7. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  8. Poly(ethyleneoxide) functionalization through alkylation

    DOEpatents

    Sivanandan, Kulandaivelu; Eitouni, Hany Basam; Li, Yan; Pratt, Russell Clayton

    2015-04-21

    A new and efficient method of functionalizing high molecular weight polymers through alkylation using a metal amide base is described. This novel procedure can also be used to synthesize polymer-based macro-initiators containing radical initiating groups at the chain-ends for synthesis of block copolymers.

  9. Synthesis and characterization of chitosan alkyl urea.

    PubMed

    Wang, Jing; Jiang, Ji-Zhou; Chen, Wei; Bai, Zheng-Wu

    2016-07-10

    Chitosan is a versatile material employed for various purposes in many fields including the development of chiral stationary phases for enantioseparation. Chitosan alkyl urea is a kind of intermediate used to prepare enantioseparation materials. In order to synthesize the intermediates, in the present work, a new way to prepare chitosan alkyl urea has been established: chitosan was first reacted with methyl chloroformate yielding N-methoxyformylated chitosan, which was then converted to chitosan alkyl urea through amine-ester exchange reaction. With a large excess of methyl chloroformate and primary amine of low stereohindrance, the amino group in chitosan could be almost completely converted to ureido group. The as-prepared chitosan alkyl urea derivatives were characterized by IR, (1)H NMR, (13)C NMR,(1)H-(1)H COSY and (1)H-(13)C HSQC NMR spectra. The chemical shifts of hydrogen and carbon atoms of glucose unit were assigned. It was found that the degree of substitution was obviously lower if cyclopropyl amine, aniline, tert-butyl amine and diethyl amine were used as reactants for the amine-ester exchange reaction. The reason was explained with the aid of theoretical calculations.

  10. 77 FR 72747 - Alkyl(C8

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-12-06

    ... Classification System (NAICS) codes is not intended to be exhaustive, but rather provides a guide to help readers.../reproductive screening test (OECD 422) toxicity study on a representative N- alkyl(C 8 -C 18... in the reproductive or developmental parameters examined. No systemic toxicity was observed in...

  11. Growth mechanisms of 2D organic assemblies generated from dialkylated melaminium derivatives: the length difference of the two alkyl chains that matters.

    PubMed

    Xu, Jun; Wu, Guanglu; Wang, Zhiqiang; Zhang, Xi

    2013-08-27

    This research is aimed to understand the growth mechanisms for self-assembly of dialkylated melamine derivatives. The dialkylated melamine derivatives with different alkyl chains (Mela-m-n) are able to self-assemble with hydrochloric acid in dichloromethane to form 2D organic assemblies, exhibiting similar lamellar structures as Mela-n·HCl with identical alkyl chains. The most interesting finding is that the growth mechanism of Mela-n·HCl with identical alkyl chains is revealed to be layer growth, while Mela-m-n·HCl with asymmetric alkyl chains adopts a spiral growth mechanism. The asymmetric alkyl chains in Mela-m-n may lead to the formation of dislocation, which is responsible for the spiral growth mechanism.

  12. Differential alkylation-based redox proteomics--Lessons learnt.

    PubMed

    Wojdyla, Katarzyna; Rogowska-Wrzesinska, Adelina

    2015-12-01

    Cysteine is one of the most reactive amino acids. This is due to the electronegativity of sulphur atom in the side chain of thiolate group. It results in cysteine being present in several distinct redox forms inside the cell. Amongst these, reversible oxidations, S-nitrosylation and S-sulfenylation are crucial mediators of intracellular redox signalling, with known associations to health and disease. Study of their functionalities has intensified thanks to the development of various analytical strategies, with particular contribution from differential alkylation-based proteomics methods. Presented here is a critical evaluation of differential alkylation-based strategies for the analysis of S-nitrosylation and S-sulfenylation. The aim is to assess the current status and to provide insights for future directions in the dynamically evolving field of redox proteomics. To achieve that we collected 35 original research articles published since 2010 and analysed them considering the following parameters, (i) resolution of modification site, (ii) quantitative information, including correction of modification levels by protein abundance changes and determination of modification site occupancy, (iii) throughput, including the amount of starting material required for analysis. The results of this meta-analysis are the core of this review, complemented by issues related to biological models and sample preparation in redox proteomics, including conditions for free thiol blocking and labelling of target cysteine oxoforms.

  13. The lower alkyl methacrylates: Genotoxic profile of non-carcinogenic compounds.

    PubMed

    Albertini, Richard J

    2017-03-01

    All of the lower alkyl methacrylates are high production chemicals with potential for human exposure. The genotoxicity of seven mono-functional alkyl esters of methacrylic acid, i.e. methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, n-, i- and t-butyl methacrylate and 2 ethyl hexyl methacrylate, as well as methacrylic acid itself, the acyl component common to all, is reviewed and compared with the lack of carcinogenicity of methyl methacrylate, the representative member of the series so evaluated. Also reviewed are the similarity of structure, chemical and biological reactivity, metabolism and common metabolic products of this group of compounds which allows a category approach for assessing genotoxicity. As a class, the lower alkyl methacrylates are universally negative for gene mutations in prokaryotes but do exhibit high dose clastogenicity in mammalian cells in vitro. There is no convincing evidence that these compounds induce genotoxic effects in vivo in either sub-mammalian or mammalian species. This dichotomy of effects can be explained by the potential genotoxic intermediates generated in vitro. This genotoxic profile of the lower alkyl methacrylates is consistent with the lack of carcinogenicity of methyl methacrylate.

  14. Characterization of esterified cassava starch with long alkyl side chains and different substitution degrees.

    PubMed

    Barrios, Simón E; Giammanco, Giuseppe; Contreras, Jesús M; Laredo, Estrella; López-Carrasquero, Francisco

    2013-08-01

    The present work describes the characterization and thermal properties of hydrophobic starch obtained by the esterification of cassava starch with acyl imidazoles, acid chlorides and methyl ester derivatives of fatty acids with n-alkyl chains with 12-22 carbon atoms, in order to compare the dependence of their properties as a function of the length of the side chain and the methodology used for their synthesis. The n-acyl starches presented degrees of substitution (DS) between 0.06 and 1.2. Most of the derivatives obtained with acyl imidazoles were found to be stable at temperatures up to 300°C, whereas those synthesized with acid chlorides or methyl ester decomposed below. Finally, when the n-acyl starches were substituted with n-alkyl side chains of 16 or more carbon atoms, they were capable to crystallize in separate paraffinic phases independent of the starch backbone.

  15. Effects of alkyl chain length on properties of 1-alkyl-3-methylimidazolium fluorohydrogenate ionic liquid crystals.

    PubMed

    Xu, Fei; Matsumoto, Kazuhiko; Hagiwara, Rika

    2010-11-15

    A series of 1-alkyl-3-methylimidazolium fluorohydrogenate salts (C(x)MIm(FH)(2)F, x=8, 10, 12, 14, 16, and 18) have been characterized by thermal analysis, polarized optical microscopy, IR spectroscopy, X-ray diffraction, and anisotropic ionic conductivity measurements. Liquid crystalline mesophases with a smectic A interdigitated bilayer structure are observed from C(10) to C(18), showing a fan-like or focal conic texture. The temperature range of the mesophase increases with the increase in the alkyl chain length (from 10.1 °C for C(10)MIm(FH)(2)F to 123.1 °C for C(18)MIm(FH)(2)F). The distance between the two layers in the smectic structure gradually increases with increasing alkyl chain length and decreases with increasing temperature. Conductivity parallel to the smectic layers is around 10 mS cm(-1) regardless of the alkyl chain length, whereas that perpendicular to the smectic layers decreases with increasing alkyl chain length because of the thicker insulating sheet with the longer alkyl chain.

  16. Alkylated lariat ethers as solvent extraction reagents: Surveying the extraction of alkali metals by bis-t-octylbenzo-14-crown-4-acetic acid by use of potentiometric two-phase titration

    SciTech Connect

    Sachleben, R.A.; Moyer, B.A.; Case, F.I.; Garmon, S.A.

    1993-01-01

    Two-phase potentiometric titrimetry was used to survey the extraction of alkali metal cations from aqueous chloride solution by the lipophilic, ionizable lariat ether bis-(t-octylbenzo)-14-crown-4-acetic acid (BOB14C4AA) in o-xylene. Analysis of the data indicates that ion-exchange extraction by the crown-carboxylic acid at low loading (i.e., low conversion of BOB14C4AA to its salt form) is stronger for lithium ion than for the other alkali metals. Little or no selectivity occurs at high loadings. In comparison with the long-chain carboxylic acid 2-methyl-2-heptylnonanoic acid (HMHN), BOB14C4AA extracts lithium and sodium at significantly lower pH; in the loading range of 0.1 to 0.7, the pH shift is 1.4-1.8 pH units for sodium ion and 1.7-2.3 pH units for lithium ion. The titration data are interpreted in terms of aggregated organic-phase species. In the case of lithium extraction, clear evidence was found for a species in which neutral BOB14C4AA participates in the organic-phase complexation of the metal cation.

  17. Identification of an Arabidopsis Fatty Alcohol:Caffeoyl-Coenzyme A Acyltransferase Required for the Synthesis of Alkyl Hydroxycinnamates in Root Waxes1[W][OA

    PubMed Central

    Kosma, Dylan K.; Molina, Isabel; Ohlrogge, John B.; Pollard, Mike

    2012-01-01

    While suberin is an insoluble heteropolymer, a number of soluble lipids can be extracted by rapid chloroform dipping of roots. These extracts include esters of saturated long-chain primary alcohols and hydroxycinnamic acids. Such fatty alcohols and hydroxycinnamic acids are also present in suberin. We demonstrate that alkyl coumarates and caffeates, which are the major components of Arabidopsis (Arabidopsis thaliana) root waxes, are present primarily in taproots. Previously we identified ALIPHATIC SUBERIN FERULOYL TRANSFERASE (At5g41040), a HXXXD-type acyltransferase (BAHD family), responsible for incorporation of ferulate into aliphatic suberin of Arabidopsis. However, aliphatic suberin feruloyl transferase mutants were unaffected in alkyl hydroxycinnamate ester root wax composition. Here we identify a closely related gene, At5g63560, responsible for the synthesis of a subset of alkyl hydroxycinnamate esters, the alkyl caffeates. Transgenic plants harboring PAt5g63560::YFP fusions showed transcriptional activity in suberized tissues. Knockout mutants of At5g63560 were severely reduced in their alkyl caffeate but not alkyl coumarate content. Recombinant At5g63560p had greater acyltransferase activity when presented with caffeoyl-Coenzyme A (CoA) substrate, thus we have named this acyltransferase FATTY ALCOHOL:CAFFEOYL-CoA CAFFEOYL TRANSFERASE. Stress experiments revealed elevated alkyl coumarate content in root waxes of NaCl-treated wild-type and fatty alcohol:caffeoyl-CoA caffeoyl transferase plants. We further demonstrate that FATTY ACYL-CoA REDUCTASEs (FARs) FAR5 (At3g44550), FAR4 (At3g44540), and FAR1 (At5g22500) are required for the synthesis of C18, C20, and C22 alkyl hydroxycinnamates, respectively. Collectively, these results suggest that multiple acyltransferases are utilized for the synthesis of alkyl hydroxycinnamate esters of Arabidopsis root waxes and that FAR1/4/5 provide the fatty alcohols required for alkyl hydroxycinnamate synthesis. PMID:22797656

  18. N-Alkyl-PEI-functionalized iron oxide nanoclusters for efficient siRNA delivery.

    PubMed

    Liu, Gang; Xie, Jin; Zhang, Fan; Wang, Zhiyong; Luo, Kui; Zhu, Lei; Quan, Qimeng; Niu, Gang; Lee, Seulki; Ai, Hua; Chen, Xiaoyuan

    2011-10-04

    Small-interfering RNA (siRNA) is an emerging class of therapeutics, which works by regulating the expression of a specific gene involved in disease progression. Despite the promises, effective transport of siRNA with minimal side effects remains a challenge. In this study, a nonviral nanoparticle gene carrier is developed and its efficiency for siRNA delivery and transfection is validated at both in vitro and in vivo levels. Such a nanocarrier, abbreviated as Alkyl-PEI2k-IO, was constructed with a core of iron oxide nanoparticles (IOs) and a shell of alkylated polyethyleneimine of 2000 Da [corrected] molecualr weight (Alkyl-PEI2k). It is found to be able to bind with siRNA, resulting in well-dispersed nanoparticles with a controlled clustering structure and narrow size distribution. Electrophoresis studies show that the Alkyl-PEI2k-IOs could retard siRNA completely at N:P ratios (i.e., PEI nitrogen to nucleic acid phosphate) above 10, protect siRNA from enzymatic degradation in serum, and release complexed siRNA efficiently in the presence of polyanionic heparin. The knockdown efficiency of the siRNA-loaded nanocarriers is assessed with 4T1 cells stably expressing luciferase (fluc-4T1) and further, with a fluc-4T1 xenograft model. Significant down-regulation of luciferase is observed, and unlike high-molecular-weight analogues, the Alkyl-PEI2k-coated IOs show good biocompatibility. In conclusion, Alkyl-PEI2k-IOs demonstrate highly efficient delivery of siRNA and an innocuous toxic profile, making it a potential carrier for gene therapy.

  19. Synthesis of an acid addition salt of delta-aminolevulinic acid from 5-bromo levulinic acid esters

    DOEpatents

    Moens, Luc

    1999-01-01

    A process of preparing an acid addition salt of delta-aminolevulinic acid comprising: dissolving a lower alkyl 5-bromolevulinate and an alkali metal diformylamide in an organic solvent selected from the group consisting of acetonitrile, methanol, tetrahydrofuran, 2-methyltetrahydrofuran and methylformate or mixtures thereof to form a suspension of an alkyl 5-(N,N-diformylamino) levulinate ester; and hydrolyzing said alkyl 5-(N,N-diformylamino) levulinate with an inorganic acid to form an acid addition salt of delta-amino levulinic acid.

  20. Synthesis of an acid addition salt of delta-aminolevulinic acid from 5-bromo levulinic acid esters

    DOEpatents

    Moens, L.

    1999-05-25

    A process is disclosed for preparing an acid addition salt of delta-aminolevulinic acid comprising. The process involves dissolving a lower alkyl 5-bromolevulinate and an alkali metal diformylamide in an organic solvent selected from the group consisting of acetonitrile, methanol, tetrahydrofuran, 2-methyltetrahydrofuran and methylformate or mixtures to form a suspension of an alkyl 5-(N,N-diformylamino) levulinate ester; and hydrolyzing the alkyl 5-(N,N-diformylamino) levulinate with an inorganic acid to form an acid addition salt of delta-amino levulinic acid.

  1. High levels of perfluoroalkyl acids in eggs and embryo livers of great cormorant (Phalacrocorax carbo sinensis) and herring gull (Larus argentatus) from Lake Vänern, Sweden.

    PubMed

    Nordén, Marcus; Berger, Urs; Engwall, Magnus

    2013-11-01

    In the eggs and developing chick livers in the two wild bird species, great cormorant and herring gull, the concentrations of a range of 15 perfluoroalkyl acids (PFAAs) were determined. Eggs of the two species were collected from Lake Vänern, Sweden, and analysed either as undeveloped egg (whole egg or separated into yolk and albumen) or incubated until start of the hatching process when the chick liver was removed and analysed. High levels of PFAAs were found in all matrixes except albumen. The predominant PFAA was perfluorooctane sulfonate (PFOS), which was found in the μg/g wet weight (ww) range in some samples of cormorant whole egg, yolk and liver and herring gull egg yolk and liver. The average concentration in yolk was 1,506 ng/g ww in cormorant and 589 ng/g ww in herring gull. The average liver concentrations of PFOS were 583 ng/g ww in cormorant and 508 ng/g ww in herring gull. At these concentrations, biochemical effects in the developing embryo or effects on embryo survival cannot be ruled out. For perfluoroalkyl carboxylates (PFCAs), the liver/egg and liver/yolk concentration ratios increased with PFCA chain length in cormorant but not in herring gull, indicating that chain length could possibly affect egg-to-liver transfer of PFCAs and that species differences may exist.

  2. In pursuit of homoleptic actinide alkyl complexes.

    PubMed

    Seaman, Lani A; Walensky, Justin R; Wu, Guang; Hayton, Trevor W

    2013-04-01

    This Forum Article describes the pursuit of isolable homoleptic actinide alkyl complexes, starting with the pioneering work of Gilman during the Manhattan project. The initial reports in this area suggested that homoleptic uranium alkyls were too unstable to be isolated, but Wilkinson demonstrated that tractable uranium alkyls could be generated by purposeful "ate" complex formation, which serves to saturate the uranium coordination sphere and provide the complexes with greater kinetic stability. More recently, we reported the solid-state molecular structures of several homoleptic uranium alkyl complexes, including [Li(THF)4][U(CH2(t)Bu)5], [Li(TMEDA)]2[UMe6], [K(THF)]3[K(THF)2][U(CH2Ph)6]2, and [Li(THF)4][U(CH2SiMe3)6], by employing Wilkinson's strategy. Herein, we describe our attempts to extend this chemistry to thorium. The treatment of ThCl4(DME)2 with 5 equiv of LiCH2(t)Bu or LiCH2SiMe3 at -25 °C in THF affords [Th(CH2(t)Bu)5] (1) and [Li(DME)2][Th(CH2SiMe3)5 (2), respectively, in moderate yields. Similarly, the treatment of ThCl4(DME)2 with 6 equiv of K(CH2Ph) produces [K(THF)]2[Th(CH2Ph)6] (3), in good yield. Complexes 1-3 have been fully characterized, while the structures of 1 and 3 were confirmed by X-ray crystallography. Additionally, the electronic properties of 1 and 3 were explored by density functional theory.

  3. Soluble Alkyl Substituted Polygermanes. Thermochromic Behavior.

    DTIC Science & Technology

    1986-07-17

    are strongly thermochromic . The effect is attributed to conformational locking of the backbone which is caused by the crystallization of the side groups...are strongly thermochromic . The effect is attributed to the conformational locking of the backbone which is caused by the crystallization of the side...SYMBOL. 02 &m A -- .- h.. .. .. . . . . . . . . ... . . . .. RJ 5008 (52258) 1/24/86 Chemis try SOLUBLE ALKYL SUBSTITUTED POLYGERMANES: THERMOCHROMIC

  4. The Scarlet Letter of Alkylation: A Mini Review of Selective Alkylating Agents

    PubMed Central

    Oronsky, Bryan T; Reid, Tony; Knox, Susan J; Scicinski, Jan J

    2012-01-01

    If there were a stigma scale for chemotherapy, alkylating agents would be ranked at the top of the list. The chemical term alkylation is associated with nonselective toxicity, an association that dates back to the use of nitrogen mustards during World War I as chemical warfare agents. That this stigma persists and extends to compounds that, through selectivity, attempt to “tame” the indiscriminate destructive potential of alkylation is the subject of this review. Selective alkylation, as it is referred to herein, constitutes an extremely nascent and dynamic field in oncology. The pharmacodynamic response to this selective strategy depends on a delicate kinetic balance between specificity and the rate and extent of binding. Three representative compounds are presented: RRx-001, 3-bromopyruvate, and TH-302. The main impetus for the development of these compounds has been the avoidance of the serious complications of traditional alkylating agents; therefore, it is the thesis of this review that they should not experience stigma by association. PMID:22937173

  5. Tetrahydrofurfuryloxide derivatives of alkyl aluminum species.

    SciTech Connect

    Boyle, Timothy J.; Avilucea, Gabriel; Bunge, Scott D.; Alam, Todd Michael; Rodriguez, Mark Andrew; Cherry, Brian Ray; Tissot, Ralph George, Jr.; Segall, Judith M.

    2004-12-01

    Tetrahydrofurfuryl alcohol (H-OTHF) was successfully reacted with a series of aluminum alkyls (AlR{sub 3}) to yield compounds of the general formula [R{sub 2}Al({mu}-OTHF)]{sub 2} where R = CH{sub 3} (1), CH{sub 2}CH{sub 3} (2), and CH{sub 2}CH(CH{sub 3}){sub 2} (3). Further, reactivity studies showed that the alkyls for 1 were easily exchanged, forming compounds of the general formula [Me(OR)Al({mu}-OTHF)]{sub 2} where OR = OC{sub 6}H{sub 3}(Me){sub 2}-2,6 (4), OC{sub 6}H{sub 3}(CMe{sub 3}){sub 2}-2,6 (5a), and OSi(C{sub 6}H5){sub 3} (6). For 5a, reflux temperatures were required to get the full exchange; otherwise the asymmetric derivative [Me(OR)Al({mu}-OTHF){sub 2}AlMe{sub 2}] (5b) was isolated. The bulk powders of 1-6 were found to be in agreement with the crystal structures on the basis of elemental analyses and multinuclear solid state NMR studies. Multinuclear solution state NMR studies indicate that the alkyl OTHF derivatives have cis/trans isomers due to the chiral proton on the OTHF ligand.

  6. Characterization of alkyl carbon in forest soils by CPMAS 13C NMR spectroscopy and dipolar dephasing

    USGS Publications Warehouse

    Kogel-Knabner, I.; Hatcher, P.G.

    1989-01-01

    Samples obtained from forest soils at different stages of decomposition were treated sequentially with chloroform/methanol (extraction of lipids), sulfuric acid (hydrolysis), and sodium chlorite (delignification) to enrich them in refractory alkyl carbon. As revealed by NMR spectroscopy, this treatment yielded residues with high contents of alkyl carbon. In the NMR spectra of residues obtained from litter samples, resonances for carbohydrates are also present, indicating that these carbohydrates are tightly bound to the alkyl carbon structures. During decomposition in the soils this resistant carbohydrate fraction is lost almost completely. In the litter samples the alkyl carbon shows a dipolar dephasing behavior indicative of two structural components, a rigid and a more mobile component. As depth and decomposition increase, only the rigid component is observed. This fact could be due to selective degradation of the mobile component or to changes in molecular mobility during decomposition, e.g., because of an increase in cross linking or contact with the mineral matter of the soil.

  7. Recovery of Alkylation Activity in Deactivated USY Catalyst Using Supercritical Fluids: A Comparison of Light Hydrocarbons

    SciTech Connect

    Daniel M. Ginosar; David N. Thompson; Kyle C. Burch

    2004-05-01

    Off-line, in-situ alkylation activity recovery from a completely deactivated solid acid catalyst was examined in a continuous-flow reaction system employing supercritical fluids (SCF). A USY zeolite catalyst was initially deactivated during the liquid phase alkylation of butene with isobutane in a single-pass reactor and then varying amounts of alkylation activity were recovered by passing supercritical fluids over the catalyst bed. A comparison of reactivation fluids on catalyst activity recovery is reported. Fluids examined included helium, propane, n-butane, isobutane, n-pentane, and isopentane. Phases studied included gas, liquid, and supercritical. As much as 82% of the fresh catalyst activity was recovered when employing supercritical isobutane. The ability of the fluid to facilitate a hydride reaction with the adsorbed deactivating high-molecular weight carbocations was indicated as an important property necessary to attain high levels of catalyst activity recovery. Activity recovery utilizing supercritical fluids that enhance reactivation by both reacting with and desorbing fouling compounds appears to be a promising technique to advance solid catalyst alkylation.

  8. A role for Saccharomyces cerevisiae Tpa1 protein in direct alkylation repair.

    PubMed

    Shivange, Gururaj; Kodipelli, Naveena; Monisha, Mohan; Anindya, Roy

    2014-12-26

    Alkylating agents induce cytotoxic DNA base adducts. In this work, we provide evidence to suggest, for the first time, that Saccharomyces cerevisiae Tpa1 protein is involved in DNA alkylation repair. Little is known about Tpa1 as a repair protein beyond the initial observation from a high-throughput analysis indicating that deletion of TPA1 causes methyl methane sulfonate sensitivity in S. cerevisiae. Using purified Tpa1, we demonstrate that Tpa1 repairs both single- and double-stranded methylated DNA. Tpa1 is a member of the Fe(II) and 2-oxoglutarate-dependent dioxygenase family, and we show that mutation of the amino acid residues involved in cofactor binding abolishes the Tpa1 DNA repair activity. Deletion of TPA1 along with the base excision repair pathway DNA glycosylase MAG1 renders the tpa1Δmag1Δ double mutant highly susceptible to methylation-induced toxicity. We further demonstrate that the trans-lesion synthesis DNA polymerase Polζ (REV3) plays a key role in tolerating DNA methyl-base lesions and that tpa1Δmag1revΔ3 triple mutant is extremely susceptible to methylation-induced toxicity. Our results indicate a synergism between the base excision repair pathway and direct alkylation repair by Tpa1 in S. cerevisiae. We conclude that Tpa1 is a hitherto unidentified DNA repair protein in yeast and that it plays a crucial role in reverting alkylated DNA base lesions and cytotoxicity.

  9. DNA-directed alkylating ligands as potential antitumor agents: sequence specificity of alkylation by intercalating aniline mustards.

    PubMed

    Prakash, A S; Denny, W A; Gourdie, T A; Valu, K K; Woodgate, P D; Wakelin, L P

    1990-10-23

    The sequence preferences for alkylation of a series of novel parasubstituted aniline mustards linked to the DNA-intercalating chromophore 9-aminoacridine by an alkyl chain of variable length were studied by using procedures analogous to Maxam-Gilbert reactions. The compounds alkylate DNA at both guanine and adenine sites. For mustards linked to the acridine by a short alkyl chain through a para O- or S-link group, 5'-GT sequences are the most preferred sites at which N7-guanine alkylation occurs. For analogues with longer chain lengths, the preference of 5'-GT sequences diminishes in favor of N7-adenine alkylation at the complementary 5'-AC sequence. Magnesium ions are shown to selectively inhibit alkylation at the N7 of adenine (in the major groove) by these compounds but not the alkylation at the N3 of adenine (in the minor groove) by the antitumor antibiotic CC-1065. Effects of chromophore variation were also studied by using aniline mustards linked to quinazoline and sterically hindered tert-butyl-9-aminoacridine chromophores. The results demonstrate that in this series of DNA-directed mustards the noncovalent interactions of the carrier chromophores with DNA significantly modify the sequence selectivity of alkylation by the mustard. Relationships between the DNA alkylation patterns of these compounds and their biological activities are discussed.

  10. Effects of alkyl parabens on plant pathogenic fungi.

    PubMed

    Ito, Shinsaku; Yazawa, Satoru; Nakagawa, Yasutaka; Sasaki, Yasuyuki; Yajima, Shunsuke

    2015-04-15

    Alkyl parabens are used as antimicrobial preservatives in cosmetics, food, and pharmaceutical products. However, the mode of action of these chemicals has not been assessed thoroughly. In this study, we determined the effects of alkyl parabens on plant pathogenic fungi. All the fungi tested, were susceptible to parabens. The effect of linear alkyl parabens on plant pathogenic fungi was related to the length of the alkyl chain. In addition, the antifungal activity was correlated with the paraben-induced inhibition of oxygen consumption. The antifungal activity of linear alkyl parabens likely originates, at least in part, from their ability to inhibit the membrane respiratory chain, especially mitochondrial complex II. Additionally, we determined that some alkyl parabens inhibit Alternaria brassicicola infection of cabbage.

  11. Alkylation damage by lipid electrophiles targets functional protein systems.

    PubMed

    Codreanu, Simona G; Ullery, Jody C; Zhu, Jing; Tallman, Keri A; Beavers, William N; Porter, Ned A; Marnett, Lawrence J; Zhang, Bing; Liebler, Daniel C

    2014-03-01

    Protein alkylation by reactive electrophiles contributes to chemical toxicities and oxidative stress, but the functional impact of alkylation damage across proteomes is poorly understood. We used Click chemistry and shotgun proteomics to profile the accumulation of proteome damage in human cells treated with lipid electrophile probes. Protein target profiles revealed three damage susceptibility classes, as well as proteins that were highly resistant to alkylation. Damage occurred selectively across functional protein interaction networks, with the most highly alkylation-susceptible proteins mapping to networks involved in cytoskeletal regulation. Proteins with lower damage susceptibility mapped to networks involved in protein synthesis and turnover and were alkylated only at electrophile concentrations that caused significant toxicity. Hierarchical susceptibility of proteome systems to alkylation may allow cells to survive sublethal damage while protecting critical cell functions.

  12. Dual platinum and pyrrolidine catalysis in the direct alkylation of allylic alcohols: selective synthesis of monoallylation products.

    PubMed

    Shibuya, Ryozo; Lin, Lu; Nakahara, Yasuhito; Mashima, Kazushi; Ohshima, Takashi

    2014-04-22

    A dual platinum- and pyrrolidine-catalyzed direct allylic alkylation of allylic alcohols with various active methylene compounds to produce products with high monoallylation selectivity was developed. The use of pyrrolidine and acetic acid was essential, not only for preventing undesirable side reactions, but also for obtaining high monoallylation selectivity.

  13. The missing member of the partially O-alkylated resorcinarene family: synthesis and conformation of methyl tetramethoxy resorcinarene.

    PubMed

    Tero, Tiia-Riikka; Suhonen, Aku; Salorinne, Kirsi; Campos-Barbosa, Hélène; Nissinen, Maija

    2013-03-01

    An improved Lewis acid catalyzed synthesis method for methyl tetramethoxy resorcinarene is described, which produced the missing lower rim methyl derivative of this partially O-alkylated resorcinarene family. Structural characterization by means of variable temperature NMR experiments and single crystal X-ray diffraction studies furthermore revealed that the resorcinarene core adopts different conformations in the solid state and in solution.

  14. Lithium perchlorate-nitromethane-promoted alkylation of anilines with arylmethanols.

    PubMed

    Zhou, Jun; Mao, Hai-Feng; Wang, Lu; Zou, Jian-Ping; Zhang, Wei

    2011-11-01

    A new application of lithium perchlorate-nitromethane (LPNM) for the formation of aromatic C-N and C-C bonds is introduced. LPNM-promoted reactions of anilines with diarylmethanols selectively generate N-alkylated anilines or mono and double Friedel-Crafts alkylation products under different conditions by changing the reaction time, reaction temperature, and the ratio of the reactants. This method does not require the use of transition metal catalysts to prepare alkylated aniline derivatives.

  15. Photochemical Production of Alkyl Nitrates in the Tropical Pacific Ocean

    NASA Astrophysics Data System (ADS)

    Dahl, E. E.; Yvon-Lewis, S. A.; Saltzman, E. S.

    2005-12-01

    Alkyl nitrates are important to the tropospheric NOx/ozone cycle because they represent a significant fraction of the reactive nitrogen (NOy). Previous work has shown that there is an oceanic source of alkyl nitrates. A photochemical mechanism for the formation of alkyl nitrates in seawater has been proposed. This mechanism involves the reaction of ROO and NO, where ROO is an alkyl peroxy radical. ROO and NO radicals in seawater are derived from the photolysis of DOM and nitrite, respectively. In this study, the photochemical production of low molecular weight alkyl nitrates (C1-C3) was observed in shipboard incubation experiments in the tropical Pacific during the PHASE 1 cruise. Seawater samples from several regions, including high and low-chlorophyll areas, were collected and incubated. Alkyl nitrate production rates as high as 2 nM/hour were observed. The production rate of alkyl nitrates was clearly dependent upon the initial concentration of nitrite, most likely as the source for NO radicals. While the magnitude of production varied between sample locations, the ratios of the production rates of the various alkyl nitrates remained relatively constant. The observed production ratios of methyl, ethyl, isopropyl, and n-propyl nitrate were 5.9:1.0:0.1:0.2. These ratios presumably reflect the speciation of peroxy radicals formed in seawater, and the yield of alkyl nitrates from the ROO+NO reaction. The observed production rate ratios are similar to the concentration ratios of alkyl nitrates observed in ambient seawater and the overlying atmosphere during the study. A comparison of the measured production rates and the observed concentrations, suggests that photochemically produced alkyl nitrates are a major source of atmospheric alkyl nitrates in the surface ocean and marine atmosphere.

  16. Effect of pH on DNA alkylation by enzyme-activated mitomycin C and porfiromycin.

    PubMed

    Yu, F; Pan, S S

    1993-06-01

    DNA adduct formation by enzyme-activated antibiotics, mitomycin C (MMC) or porfiromycin (PFM), at pH 7.6 or pH 6.0 under anaerobic conditions was analyzed by a 32P-postlabeling method. Antibiotic activation by rat liver NADPH-cytochrome P-450 reductase (EC 1.6.2.4) and bovine milk xanthine oxidase (EC 1.2.3.2) produced similar results. Five 32P-labeled MMC adducts were separated by thin layer chromatography and high performance liquid chromatography from DNA alkylated at either pH. Four of the radioactive spots separated by thin layer chromatography were identified as two monofunctional monoadducts [1" alpha and 1" beta forms of N2-(2" beta,7"-diaminomitosen-1"-yl)-2'-deoxyguanylic acid], one bifunctional monoadduct [N2-(10"-decarbamoyl-2",7"-diaminomitosen-1" alpha-yl)-2'-deoxyguanylic acid], and one cross-linked adduct [N2-(2" beta,7"-diamino-10"-deoxyguanyl-N2-yl-mitosen- 1" alpha-yl)-2'-deoxyguanylic acid]. One minor radioactive spot was not identified. By comparing DNA alkylated at the two pH values, based on equal amounts of 32P radioactivity, similar amounts of cross-links were detected. However, the DNA showed different ratios of the alpha and beta isomers of the monofunctional monoadduct. Furthermore, the DNA alkylated at pH 6.0 showed more bifunctional monoadducts than did the DNA alkylated at pH 7.6. Analysis of alkylated DNA by enzyme-activated PFM showed a similar spectrum of DNA adduct formation. The effect of pH on the distribution of the five PFM-DNA adducts was similar to that observed for the five MMC-DNA adducts. The distribution of adducts in DNA alkylated at the same pH was similar irrespective of which enzyme activated MMC or PFM. The pH of the reaction during DNA and MMC interaction was the determining factor for the quantitative distribution of the adducts. This pH effect may be important for the cytotoxicity of MMC and PFM in tumor cells that have high levels of reductive enzymes with low optimal pH values.

  17. Hyaluronan derivatives: Alkyl chain length boosts viscoelastic behavior to depolymerization.

    PubMed

    Pavan, Mauro; Galesso, Devis; Menon, Giampaolo; Renier, Davide; Guarise, Cristian

    2013-09-12

    Five amide derivatives of Hyaluronic Acid (HA) were synthesized with C8, C12, C15, C16 and C18 linear alkyl-amines. These polymers (Hyadd) were tested against thermal, oxidative and hyaluronidase degradation by means of rheological experiments and SEC analysis and compared to non-modified HA. First of all, no free hexadecylamine was detected in the treated samples, meaning that under these stressing conditions only cleavage of glycosidic bonds occurs. Then, viscoelastic properties were assessed during thermal degradation and their variation as a function of time was expressed by means of a decay constant k(G'): while no significant difference in the decrease rate was observed between Hyadd-C8 and Hyadd-C12, a marked stabilization of viscoelastic properties during thermal treatment was detected for Hyadd-C15, Hyadd-C16 and Hyadd-C18. On the other hand, no difference was observed between the MW decrease rate (kMW decay constant) of HA and Hyadd-C12 to-C18; the depolymerization takes place on the backbone of the polymers independently whether they are derivatized or not, but longer alkyl chains lead to higher viscoelasticity in the depolymerized products. Finally, both oxidative and enzymatic degradation were carried out analyzing the changes in elastic modulus and in dynamic viscosity: once again, the amide side chain came out with similar behavior to chemical cross-linked HA (HBC) and with improved performances respect to linear HA in terms of preservation of viscoelasticity after chain depolymerization.

  18. Neighbor-directed Histidine N(τ)–Alkylation: A Route to Imidazolium-containing Phosphopeptide Macrocycles

    PubMed Central

    Qian, Wen-Jian; Park, Jung-Eun; Grant, Robert; Lai, Christopher C.; Kelley, James A.; Yaffe, Michael B.; Lee, Kyung S.; Burke, Terrence R.

    2016-01-01

    Our recently discovered, selective, on-resin route to N(τ)-alkylated imidazolium-containing histidine residues affords new strategies for peptide mimetic design. In our current work, we demonstrate the use of this chemistry to prepare a series of macrocyclic phosphopeptides, in which imidazolium groups serve as ring-forming junctions. Interestingly, these cationic moieties subsequently serve to charge-mask the phosphoamino acid group that directed their formation. Neighbor-directed histidine N(τ)-alkylation opens the door to new families of phosphopeptidomimetics for use in a range of chemical biology contexts. PMID:26152807

  19. Alkyl Chlorides as Hydrogen Bond Acceptors

    SciTech Connect

    Nadas, Janos I; Vukovic, Sinisa; Hay, Benjamin

    2012-01-01

    To gain an understanding of the role of an alkyl chloride as a hydrogen bond acceptor, geometries and interaction energies were calculated at the MP2/aug-cc-pVDZ level of theory for complexes between ethyl chloride and representative hydrogen donor groups. The results establish that these donors, which include hydrogen cyanide, methanol, nitrobenzene, pyrrole, acetamide, and N-methylurea, form X-H {hor_ellipsis} Cl hydrogen bonds (X = C, N, O) of weak to moderate strength, with {Delta}E values ranging from -2.8 to -5.3 kcal/mol.

  20. Determination of reaction rate constants for alkylation of 4-(p-nitrobenzyl) pyridine by different alkylating agents.

    PubMed

    Walles, S A

    1980-02-01

    The rate constants have been determined for the reaction between some different alkylating agents and 4-(p-nitrobenzyl) pyridine (NBP) in methanol. These constants have been compared with those for alkylation of aniline in water. All the constants were lower in methanol than in water but in different degrees. The rate constants of the different alkylating agents have been calculated at a nucleophilic strength n=2. The genetic risk defined as the degree of alkylation of a nucleophile (n=2) is equivalent to the rate constant kn=2 and the target dose. The dependence of the genetic risk on the rate constant (kn=2) is discussed.

  1. Water extracts of tree Hypericum sps. protect DNA from oxidative and alkylating damage and enhance DNA repair in colon cells.

    PubMed

    Ramos, Alice A; Marques, Filipe; Fernandes-Ferreira, Manuel; Pereira-Wilson, Cristina

    2013-01-01

    Diet may induce colon carcinogenesis through oxidative or alkylating DNA damage. However, diet may also contain anticarcinogenic compounds that contribute to cancer prevention. DNA damage prevention and/or induction of repair are two important mechanisms involved in cancer chemoprevention by dietary compounds. Hypericum sps. are widely used in traditional medicine to prepare infusions due to their beneficial digestive and neurologic effects. In this study, we investigated the potential of water extracts from three Hypericum sps. and some of their main phenolic compounds to prevent and repair oxidative and alkylating DNA damage in colon cells. The results showed that water extracts of Hypericum perforatum, Hypericum androsaemum, Hypericum undulatum, quercetin and rutin have protective effect against oxidative DNA damage in HT29 cells. Protective effect was also observed against alkylating DNA damage induced by methyl-methanesulfonate, except for H. androsaemum. With regard to alkylating damage repair H. perforatum, H. androsaemum and chlorogenic acid increased repair of alkylating DNA damage by base excision repair pathway. No effect was observed on nucleotide excision repair pathway. Antigenotoxic effects of Hypericum sps. may contribute to colon cancer prevention and the high amount of phenolic compounds present in Hypericum sps. play an important role in DNA protective effects.

  2. Microstructure of Hydrophobically Modified Alkyl Acrylamide Hydrogels

    NASA Astrophysics Data System (ADS)

    Tian, Jun; Seery, Thomas A. P.; Ho, Derek L.; Weiss, R. A.

    2004-03-01

    Hydrophobically modified water-soluble acrylamide polymers have a variety of applications, including viscosity thickeners, microencapsulation, biosensors and controlled drug delivery systems. The microstructure of copolymer hydrogels of N,N-dimethylacrylamide (DMA) or N-isopropylacrylamide(NIPA) modified with 2-(N-ethylfluorooctanesulfonamido)ethyl acrylate, FOSA, was studied by small angle x-ray (SAXS) and neutron scattering (SANS). Swelling and DSC measurements showed that FOSA/NIPA gels exhibited a volume phase transition (VPT), but that FOSA/DMA gels did not. A modified interacting core-shell model was used to explain the SAXS and SANS data for both gels. The crosslink junctions of the gel consisted of nanophase-separated FOSA domains as the core surrounded by a water-poor layer of the alkyl acrylamide. These nanodomains were dispersed in a matrix of water-swollen alkyl acrylamide that had large scale heterogeneities. The average spherical core radius ranged from 1 to 3 nm and the average shell thickness ranged from 1 to 1.5 nm; the aggregation number ranged from 10 to 200.

  3. ESCHERICHIA COLI Gene Induction by Alkylation Treatment

    PubMed Central

    Volkert, Michael R.; Nguyen, Dinh C.; Beard, K. Christopher

    1986-01-01

    Searches for alkylation-inducible (aid) genes of Escherichia coli have been conducted by screening random fusions of the Mu-dl(ApR lac) phage for fusions showing increased β-galactosidase activity after treatment with methylating agents, but not after treatments with UV-irradiation. In this report we describe gene fusions that are specifically induced by alkylation treatments. Nine new mutants are described, and their properties are compared with the five mutants described previously. The total of 14 fusion mutants map at five distinct genetic loci. They can be further subdivided on the basis of their induction by methyl methanesulfonate (MMS) and N-methyl-N'-nitro-N-nitrosoguanidine (MNNG). alkA, aidB and aidD are induced by both agents and appear to be regulated by ada. Neither aidC nor aidI is regulated by ada. Moreover, since aidC is induced only by MNNG and aidI is induced only by MMS, these two genes are likely to be individually regulated. Thus, there appear to be at least three different regulatory mechanisms controlling aid genes. PMID:3080354

  4. Escherichia coli gene induction by alkylation treatment.

    PubMed

    Volkert, M R; Nguyen, D C; Beard, K C

    1986-01-01

    Searches for alkylation-inducible (aid) genes of Escherichia coli have been conducted by screening random fusions of the Mu-dl(ApR lac) phage for fusions showing increased beta-galactosidase activity after treatment with methylating agents, but not after treatments with UV-irradiation. In this report we describe gene fusions that are specifically induced by alkylation treatments. Nine new mutants are described, and their properties are compared with the five mutants described previously. The total of 14 fusion mutants map at five distinct genetic loci. They can be further subdivided on the basis of their induction by methyl methanesulfonate (MMS) and N-methyl-N' -nitro-N-nitrosoguanidine (MNNG). alkA, aidB and aidD are induced by both agents and appear to be regulated by ada. Neither aidC nor aidI is regulated by ada. Moreover, since aidC is induced only by MNNG and aidI is induced only by MMS, these two genes are likely to be individually regulated. Thus, there appear to be at least three different regulatory mechanisms controlling aid genes.

  5. Partial Crystallinity in Alkyl Side Chain Polymers.

    NASA Astrophysics Data System (ADS)

    Sahni, Vasav; Prasad, Shishir; Villate, Johanna; Jiang, Zhang; Sinha, Sunil; Dhinojwala, Ali

    2009-03-01

    Surface freezing is the formation of a crystalline monolayer at the free surface of a melt at a temperature Ts, a few degrees above the bulk freezing temperature, Tb. This effect, i.e. Ts> Tb, common to many chain molecules, is in marked contrast with the surface melting effect, i.e. Ts<=Tb, shown by almost all other materials. Various theoretical and experimental studies have been done to characterize the monolayer formed when the surface freezes before the bulk. We have studied the structure of a novel crystalline surface monolayer on top of a disordered melt of the same material (poly(n-alkyl acrylate)s) using grazing incidence x-ray diffraction. The grazing incidence x-ray diffraction, surface tension, and bulk latent heat results show that there is partial side-chain crystallinity. Also, the surface tension results explain the trend of the difference between the surface order-to-disorder transition temperature and the bulk melting temperature (δT) as a function of side chain length. The behavior of the crystal length, crystal spacing and tilt with varying alkyl chain length and temperature was also studied.

  6. The photodissociation dynamics of alkyl radicals

    SciTech Connect

    Giegerich, Jens; Fischer, Ingo

    2015-01-28

    The photodisscociation dynamics of the alkyl radicals i-propyl (CH(CH{sub 3}){sub 2}) and t-butyl (C(CH{sub 3}){sub 3}) are investigated by H-atom photofragment imaging. While i-propyl is excited at 250 nm, the photodynamics of t-butyl are explored over a large energy range using excitation wavelengths between 347 nm and 233 nm. The results are compared to those obtained previously for ethyl, CH{sub 3}CH{sub 2}, and to those reported for t-butyl using 248 nm excitation. The translational energy (E{sub T}) distribution of the H-atom photofragments is bimodal and appears rather similar for all three radicals. The low E{sub T} part of the distribution shows an isotropic photofragment angular distribution, while the high E{sub T} part is associated with a considerable anisotropy. Thus, for t-butyl, two H-atom loss channels of roughly equal importance have been identified in addition to the CH{sub 3}-loss channel reported previously. A mechanism for the photodissociation of alkyl radicals is suggested that is based on interactions between Rydberg- and valence states.

  7. Solid catalyzed isoparaffin alkylation at supercritical fluid and near-supercritical fluid conditions

    DOEpatents

    Ginosar, Daniel M.; Fox, Robert V.; Kong, Peter C.

    2000-01-01

    This invention relates to an improved method for the alkylation reaction of isoparaffins with olefins over solid catalysts including contacting a mixture of an isoparaffin, an olefin and a phase-modifying material with a solid acid catalyst member under alkylation conversion conditions at either supercritical fluid, or near-supercritical fluid conditions, at a temperature and a pressure relative to the critical temperature(T.sub.c) and the critical pressure(P.sub.c) of the reaction mixture. The phase-modifying phase-modifying material is employed to promote the reaction's achievement of either a supercritical fluid state or a near-supercritical state while simultaneously allowing for decreased reaction temperature and longer catalyst life.

  8. Alkyl ammonium cation stabilized biocidal polyiodides with adaptable high density and low pressure.

    PubMed

    He, Chunlin; Parrish, Damon A; Shreeve, Jean'ne M

    2014-05-26

    The effective application of biocidal species requires building the active moiety into a molecular back bone that can be delivered and decomposed on demand under conditions of low pressure and prolonged high-temperature detonation. The goal is to destroy storage facilities and their contents while utilizing the biocidal products arising from the released energy to destroy any remaining harmful airborne agents. Decomposition of carefully selected iodine-rich compounds can produce large amounts of the very active biocides, hydroiodic acid (HI) and iodine (I2). Polyiodide anions, namely, I3(-), I5(-), which are excellent sources of such biocides, can be stabilized through interactions with large, symmetric cations, such as alkyl ammonium salts. We have designed and synthesized suitable compounds of adaptable high density up to 3.33 g cm(-3) that are low-pressure polyiodides with various alkyl ammonium cations, deliverable iodine contents of which range between 58.0-90.9%.

  9. Intramolecular alkylative arylation of oxabicylic alkene: a potential diene approach for the synthesis of estrone and analogous steroid structures.

    PubMed

    Li, Wei-Dong Z; Wei, Kun

    2004-04-15

    Regioselective and stereospecific intramolecular alkylative arylation of unsaturated oxabicyclic diol 6, mediated by Lewis acid or strong protic acid to give the tetracyclic products 7a and 7b, as shown above, represents the first example of an electrophilic (cationic in character) ring-opening-cyclization of oxabicyclic alkene. This constitutes the key cyclization step for a long-standing and potentially useful diene approach for the synthesis of estrone and analogous steroid structures. [structure: see text

  10. 40 CFR 721.6070 - Alkyl phosphonate ammonium salts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkyl phosphonate ammonium salts. 721... Substances § 721.6070 Alkyl phosphonate ammonium salts. (a) Chemical substances and significant new uses... salts (PMNs P-93-725 and P-93-726) are subject to reporting under this section for the significant...

  11. 40 CFR 721.6070 - Alkyl phosphonate ammonium salts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl phosphonate ammonium salts. 721... Substances § 721.6070 Alkyl phosphonate ammonium salts. (a) Chemical substances and significant new uses... salts (PMNs P-93-725 and P-93-726) are subject to reporting under this section for the significant...

  12. 40 CFR 721.2155 - Alkoxyamino-alkyl-coumarin (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkoxyamino-alkyl-coumarin (generic... Substances § 721.2155 Alkoxyamino-alkyl-coumarin (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as...

  13. 40 CFR 721.2155 - Alkoxyamino-alkyl-coumarin (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkoxyamino-alkyl-coumarin (generic... Substances § 721.2155 Alkoxyamino-alkyl-coumarin (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as...

  14. 40 CFR 721.2155 - Alkoxyamino-alkyl-coumarin (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkoxyamino-alkyl-coumarin (generic... Substances § 721.2155 Alkoxyamino-alkyl-coumarin (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as...

  15. 40 CFR 721.2155 - Alkoxyamino-alkyl-coumarin (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkoxyamino-alkyl-coumarin (generic... Substances § 721.2155 Alkoxyamino-alkyl-coumarin (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as...

  16. 40 CFR 721.2155 - Alkoxyamino-alkyl-coumarin (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkoxyamino-alkyl-coumarin (generic... Substances § 721.2155 Alkoxyamino-alkyl-coumarin (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as...

  17. 40 CFR 721.10317 - Alkyl phosphate derivative (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl phosphate derivative (generic... Specific Chemical Substances § 721.10317 Alkyl phosphate derivative (generic). (a) Chemical substance and... phosphate derivative (PMN P-02-1040) is subject to reporting under this section for the significant new...

  18. 40 CFR 721.10317 - Alkyl phosphate derivative (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkyl phosphate derivative (generic... Specific Chemical Substances § 721.10317 Alkyl phosphate derivative (generic). (a) Chemical substance and... phosphate derivative (PMN P-02-1040) is subject to reporting under this section for the significant new...

  19. 40 CFR 721.10317 - Alkyl phosphate derivative (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkyl phosphate derivative (generic... Specific Chemical Substances § 721.10317 Alkyl phosphate derivative (generic). (a) Chemical substance and... phosphate derivative (PMN P-02-1040) is subject to reporting under this section for the significant new...

  20. Organocatalytic enantioselective indole alkylations of alpha,beta-unsaturated ketones.

    PubMed

    Chen, Wei; Du, Wei; Yue, Lei; Li, Rui; Wu, Yong; Ding, Li-Sheng; Chen, Ying-Chun

    2007-03-07

    The C3-selective enantioselective Michael-type Friedel-Crafts alkylations of indoles with nonchelating alpha,beta-unsaturated alkyl ketones, catalysed by a chiral primary amine derived from natural cinchonine, were investigated. The reactions, in the presence of 30 mol% catalyst, were smoothly conducted at 0 to -20 degrees C. Moderate to good ee (47-89%) has been achieved.